US011311473B2

( 12) United States Patent ( 10 ) Patent No .: US 11,311,473 B2

Fischer et al . (45) Date of Patent : *Apr . 26 , 2022
(54) USE OF A BIO - BASED POLYMER IN A 2,905,565 A 9/1959 Dietz
COSMETIC , DERMATOLOGICAL OR 3,052,628 A 9/1962 Stanberry, Jr.
3,236,733 A 2/1966 Karsten
PHARMACEUTICAL COMPOSITION 3,509,113 A 4/1970 Monagle
3,544,597 A 12/1970 Killam
( 71 ) Applicant: Clariant International Ltd. , Muttenz 3,753,196 A 8/1973 Kurtz
( CH ) 3,761,418 A 9/1973 Parran
3,937,721 A 2/1976 Schroeck
( 72 ) Inventors : Dirk Fischer , Hahnheim ( DE ) ; 3,960,918 A 6/1976 Schroeck
Christoph Kayser, Mainz (DE ); 4,015,991 A 4/1977 Persinski
4,138,430 A 2/1979 Stiles
Gundula Starkulla , Mainz (DE ) 4,323,683 A 4/1982 Bolich , Jr.
4,342,653 A 8/1982 Halverson
( 73 ) Assignee : CLARIANT INTERNATIONAL LTD , 4,345,080 A 8/1982 Bolich , Jr.
Muttenz ( CH ) 4,379,753 A 4/1983 Bolich , Jr.
4,470,982 A 9/1984 Winkler
( * ) Notice: Subject to any disclaimer, the term of this 4,487,864 A 12/1984 Bermudez
patent is extended or adjusted under 35 ( Continued )
U.S.C. 154 (b ) by 0 days.
FOREIGN PATENT DOCUMENTS
This patent is subject to a terminal dis
claimer. CN 101066940 A 11/2007
CN 101636381 A 1/2010
( 21 ) Appl. No .: 16 /468,659 (Continued )
( 22 ) PCT Filed : Dec. 4 , 2017 OTHER PUBLICATIONS
(86) PCT No .: PCT / EP2017 /081417 Adhikary et al , Synthesis, characterization , and application of
$ 371 (c ) ( 1 ) , amylopectin -graft-poly ( AM - co - AMPS ), Journal of Applied Poly
( 2 ) Date: Jun . 11 , 2019 mer Science (2012 ) , 126(S1 ) , 6 pages .
Anonymous, “ Bio - based material -Wkipedia, the free encyclope
( 87 ) PCT Pub . No .: WO2018 /108611 dia ” , (Mar. 12 , 2015 ) , URL : https://en.wikipedia.org/wiki/Bio-based
g

PCT Pub . Date : Jun . 21 , 2018 material, ( Sep. 1 , 2016 ) , XP055299147 .

(Continued )
( 65 ) Prior Publication Data
US 2020/0078287 A1 Mar. 12 , 2020 Primary Examiner — Jyothsna A Venkat
( 30 ) Foreign Application Priority Data (74 ) Attorney, Agent, or Firm — Tod A. Waldrop
Dec. 12 , 2016 (EP ) 16203549 ( 57 ) ABSTRACT
( 51 ) Int . Ci . The present invention relates to the use of a polymer in a
A61Q 5700 ( 2006.01 ) cosmetic , dermatological or pharmaceutical composition,
A610 19/00 (2006.01 ) wherein the polymer is crosslinked or non -crosslinked,
A61K 8/81 ( 2006.01)
A61K 8/04 (2006.01 ) characterized in that the polymer comprises at least 9.49
A61K 8/06 ( 2006.01 ) mol- % of repeating units ( a) according to Formula ( 1 )
A61K 4732 (2006.01 ) wherein at least 10 wt .- % , preferably at least 20 wt .- % of the
( 52) U.S. CI . repeating units according to Formula ( 1 ) comprise from 28
CPC A61K 8/8158 (2013.01 ) ; A61K 8/042 wt .- % to 100 wt .- % bio -based carbon content, relative to the
(2013.01 ) ; A61K 8/062 (2013.01 ) ; A61K 47/32 total mass of carbon in the repeating unit according to
(2013.01 ) ; A61Q 5/00 (2013.01 ) ; A61Q 19/00 Formula ( 1 ) , measured according to standard ASTM D6866
( 2013.01 ) ; A61K 2800/10 (2013.01 ) ; A61K 12 , Method B
2800/48 (2013.01 )
( 58 ) Field of Classification Search
None (
)
1
1
See application file for complete search history. Hz qR' +
+ CH2 - ÇR ! +
( 56 )

2,614,989
References Cited
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 US 11,311,473 B2
Page 2

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U.S. Patent Apr. 26 , 2022 Sheet 1 of 3 US 11,311,473 B2

FIG . 1
30000

25000

20000

15000

10000

5000

0
0,5 1 1,5 N 2,5
X
U.S. Patent Apr. 26 , 2022 Sheet 2 of 3 US 11,311,473 B2

FIG . 2

30000

25000

20000

15000
1

10000

5000

0
0 2 4 6 8 10 12 14
U.S. Patent Apr. 26 , 2022 Sheet 3 of 3 US 11,311,473 B2

FIG . 3

80000
70000
60000
50000
40000
30000
20000
10000
0
N 66 8 10 12 14
X
 US 11,311,473 B2
1 2
USE OF A BIO -BASED POLYMER IN A material for polyisobutene rubbers and other downstream
COSMETIC , DERMATOLOGICAL OR products such as tert. -butanol, iso -octanol, branched alkanes
PHARMACEUTICAL COMPOSITION or branched alcohols. WO 2016/042011 (Global Bioener
gies ) describes an enzymatic method for the production of
FIELD OF THE INVENTION 5 isobutene from 3 -methylcrotonyl - CoA . WO 2014/004616
(Gevo Inc ) discloses the synthesis of isobutanol by recom
The present invention relates to the use of a polymer in a binant yeast microorganisms. The catalytic dehydration
cosmetic, dermatological or pharmaceutical composition , leads to isobutene .
wherein the polymer is crosslinked or non -crosslinked , WO 2015/034948 (MYRIANT CORP ) describes the syn
characterized in that the polymer comprises at least 9.49 10 thesis of bio -based acrylic acid by dehydration of 1,3
mol- % of repeating units (a ) according to Formula ( 1 ) , propandiol and subsequent oxidation of the allylic alcohol .
wherein at least 10 wt .- % , preferably at least 20 wt .- % of the Nevertheless, the availability of more renewable poly
repeating units according to Formula ( 1 ) comprise from 28 mers suitable for use as components in cosmetic, dermato
wt .- % to 100 wt .- % bio -based carbon content. logical or pharmaceutical composition e.g. as thickening
15 agents, is highly limited . Furthermore, there is a need for
BACKGROUND OF THE INVENTION components that can be used as thickening agents and
rheology modifiers , where such components that are not
Many materials employed for use as thickeners or rheol- only more renewable , but also provide excellent perfor
ogy modifiers are traditionally derived from crude oil . mance in cosmetic , dermatological or pharmaceutical com
Environmental, economic and sustainability questions are 20 position . There is a need , therefore, for providing polymers
restricting the use of products derived from this limited that can provide the excellent performance of modern poly
resource : synthetic surfactants , for example, have been mers yet from more sustainable sources.
blamed for environmental incidents, particularly vis - à - vis
aquatic problems in rivers and lakes. Therefore, there is a SUMMARY OF THE INVENTION
desire to identify more sustainable and biodegradable, yet 25
gentle and effective materials . Indeed , consumers are very In aa first aspect , the present invention relates to the use of
interested in “ natural” products including products with a a polymer in a cosmetic , dermatological or pharmaceutical
high percentage of " natural " compounds and /or compounds composition, wherein the polymer is crosslinked or non
that are derived from renewable materials. Consumers per- crosslinked, characterized in that the polymer comprises at
ceive compounds derived from natural materials to be 30 least 9.49 mol-% of repeating units (a) according to Formula
gentler and more environmentally friendly . Recent industrial ( 1 ) wherein at least 10 wt .- % , preferably at least 20 wt .- %
developments in “ bio -based ” chemicals are summarised, for of the repeating units according to Formula ( 1 ) comprise
example, in de Jong et al , “ Product developments in the from 28 wt .- % to 100 wt .- % bio - based carbon content,
bio -based chemicals arena ” , Biofuels, Bioprod. Bioref. relative to the total mass of carbon in the repeating unit
6 : 606-624 (2012). 35 according to Formula ( 1 ) , measured according to standard
Recently, classical monomers such as ethylene, acrylic ASTM D6866-12 , Method B ;
acid or methyl methacrylate have been disclosed as being
produced with renewable raw materials . US 2014/0154758
(Arkema ) discloses the preparation of methyl methacrylate 1
(
)(1
wherein the method comprises the use of acetone cyanohy- 40 + CH2 - ÇR ! +
drin as a raw material, said acetone cyanohydrin being
obtained by condensing cyanohydric acid in acetone , and the -O Q +
methyl methacrylate is prepared using a process involving R2
the addition of methanol. Acetone and methanol can be
sourced from renewable feedstock . DE 2655891 (DU 45
PONT ) discloses the oxidation from 1 -propanol to acrylates. wherein
U.S. Pat . No. 4,138,430 ( DU PONT ) discloses the ammoxi- R and R2 are independently selected from H , methyl or
dation of 1 -propanol to form acrylonitrile . ethyl; A is a linear or branched C - C12 -alkyl group ; and Q *
Different synthetic routes for the synthesis of bio -based is H , NH4+ , organic ammonium ions [NHR RÖR? ] *
acrylonitrile are described by M. Olga Guerrero - Péreza and 50 wherein R5 , R , and R ’ independently of one another may be
Miguel A. Bañares in Catalysis Today 239 ( 2015 ) 25-30 . hydrogen, a linear or branched alkyl group having 1 to 22
The process for the direct production of acrylonitrile from carbon atoms, a linear or branched , singularly or multiply
glycerol was described recently by M. O. Guerrero -Pérez , unsaturated alkenyl group having 2 to 22 carbon atoms , a
M. A. Bañares , ChemSusChem 1 (2008 ) 511 and by M. A. Co - C22 alkylamidopropyl group , a linear mono-hydroxyal
Bañares, M. O. Guerrero -Pérez, Appl. Catal . B (2013 ), as 55 kyl group having 2 to carbon atoms or a linear or branched
well as in US 20100048850A1 (Arkema) and WO dihydroxyalkyl group having 3 to carbon atoms , and where
2009063120A1 ( CONSEJO SUPERIOR DE INVESTIGA- at least one of the radicals RS , Ró , and R7 is not hydrogen,
CIONES CIENTÍFICAS ). or Q * is Li * , Na + , K+ , 1/2 Ca++ , 1/2 Mg ++ , 1/2 Zn++ , 1/3 Al *** ,
Bio -based propylene can directly been used in the so- or combinations thereof.
called SOHIO process to form acrylonitrile. U.S. Pat . No. 60 Other aspects relate to compositions
? , methods, uses , and
2,904,580 (STANDARD OIL CO ) describes the ammoxi processes related to the polymer disclosed in the first aspect .
dation of propylene according to the so - called SOHIO
process. BRIEF DESCRIPTION OF THE FIGURES
WO 2014086780 (Global Bioenergies) discloses a fer
mentation method for several olefins including propene and 65 FIG . 1 : Viscosity dependence on polymer concentration;
isobutene. Propene can be used as a raw material for the measured in deionized water (Brookfield RVDV - 1, 20 ° C. ,
ammoxidation to acrylonitrile. Isobutene is an important raw 20 rpm ). The x - axis shows the concentration of polymer in
 US 11,311,473 B2
3 4
wt .- % . The y - axis shows the viscosity in mPa.s. Polymer than one species fall within the scope of the ingredient
B1 / 16 ( according to the invention ; solid line ) and a com- definition, the total amount of all ingredients fitting that
parative polymer B1 / 16 # are compared ( broken line ). definition, in the composition . For example, if the compo
FIG . 2 : Viscosity dependence on pH ; 1.0 wt . % polymer sition comprises from 1 % to 5 % fatty alcohol , then a
measured in deionized water ( Brookfield RVDV -1, 20 ° C. , 5 composition comprising 2 % stearyl alcohol and 1 % cetyl
20 rpm ). The x - axis shows the pH . The y - axis shows the alcohol and no other fatty alcohol , would fall within this
viscosity in mPa.s. Polymer B1 / 16 ( according to the inven- scope .
The following acronyms are used herein :
tion ; solid line) and a comparative polymer B1 / 16 # are
compared (broken line ). ACDMT = acryloyldimethyltaurate ; AM - acrylamide;
FIG . 3 : Viscosity dependence on pH ; 1.0 wt . % polymer 10 AN = acrylonitrile ; tBAM = tert.-butyl acrylamide;
measured in deionized water (Brookfield RVDV - 1, 20 ° C. , IBSA = isobutene sulfonic acid ; IBDSA = 2 -methylidene- 1,3
20 rpm ). The x - axis shows the pH . The y - axis shows the propylenedisulfonic acid . Unless otherwise stated , " viscos
viscosity in mPa.s. Polymer A1 /2 ( according to the inven- ity” herein is measured at 20 ° C. viscosity in centipoise (CP )
tion ; solid line ) and a comparative polymer A1 /2 # are or mPa.s using a Brookfield viscometer model LV , RVT
compared (broken line ). 15 DV - II or LVT DV - II with 10-90 % torque at 20 rpm .
“ Molecular weight ” or “M.Wt.” “ M ”, “Mw ” or “ MW ”
w
DETAILED DESCRIPTION OF THE and grammatical equivalents mean the weight average
INVENTION molecular weight, unless otherwise stated . Also relevant for
the determination of the molecular weight distribution is the
Definitions and General 20 number average molecular weight “ Mn ” , “ M ,” and gram n
matical equivalents , and the polydispersity “ D ” or “ PD " .
In this document, including in all embodiments of all The weight average molecular weight can be measured by
aspects of the present invention , the following definitions gel permeation chromatography ( GPC ) , also referred to as
apply unless specifically stated otherwise . All percentages size exclusion chromatography ( SEC ) . The molecular
are by weight ( w / w ) of the total composition. " wt.- % ” 25 weight of polymers and its measurement is described in the
means percentage by weight; “ vol.- % ” means percentage by textbook “ Principles of Polymerization " by Georg Odian ,
volume ; “ mol- % ” means percentage by mole . All ratios are third edition, Wiley - Interscience , New York , in chapter 1-4 ,
weight ratios. References to “parts ' e.g. a mixture of 1 part page 19 to 24 , ISBN 0-471-61020-8 . The process to deter
X and 3 parts Y, is a ratio by weight. “ QS” or “ QSP ” means mine the weight average molecular weight is described in
sufficient quantity for 100 % or for 100 g . +/- indicates the 30 detail in chapter 3 of Makromolekulare Chemie: Eine
standard deviation . All ranges are inclusive and combinable . Einführung" by Bernd Tieke, Wiley - VCH , 2. vollständig
The number of significant digits conveys neither a limitation üiberarbeitete und erweiterte Auflage ( 3. Nachdruck 2010 )
on the indicated amounts nor on the accuracy of the mea- ISBN - 13 : 978-3-527-31379 page 259-261 .
surements. All numerical amounts are understood to be Determination of molecular weight and distribution of
modified by the word “ about ” . All measurements are under- 35 ACDMT samples by GPC was determines under the fol
stood to be made at 23 ° C. and at ambient conditions, where lowing conditions.
“ ambient conditions” means at 1 atmosphere ( atm ) of pres- Column : PSS Suprema 30,000 Å 10 um , 300 mmx8 mm
sure and at 50% relative humidity. “ Relative humidity ” Detector : RID
refers to the ratio ( stated as a percent) of the moisture Oven temperature: 23 ° C.
content of air compared to the saturated moisture level at the 40 Flow : 1 mlmin
/
same temperature and pressure. Relative humidity can be Injection volume: 20 ul
measured with a hygrometer, in particular with a probe Eluent: 0.07 mol /I disodium hydrogen phosphate in water
hygrometer from VWR® International. Herein “ min ” means Calibration method : Conventional poly ( styrene sulfonate )
" minute " or " minutes " . Herein “ mol” means mole . Herein sodium salt calibration Sample preparation : Weigh approx .
“ g” following a number means “ gram ” or “ grams ”. “ Ex . ” 45 10 mg sample in 10 ml 0.07 mol/I disodium hydrogen
means “ example ” . All amounts as they pertain to listed phosphate in water and shake for 15 min .
ingredients are based on the active level ( “ solids ' ) and do not “ Water- soluble ” refers to any material that is sufficiently
include carriers or by -products that may be included in soluble in water to form aa clear solution to the naked eye at
commercially available materials . Herein , " comprising" a concentration of 0.1 % by weight of the material in water
means that other steps and other ingredients can be in 50 at 25 ° C. The term “ water-insoluble” refers to any material
addition . “ Comprising” encompasses the terms " consisting that is not " water - soluble ” .
of" and " consisting essentially of " . The compositions, for- “ Substantially free from ” or “ substantially free of means
mulations, methods, uses , kits , and processes of the present less than 1 % , or less than 0.8 % , or less than 0.5 % , or less
invention can comprise , consist of, and consist essentially of than 0.3 % , or about 0 % , by total weight of the composition
the elements and limitations of the invention described 55 or formulation .
herein , as well as any of the additional or optional ingredi- “ Monomer ” means a discrete, non -polymerised chemical
ents, components , steps, or limitations described herein . moiety capable of undergoing polymerisation in the pres
Embodiments and aspects described herein may comprise or ence of an initiator or any suitable reaction that creates a
be combinable with elements , features or components of macromolecule e.g. such as polycondensation , polyaddition,
other embodiments and / or aspects despite not being 60 radical, anionic or cationic polymerization. “ Unit ” means a
expressly exemplified in combination , unless an incompat- monomer that has already been polymerised i.e. is part of a
ibility is stated . “ In at least one embodiment ” means that one polymer.
or more embodiments, optionally all embodiments or a large “ Polymer ” means a chemical formed from the polymeri
subset of embodiments, of the present invention has/have sation of two or more monomers. The term “ polymer ” shall
the subsequently described feature. Where amount ranges 65 include all materials made by the polymerisation of mono
are given , these are to be understood as being the total mers as well as natural polymers . Polymers made from only
amount of said ingredient in the composition, or where more one type of monomer are called homopolymers . Herein , a
 US 11,311,473 B2
5 6
polymer comprises at least two monomers . Polymers made such microbes are commercially available. ACDMT itself is
from two or more different types of monomers are called not similar to any other products that typical microbes would
copolymers . The distribution of the different monomers can produce naturally. Furthermore , there are few natural micro
be random , alternating or block - wise (i.e. block copolymer ). bial pathways capable of converting sulfonic acid groups.
The term “ polymer” used herein includes any type of 5 Therefore, the person skilled in the art naturally has a bias
polymer including homopolymers and copolymers. in his mind that it would be difficult to produce bio - based
" Fuming sulfuric acid ” herein means a solution of sulfur ACDMT in view of its more synthetic -type chemical moi
trioxide in sulfuric acid . Fuming sulfuric acid is also known eties . The person skilled in the art may, however, consider
as oleum and is identified by the CAS number 8014-95-7 , that the reaction of acrylic acid with taurine as bio -based
and can be described by the formula H2SO4.xSO , where x 10 materials could form the corresponding acryl-amido taurate
is the molar free sulfur trioxide content. compound, which is a similar structure as compared to
The “ biobased content " is reported in ASTM D6866-12 , ACDMT. However, the reactants would preferentiality react
Method B ( see section 3.3.9 of ASTM D6866-12 ) . to form a Michael adduct, rather than an acryl- amido taurate
“ Biobased carbon content” , “ biobased content” , “ biogenic compound . Hence , it would be known to the person skilled
carbon content ”, “ bio -based content” , “ biomass - derived car- 15 in the art that synthesising bio - based ACDMT is no trivial
bon ” herein refer to the same thing and are all measured in matter.
wt .- % . Herein , the term “ bio -based carbon content is used . Bianca et al (Appl Microbiol Biotechnol (2012 ) 93: 1377
ASTM D6866-12 , Method B lab results report the percent- 1387 ) states that a high level of impurities are produced
age of bio -based carbon content relative to total carbon, and when bio -based isobutene is synthesised ( 2/3 carbon diox
not to total mass of the sample or molecular weight. A 20 ide ) . WO 2014086780A2 on pages 5 and 6 mentions various
comment on bio - based carbon content calculation : Presently by -products and impurities that may result from when the
ASTM D6866-12 , Method B ( see section 9 of ASTM bio -based isobutene is synthesised. Indeed , on page 14 of
D6866-12 ) requires the percent modern carbon value (PMC ) WO 2014086780A2 it states “ The fermentation off -gas (i.e.
reported to be multiplied by a correction factor of 0.95 to a gas stream originating from the fermenter) typically com
account for excess carbon - 14 in the atmosphere due to 25 prises the hydrocarbon as the desired product and the
nuclear weapons testing. However, a revision is pending for intermediate together with additional gaseous components.
ASTM D6866-12 , Method B to update the correction factor Generally, the total content of the desired product, such as
to 0.98 due to ongoing decrease in excess atmospheric isobutene , and the intermediate, such as acetone , in the
14CO2 . For the purposes of accuracy, the new correction fermentation off -gas is in a range of 3 to 30 vol .- % ,
factor of 0.98 is often reported in the field e.g. by suppliers . 30 preferably 3 to 20 vol .- % . ” . In other words , it is known in the
Generally, results below ~20% bio - based carbon will not be art that a very low yield results when known bio - based
affected . However, results close to 100 % will be ~2-3 % isobutene synthesis processes are employed, as well as that
bio -based carbon higher using the 0.98 factor vs 0.95 . a significant level of by -products is produced. Indeed, nor
Results between ~20-90% will increase by 0-3 % . Hence the mally at least 98 % , typically at least 99.5 % purity of
term “ bio - based carbon content” as used herein is defined by 35 isobutene is used in conventional synthesis techniques .
the equation : Surprisingly, it is possible to produce bio -based ACDMT
Bio - based carbon content= pMC * 0.95 ( % )
despite using bio -based components that are typically
impure in view of the microbes that produce the bio - based
A review on measurement methods of bio -based carbon component creating by -products as a result of their natural
content for biomass - based chemicals and plastics is given by 40 enzymatic action . International patent application PCT/
Massao Kunioka in Radioisotopes, 62 , 901-925 (2013 ) . EP2017/ 064977 (claiming priority from European patent
" Hair ” means mammalian keratin fibres including scalp application 16175218.3 filed on 20 Jun . 2016 ) in the name
hair, facial hair and body hair. It includes such hair still being of Clariant International Ltd , the disclosure of which is
attached to a living subject and also hair that has been incorporated herein by reference, discloses the synthesis of
removed therefrom such as hair swatches and hair on a 45 bio -based acryloyldimethyltaurate, which can be used as a
doll /mannequin . In at least one embodiment, “ hair ” means monomer for the polymer according to the present inven
human hair . “ Hair shaft” or “ hair fibre ” means an individual tion .
hair strand and may be used interchangeably with the term Furthermore it has surprisingly been found that polymers
" hair." containing such novel bio - based components can be synthe
“ Cosmetically acceptable ” means that the compositions, 50 sised . Such polymers may be, for example, crosslinked
formulations or components described are suitable for use in copolymers .
contact with human keratinous tissue without undue toxicity, The present invention relates inter alia to a cosmetic or
incompatibility, instability, allergic response, and the like . dermatological composition comprising polymers compris
All compositions and formulations described herein which ing at least one unit from bio -based ACDMT or similar
have the purpose of being directly applied to keratinous 55 compounds. The bio -based ACDMT is characterized in that
tissue are limited to those being cosmetically acceptable . at least one portion of the carbons thereof is biologically
sourced and, more specifically, in that it can contain between
Explanation of and Benefits Provided by the 38 wt .- % and 100 wt .- % bio - based carbon content in relation
Invention to total carbon weight according to the ASTM D6866-12 ,
60 Method B standard . The preparation method of ACDMT
Surprisingly, it has now been found that it is possible to typically comprises the use of acrylonitrile, isobutene and a
synthesise good quality bio -based ACDMT at acceptable mixture of sulfuric acid and fuming sulfuric acid comprising
yields . This bio - based ACDMT can be used for synthesising sulfur trioxide. Preferably, at least one of the raw materials,
a polymer for use in the cosmetic or dermatological com- acrylonitrile or isobutene , are of bio -based origin . The
position according to the present invention. 65 bio- based ACDMT is suitable to make polymers comprising
Indeed , when considering genetically engineered a bio -based carbon content stemming from its bio - based
microbes for use in creating bio -based ACDMT, currently no ACDMT share. The present invention provides the use of
 US 11,311,473 B2
7 8
such polymers in a cosmetic , dermatological or pharmaceu-
a kyl group having 2 to carbon atoms or a linear or branched
tical composition and the compositions themselves. dihydroxyalkyl group having 3 to carbon atoms , and where
ACDMT ( see Formula [ 3 ] ) consists of seven carbon at least one of the radicals RS , R ' , and R’ is not hydrogen ,
9

atoms . Preferably a minimum of three, preferably four and or Q+ is Li+ , Na+ , K+ , 12 Cat+ , 12 Mg++ , 12 Zn ++, 13 A1+++
++

most preferred all seven carbon atoms of the ACDMT 5 or combinations thereof.
molecule can become renewable , bio - based carbon atoms . In For brevity, cosmetic , dermatological or pharmaceutical
this way, a high proportion of bio - based and / or biodegrad- composition is referred to simply as “ composition ” herein .
able ( polymer ) products made from the bio - based monomer In at least one embodiment, the composition is for treating
ACDMT are recyclable and part of the natural carbon cycle . 10
keratinous material, preferably for treating hair and / or skin .
If these kinds of products are incinerated or biodegraded, the In at least one embodiment, the use of the polymer according
quantity of carbon dioxide that is emitted corresponds to the to the first aspect is as a thickening agent or rheology
quantity fixed by photosynthesis during biomass growth . modifier in a cosmetic , dermatological or pharmaceutical
composition.
15 In at least one embodiment, the composition comprises a
CH3
(3 ) cosmetically acceptable component. Suitable cosmetically
acceptable components are mentioned in the second
SO3- Xt aspect — such cosmetically acceptable components are com
H3C patible and combinable with the first aspect . In at least one
20 embodiment, the cosmetically acceptable component is
selected from the group consisting of surfactants, auxiliaries,
To date several high performance water soluble or water hair conditioning agents, hairstyling polymers, and combi
swellable polymers such as Fluid Loss Additives for the nations thereof. Surfactants, auxiliaries, hair conditioning
construction and (oil and gas ) well construction industry as agents and hairstyling polymers are disclosed in the second
well as rheology modifiers, comprise ACDMT. Independent 25 aspect — such cosmetically acceptable components are com
from the excellent performance in their applications , such patible and combinable with the first aspect .
polymers have so - far all been made from petrochemical In at least one embodiment, the composition is selected
based, fossil hydrocarbon based ACDMT. The present from the group consisting of shampoo, body wash , facial
invention provides new polymers comprising units from cleanser, face mask, bubble bath , intimate wash , bath oil ,
bio -based ACDMT or similar compounds (see Formula ( 1 )) , 30 cleansing milk, micellar water, make - up remover, cleansing
thus giving access to the use of such polymers in aa cosmetic , wipes , hair mask , perfume, liquid soap , shaving soap , shav
dermatological or pharmaceutical composition and the com ing foam , cleansing foam , day cream , anti-ageing cream ,
positions themselves. Such new compositions having the body milk , body lotion , body mousse , face serum , eye
excellent performance benefits that compositions absent of cream , sunscreen lotion , sun cream , face cream , after -shave
bio -based polymers are already known for. 35 lotion, pre -shaving cream , depilatory cream , skin -whitening
The details of the invention and its aspects are provided gel, self-tanning cream , anti -acne gel, mascara, foundation,
hereinafter. primer, concealer, blush , bronzer, blemish balm (bb ) cream ,
First Aspect eyeliner, night cream , eye brow gel , highlighter, lip stain ,
The first aspect relates to the use of a polymer in a hand sanitizer, hair oil , nail varnish remover , conditioner,
cosmetic , dermatological or pharmaceutical composition, 40 hair styling gel , hair styling cream , anti- frizz serum , scalp
wherein the polymer is crosslinked or non -crosslinked , treatment, hair colorant, split end fluid , deodorant, antiper
characterized in that the polymer comprises at least 9.49 spirant, baby cream , insect repellent, hand cream , sunscreen
mol- % of repeating units ( a) according to Formula ( 1 ) gel , foot cream , exfoliator, body scrub , cellulite treatment,
wherein at least 10 wt .- % , preferably at least 20 wt .- % of the bar soap , cuticle cream , lip balm , hair treatment, eye
repeating units according to Formula ( 1 ) comprise from 28 45 shadow, bath additive, body mist , eau de toilette, mouth
wt .- % to 100 wt .- % bio -based carbon content, relative to the
wash , toothpaste, lubricating gel , moisturizer, serum , toner,
total mass of carbon in the repeating unit according to aqua sorbet, cream gel , styling mousse , dry shampoo , lip
Formula ( 1 ) , measured according to standard ASTM D6866- stick , lip gloss , hydro - alcoholic gel , body oil , shower milk ,
12 , Method B ; illuminator, lip crayon , hair spray, combing cream , and
50 sunblock .
The first aspect relates to the use of a polymer in a
(1) composition as defined herein . In at least one embodiment,
FCH2 -ÇR ! + the composition comprises at least 0.1 wt .- % , or at least 0.2

wherein
N - A
R2 1+ Q+
wt .- % , or at least 0.3 wt .- % , or at least 0.4 wt .- % , or at least
55 0.5 wt .- % , or at least 0.6 wt .- % , or at least 0.7 wt .- % , or at
least 0.8 wt .- % , or at least 0.9 wt .- % , or at least 1.0 wt .- % ,
or at least 1.1 wt .- % , or at least 1.2 wt .- % , or at least 1.3
wt .- % , or at least 1.4 wt .- % , or at least 1.5 wt .- % , or at least
1.6 wt .- % , or at least 1.5 wt .- % , or at least 1.6 wt .- % , or at
R ! and Rº are independently selected from H , methyl or 60 least 1.7 wt .-% , or at least 1.8 wt .-% , or at least 1.9 wt.-% ,
ethyl; A is aa linear or branched C - C12 - alkyl group ; and Q * or at least 2.0 wt .- % of the polymer.
is H * , NH4+, organic ammonium ions [NHR?R?R ] *
> In at least one embodiment, the polymer is aa crosslinked
wherein R” , Rº , and R independently of one another may be or non - crosslinked homopolymer . In at least one embodi
hydrogen, a linear or branched alkyl group having 1 to 22 ment, the polymer is aa crosslinked or non - crosslinked copo
carbon atoms, a linear or branched , singularly or multiply 65 lymer. In at least one embodiment, the polymer has a weight
unsaturated alkenyl group having 2 to 22 carbon atoms , a average molecular weight of at least 700 g /mol, preferably
C6 - C22 alkylamidopropyl group , a linear mono -hydroxyal- from 700 g /mol to 10 million g/mol .
 US 11,311,473 B2
9 10
In at least one embodiment, the polymer is a derived In at least one embodiment, the polymer comprises at
natural cosmetic ingredient. According to ISO 16128-1 : 2016 least one repeating unit according to Formula ( 1 ) . In at least
( E) a polymer is a derived natural cosmetic ingredient if it one embodiment, the polymer comprises two or more dif
is of greater than 50 % natural origin by renewable carbon ferent repeating units according to Formula ( 1 ) , such as
content . The degree of natural origin can be quantified by 5 repeating units according to Formula ( 1 ) having different Q*
renewable carbon content according to analytical procedure counterions .
ASTM 6866-12 , Method B. In at least one embodiment, the repeating units according
Units (a) to Formula ( 1 ) have a degree of neutralisation of between 0
In at least one embodiment, the polymer comprises from
9.49 mol- % to 98 mol- % , preferably from 27.5 mol- % to 10 mol- % and 100 mol- % . In at least one embodiment, the
repeating units according to Formula ( 1 ) have a degree of
97.4 mol- % of repeating units (a ) according to Formula ( 1 ) neutralisation of from 50.0 to 100 mol- % , preferably from
wherein at least 10 wt .- % , preferably at least 20 wt .- % of the 80 mol- % to 100 mol- % , more preferably from 90.0 to 100
repeating units (a ) according to Formula ( 1 ) comprise from mol- % , even more preferably from 95.0 to 100 mol- % .
28 wt .- % to 100 wt .- % bio - based carbon content, relative to
the total mass of carbon in the repeating unit according to 15 Particular preference being given to a degree of neutralisa
tion of more than 80 mol- % , more preferably more than 90
Formula ( 1 ) , measured according to standard ASTM D6866 mol- % , even more preferably more than 95 mol- % . The
12 , Method .
In at least one embodiment, the polymer comprises from degree of neutralisation is important in view of the molecu
40 to 98 mol- % , preferably from 55 mol- % to 98 mol- % of lar weight of the polymer and the yield of polymer produced .
repeating units ( a) according to Formula ( 1 ) wherein at least 20 The repeating units according to Formula ( 1 ) comprise
10 wt .- % , preferably at least 20 wt .- % of the repeating units from 28 wt .- % to 100 wt .- % bio - based carbon content,
( a) according to Formula ( 1 ) comprise from 28 wt .- % to 100
be relative to the total mass of carbon in the repeating unit
wt .- % bio - based carbon content, relative to the total mass of according to Formula ( 1 ) , measured according to standard
carbon in the repeating unit according to Formula ( 1 ) , ASTM D6866-12 , Method B. In at least one embodiment,
measured according to standard ASTM D6866-12 , Method. 25 the repeating unit comprises from 35 wt .-% , preferably from
In at least one embodiment, the polymer comprises from 40 wt .- % , more preferably from 54 wt .- % , even more
90 mol- % to 99.9 mol- % , preferably from 95 mol- % to 99.5 preferably from 57 wt .- % to 100 wt .- % , most preferably
mol- % of repeating units ( a) according to Formula ( 1 ) about 100 wt .- % , by mass of bio -based carbon content,
wherein at least 10 wt .- % , preferably at least 20 wt .- % of the relative to the total mass of carbon in the repeating unit
repeating units (a) according to Formula ( 1 ) comprise from 30 according to Formula ( 1 ) , measured according to standard
28 wt .- % to 100 wt .- % bio - based carbon content, relative to ASTM D6866-12 , Method B.
the total mass of carbon in the repeating unit according to In at least one embodiment, the repeating units according
Formula ( 1 ) , measured according to standard ASTM D6866 to Formula ( 1 ) result from the incorporation of a monomer
12 , Method . selected from the group consisting of acryloyldimethyltau
In at least one embodiment, the polymer comprises at 35 rates , acryloyl- 1,1 -dimethyl -2 -methyltaurates (ACDMT),
least 99 mol- % , preferably about 100 mol- % of repeating acryloyltaurates , acryloyl - N -methyltaurates, and combina
units ( a) according to Formula ( 1 ) wherein at least 10 wt .- % , tions thereof. Preferably the repeating units according to
Formula ( 1 ) result from the incorporation of acryloyldim
preferably at least 20 wt .- % of the repeating units (a ) ethyltaurate
according to Formula ( 1 ) comprise from 28 wt .- % to 100 .
wt .- % bio - based carbon content, relative to the total mass of 40 In at least one embodiment, the polymer comprises from
carbon in the repeating unit according to Formula ( 1 ) , 55 mol- % to 98 mol- % of repeating units according to
measured according to standard ASTM D6866-12 , Method . Formula ( 1 ) wherein at least 30 wt .- % , preferably at least 50
In at least one embodiment, the polymer comprises at least wt .- % , more preferably at least 70 wt .- % of the repeating
99 mol- % , preferably about 100 mol- % of repeating units (a ) units comprises from 28 wt .- % to 100 wt .- % bio - based
according to Formula ( 1 ) wherein at least 50 wt.- % , pref- 45 repeating
carbon content , relative toto Formula
unit according the total( 1mass of carbon
) , measured in the
according
erably at least 80 wt .- % of the repeating units (a ) according
to Formula ( 1 ) comprise from 28 wt .- % to 100 wt .- % to standard ASTM D6866-12 , Method B.
bio -based carbon content, relative to the total mass of carbon Preferably the repeating units according to Formula ( 1 )
in the repeating unit according to Formula ( 1 ) , measured are formed by polymerization of a compound according
according to standard ASTM D6866-12 , Method . 50 Formula ( 3 ) . More preferably the compound according to
In at least one embodiment, the polymer comprises at Formula ( 3 ) is ACDMT.
least one repeating unit according to Formula ( 1 ) wherein R
and R’ are independently selected from H , methyl or ethyl; (3 )
A is a linear or branched C , -C12 - alkyl group ; and Q * is H * ,
++ H CH3
NH4 * , Li * , Na + , K+ , 1/2 Ca +, 1/2 Mg ++ , 1/2 Zn++ , 13 A1 +++ , or 55
combinations thereof, preferably wherein Q + is Na + or SO3 x +
NH4 * . NH4 + is preferred because it is more soluble the H3C
favored solvent used in the polymer synthesis. Nat is
preferred because of reduced likelihood of unpreferred gases
being produced during synthesis and also due to economic 60 wherein X is a proton .
advantages. In at least one embodiment, the compound according to
In at least one embodiment, Q * is NH4 * . In at least one Formula ( 3 ) comprises from 28 wt .- % to 100 wt .- % bio
embodiment, Q7 is selected from the group monoalkylam- based carbon content, relative to the total mass of carbon in
monium , dialkylammonium , trialkylammonium and / or tet- the compound , measured according to standard ASTM
raalkylammonium salts , in which the alkyl substituents of 65 D6866-12 , Method B. In at least one embodiment, the
the amines may independently of one another be (C to compound comprises from 35 wt .- % , preferably from 40
C22 ) -alkyl radicals or ( C2 to C10 )-hydroxyalkyl radicals. wt .- % , more preferably from 54 wt .- % , even more prefer
 US 11,311,473 B2
11 12
ably from 57 wt .- % to 100 wt .- % , most preferably about 100 In at least one embodiment, the crosslinking or branching
wt .- % , by mass of bio - based carbon content, relative to the units result from the incorporation of a monomer according
total mass of carbon in the compound, measured according to Formula ( 4 )
to standard ASTM D6866-12 , Method B. Preferably the
compound according to Formula ( 3 ) is ACDMT. 5

The bio -based carbon content, relative to the total mass of )

4
(
carbon in the compound or unit , is measured according to CR2
standard ASTM D6866-12 , Method B. More details on the
analytical procedure for determination of bio -based carbon 10 H2C + D CH2
content: the provided sample material does not undergo any
pre - treatment procedure and is converted to graphite as is + OFEJR - ÇR!
using the following procedure : Depending on the estimated CR2 C - F1.0
H2
amount of carbon content, typically a few milligrams of CH2 CR2
sample material is combusted in an elemental analyzer ( EA) . 15
+
The resulting gas mixture is cleaned and CO2 is automati CH2
cally separated by the EA using the purge and trap technol
ogy. The remaining Co ,2 is transferred into a custom -made
+
graphitization system , converted into carbon ( graphite) cata
lytically using H , and an iron -powder catalyst . The 14C 20 wherein
determination of the graphite is performed at the Klaus- R ' is independently selected from H , methyl or ethyl; and
Tschira - Archaeometrie - Center using an accelerator mass R² is a linear or branched alkyl group having 1 to 6 carbon
spectrometer (AMS ) of the type MICADAS (developed at atoms , or is a linear or branched , mono- or polyunsatu
the ETH Zurich, Switzerland ). rated alkylene group having 2 to 6 carbon atoms ;
Units ( b ) 25
In at least one embodiment, the polymer comprises cross D , E , and F are independently methyleneoxy CH2O ),
linking or branching units ( b ) , wherein the crosslinking or ethyleneoxy ( CH2 - CH2–0– ), propyleneoxy (CH
branching units result from the incorporation of a monomer ( CH3)-CH2-0– ), a linear or branched alkylene group
comprising at least two olefinically unsaturated double 30 having 1 to 6 carbon atoms , a linear or branched, singu
bonds. In at least one embodiment, the polymer comprises larly or multiply unsaturated alkenylene group having 2 to
from 0.01 mol- % to 5 mol % , preferably 0.01 mol- % to 4 6 carbon atoms , a linear mono -hydroxyalkylene group
mol- % , more preferably from 0.01 mol- % to 2 mol- % of having 2 to 6 carbon atoms or a linear or branched
crosslinking or branching units . dihydroxyalkylene group having 3 to 6 carbon atoms; and
In at least one embodiment, the crosslinking or branching o , p , and q each independently are an integer from 1 to 50 .
units comprise least one oxygen , nitrogen , and sulfur or 35 A monomer according to Formula ( 4 ) has the advantage
phosphorus atom . In at least one embodiment, the crosslink that a polymer can be predicted as being highly branched .
ing or branching units result from monomers having a In at least one embodiment, the crosslinking or branching
molecular weight of less than 500 g /mol. In at least one units result from the incorporation of a monomer selected
embodiment, the units ( b ) are bifunctional or trifunctional 40 from the group consisting of methylenebisacrylamide; meth
crosslinking agents . ylenebismethacrylamide; esters of unsaturated monocarbox
In at least one embodiment, the polymer comprises two or ylic and polycarboxylic acids with polyols , preferably di
more different crosslinking or branching units. In at least one acrylates and tri -acrylatees and -methacrylates ( e.g. glycerol
embodiment, the crosslinking or branching units result from propoxylate triacrylatee [GPTA ] ), more preferably butane
the incorporation of a monomer according to Formula (2 ) : 45 diol and ethylene glycol diacrylate and poly ethylene glycol
diacrylate and -methacrylate, trimethylolpropane triacrylate
(2)
( TMPTA ) and trimethylolpropane trimethacrylate
( TMPTMA ); allyl compounds, preferably allyl (methacry
CR late , triallyl cyanurate , diallyl maleate, polyallyl esters ,
50 tetraallyloxyethane, triallylamine, tetraallylethylenedi
H2C -R2 amine ; allyl esters of phosphoric acid ; and / or vinylphospho
-CR nic acid derivatives. The choice of crosslinking or branching
CH2
units is important in view of the flexibility of the crosslinks
between the main chains of the polymer which affects the
55 final performance of the polymer.
wherein In at least one embodiment, the crosslinking or branching
R is independently selected from H , methyl or ethyl; and units result from the incorporation of a crosslinker selected
R² is aa linear or branched alkyl group having 1 to 6 carbon from the group consisting of trimethylolpropane triacrylatee
atoms, or is a linear or branched , mono- or polyunsatu- ( TMPTA ) and / or glycerol propoxylate triacrylate (GPTA ).
rated alkylene group having 2 to 6 carbon atoms, 60 Particularly preferred as crosslinkers for the polymers of the
( CH , CH - ), n invention are glycerol propoxylate triacrylate (GPTA ), trim
n is a integer from 1 to 100 . ethylolpropane triacrylate ( TMPTA ), pentaerythritol diacry
A monomer according to Formula (2 ) has the advantage late mono stearate (PEAS ) , hexanediol diacrylate (HDDA) ,
that the polymer can be predicted as being more brush -like . poly ethylene glycol diacrylate (PEG - DA) and hexanediol
However, brush - like polymers show different properties, 65 dimethacrylate (HDDMA ). Especially preferred is glycerol
versus linear ones . For example , depending on the different propoxylate triacrylatee (GPTA ) and trimethylolpropane
comonomer units the solubility can be in- or decreased . triacrylatee ( TMPTA ).
 US 11,311,473 B2
13 14
Units (C) wherein at least one of RS , R and R’ is not hydrogen,
In at least one embodiment, the polymer at least one or Z + is Li + , Na+ , K+ , 1/2 Ca ++ , 1/2 Mg ++ , 1/2 Zn ++, 1/3
repeating neutral structural unit (c ) . In at least one embodi A1 +++ , or combinations thereof. In at least one embodi
ment, the polymer comprises (c ) from 0.99 mol- % to 59.99 ment, the Zt is H * , NH4* , Li + , Na + , K+ , 1/2 Ca++ , 1/2
mol- % , preferably from 1.99 mol- % to 44.99 mol- % of 5 Mg ++ , 1/2 Zn ++, or 11 A1 +++ , preferably H + , NH4+ ?, Li * ,
9

repeating neutral structural units ; wherein the repeating Na+ or K+ .

neutral units comprises up to 100 wt .- % bio - based carbon
content, relative to the total mass of carbon in the repeating leastIn one at least one embodiment, the polymer comprises at
repeating anionic structural unit selected from the
unit , measured according to standard ASTM D6866-12 , 10 group consisting of acrylic acid or acrylate methacrylic acid
Method B.
In at least one embodiment, the polymer comprises at or methacrylate , itaconic acid or itaconate, carboxyethyl
least one repeating neutral structural unit selected from the acrylic acid or carboxyethylacrylate , carboxyethylacrylic
group consisting of N -vinylformamide, N -vinylacetamide , acid oligomers or carboxyethylacrylate oligomers , 2-propy
N -methyl - N -vinylformamide, N -methyl - N -vinylacetamide, lacrylic acid or 2 - propylacrylate, 2 -ethylacrylic acid or
N - vinyl- 2 -pyrrolidone, N -vinylcaprolactam , vinylacetate , 15 2 -ethylacrylate, and their respective alkali or alkaline earth
N , N -dimethylacrylamide, N - isopropylacrylamide, acrylam- metal salts . In at least one embodiment, the polymer com
ide , methylacrylate, behenylpolyethoxy-(25 ) -methacrylate , prises at least one repeating anionic structural unit selected
laurylpoly - ethoxy-( 7 )-methacrylate, cetylpolyethoxy-( 10 )- from the group consisting of acrylic acid or acrylate meth
methacrylate, stearylpoly - ethoxy- ( 8 ) -methacrylate, acrylic acid or methacrylate, itaconic acid or itaconate ,
methoxypoly
thereof.
- ethoxy-( 12 ) -methacrylate, and combinations 20 carboxyethylacrylic acid or carboxyethylacrylate, carboxy
ethylacrylic acid oligomers or carboxyethylacrylate oligom
Units ( d )
In at least one embodiment, the polymer comprises at ers , and their respective alkali or alkaline earth metal salts .
least one repeating anionic structural unit . In at least one becauserepeating
These
they can
anionic structural units are preferred
easily be synthesised from bio -based
embodiment, the polymer comprises from 1.98 mol- % to 20 25 sources .
mol- % , preferably from 2.5 mol- % to 18 mol- % ofrepeating
anionic structural units , wherein the repeating anionic struc- Optional Units
tural units result from the incorporation of a monomer In at least one embodiment, the polymer comprises at
comprising at least one carboxylate anion , and wherein the least one optional unit . In at least one embodiment, the
repeating anionic structural units are different from units (a) 30 optional unit results from the incorporation of a monomer
and wherein the repeating anionic structural units comprises selected from the group consisting of unsaturated carboxylic
up to 100 wt .- % bio - based carbon content, relative to the acids and their anhydrides and salts , and also their esters
total mass of carbon in the repeating unit, measured accord with aliphatic , olefinic , cycloaliphatic, arylaliphatic or aro
ing to standard ASTM D6866-12 , Method B.
In at least one embodiment, the repeating anionic struc- 35 matic at
alcohols having a carbon number of from 1 to 22. In
least one embodiment, the optional unit results from the
tural unit results from the incorporation of monomers incorporation of at least one monomer selected from the
according to formula ( A ): group consisting of functionalised (meth )acrylic acid esters ,
acrylic or methacrylic acid amides , polyglycol acrylic or
methacrylic acid esters , polyglycol acrylic or methacrylic
( A ) 40 acid amides, dipropyleneglycolacrylic or methacrylic acid
X - R1
esters, dipropylenglycolacrylic or methacrylic acid amides,
H2C = C ethoxylated fatty alcohol acrylates or methacrylates,
0 propoxylated fatty alcohol acrylates or linear or cyclic
45 N -vinylamides or N -methylvinyl amides .
M -O Z In at least one embodiment, the optional unit results from
the incorporation of monomers according to formula ( A ):
wherein
Rl and R3 are H , methyl or ethyl, or C ( O ) O - Z + ;
X , Y are selected from a covalent bond , O , CH2 , C (O ) O , 50 (A)
X - R
OC ( O ) , C (O )NR or NRC( O );
M are selected from a covalent bond , [C (O )O CH2 H2C ==
CH2] n , a linear or branched alkylene group with 1 to 6 Y 0
carbon atoms, a linear or branched, mono- or polyunsatu | 11
rated alkenylene group with 2 to 6 carbon atoms , a linear 55 M — C — 0 Z+
mono -hydroxyalkylene group with 2 to 6 carbon atoms or
a linear or branched di -hydroxyalkylene group with 3 to
6 carbon atoms; wherein :
n is an integer from 1 to 5 ; and
Zt is H * , NH4 +, an organic ammonium ion [HNRRÓR ? ]+ 60 X , OCY are selected from a covalent bond , O , CH2 , C (O ) O ,
( O ), C (O )NR or NRC (O );
wherein RS , R and R7 are independently hydrogen , a
linear or branched alkyl group with 1 to 22 carbon R1 and R3 are H , methyl or ethyl, or C (O ) O - Z + ;
atoms , a linear or branched , mono- or polyunsaturated M is selected from a covalent bond , — [C ( O )O CH2
alkenyl group with 2 to 22 carbon atoms , a Co6 to C22 CH2 ] n-, a linear or branched alkylene group with 1 to 6
alkylamidopropyl group , a linear mono -hydroxyalkyl 65 carbon atoms, a linear or branched, mono- or polyunsatu
group with 2 to 10 carbon atoms or a linear or branched rated alkenylene group with 2 to 6 carbon atoms , a linear
di-hydroxyalkyl group with 3 to 10 carbon atoms , and mono -hydroxyalkylene group with 2 to 6 carbon atoms or
 US 11,311,473 B2
15 16
a linear or branched di -hydroxyalkylene group with 3 to methacrylate, laurylpolyethoxy- (23 ) -acrylate, cetylpoly
6 carbon atoms; ethoxy-( 2 ) -methacrylate , cetylpolyethoxy-( 2 ) -acrylate,
n is an integer from 1-5 , and cetylpolyethoxy- ( 7 ) -methacrylate, cetylpolyethoxy-( 7 )
Zt is H * , NH . , an organic ammonium ion [HNR RR ? * acrylate, cetylpolyethoxy- (10 )-methacrylate, cetylpoly
>

wherein RS , R and R7 are independently hydrogen , a 5 ethoxy- ( 10 ) -acrylate, cetylpolyethoxy- (12 ) -methacrylate,
linear or branched alkyl group with 1 to 22 carbon cetylpolyethoxy- (12 ) -acrylate cetylpoly - ethoxy-( 16 ) -meth
atoms , a linear or branched, mono- or polyunsaturated acrylate, cetylpolyethoxy- ( 16 ) -acrylate cetyl polyethoxy
alkenyl group with 2 to 22 carbon atoms , a Co to C22 ( 20 ) -methacrylate, cetylpolyethoxy-(20 )-acrylate, cetylpo
6
alkylamidopropyl group , a linear mono -hydroxyalkyl lyethoxy- ( 25 ) -methacrylate , cetylpolyethoxy- (25 )-acrylate,
group with 2 to 10 carbon atoms or a linear or branched 10 cetylpolyethoxy- ( 25 ) -methacrylate , cetylpolyethoxy-(25 )
di-hydroxyalkyl group with 3 to 10 carbon atoms, and acrylate, stearylpolyethoxy - 7 )-methacrylate, stearylpoly
wherein at least one of RS , RÓ and R7 is not hydrogen, ethoxy- ( 7 ) -acrylate, stearylpoly - ethoxy- ( 8 ) -methacrylate,
or Z * is Li * , Na+ , K+ , 1/2 Ca ++ , 1/2 Mg++ , 1/2 Zn ++, 1/3 stearyl polyethoxy- ( 8 )-acrylate, stearylpolyethoxy-( 12 )
A1 +++ , or combinations thereof. In at least one embodi
9
ment,, the Z * is H *+, NH , +, Li+*, Na+, K+, 12 Ca++, 12 15 ethoxy-
methacrylate , stearylpolyethoxy-( 12 )-acrylate, stearylpoly
( 16 ) -methacrylate, stearylpolyethoxy- (16 ) -acrylate,
Mg ++, 1/2 Zn ++, or 1/3 A1+++, preferably H + , NH4 +, Li * ,
+

stearylpolyethoxy- (22 ) -methacrylate, stearyl poly -ethoxy

Na + or K+ .
In at least one embodiment, the optional unit results from (22 ) -acrylate , stearylpolyethoxy- (23 )-methacrylate,
the incorporation of a monomer according to formula (A) stearylpolyethoxy- (23 ) -acrylate, stearylpolyethoxy-(25)
wherein X is a covalent bond or is CH2. In at least one 20 methacrylate, stearylpolyethoxy-(25 ) -acrylate, tridecyl
embodiment, the optional unit results from the incorporation polyethoxy- ( 7 ) -methacrylate , tridecylpolyethoxy-(7 ) -acry
of a monomer according to formula ( A ) wherein Y is a late , tridecylpolythoxy- ( 10 ) -methacrylate , tridecylpoly
covalent bond , CH ,, C ( O ) O , or C ( O )NR3 . In at least one ethoxy- ( 10 )-acrylate, tridecylpolyethoxy- ( 12 ) -methacrylate,
embodiment, the optional unit results from the incorporation tridecylpolyethoxy- (12 ) -acrylate, tridecylpolyethoxy-( 16 )
of a monomer according to formula ( A ) wherein M is a 25 methacrylate, tridecylpolyethoxy-(16 )-acrylate, tridecylpo
covalent bond, [ C ( O ) O - CH2 - CH21n- , a linear or lyethoxy- ( 22 ) -methacrylate, tridecylpoly -ethoxy- (22 )-acry
branched alkylene group with 1 to 6 carbon atoms . In at least late , tridecylpolyethoxy- (23 ) -methacrylate,
one embodiment, the optional unit results from the incor tridecylpolyethoxy- ( 23 )-acrylate, tridecylpoly -ethoxy-( 25 )
poration of a monomer according to formula ( A ) wherein R ! methacrylate , tridecylpolyethoxy-( 25 ) -acrylate, methoxy
is H , methyl or ethyl; X is a covalent bond or is CH2 ; Y is 30 polyethoxy- ( 7 ) -methacrylate, methoxy -polyethoxy-(7 )
a covalent bond, CH,, C (O)O , or C (O )NR ; R3 is H , methyl acrylate, methoxypoly - ethoxy- (12 ) -methacrylate ,
or ethyl; M is a covalent bond , [C (O )O CH2 CH2]n methoxypolyethoxy- (12 )-acrylate, methoxypolyethoxy
a linear or branched alkylene group with 1 to 6 carbon ( 16 ) -methacrylate, methoxypolyethoxy- ( 16 ) -acrylate ,
atoms ; Z + is H * , NH4 + , Li * , Na , K+ , 1/2 Ca ++ , 1/2 Mg++ , 1/2 methoxypolyethoxy- ( 25 ) -methacrylate, methoxy - poly
Zn++ , or 1/3 A1 +++ , or combinations thereof. 35
ethoxy-( 25 ) -acrylate, acrylic acid , ammonium acrylate,
In at least one embodiment, the optional unit results from sodium acrylate, potassium acrylate, lithium acrylate , zinc
the incorporation of a monomer selected from the group acrylate, calcium acrylate , magnesium acrylate , zirconium
consisting of N -vinylformamide, N - vinylacetamide, N
methyl- N - vinylformamide, N -methyl - N -vinylacetamide, acrylate, methacrylic acid, ammonium methacrylate , sodium
N - vinyl- 2 -pyrrolidone (NVP ), N vinylcaprolactam , vinylac- 40 methacrylate, potassium methacrylate, lithium methacrylate,
etate, methylvinylether, ethylvinylether, methylallylether, calcium methacrylate, magnesium methacrylate, zirconium
ethylmethallylether, styrol, acetoxystyrol, methylmethally- methacrylate, zinc methacrylate, 2 -carboxyethylacrylate,
lether, ethylallylether, tert - butylacrylamide, N , N -diethyl- ammonium 2 - carboxyethylacrylate, sodium 2-carboxyethy
acrylamide, N ,N -dimethylacrylamide, N ,N -dimethylmeth- lacrylate , potassium 2 - carboxyethylacrylate, lithium 2 car
acrylamide, N , N -dipropylacrylamide, 45 boxyethylacrylate , zinc 2 - carboxyethylacrylate, calcium
N - isopropylacrylamide, N -propylacrylamide, acrylamide, 2 -carboxyethylacrylate, magnesium 2 -carboxyethylacrylate ,
methacrylamide, methylacrylate, methymethylacrylate, tert- zirconium 2 -carboxyethylacrylate, 2 -carboxyethylacrylate
butylacrylate, tert-butylmethacrylate, n -butylacrylate, oligomere , ammonium 2 - carboxyethylacrylate - oligomers,
n -butylmethacrylate, laurylacrylate,, laurylmethacrylate , sodium 2 -carboxyethylacrylate - oligomers, potassium 2 - car
behenylacrylate , behenylmethacrylate, cetylacrylate, cetyl- 50 boxyethylacrylate -oligomers, lithium 2 carboxyethylacry
methacrylate, stearylacrylate, stearylmethacrylate, tridecy- late - oligomers , zinc 2 - carboxyethylacrylate -oligomers, cal
lacrylate , tridecylmethacrylate, polyethoxy-(5 ) -methacry- cium 2 -carboxyethylacrylate -oligomers, magnesium
late , polyethoxy- (5 ) -acrylate , polyethoxy-( 10 )- 2 -carboxyethylacrylate -oligomers, zirconium 2 -carboxy
methacrylate, polyethoxy- ( 10 )-acrylate, ethylacrylate -oligomers, itaconic acid , sodium itaconate,
behenylpolyethoxy-( 7) -methacrylate, behenylpolyethoxy- 55 potassium itaconate, lithium itaconate, calcium itaconate,
( 7 ) -acrylate, behenylpolyethoxy- ( 8 )-methacrylate, behe- magnesium itaconate, zirconium itaconate , zinc itaconate ,
nylpoly - ethoxy- ( 8 ) -acrylate, behenylpolyethoxy-( 12)-meth- 2 -ethylacryl acid , ammonium 2 - ethylacrylate, sodium
acrylate, behenylpoly -ethoxy- ( 12 ) -acrylate, 2 -ethylacrylate , potassium 2 -ethylacrylate , lithium 2 - ethyl
behenylpolyethoxy- ( 16 ) -methacrylate, behenylpolyethoxy- acrylate, calcium 2 - ethylacrylate, magnesium 2 -ethylacry
( 16 ) -acrylate, behenylpolyethoxy- (25 ) -methacrylate, behe- 60 late , zirconium 2 - ethylacrylate, zinc 2 -ethylacrylate, 2-pro
nylpolyethoxy-(25 ) -acrylate , laurylpoly -ethoxy-(7)-meth- pylacryl acid , ammonium 2 -propylacrylate , sodium
acrylate, laurylpolyethoxy- ( 7 ) -acrylate, laurylpolyethoxy- 2 -propylacrylate , potassium 2 -propylacrylate, lithium 2 -pro
( 8 ) -methacrylate, laurylpolyethoxy-(8 ) -acrylate, pylacrylate, calcium 2 - propylacrylate, magnesium 2 -propy
laurylpolyethoxy-(12 ) -methacrylate, laurylpolyethoxy-(12 )- lacrylate, magnesium 2 -propylacrylate, zirconium 2 -propy
acrylate, laurylpolyethoxy-(16 ) -methacrylate, laurylpoly- 65 lacrylate, zinc 2 -propylacrylate, glycerin propoxylate
ethoxy- ( 16 ) -acrylate, laurylpolyethoxy- (22 ) -methacrylate, triacrylate (GPTA ), trimethylolpropane triacrylate
lauryl polyethoxy-(22 ) -acrylate, laurylpolyethoxy-(23 )- ( TMPTA ), pentaerythritoldiacrylate monostearate ( PEAS ) ,
 US 11,311,473 B2
17 18
polyethyleneglycol diacrylate, hexanediol diacrylate wherein :
( HDDA) , hexanediol dimethacrylate (HDDMA ), and com-
binations thereof.
Rl and R2 are independently selected from H , methyl or
In a preferred embodiment, the optional unit results from ethyl; A is a linear or branched C - C12 - alkyl group ; and
the incorporation of a monomer selected from the group 5 Q + is H+ , NH4+ , organic ammonium ions
consisting of glycerine propoxylate triacrylate (GPTA ) and [NHR RØR ?]* wherein R " , Rº , and Rindependently of
trimethylolpropantriacrylate ( TMPTA ). one another may be hydrogen , a linear or branched
In a preferred embodiment, the optional unit results from alkyl group having 1 to 22 carbon atoms , a linear or
the incorporation of a monomer selected from the group branched, singularly or multiply unsaturated alkenyl
consisting of N -vinylformamide, N -vinylacetamide, group having 2 to 22 carbon atoms, a C6 - C22 alkylami
N -methyl- N -vinylacetamide, N - vinyl-2 -pyrrolidone (NVP ), 10 dopropyl group , a linear mono -hydroxyalkyl group
N , N -diethylacrylamide, acrylamide, methacrylamide, having 2 to carbon atoms or a linear or branched
methylacrylate , methylmethylacrylate , tert -Butylacrylate, dihydroxyalkyl group having 3 to carbon atoms, and
acrylic acid , methacrylic acid , 2 -carboxyethylacrylate, where at least one of the radicals RS , R " , and R7 is not
2 -carboxyethylacrylate oligomers, itaconic acid glycerine hydrogen, or Q * is Li + , Na+ , K+ , 1/2 Ca ++ , 12 Mg++ , 1/2
propoxylate triacrylate (GPTA ), trimethylolpropane triacry 15
> 2

Zn ++ , 1/3 A1 +++ or combinations thereof; and

2

late ( TMPTA ), pentaerythritol diacrylate monostearate ( b ) optionally from 0.01 mol- % to 10 mol- % , preferably
( PEAS ) and polyethyleneglycol diacrylate. from 0.01 mol- % to 5 mol- % of crosslinking or branching
In at least one embodiment, the optional unit results from units , wherein the crosslinking or branching units result
the incorporation of a monomer selected from the group 20 from the incorporation of a monomer comprising at least
consisting of acrylic acid , methacrylic acid , styrenesulfonic two olefinically unsaturated double bonds .
acid, maleic acid , fumaric acid, crotonic acid , itaconic acid , In at least one embodiment, the polymer comprises from
and senecic acid . In at least one embodiment, the optional 96 mol- % to 99.7 mol- % , preferably from 97 mol- % to 99.5
unit results from monomers selected from the group con mol- % units ( a) and from 0.3 mol- % to 4 mol- % , preferably
sisting of open- chain N -vinyl amides, preferably N -vinyl from 0.5 mol- % to 3 mol- % units (b ) . In at least one
formamide (VIFA ), N - vinylmethylformamide, N - vinylm 25 embodiment, the polymer comprises units ( a) and (b ) , such
ethylacetamide ( VIMA ) and N -vinylacetamides ; cyclic that the sum thereof is at least 99 mol- % , by total weight of
N - vinyl amides ( N -vinyl lactams) with a ring size of 3 to 9 , the polymer.
preferably N - vinylpyrrolidones (NVP ) and N -vinylcapro In a preferred embodiment, the first aspect relates to the
lactam ; amides of acrylic and methacrylic acid, preferably
acrylamide, methacrylamide, N , N -dimethylacrylamide, 30 use of a polymer in a cosmetic , dermatological or pharma
ceutical composition, wherein the polymer is crosslinked or
N , N -diethylacrylamide, and N , N -diisopropylacrylamide; non -crosslinked, characterized in that the polymer com
alkoxylated acrylamides and methacrylamides , preferably prises:
hydroxyethyl methacrylate, hydroxymethylmethacrylamide; a ) from 40 mol- % to 98 mol- % , preferably from 55 mol- %
hydroxyethylmethacryl amide , hydroxypropylmethacrylam 35 to 98 mol- % repeating units according to Formula ( 1 )
ide , and mono [ 2- (methacryloyloxy ) ethyl ]succinate ; N , N - di wherein at least 10 wt .- % , preferably at least 20 wt .- % of
methylaminomethacrylate ; diethylaminomethylmethacry the repeating units comprises from 28 wt .- % to 100 wt .- %
late ; acrylamideo- and methacrylamideoglycolic acid ; 2 bio - based carbon content, relative to the total mass of
and 4 - vinylpyridine; vinyl acetate ; glycidyl methacrylate; carbon in the repeating unit according to Formula ( 1 ) ,
styrene; acrylonitrile; vinyl chloride ; stearyl acrylate; lauryl measured according to standard ASTM D6866-12 ,
methacrylate ; vinylidene chloride; tetrafluoroethylene ; and 40 Method B ;
combinations thereof.
Example Embodiments of the First Aspect (1 )
45 + CH2 - ÇR ! +
In a preferred embodiment, the first aspect relates to the
use of a polymer in a cosmetic , dermatological or pharma -A - S -O Q +
ceutical composition, wherein the polymer is crosslinked or
non - crosslinked , characterized in that the polymer com
prises:
R2
50
a ) from 90 mol- % to 99.9 mol- % , preferably from 95 mol- % wherein :
to 99.5 mol- % of repeating units according to Formula ( 1 ) Rl and R2 are independently selected from H , methyl or
wherein at least 10 wt .- % , preferably at least 20 wt .- % of ethyl; A is aa linear or branched C1 - C12 - alkyl group; and
the repeating units according to Formula ( 1 ) comprise Q + is H *, NHL *, organic
organic ammonium ions
from 28 wt .- % to 100 wt .- % bio -based carbon content, 55 NHR RR? * wherein R , RC , and R' independently of
relative to the total mass of carbon in the repeating unit one another may be hydrogen, a linear or branched
according to Formula ( 1 ) , measured according to standard alkyl group having 1 to 22 carbon atoms , a linear or
ASTM D6866-12 , Method B ; branched , singularly or multiply unsaturated alkenyl
group having 2 to 22 carbon atoms, a Co - C22 alkylami
(1) 60 dopropyl group , a linear mono -hydroxyalkyl group
13 =- ¢R! + having 2 to carbon atoms or a linear or branched
dihydroxyalkyl group having 3 to carbon atoms, and
1
R2 1 00+
65
where at least one of the radicals RS , R " , and R7 is not
hydrogen, or Q * is Li * , Na , K+ , 1/2 Ca ++ , 12 Mg++ , 1/2
2

Zn ++, 1/3 A1 +++ , or combinations thereof;

.

( b ) optionally from 0.01 mol- % to 5 mol- % , preferably from

0.01 mol- % to 3 mol- % crosslinking or branching units ,
 US 11,311,473 B2
19 20
wherein the crosslinking or branching units result from wherein the crosslinking or branching units result from
the incorporation of a monomer comprising at least two the incorporation of a monomer comprising at least two
olefinically unsaturated double bonds ; and olefinically unsaturated double bonds ;
( c ) optionally from 0.99 mol- % to 59.99 mol- % , preferably (c ) optionally from 0.01 mol- % to 88.52 mol- % , preferably
from 1.99 mol- % to 44.99 mol- % of repeating neutral 5 from 0.05 mol- % to 72.4 mol- % of repeating neutral
structural units wherein at least 10 wt .- % , preferably at structural units , preferably wherein at least 10 wt .- % ,
least 20 wt .- % of the neutral structural units comprises preferably at least 20 wt .- % of the repeating neutral
from 0 wt .- % to 100 wt .- % bio - based carbon content, structural units comprises from 0 wt .- % to 100 wt .- %
relative to the total mass of carbon in the repeating unit, 10
bio - based carbon content, relative to the total mass of
measured according to standard ASTM D6866-12 , carbon in the repeating neutral structural unit, measured
Method B. according to standard ASTM D6866-12 , Method B ;
In at least one embodiment, the polymer comprises from (d) optionally from 1.98 mol- % to 20 mol- % , preferably
45 mol- % to 97 mol- % , preferably from 65 mol- % to 96 from 2.5 mol- % to 18 mol- % of repeating anionic struc
mol- % units ( a) , from 0.25 mol- % to 4 mol- % , preferably 15
tural units , wherein the repeating anionic structural units
from 0.3 mol- % to 3 mol- % units (b ) , from 2 mol- % to 54.7 result from the incorporation of a monomer comprising at
mol - %% , preferably from 2.5 mol- % to 34.5 mol- % units least one carboxylate anion , and wherein the repeating
( c ) . In at least one embodiment, the polymer comprises units anionic structural units are different from units ( a) and
( a) , (b ) and (c ) such that the sum thereof is at least 99 mol- % , preferably wherein at least 10 wt .- % , preferably at least
by total weight of the polymer. 20
20 wt .- % of the repeating anionic structural units com
In at least one embodiment, the polymer comprises from prise from 0 wt .- % to 100 wt .- % bio - based carbon con
70 mol- % to 98 mol- % , preferably from 73 mol- % to 96 tent, relative to the total mass of carbon in the repeating
mol- % units ( a) , from 0.6 mol- % to 2.5 mol- % , preferably anionic structural unit , measured according to standard
from 0.75 mol- % to 2 mol- % units ( b ), from 1.4 mol- % to ASTM D6866-12 , Method B.
54.7
( C ) . Inmol- % ,preferably
at least from 2.5, themol-polymer
one embodiment % to 34.5comprises
mol-% units
units 25 37Inmol-at least one embodiment, the polymer comprises from
% to 96.4 mol-% , preferably from 43 mol- % to 95.3
( a) , (b ) and (c ) such that the sum thereof is at least 99 mol- % , mol- % units ( a) , from 0.1 mol- % to 3 mol- % , preferably
9

by total weight of the polymer. from 0.2 mol- % to 2 mol- % units ( b ), from 0.1 mol- % to
In a preferred embodiment, the first aspect relates to the 59.3 mol- % , preferably from 0.5 mol- % to 52.8 mol- % units
(c ) , and from 3.5 mol- % to 16 mol- % , preferably from 4
use of a composition
ceutical polymer in ,a wherein
cosmeticthe
, dermatological orpharma-or
polymer is crosslinked 30 mol- % to 14 mol- % units ( d). In atleast one embodiment,
non -crosslinked, characterized in that the polymer com the polymer comprises units (a ) , ( b ), (c ) and (d) such that the
prises: sum thereof is at least 99 mol- % , by total weight of the
a ) from 9.49 mol- % to 98 mol- % , preferably from 27.5 polymer.
mol-
mula%( 1 to) wherein
97.4 mol-at least
% repeating
10 wt .- %units accordingat toleastFor-20
, preferably 35 70Inmol-
at least one embodiment, the polymer comprises from
% to 94.5 mol-% , units (a), from 0.35 mol- % to 1.5
wt .- % of the repeating units according to Formula ( 1 ) mol- % , units (b ) , from 0.65 mol- % to 25.65 mol- % units ( c ) ,
comprise from 28 wt .- % to 100 wt .- % bio - based carbon and from 4.5 mol- % to 12 mol- % units ( d ). In at least one
content, relative to the total mass of carbon in the repeat embodiment, the polymer comprises units ( a ) , ( b ), ( c ) and
ing unit according to Formula ( 1 ) , measured according to 40 (d) such that the sum thereof is at least 99 mol- % , by total
standard ASTM D6866-12 , Method B ; weight of the polymer .
In a preferred embodiment, the first aspect relates to the
use of the cosmetic, dermatological or pharmaceutical com
(1) position according to the second aspect .
-CH2 - CR ! + 45
Second Aspect
A second aspect relates to a cosmetic, dermatological or
N - A - S 0 0
pharmaceutical composition comprising:
(I ) a polymer;
R2 ( II ) a cosmetically acceptable component;
50
wherein the polymer is crosslinked or non -crosslinked ,
wherein : characterized in that the polymer comprises at least
R and R2 are independently selected from H , methyl or 9.49 mol- % of repeating units (a ) according to Formula
ethyl; A is aa linear or branched C1 -C12 -alkyl group ; and ( 1 ) wherein at least 10 wt .- % , preferably at least 20
Q + is H + , NH4 + , organic ammonium ions (NHRSRØR ? ] wt .- % of the repeating units (a ) according to Formula
( 1 ) comprise from 28 wt .- % to 100 wt .- % bio -based
wherein RS , R? , and R7 independently of one another 55 carbon content, relative to the total mass of carbon in
may be hydrogen, a linear or branched alkyl group the repeating unit according to Formula ( 1 ) , measured
having 1 to 22 carbon atoms, a linear or branched , according to standard ASTM D6866-12 , Method B ;
singularly or multiply unsaturated alkenyl group hav
ing 2 to 22 carbon atoms, a C6 - C22 alkylamidopropyl
group , a linear mono -hydroxyalkyl group having 2 to 60 (1 )
carbon atoms or a linear or branched dihydroxyalkyl CH2 - ÇR !+
group having 3 to carbon atoms , and where at least one
of the radicals RS , R " , and R7 is not hydrogen, or Q is
Li + , Na + , K+ , 1/2 Ca++ , 122 Mg ++ , 1/2 Zn++ , 1/3 A1 +++ , or
combinations thereof;
2

(b ) optionally from 0.01 mol- % to 5 mol- % , preferably from

0.01 mol- % to 4 mol- % crosslinking or branching units ,
65
N - A

R2 + O 0+
 US 11,311,473 B2
21 22
wherein : sodium myreth sulfate , and mixtures thereof. Typical
R and R2 are independently selected from H , methyl or anionic surfactants for use in compositions of the invention
ethyl; A is aa linear or branched C -C12 - alkyl group ; and include sodium oleyl succinate , ammonium lauryl sulpho
Q + is H * , NH4+ , organic ammonium ions
2 succinate, sodium lauryl sulphate, sodium lauryl ether sul
[NHRR?R ]]* wherein R5 , R , and R? independently of 5 phate, sodium lauryl ether sulphosuccinate, ammonium lau
>

one another may be hydrogen , a linear or branched ryl sulphate , ammonium lauryl ether sulphate, sodium
alkyl group having 1 to 22 carbon atoms , a linear or dodecyl benzene sulphonate, triethanolamine dodecylben
branched , singularly or multiply unsaturated alkenyl zene sulphonate , sodium cocoyl isethionate , sodium lauryl
group having 2 to 22 carbon atoms , a C. - C22 alkylami- isethionate, lauryl ether carboxylic acid and sodium N - lauryl
dopropyl group, a linear mono -hydroxyalkyl group 10 sarcosinate. Preferred anionic surfactants are selected from
having 2 to carbon atoms or a linear or branched sodium lauryl sulphate and sodium lauryl ether sulphate ( n )
dihydroxyalkyl group having 3 to carbon atoms, and EO , (where n is from 1 to 3 ) ; more preferably sodium lauryl
where at least one of the radicals RS , R " , and R7 is not ether sulphate ( n )EO , (where n is from 1 to 3 ) ; most prefer
hydrogen, or Q + is Li + , Na + , K+ , 1/2 Ca ++ , 1/2 Mg ++ , 1/2 ably sodium lauryl ether sulphate ( n )EO where n = 1 . Prefer
2

Zn ++, 1/3 A1 +++ , or combinations thereof. 15 ably the level of alkyl ether sulphate is from 0.5 wt .- % to 25
In at least one embodiment, the polymer is the polymer wt.- % of the total composition, more preferably from 3
according to the first aspect . wt .- % to 18 wt .- % , most preferably from 6 wt .- % to 15
The cosmetic , dermatological or pharmaceutical compo- wt .- % of the total composition.
sition or for brevity herein " composition ” , comprises a The total amount of anionic surfactant in the composition
cosmetically acceptable component. In at least one embodi- 20 may range from 0.5 wt .- % to 45 wt .- % , more preferably
ment, the cosmetically acceptable component is selected from 1.5 wt .- % to 20 wt .- % .
from the group consisting of surfactants, auxiliaries, hair In at least one embodiment, the composition comprises a
conditioning agents, hairstyling polymers, and combinations fatty acyl isethionate. In at least one embodiment, the
thereof. composition comprises fatty acyl isethionate at a level of
Surfactant 25 from 1 to 10 wt .- % , more preferably from 2 to 8 wt .- % , most
In at least one embodiment , the composition comprises a preferably from 2.5 to 7.5 wt.- % . A preferred fatty acyl
surfactant. In at least one embodiment, the composition isethionate product comprises fatty acyl isethionate surfac
comprises a surfactant system comprising a plurality of tant at a level of from 40 to 80 wt .- % of the product, as well
different surfactants. In at least one embodiment, the sur- as free fatty acid and / or fatty acid salt at a level of from 15
factant system comprises a surfactant selected from the 30 to 50 wt .- % . Preferably, greater than 20 wt .- % and less than
group consisting of anionic surfactants , cationic surfactants, 45 wt .- % , more preferably greater than 25 wt .- % and less
non - ionic surfactants , zwitterionic surfactants and /or than 45 wt .- % of the fatty acyl isethionate are of chain length
amphoteric surfactants. In at least one embodiment, the greater than or equal to C and greater than 50 wt .- % ,
surfactant is selected from the group consisting of anionic preferably greater than 60 wt .- % of the free fatty acid / soap
surfactants, cationic surfactants, non - ionic surfactants, zwit- 35 is of chain length C6 to C20 . In addition , the composition
terionic surfactants and / or amphoteric surfactants. may contain isethionates salts which are present typically at
In at least one embodiment, the composition comprises a levels less than 5 wt .- % , and traces (less than 2 wt .- % ) of
total amount of surfactant of from 0.01 wt .- % to 70 wt .- % , other impurities. Preferably, a mixture of aliphatic fatty
from 0.1 wt .- % to 40 wt .- % , from 1 wt .- % to 30 wt .- % , from acids is used for the preparation of commercial fatty acyl
2 wt .- % to 20 wt .- % . 40 isethionates surfactants. The resulting fatty acyl isethionate
In at least one embodiment, the composition comprises an surfactants (e.g. , resulting from reaction of alkali metal
anionic surfactant. In at least one embodiment, the compo- isethionate and aliphatic fatty acid) preferably should have
sition comprises an anionic surfactant as cosmetically more than 20 wt .- % , preferably more than 25 wt .- % , but no
acceptable component ( II ) . In at least one embodiment, the more than 45 wt .- % , preferably 35 wt .- % (on basis of fatty
anionic surfactant is selected from the group consisting of 45 acyl isethionates reaction product) of fatty acyl group with
(C10 -C20 ) -alkyl and alkylene carboxylates, alkyl ether car- 16 or greater carbon atoms to provide both excellent lather
boxylates, fatty alcohol sulfates, fatty alcohol ether sulfates , and mildness of the resulting fatty acyl isethionate product.
alkylamide sulfates and sulfonates, fatty acid alkylamide These longer chain fatty acyl isethionate surfactants and
polyglycol ether sulfates, alkanesulfonates and hydroxyal- fatty acids , i.e. fatty acyl group and fatty acid with 16 or
kanesulfonates, olefinsulfonates, acyl esters of isethionates, 50 more carbons, can typically form insoluble surfactant / fatty
Q - sulfo fatty acid esters , alkylbenzenesulfonates, alkyl-phe- acid crystals in water at ambient temperatures.
nol glycol ether sulfonates, sulfosuccinates, sulfosuccinic In at least one embodiment, the composition comprises an
monoesters and diesters , fatty alcohol ether phosphates, acylglycinate surfactant. In at least one embodiment, the
protein /fatty acid condensation products , alkyl monoglycer- acylglycinate surfactant conforms to the formula (Y) :
ide sulfates and sulfonates, alkylglyceride ether sulfonates, 55
fatty acid methyltaurides, fatty acid sarcosinates, sulforici
noleates , acylglutamates, and mixtures thereof. The anionic

hy
(Y)
surfactants ( and their mixtures) can be used in the form of
their water - soluble or water - dispersible salts , examples
being the sodium , potassium , magnesium , ammonium , 60 Rla N
Bet
mono- , di-, and triethanolammonium , and analogous alky H
lammonium salts . In at least one embodiment, the anionic
surfactant is the salt of an anionic surfactant comprising 12
to 14 carbon atoms. In at least one embodiment, the anionic wherein
surfactant is selected from the group consisting of sodium 65 Rla is a linear or branched, saturated alkanoyl group having
lauryl sulfate, sodium laureth sulfate, sodium tridecyl sul- 6 to 30 , preferably 8 to 22 , particularly preferably 8 to 18 ,
fate, sodium trideceth sulfate, sodium myristyl sulfate , carbon atoms or is a linear or branched , mono- or polyun
 US 11,311,473 B2
23 24
saturated alkenoyl group having 6 to 30 , preferably 8 to 22 particular addition products of from 2 to 30 mol of ethylene
and particularly preferably 12 to 18 carbon atoms, and Qat oxide and / or 1 to 5 mol of propylene oxide onto C8- to
is aa cation . In at least one embodiment, Qat is selected from C22- fatty alcohols , onto C12- to C22 - fatty acids or onto
the group consisting of Li + , Na + , K+ , Mg ++ , Ca++ , A1 +++ , alkyl phenols having 8 to 15 carbon atoms in the alkyl group ,
NH4+, a monoalkylammmonium ion , a dialkylammonium 5 C12- to C22 - fatty acid mono- and diesters of addition
9

ion , a trialkylammonium ion and a tetraalkylammonium ion , products of from 1 to 30 mol of ethylene oxide onto glycerol,
or combinations thereof. Optionally Riala is independently addition products of from 5 to 60 mol of ethylene oxide onto
from one another, are (C7 -C22 ) -alkyl radicals or (C2- C10) esters castor oil or onto hydrogenated castor oil , fatty acid sugar
hydroxyalkyl radicals . In at least one embodiment, the 10 C22 - fatty , in particular esters of sucrose and one or two C8- to
acylglycinate surfactant is selected from sodium acids , INCI : Sucrose Cocoate, Sucrose Dilaurate ,
cocoylglycinate and potassium cocoylglycinate . Sucrose Distearate , Sucrose Laurate, Sucrose Myristate ,
In at least one embodiment, the composition comprises a Sucrose Oleate , Sucrose Palmitate, Sucrose Ricinoleate ,
glutamate surfactant corresponding to formula (Z ) or a salt to C22 -fatty acids, esters
Sucrose Stearate of sorbitan and one , two or three C8
and a degree of ethoxylation of from 4 to
thereof:
15 20 , polyglyceryl fatty acid esters , in particular of one , two or
more C8- to C22 - fatty acids and polyglycerol having pref
(Z) erably 2 to 20 glyceryl units , alkyl glucosides, alkyl oligo
R - CO - NH - CH - COOH glucosides and alkyl polyglucosides having C8 to C22 - alkyl
R' groups, e.g. decylglucoside or laurylglucoside, and mixtures
20 thereof.
In at least one embodiment, the non - ionic surfactant is
wherein selected from the group consisting of fatty alcohol ethoxy
R' is HOOC - CH2 - CH2 or M* -OOC-CH2CH2 lates (alkylpolyethylene glycols ), alkylphenol polyethylene
wherein M is a cation; and wherein R is a linear or glycols, alkylmercaptan polyethylene glycols , fatty amine
branched , saturated alkanoyl group having 6 to 30 , prefer- 25 ethoxylates (alkylaminopolyethylene glycols ) , fatty acid
ably 8 to 22 , more preferably 8 to 18 , carbon atoms or is a ethoxylates ( acylpolyethylene glycols ) , polypropylene gly
linear or branched , mono- or polyunsaturated alkenoyl col ethoxylates (Pluronics® ) , fatty acid alkylol amides,
group having 6 to 30 , preferably 8 to 22 and more preferably ( fatty acid amide polyethylene glycols ) , N -alkyl-, N -alkoxy
12 to 18 carbon atoms. In at least one embodiment, M * is a polyhydroxy -fatty acid amide , sucrose esters, sorbitol esters ,
metal cation . In at least one embodiment, M+ is selected 30 polyglycol ethers , and mixtures thereof.
from the group consisting of Li * , Na , K + , Mg **, Catt ,
2 In at least one embodiment, the composition comprises a
Al *** , NH4 + , a monoalkylammmonium ion , a dialkylam- fatty N -methyl - N -glucamide surfactant. In at least one
monium ion, a trialkylammonium ion and a tetraalkylam- embodiment, the fatty N -methyl - N - glucamide surfactant
monium ion , or combinations thereof. In at least one conforms to the formula ( X ) :
embodiment, the glutamate surfactant is selected from 35
sodium cocoyl glutamate and potassium cocoyl glutamate.
In at least one embodiment, the composition comprises a
non - ionic surfactant. The non - ionic surfactants may be pres
ent in the range 0 to 5 wt .- % . The non - ionic surfactants that
can be included in the compositions herein include conden-
sation products of aliphatic primary or secondary linear or
branched chain alcohols or phenols with alkylene oxides ,
usually ethylene oxide and generally having from 6 to 30
ethylene oxide groups. Alkyl ethoxylates are particularly
40

wherein
R dy OH

OH
OH

OH
OH
(X)

preferred. Most preferred are alky ethoxylates having the 45 R is a linear or branched alkyl or alkenyl group having from
formula R— (OCH2CH2) , OH , where R is an alkyl chain of 3 to 30 carbon atoms . In at least one embodiment, R is an
C12 to C15 , and n is 5 to 9. Other suitable nonionic alkyl group having from 3 to 30 carbon atoms . In at least one
surfactants include mono- or di -alkyl alkanolamides . embodiment, R is a saturated aliphatic hydrocarbon group
Examples include coco mono- or di - ethanolamide and coco which can be linear or branched and can have from 3 to 20
mono - isopropanolamide. 50 carbon atoms in the hydrocarbon chain , preferably linear or
Further nonionic surfactants which can be included in branched . Branched means that a lower alkyl group such as
compositions of the invention are the alkyl polyglycosides methyl, ethyl or propyl is present as substituent on a linear
(APGs ) . Typically, APG is one which comprises an alkyl alkyl chain . Suitable fatty N -methyl - N - glucamide surfac
group connected ( optionally via a bridging group ) to a block tants are described in WO2013 / 178700 and EP0550637 ,
of one or more glycosyl groups . 55 which are incorporated herein by reference . In at least one
In at least one embodiment, the non- ionic surfactant has embodiment, the fatty N -methyl- N - glucamide surfactant is
an HLB (Hydrophilic Lipophilic Balance ) of greater than selected from those conforming to formula (X ) , wherein R
12. Optionally, the non - ionic surfactant is selected from the is C12 alkyl or C14 alkyl. In at least one embodiment, the
group consisting of ethoxylated or ethoxylated /propoxylated fatty N -methyl- N - glucamide surfactant is selected from
fatty alcohols with a fatty chain comprising from 12 to 22 60 those conforming to formula ( X ), wherein R is C16 alkyl or
carbon atoms, ethoxylated sterols, such as stearyl- or lauryl C18 alkyl.
alcohol ( EO - 7 ) , PEG - 16 soya sterol or PEG - 10 soya sterol, Amphoteric or zwitterionic surfactant( s) can be included
polyoxyethylene polyoxypropylene block polymers (polox- in the composition in an amount ranging from 0.5 wt .- % to
amers ), and mixtures thereof. about 8 wt .- % , preferably from 1 wt .- % to 4 wt .- % of the
In at least one embodiment, the non - ionic surfactant is 65 total composition.
selected from the group consisting of ethoxylated fatty In at least one embodiment, the amphoteric surfactants are
alcohols , fatty acids , fatty acid glycerides or alkylphenols, in selected from the group consisting of N- (C12- C18 ) -alkyl
 US 11,311,473 B2
25 26
B - aminopropionates and N- ( C12- C18)-alkyl-B -iminodipro- ing agents and reducing agents. In at least one embodiment,
pionates as alkali metal salts and mono-, di-, and trialky- the cosmetically acceptable component is an auxiliary or
.
lammonium salts ; N -acylaminoalkyl-N , N- mixture of auxiliaries.
dimethylacetobetaine, preferably N - C -Cs)- In at least one embodiment, the composition comprises an
acylaminopropyl - N , N -dimethylacetobetaine, ( C12 - C18 ) - 5 oily substance or wax . Preferably the oily substance or wax
alkyl -dimethyl - sulfopropylbetaine, amphosurfactants based is selected from the group consisting of silicone oils , volatile
on imidazoline ( trade name: Miranol® , Steinapon® ), pref- or nonvolatile, linear, branched or cyclic , optionally with
erably the sodium salt of 1- (ß -carboxymethyloxyethyl)-1- organic modification ; phenylsilicones; silicone resins and
( carboxymethyl)-2 -laurylimidazolinium ; amine oxide , e.g. , silicone gums ; mineral oils such as paraffin oil or vaseline
(C12 - C18 ) -alkyl -dimethyl -amine oxide , fatty acid amidoal- 10 oil ; oils of animal origin such as perhydrosqualene, lanolin ;
kyldimethylamine oxide , and mixtures thereof. oils of plant origin such as liquid triglycerides, e.g. , sun
In at least one embodiment, the composition comprises a flower oil , corn oil , soybean oil , rice oil , jojoba oil , babassu
betaine surfactant. Optionally, the betaine surfactant is oil , pumpkin oil , grapeseed oil , sesame oil , walnut oil ,
selected from C8- to C18 -alkylbetaines. In at least one apricot oil , macadamia oil , avocado oil , sweet almond oil ,
embodiment, the betaine surfactant is selected from the 15 lady’s - smock oil , castor oil , triglycerides of caprylic /capric
group consisting of cocodimethylcarboxymethylbetaine, acids , olive oil , peanut oil , rapeseed oil , argan oil , abyssinian
lauryldimethylcarboxymethylbetaine, lauryldimethylal- oil , and coconut oil ; synthetic oils such as purcellin oil ,
phacarboxyethylbetaine, cetyldimethylcarboxymethyl- isoparaffins, linear and / or branched fatty alcohols and fatty
betaine, oleyldimethylgammacarboxypropylbetaine and lau- acid esters , preferably guerbet alcohols having 6 to 18 ,
rylbis ( 2 -hydroxypropyl) alphacarboxyethylbetaine and 20 preferably 8 to 10 , carbon atoms ; esters of linear ( Co - C13 )
combinations thereof. Optionally, the betaine surfactant is fatty acids with linear ( Co - C20 ) fatty alcohols; esters of
selected from C8- to C18 - sulfobetaines. In at least one branched (C8 - C13 ) carboxylic acids with linear ( Co - C20 )
embodiment, the betaine surfactant is selected from the fatty alcohols, esters of linear (C6 - C18 ) fatty acids with
group consisting of cocodimethylsulfopropylbetaine, branched alcohols, especially 2 - ethylhexanol; esters of lin
stearyldimethylsulfopropylbetaine, lauryldimethyl- sulfoeth- 25 ear and / or branched fatty acids with polyhydric alcohols
ylbetaine, laurylbis ( 2 -hydroxyethyl) sulfopropylbetaine, and ( such as dimerdiol or trimerdiol, for example ) and / or guerbet
combinations thereof. Optionally , the betaine surfactant is alcohols ; triglycerides based on ( C6 - C10 ) fatty acids ; esters
selected from carboxyl derivatives of imidazole , the C8- to such as dioctyl adipate , diisopropyl dimer dilinoleate; pro
C18 - alkyldimethylammonium acetates , the C8- to C18- pylene glycols /dicaprylate or waxes such as beeswax , par
alkyldimethylcarbonylmethylammonium salts , and the C8- 30 affin wax or microwaxes , alone or in combination with
to C18 - fatty acid alkylamidobetaines, and mixtures thereof. hydrophilic waxes, such as cetylstearyl alcohol , for
Optionally, the C8- to C18 - fatty acid alkylamidobetaine is example ; fluorinated and perfluorinated oils ; fluorinated
selected from conut fatty acid amidopropylbetaine, N - co- silicone oils ; mixtures of the aforementioned compounds.
conut fatty acid amidoethyl -N-[ 2- ( carboxymethoxy )ethyl] In at least one embodiment, the composition comprises an
glycerol (CTFA name : Cocoamphocarboxyglycinate ), and 35 oily substance , which is any fatty substance which is liquid
mixtures thereof. A particularly preferred amphoteric or at room temperature ( 25 ° C. ) . In a preferred embodiment,
zwitterionic surfactant is cocamidopropyl betaine . Mixtures the oily substance is selected from the group consisting of
of any of the foregoing amphoteric or zwitterionic surfac- sweet almond oil , caprylic /capric triglycerides , dimethicone,
tants may also be suitable . Preferred mixtures are those of mineral oil , squalane, castor oil , isopropyl isostearate, jojoba
cocamidopropyl betaine with further amphoteric or zwitte- 40 oil , dicaprylyl carbonate, isohexadecane, C12-15 alkyl ben
rionic surfactants as described above . A preferred further zoate , and combinations thereof. In at least one embodiment,
amphoteric or zwitterionic surfactant is sodium cocoam- the composition comprises from 0.001 wt % to 60 wt % ,
phoacetate. preferably from 0.05 wt % to 50 wt % , even more preferably
Auxiliary from 0.1 wt % to 40 wt % of at least one oily substance.
In at least one embodiment, the composition comprises at 45 In a preferred embodiment, the wax is selected from the
least one additive common in cosmetology, pharmacy, and group consisting of carnauba wax , beeswax , candelilla wax ,
dermatology, which are hereinafter called auxiliaries . In at synthetic wax , polyethylene, paraffin wax , microcrystalline
least one embodiment, the composition comprises an aux- wax , hydrogenated vegetable oil , hydrogenated castor oil ,
iliary. In at least one embodiment, the auxiliary is cosmeti- rice bran wax , cetyl dimethicone, bis - PEG - 18 methyl ether
cally acceptable . In at least one embodiment, the auxiliary is 50 dimethyl silane, and combinations thereof. In at least one
selected from the group consisting of oily substances , embodiment, the composition comprises from 0.001 wt % to
waxes , emulsifiers, coemulsifiers, solubilizers, cationic 30 wt % , preferably from 0.05 wt % to 20 wt % , even more
polymers , film formers, superfatting agents, refatting agents, preferably from 0.1 wt % to 10 wt % of at least one wax .
foam stabilizers , stabilizers, active biogenic substances , In at least one embodiment, the composition comprises an
preservatives, preservation boosting ingredients, anti-fungal 55 emulsifier, coemulsifier or solubilizer. Non-ionic , anionic ,
substance, anti- dandruff agents, dyes or pigments, particu- cationic or amphoteric surface active compounds can be
late substances, opacifiers, abrasives, absorbents, anticaking used as emulsifiers, coemulsifiers and solubilizers.
agents , bulking agents, pearlizing agents , direct dyes, per- As nonionogenic surface active compounds, consider
fumes or fragrances , carriers, solvents or diluents, propel- ation may preferably be given to : addition products of 0 to
lants , functional acids , active ingredients, skin -brightening 60 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide on
agents, self -tanning agents, exfoliants, enzymes , anti - acne linear fatty alcohols with 8 to 22 carbon atoms , on fatty acids
agents , deodorants and anti-perspirants, viscosity modifiers, with 12 to 22 carbon atoms , on alkyl phenols with 8 to 15
thickening and gelling agents , pH adjusting agents, buffering carbon atoms in the alkyl group and on sorbitan or sorbitol
agents, anti -oxidants, chelants, astringents, sunscreens, sun esters; (C12 -C18 ) -fatty acid mono- and diesters of addition
protection agents, UV filters, skin conditioning agents , 65 products of 0 to 30 mol ethylene oxide on glycerol; glycerol
emollients, humectants, occlusive agents , pediculocides , mono- and diesters and sorbitan mono- and diesters of
anti - foaming agents , flavouring agents, electrolytes, oxidiz- saturated and unsaturated fatty acids with 6 to 22 carbon
 US 11,311,473 B2
27 28
atoms and optionally their ethylene oxide addition products ; polyquaterniums, carboxyvinyl polymers, such as carbom
addition products of 15 to 60 mol ethylene oxide on castor ers and salts thereof, polysaccharides, for example polydex
oil and / or hardened castor oil ; polyol and especially trose and glucan, vinyl acetate / crotonate .
polyglycerol esters , e.g. polyglycerol polyricinoleate and In at least one embodiment, the composition comprises a
polyglycerol poly - 12 -hydroxystearate . Ethoxylated fatty 5 superfatting agent and / or a refatting agent. As superfatting
amines , fatty acid amides, fatty acid alkanolamides and agents it is possible to use substances such as , for example,
mixtures of compounds from several of these classes of lanolin , polyethoxylated lanolin derivatives, lecithin , leci
substances are also preferably suitable . Polymeric ethers thin derivatives, non - ethoxylated and polyethoxylated or
formed by block polymerization of ethylene or propylene acylated lanolin and lecithin derivatives, polyol fatty acid
oxide known as poloxamers are also suitable . 10 esters such as glyceryl oleate , mono- , di- and triglycerides
Suitable ionogenic coemulsifiers are e.g. anionic emulsi- and / or fatty acid alkanolamides, can preferably be used as
fiers , such as mono-, di- or triphosphoric acid esters, soaps overfatting agents or refatting agents . These compounds can
( e.g. sodium stearate ), fatty alcohol sulfates as well as also simultaneously serve as foam stabilizers. In a preferred
cationic emulsifiers such as mono- , di- and tri -alkyl quats embodiment, the superfatting agent and /or a refatting agent
and polymeric derivatives thereof. Amphoteric emulsifiers 15 is selected from the group consisting of, lanolin , glyceryl
that are available are preferably alkyl aminoalkyl carboxylic ricinoleate, PEG - 8 glyceryl laurate, glyceryl Oleate , coc
acids , betaines, sulfobetaines and imidazoline derivatives . amide MEA , PEG - 75 lanolin , and combinations thereof.
Fatty alcohol ethoxylates are used especially preferably . In at least one embodiment , the composition comprises a
Fatty acid ethoxylates are also preferred. Sodium laureth- stabiliser. As stabiliser it is possible to use metal salts of fatty
11 -carboxylate can be used advantageously as ethoxylated 20 acids , such as magnesium , aluminum and/or zinc stearate,
alkyl ether carboxylic acid or salts thereof. Polyethylene for example. In a preferred embodiment, the stabilizer is
glycol ( 60) evening primrose glycerides can be used advan- selected from the group consisting of, aluminum stearate ,
tageously as ethoxylated triglycerides. aluminum isostearates /myristates, magnesium stearate ,
In at least one embodiment, the composition comprises magnesium cocoate, zinc palmitate , zinc stearate, and com
from 0.1 wt % to 20 wt % , preferably from 0.5 wt % to 10 25 binations thereof.
wt % , even more preferably from 1.0 wt % to 5.0 wt % of In at least one embodiment, the composition comprises a
at least one emulsifier, coemulsifier and /or solubilizer. biogenic substance.
In at least one embodiment, the composition comprises a In at least one embodiment, the composition comprises a
cationic polymer. Suitable cationic polymers include those preservative, preservation boosting ingredient, anti- fungal
known under the INCI designation “ polyquaternium ” , espe- 30 agent, and / or anti- dandruff agent. In at least one embodi
cially polyquaternium - 31 , polyquaternium - 16 , polyquater- ment, the preservative is selected from the group consisting
nium-24 , Polyquaternium - 7 , polyquaternium - 22 , poly- of benzyl alcohol , piroctone olamine, phenoxyethanol, para
quaternium -39, polyquaternium -28, polyquaternium - 2, bens, pentanediol, benzoic acid / sodium benzoate , sorbic
polyquaternium - 10 , polyquaternium - 1, and also polyquater- acid / potassium sorbate, and combinations thereof. Other
nium - 37 & mineral oil & PPG trideceth ( Salcare SC95 ) , 35 organic acids can also be used to provide antimicrobial
PVP -dimethylaminoethyl methacrylate copolymer, guar-hy- protection. In at least one embodiment, the preservation
droxypropyltriammonium chlorides, and also calcium alg- boosting ingredient is selected from the group consisting of
inate and ammonium alginate. It is additionally possible to anisic acid , lactic acid , sorbitan caprylate, ethylhexylglyc
employ cationic cellulose derivatives; cationic starch ; copo-erin , caprylyl glycol , octanediol, and mixtures thereof. A
lymers of diallylammonium salts and acrylamides ; quater- 40 suitable preservation boosting ingredient is also disclosed in
nized vinylpyrrolidone / vinylimidazole polymers; condensa- International patent application PCT/EP2017/ 065927
tion products of polyglycols and amines; quaternized ( claiming priority from European patent application
collagen polypeptides ; quaternized wheat polypeptides; 16176830.4 filed on 29 June 2016 ) by Clariant International
polyethyleneimines; cationic silicone polymers, such as Ltd ( see in particular claim 1 therein ), which is incorporated
amidomethicones, for example; copolymers of adipic acid 45 herein by reference. In at least one embodiment, the com
and dimethylaminohydroxypropyldiethylenetriamine; position comprises 0.01 to 5.0 wt % , particularly preferably
polyaminopolyamide and cationic chitin derivatives, such as from 0.05 wt % to 1.0 wt % of at least one preservative.
chitosan , for example. Suitable preservatives include the substances listed in the
In at least one embodiment, the composition comprises a International Cosmetic Ingredient Dictionary and Hand
film former. Film formers are materials which produce a 50 book , 9th Edition with the function “ preservatives ” . In at
continuous film on skin , hair, or nails such as synthetic or least one embodiment, the preservative is selected from the
natural polymers and their derivatives. The compositions group consisting of phenoxyethanol, benzyl paraben, butyl
according to the invention can contain film formers , which paraben, ethyl paraben , isobutyl paraben, isopropyl paraben,
are , depending on the intended use , selected from salts of methyl paraben , propyl paraben , iodopropynyl butylcarbam
phenylbenzimidazole sulfonic acid, water- soluble polyure- 55 ate , methyldibromoglutaronitrile, DMDM hydantoin and
thanes , for example C10 -polycarbamyl polyglyceryl ester, combinations thereof. In at least one embodiment, the com
polyvinyl alcohol , polyvinylpyrrolidone (PVP ) copolymers , position comprises a preservative selected from the group
vinylpyrrolidone/vinyl acetate copolymer or PVP/ eicosene consisting of cetyltrimethyl ammonium chloride , cetylpyri
copolymers, vinylpyrrolidone /alkene copolymers, for dinium chloride, benzethonium chloride, diisobutylethoxy
example VP / eicosene copolymer or VP /hexadecene copo- 60 ethyldimethyl benzylammonium chloride , sodium N - lauryl
lymer, PVM /MA copolymer or esters thereof, maleinized sarcosinate, sodium - N -palmethyl sarcosinate, lauroyl sar
polypropylene polymers, water - soluble acrylic acid poly- cosine , N -myristoylglycine, potassium - N - laurylsarcosine,
mers /copolymers or esters or salts thereof, for example trimethylammonium chloride , sodium aluminium chlorohy
partial -ester copolymers of acrylic /methacrylic acid , poly- droxylactate, triethylcitrate, tricetylmethylammonium chlo
alkylsilsesquioxanes , polyacrylamide, water -soluble cellu- 65 ride, 2,4,4 - trichloro - 2 -hydroxydiphenylether ( Triclosan ),
1

lose , for example

e hydroxymethylcellulose, hydroxyethylcel- phenoxyethanol, 1,5 -pentandiol, 1,6 -hexandiol, 3,4,4'
lulose , hydroxypropylcellulose, water - soluble quaterniums, trichlorocarbanilide ( Triclocarban ), diaminoalkylamide,
 US 11,311,473 B2
29 30
L - lysine hexadecylamide, heavy metal citrate salts , salicy- 25 wt % , preferably from 0.1 wt % to 15 wt % , even more
late , piroctose, zinc salts , pyrithione and its heavy metal preferably from 0.5 wt % to 10 wt % of at least one pigment.
salts , zinc pyrithione, zinc phenol sulfate , farnesol, keto- In at least one embodiment, the inorganic pigment is
conazol , oxiconazol, bifonazole , butoconazole , cloconazole , selected from the group consisting of chalk, ochre , umber,
clotrimazole , econazole , enilconazole, fenticonazole, iso- 5 green earth , burnt sienna, graphite , and combinations
conazole , miconazole , sulconazole , tioconazole , flucona- thereof. The pigments may be white pigments, such as , for
zole , itraconazole, terconazole , naftifine, terbinafine, sele- example, titanium dioxide or zinc oxide , black pigments,
nium disulfide, piroctone olamine (Octopirox® ), such as , for example, iron oxide black , colored pigments,
methylchloroisothiazolinone, methyl isothiazolinone, meth- such as , for example , ultramarine or iron oxide red , lustre
yldibromo glutaronitrile, silver chloride (AgCl), diazolidinyl 10 pigments, metal effect pigments, pearlescent pigments, and
urea , imidazolidinyl urea , dehydroacetic acid , undecylenic fluorescent or phosphorescent pigments, where preferably at
acid , chlorphenesin , proprionic acid , salicylic acid , chlorox- least one pigment is aa colored, nonwhite pigment.
ylenol , sodium salts of diethylhexylsulfosuccinate, sodium- In at least one embodiment, the composition comprises a
benzoate, phenoxyethanol, (RS)-1-(4 -chlorophenoxy )-1- particulate substance . In at least one embodiment, the com
imidazol - 1 -yl - 3,3 -dimethylbutan - 2 -one ( climbazole ), 15 position comprises at least one particulate substance . Suit
benzyl alcohol, phenoxyisopropanol, parabens such as able substances are , for example, substances which are solid
butyl-, ethyl-, methyl- and propylparaben and their salts , at room temperature ( 25 ° C. ) and are in the form of particles.
2 -Bromo - 2 -nitropropane - 1,3 -diol, polyaminopropyl bigua- Suitable substances are, for example, substances which
nide , phenoxyisopropanol, iodopropynyl butylcarbamate, serve as opacifiers, abrasives , absorbents, anti -caking
benzalkonium chloride, benzethonium chloride , pentandiol, 20 agents , bulking agents or performance fillers. In at least one
1,2 - octanediol, ethylhexylglycerin, sorbic acid , benzoic embodiment, the particulate substance is selected from the
acid , lactic acid , imidazolidinyl urea , diazolidinyl urea , group consisting of silica , silicates ( e.g. sepiolite, mont
dimethylol dimethyl hydantoin ( DMDMH ) , chlorhexidine, morillonite , bentonite, kaolin , hectorite ), aluminates, clay
sodium salts of hydroxymethyl glycinate, hydroxyethylgly- earths, mica , talc , starch, perlite, charcoal, pulp powder, seed
cine of sorbic acid, and combinations thereof. In at least one 25 powder, insoluble salts , in particular insoluble inorganic
embodiment, the preservative is selected from the group metal salts , metal oxides ( e.g. titanium dioxide ) , minerals
consisting of phenoxyethanol, benzyl paraben, butyl para- and insoluble polymer particles , such as polyamide deriva
ben, ethyl paraben , isobutyl paraben , isopropyl paraben, tives ( e.g. nylon - 12 , nylon - 6 , polyamide - 5 ), silicones (e.g.
methyl paraben, propyl paraben, iodopropynyl butylcarbam- polymethylsilsesquioxane ), polyesters ( e.g. polyester- 12 ),
ate , methyldibromoglutaronitrile, DMDM hydantoin and 30 polyethylene and polymethyl methacrylates.
combinations thereof. In at least one embodiment, the com- In at least one embodiment , the composition comprises
position is substantially free of parabens. pearlizing agents. In at least one embodiment, the compo
In at least one embodir the composition comprises sition comprises at least one pearlizing agent. In least one
from 0.1 wt % to 5.0 wt % antimicrobial agents. In at least embodiment, the particulate substance is selected from the
one embodiment, the antimicrobial agent is chlorhexidine . 35 group consisting of, fatty acid monoalkanolamides, fatty
In at least one embodiment, the composition comprises an acid dialkanolamides, monoesters or diesters of alkylene
anti- fungal substance . In at least one embodiment, the glycols , especially ethylene glycol and / or propylene glycol
anti- fungal substance is selected from the group consisting or oligomers thereof, with higher fatty acids , e.g. palmitic
of ketoconazole , oxiconazole , bifonazole , butoconazole , acid, stearic acid and behenic acid , monoesters or polyesters
cloconazole , clotrimazole, econazole , enilconazole , fenti- 40 of glycerol with carboxylic acids , fatty acids and metal salts
conazole , isoconazole , miconazole , sulconazole , tiocona- thereof, ketosulfones or mixtures of the aforementioned
zole , fluconazole, itraconazole, terconazole, naftifine, terbi- compounds.
nafine, zinc pyrithione, piroctone olamine (Octopirox® ) , In at least one embodiment, the composition comprises a
( RS )-1- ( 4 -chlorophenoxy )-1 - imidazol- 1 -yl-3,3 -dimethylbu- direct dye. In at least one embodiment, the composition
tan - 2 - one ( climbazole ), and combinations thereof. In at least 45 comprises at least one direct dye. Preferred among the direct
one embodiment, the composition comprises a total amount dyes are the following compounds, alone or in combination
of anti -fungal substance in the composition of from 0.1 wt with one another: hydroxyethyl- 2 - nitro - p - toluidine, 2 -hy
% to 1.0 wt % . In at least one embodiment, the composition droxyethylpicramic acid , 4 - nitrophenylaminourea, tri (4
comprises pyridinethione anti -dandruff particulates, for amino - 3 -methylphenyl ) carbenium chloride (Basic Violet 2 ) ,
example 1 -hydroxy - 2 -pyridinethione salts , are highly pre- 50 1,4 - di - amino - 9,10 - anthracenedione (Disperse Violet 1 ) ,
ferred particulate anti - dandruff agents. The concentration of 1- ( 2 -hydroxy - ethyl ) amino - 2 -nitro -4- [di( 2 -hydroxyethyl)
pyridinethione anti -dandruff particulate may ranges from amino ]benzene (HC Blue No. 2 ) , 4- [ethyl- ( 2 -hydroxyethyl)
0.1 % to 4.0 % , by weight of the formulation , preferably from amino ] -1 - [ ( 2 -hydroxyethyl) amino ] -2 -nitrobenzene hydro
0.1 % to 3.0 % , more preferably from 0.3 % to 2.0% . Pre- chloride ( HC Blue No. 12 ) , 1 -amino - 4- [di ( 2 -hydroxyethyl)
ferred pyridinethione salts include those formed from heavy 55 amino ) -2 -nitrobenzene hydrochloride (HC Red No. 13 ) ,
metals such as zinc, tin , cadmium , magnesium , aluminum 4 - amino - 1- ( 2 -hydroxyethyl )amino ) -2 -nitrobenzene (HC
and zirconium , preferably zinc , more preferably the zinc salt Red No. 3 ) , 4 - amino - 3 -nitrophenol, 4 - [ ( 2 -hydroxyethyl)
of 1 -hydroxy - 2 -pyridinethione ( known as " zinc pyridi- amino ] -3 -nitrophenol, 1- amino -5 -chloro -4 -[( 2,3 - dihydroxy
nethione ” or “ ZPT” ), more preferably 1-hydroxy -2 -pyridi- propyl )amino ] -2 - nitrobenzene ( HC Red No. 10 ) , 5 -chloro
nethione salts in platelet particle form . Salts formed from 60 1,4- [ di ( 2,3 -dihydroxypropyl )amino ] -2 -nitrobenzene (HC
Red No. 11 ) , 2 -chloro -6 - ethylamino - 4 -nitrophenol,
In at least one embodiment, the composition comprises a 2 -amino - 6 -chloro - 4 -nitrophenol6,
other cations , such as sodium , may also be suitable .
4 - [ ( 2 -hydroxyethyl)
dye or pigment. In at least one embodiment, the composition amino ]-3 -nitro - 1 - trifluoromethylbenzene ( HC Yellow No.
comprises at least one dye or pigment. Suitable dyes and 13 ) , 8 -amino -2-bromo-5 -hydroxy-4 - imino -6 - {[3-(trimeth
pigments are disclosed in WO02013 /017262A1 in the table 65 ylammonio )-phenyl] amino }-1 (4H ) -naphthalenone chloride
spanning pages 36 to 43. In at least one embodiment, the (C.I. 56059 ; Basic Blue No. 99 ) , 1 -[(4 -aminophenyl) azo )
composition comprises a total amount of from 0.01 wt % to 7- ( trimethylammonio ) -2 -naphthol chloride ( C.I. 12250 ;
 US 11,311,473 B2
31 32
Basic Brown No. 16 ) , 1 -[(4 -amino -2 -nitrophenyl)azo ] -7- propellants are selected from the group consisting of air,
( trimethylammonio ) -2 -naphthol chloride ( Basic Brown No. nitrogen (N2), nitrous oxide (N2O ), carbon dioxide ( CO2 ) ,
17 ) , 2 -hydroxy - 1-[ (2 -methoxyphenyl)azo ]-7-(trimethylam- and mixtures thereof. In at least one embodiment, the
monio )naphthalene chloride (C.I. 12245 ; Basic Red No. 76 ) , liquefied gas propellants are selected from the group con
3 -methyl- 1 -phenyl - 4 - { [ 3- (trimethylammonio )phenyl] 5 sisting of dimethylether ( DME ) , 1,1 -difluoroethane (HFC
azo }pyrazol-5 -one chloride ( C.I. 12719 ; Basic Yellow No. 152a ) , 1,1,1,2 - tetrafluoroethane ( HFC - 134a ) , pentane , n -bu
57 ) and 2,6 -diamino - 3 - [ (pyridin - 3 -yl) azo ]pyridine as well tane , iso -butane, propane, trans - 1,3,3,3 - tetrafluoropropene
as the salts thereof. (HF0-1234ze) , and mixtures thereof.
In at least one embodiment, the composition comprises a In at least one embodiment, the composition comprises a
perfume or fragrance ingredient. Individual fragrance com- 10 functional acid or an active ingredient. Functional acids and
pounds, e.g. the synthetic products of the type of esters , active ingredients are substances used to impart a clinical
ethers, aldehydes, ketones, alcohols and hydrocarbons can functionality to the skin or hair upon application. Functional
be used as fragrance or perfume oils . Fragrance compounds acids and active ingredients are for example used as exfo
of the ester type are e.g. benzyl acetate , phenoxyethyl liants, skin -brightening agents, self - tanning agents, anti
isobutyrate , p - tert -butylcyclohexyl acetate, linalyl acetate , 15 acne agents and anti-ageing agents.
dimethylbenzylcarbinyl acetate , phenylethyl acetate , linalyl In at least one embodiment, the composition comprises a
benzoate , benzyl formate , ethyl -methylphenyl glycinate , 2 deodorant or an anti -perspirants . In at least one embodiment,
allylcyclohexyl propionate, styrallyl propionate and benzyl the composition comprises a deodorising agent. In at least
salicylate. Perfume oils can also contain mixtures of natural one embodiment, the deodorising agent is selected from the
odoriferous substances that can be obtained from vegetable 20 group consisting of allantoin , bisabolol , and combinations
or animal sources . Essential oils of lower volatility, which thereof. The composition may comprise an antiperspirant.
are used mostly as flavor components, are also suitable as As antiperspirant it is possible to use aluminium chloride ,
perfume oils . aluminum chloride hydroxide, aluminum chloride dihydrox
In at least one embodiment, the composition comprises a ide , aluminum chlorohydrex polyethylene glycol complex,
carrier, solvent or diluent. In at least one embodiment, the 25 magnesium zirconium complexes or aluminum zirconium
composition comprises a solvent, wherein the solvent com- chloride hydroxide, for example.
prises water and / or alcohol . Solvent is useful for providing In at least one embodiment, the composition comprises at
the compounds used in present invention in liquid form . In least one viscosity modifier or thickening and / or gelling
at least one embodiment, the solvent is cosmetically accept- agent. The desired viscosity and rheology profile of the
able . In at least one embodiment, the composition comprises 30 compositions can be adjusted by adding further thickeners
at least 10 wt % water. Water is useful for economic reasons and gelling agents. The viscosity -modifying substance is
but also because it is cosmetically acceptable. Optionally the preferably a thickening polymer. In at least one embodiment,
composition comprises water- miscible or water - soluble sol- the thickening polymer selected from the group consisting
vents such as lower alkyl alcohols . In at least one embodi- of: copolymers of at least one first monomer type , which is
ment, the composition comprises C1 - C5 alkyl monohydric 35 chosen from acrylic acid and methacrylic acid, and at least
alcohols , preferably C2 - C3 alkyl alcohols. The alcohols one second monomer type , which is chosen from esters of
which may be present are in particular lower monohydric or acrylic acid and ethoxylated fatty alcohol , crosslinked poly
polyhydric alcohols having 1 to 4 carbon atoms customarily acrylic acid , crosslinked copolymers of at least one first
used for cosmetic purposes, such as preferably ethanol and monomer type, which is chosen from acrylic acid and
isopropanol . Optionally, the composition comprises a water- 40 methacrylic acid , and at least one second monomer type ,
soluble polyhydric alcohol . In at least one embodiment, the which is chosen from esters of acrylic acid with C10- to
water - soluble polyhydric alcohols are polyhydric alcohols C30 - alcohols ; copolymers of at least one first monomer
having two or more hydroxyl groups in the molecule . In a type , which is chosen from acrylic acid and methacrylic
preferred embodiment, the composition comprises a solvent acid, and at least one second monomer type, which is chosen
selected from the group consisting ofwater, glycols , ethanol, 45 from esters of itaconic acid and ethoxylated fatty alcohol ;
and combinations thereof. In a preferred embodiment, the copolymers of at least one first monomer type , which is
composition comprises an aqueous , alcoholic or aqueous- chosen from acrylic acid and methacrylic acid , at least one
alcoholic solvent, and wherein the aqueous, alcoholic or second monomer type , which is chosen from esters of
aqueous-alcoholic solvent comprises water, ethanol, propa- itaconic acid and ethoxylated C10- to C30 - alcohol and a
nol , isopropanol , 1,2 -propylene glycol , 1,3 - propylene gly- 50 third monomer type , chosen from C1 - to C4 - aminoalkyl
col , isobutanol, butanol, butyl glycol , butyl diglycol , glyc- acrylates; copolymers of two or more monomers chosen
erol, or a mixture thereof; preferably wherein the aqueous , from acrylic acid , methacrylic acid , acrylic esters and meth
alcoholic or aqueous -alcoholic solvent comprises water, acrylic esters ; copolymers of vinylpyrrolidone and ammo
ethanol, propanol, isopropanol, 1,2 -propylene glycol , 1,3- nium acryloyldimethyltaurate ; copolymers of ammonium
propylene glycol , glycerol, or mixtures thereof. Natural 55 acryloyldimethyltaurate and monomers chosen from esters
solvents can also be used . In at least one embodiment, the of methacrylic acid and ethoxylated fatty alcohols, hydroxy
composition comprises a solvent selected from the group ethylcellulose, hydroxypropylcellulose, hydroxypropylguar,
consisting of plant oil , honey, plant -derived sugar compo- glyceryl polyacrylate, glyceryl polymethacrylate, copoly
sitions , and mixtures thereof. In at least one embodiment, the mers of at least one C2-, C3- or C4 - alkylene and styrene ,
composition comprises from 0.5 wt % to 90 wt % , preferably 60 polyurethanes, hydroxypropyl starch phosphate , polyacryl
from 1.0 wt % to 80 wt % , even more preferably from 5.0 amide, copolymer of maleic anhydride and methyl vinyl
wt % to 70 wt % of at least one carrier, solvent and / or ether crosslinked with decadiene, carob seed flour, gums
diluent . such as guar gum , karaya gum , xanthan gum or dehydroxan
In at least one embodiment, the composition comprises a than gum , carrageenan , hydrolyzed corn starch ; copolymers
propellant. In at least one embodiment, the propellant is 65 of polyethylene oxide, fatty alcohols and saturated methyl
selected from compressed gas propellants and liquefied gas enediphenyl diisocyanate (e.g. PEG - 150 / stearyl alcohol /
propellants . In at least one embodiment, the compressed gas SMDI copolymer ), and mixtures thereof. In a preferred
 US 11,311,473 B2
33 34
embodiment, the viscosity modifier or thickening and / or agents and UV filters are disclosed in Wo02013 /017262A1
gelling agent is selected from the group consisting of ( published on 7 Feb. 2013 ) , from page 32 , line 11 to the end
carbomers, acrylates copolymers , xanthan gum , hydroxy- of page 33. The photoprotective substances include, in
ethylcellulose, laureth - 2 , and combinations thereof. particular, all of the photoprotective substances specified in
In at least one embodiment, the composition comprises an 5 EP1084696 , which is incorporated herein by reference . In
alkalizing agent or pH adjusting agent. In at least one another preferred embodiment of the invention , the compo
embodiment, ammonia or caustic soda is suitable, but water- sitions according to the invention contain one or more
soluble, physiologically tolerable salts of organic and inor- substances selected from inorganic and organic UV filters
ganic bases can also be considered . Optionally, the pH and especially preferably are in the form of sunscreen
adjusting agent is selected from ammonium hydrogen car- 10 compositions.
bonate , ammonia, monoethanolamine , ammonium hydrox- In at least one embodiment, the composition comprises a
ide , ammonium carbonate . In at least one embodiment, the skin conditioning agent. Skin conditioning agents such as
alkalizing agents is selected from the group consisting of emollients, humectants and occlusive agents are ingredients
2 -amino - 2 -methyl - 1 -propanol, 2 -amino - 2-methyl-1,3 -pro- which help to maintain the soft and smooth appearance of
panediol, 2 -amino - 2 - ethyl- 1,3 -propanediol, tris (hydroxyl- 15 the skin or which help to improve the condition of dry or
methyl)-aminomethane, 2 - amino - 1 -butanole , tris- (2 - hy- damaged skin . In at least one embodiment, the skin condi
droxypropyl ) -amine, 2,2 - iminobisethanol, lysine , iminourea tioning agent is selected from the group consisting of oily
( guanidine carbonate ), tetrahydro - 1,4 -oxazine, 2 - amino - 5- substances ( description see above ), functional acids or
guanidin -valeric acid , 2 - aminoethansulfonic acid, dietha- active ingredients ( description see above ) , fatty acid N - al
nolamine, triethanolamine, N -methyl ethanolamine, isopro- 20 kylpolyhydroxyalkyl amides , fatty acids , triglycerides, pan
panolamine, diisopropanolamine , triisopropanolamine , thenol, allantoin , bisabolol, glycerol, sorbitol, urea and
glucamine, sodium hydroxide, potassium hydroxide , lithium derivatives thereof, trehalose , erythrulose , pyrrolidone car
hydroxide and magnesium oxide, and mixtures thereof. To boxylic acid ( PCA) and its salts , polyglucuronic acid , glu
establish an acidic pH value , an acid can be included . conolactone , petrolatum , ubichinon - 10 and ubiquinol. In a
In at least one embodiment, the composition / formulation 25 preferred embodiment, the skin conditioning agent is
comprises an anti -oxidant. In at least one embodiment, the selected from the group consisting of urea , glycerine, pyr
anti - oxidant is selected from the group consisting of amino rolidone carboxylic acid ( PCA) and its salts , panthenol,
acids , peptides , sugars , imidazoles , carotinoids, carotenes, petrolatum , and combinations thereof.
chlorogenic acid , lipoic acid, thiols , thiol glycosyl esters , In at least one embodiment, the composition comprises an
thiol N - acetyl esters , thiol methyl esters , thiol ethyl esters , 30 anti - foaming agent. Antifoams are chemicals which reduce
thiol propyl esters , thiol amyl esters , thiol butyl esters, thiol the tendency of finished products to generate foam on
lauryl esters, thiol palmitoyl esters , thiol oleyl esters , thiol shaking or agitation . In at least one embodiment, the anti
linoleyl esters , thiol cholesteryl esters , thiol glyceryl esters , foaming agent is selected from the group consisting of
dilaurylthiodipropionate, distearylthiodipropionate, thiodi- alcohols ( e.g. ethanol, isopropyl alcohol or propyl alcohol ),
propionic acid , metal chelators , hydroxy acids , fatty acids , 35 alkoxylated alcohols ( e.g. laureth - 5 butyl ether ), silicon oils
folic acids , vitamin C , tocopherol, vitamin A , stilbenes , and resins (e.g. dimethicone and its derivatives such as cetyl
derivatives and combinations thereof. dimethicone , phenyl dimethicone, PEG /PPG - 12 / 18 dimethi
In at least one embodiment, the composition / formulation cone and hydrogen trifluoropropyl dimethicone, trimethyl
comprises a chelant. In at least one embodiment, the chelant siloxysilicate /dimethicone crosspolymer or polysilicone -10 )
is selected from the group consisting of EDTA , caprylhy- 40 and hydrophobic silica derivatives ( e.g. silica silylate ).
droxamic acid, oxalate derivatives, disodium hydroxyethyl- In at least one embodiment, the composition comprises a
iminodiacetate, galacturonic acid and derivatives, glu- flavouring agent. In at least one embodiment, the flavouring
curonic acid and derivatives, lauroyl ethylenediamine agent is selected from the group consisting of 1 -acetonaph
triacetic acid , methyl dihydroxybenzoate, trisodium ethyl- thalene, 1 - decen - 3 - ol , p -methylbenzaldehyde, p -prope
enediamine disuccinate, phytic acid, itaconic acid, propane 45 nylphenyl methyl ether, aspartame, benzaldehyde, bromo
tricarboxylic acid , citric acid and derivatives ( e.g. diammo- cinnamal, calcium cyclohexylsulfamate, calcium
nium citrate , bismuth citrate and acetyl trihexyl citrate o -benzolufimide, carvone , cinnamic aldehyde, 3,7 -dim
2,6 -dicarboxy pyridine ), phosphoric and phosphonic acid ethyl - 6 -octenoic acid , fruit sugar, glucose , glucosyl stevio
derivatives (e.g. diethylenetriamine pentamethylene phos- side , honey , 3 -methyl - 1 -butanol, 4 -hydroxy -3 -methoxy - 1
phonic acid , disodium azacycloheptane diphosphonate, 50 propenylbenzene, malt sugar, menthol, eucalyptol, thymol,
glycereth - 26 phosphate, disodium pyrophosphate, disodium potassium 6 -methyl - 1,2,2 -oxathiazin - 4 (3H ) -one 2,2'-diox
salicylphosphate , aminotrimethylene phosphonic acid , ide , isodulcitol, saccharine, stevioside , 1',4,6 -trichloro - ga
phosphonobutanetricarboxylic acid, potassium trisphospho- lacto -sucrose, sorbitol, saccharose , sodium saccharin ,
nomethylamine oxidebeta - alanine diacetic acid or cyclo- methyl salicylate vanillaldehyde, xylite , xylose and plant
hexanediamine tetraacetic acid) . In at least one embodiment, 55 extracts .
the chelant is selected from the group consisting EDTA , In at least one embodiment, the composition comprises an
oxalate derivatives, disodium salicylphosphate, and combi- electrolyte. In at least one embodiment, the electrolyte is
nations thereof. selected from the group consisting of salts preferably ammo
In at least one embodiment, the composition comprises an nium or metal salts , especially preferably halides , for
astringent. In at least one embodiment, the astringent is 60 example CaCl2 , MgCl2 , LiCl , KCl and NaCl , carbonates ,
selected from the group consisting of magnesium oxide, hydrogen carbonates, phosphates, sulfates, nitrates, espe
aluminium oxide , titanium dioxide , zirconium dioxide , zinc cially preferably sodium chloride, sodium fluoride, sodium
oxide , oxide hydrates, aluminium oxide hydrate ( boehmite) monofluorophosphate, stannous fluoride, and / or organic
and hydroxide, chlorohydrates of calcium , magnesium , alu- salts .
minium , titanium , zirconium or zinc .
9 65 In at least one embodiment, the composition comprises an
In at least one embodiment, the composition comprises a oxidizing or reducing agent. In at least one embodiment, the
sun protection agent and / or UV filter. Suitable sun protection oxidizing or reducing agent is selected from the group
 US 11,311,473 B2
35 36
consisting of ammonium persulfate, calcium peroxide, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or
hydrogen peroxide, hypochlorous acid, sodium hypochlo- alkylaryl group having up to 22 carbon atoms ;
rite , potassium monopersulfate, sodium carbonate peroxide , X is selected from the group consisting of: halogen, acetate ,
ammonium thioglycolate, cysteine, glutathione , hydroqui- citrate , lactate , glycolate, phosphate , nitrate , sulfonate, sul
none, mercaptopropionic acid , superoxide dismutase, thio- 5 fate, alkylsulfate, alkyl sulfonate radicals, and combinations
thereof.
glycerin , thioglycolic acid, thiolactic acid , sodium sulfite ,
sodium thioglycolate , potassium thioglycolate , and cysteine. In at least one embodiment, the cationic surfactant is
Hair Conditioning Agent selected from the group consisting of cetyltrimonium chlo
In at least one embodiment, the composition comprises a ride (CTAC ), stearyltrimonium chloride (STAC ), behentri
hair conditioning agent. In at least one embodiment, the hair 10 monium( SAPDMA
methosulfate, stearoylamidopropyldimethyl amine
), distearyldimethylammonium chloride, and
conditioning agent is a water insoluble, water dispersible , mixtures thereof .
non- volatile , liquid that forms emulsified , liquid particles. In Hairstyling Polymers
at least one embodiment, the hair conditioning agent is a In at least one embodiment, the composition comprises a
silicone ( e.g. , silicone oil , cationic silicone, silicone gum , 15 hairstyling polymer. In at least one embodiment, the hair
high refractive silicone , and silicone resin ), an organic styling polymer is selected from the group consisting of:
conditioning oil ( e.g. , hydrocarbon oils , polyolefins, and amphoteric hairstyling polymers , zwitterionic hairstyling
fatty esters ), or combinations thereof. polymers, anionic hairstyling polymers, non - ionic hairstyl
In at least one embodiment, the hair conditioning agent is ing polymers, cationic hairstyling polymers, and mixtures
a silicone , and wherein the composition comprises from 20 thereof. In at least one embodiment, the composition com
0.01 % to 10% , or from 0.1 % to 5 % silicone hair condition- prises from 0.01 % to 20 % , or from 0.01 % to 16 % , or from
ing agent, by total weight of the composition . Suitable 0.01 % to 10 % , or from 1 % to 8 % , or from 2 % to 6 % of
silicone hair conditioning agents, and optional suspending hairstyling polymer.
agents for the silicone, are described in U.S. Pat. No. Cosmetic , Dermatological or Pharmaceutical Compositions
5,104,646 . In at least one embodiment, the composition 25 In at least one embodiment, the cosmetic , dermatological
comprises a silicone gum selected from the group consisting or pharmaceutical composition according ato the invention
of polydimethylsiloxane, ( polydimethylsiloxane ) (methylvi comprise the one or more polymers ( I ) in a total amount of
nylsiloxane) copolymer, poly ( dimethylsiloxane) (diphenyl from 0.01 to 10 wt % , preferably from 0.1 to 5.0 wt % , even
siloxane) (methylvinylsiloxane ) copolymer, and mixtures more preferably from 0.25 to 2.0 wt % . In at least one
thereof. In at least one embodiment, the composition com 30 cal
embodiment, the cosmetic , dermatological or pharmaceuti
prises a terminal aminosilicone . “ Terminal aminosilicone” % , compositions comprise further from 0.5 wt % to 90 wt
as defined herein means silicone comprising one or more preferably from 5.0 wt1.0% wt 70%wtto%80of at
preferably from wt % , even more
least one carrier,
amino groups at one or both ends of the silicone backbone . solvent and / or diluent. Carriers, solvents and / or diluents are
highIn melting
at least one
pointembodiment , the composition
fatty compound comprises
. The high melting pointa 35 listed above. In at least one embodiment, the carrier, solvent
and / or diluent is selected from the group consisting of water,
fatty compound has a melting point of 25 ° C. or higher. In glycols , ethanol, and combinations thereof.
at least one embodiment, the high melting point fatty com In at least one embodiment, the composition is selected
pound is selected from the group consisting of a fatty from the group consisting of shampoo, body wash , facial
alcohol , fatty acid, fatty alcohol derivative, fatty acid deriva- 40 cleanser, face mask, bubble bath , intimate wash , bath oil ,
tive , and mixtures thereof. Non - limiting examples of the cleansing milk , micellar water, make-up remover , cleansing
-
high melting point compounds are found in International wipes , hair mask , perfume, liquid soap , shaving soap , shav
Cosmetic Ingredient Dictionary, Fifth Edition , 1993 , and ing foam , cleansing foam , day cream , anti -ageing cream ,
CTFA Cosmetic Ingredient Handbook, Second Edition, body milk , body lotion , body mousse , face serum , eye
1992. The composition may comprise from 0.1 % to 40 % , or 45
from 1 % to 30 % , or from 1.5 % to 16 % , or from 1.5 % to 8 %
cream , sunscreen lotion, sun cream , face cream , after - shave
of a high melting point fatty compound, by total weight of lotion, pre - shaving cream , depilatory cream , skin -whitening
the composition. gel , self -tanning cream , anti - acne gel , mascara, foundation ,
In at least one embodiment, the composition comprises a primer, concealer, blush , bronzer, blemish balm (bb ) cream ,
eyeliner, night cream , eye brow gel , highlighter, lip stain ,
cationic surfactant. In an embodiment, cationic surfactant is 50
according to Formula (C ) :
hand sanitizer, hair oil , nail varnish remover, conditioner,
hair styling gel , hair styling cream , anti- frizz serum , scalp
treatment, hair colorant, split end fluid , deodorant, antiper
(C)
spirant, baby cream , insect repellent, hand cream , sunscreen
R71 gel , foot cream , exfoliator, body scrub , cellulite treatment,
55 bar soap , cuticle cream , lip balm , hair treatment, eye
R72 — Nle> R73 x shadow , bath additive, body mist , eau de toilette , mouth
R74 wash , toothpaste, lubricating gel , moisturizer, serum , toner,
aqua sorbet, cream gel , styling mousse , dry shampoo, lip
stick , lip gloss , hydro - alcoholic gel , body oil , shower milk ,
wherein 60 illuminator, lip crayon , hair spray , combing cream , and
at least one of R71 , R7 ?, R73 and R74 is selected from an
2 sunblock .
aliphatic group of from 8 to 30 carbon atoms, an aromatic , In at least one embodiment, the cosmetic , dermatological
alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl, or or pharmaceutical composition is for use on skin . In at least
an alkylaryl group having up to 22 carbon atoms; one embodiment, the composition is for use on the face , the
the remainder of R71 , R72 , R73 and R74 are independently 65
2 neck , the body and / or around the eye area . In at least one
selected from the group consisting of an aliphatic group embodiment, the composition is an emulsion or gel , prefer
consisting of from 1 to 22 carbon atoms, and an aromatic, ably an oil - in -water (o /w ) , cream gel , hydro -alcoholic gel or
 US 11,311,473 B2
37 38
hydrogel composition . In a preferred embodiment, the com- thickening and / or gelling agent. Viscosity modifiers or
position has a viscosity from 100 000 to 200 000 mPa.s , thickening and / or gelling agents are listed above. Optionally
preferably from 1 000 to 100 000 mPa.s , even more pref- the skin -whitening composition comprises from 0.01 wt %
erably from 2000 to 50 000 mPa.s and very preferably from to 5.0 wt % , preferably from 0.1 wt % to 3.0 wt % , even
5000 to 30 000 mPa.s (measured at 25 ° C. , Brookfield RVT, 5 more preferably from 0.4 wt % to 1.0 wt % of at least one
T - C spindle at 20 revolutions per minute ). preservative or preservation boosting ingredient. Preserva
In at least one embodiment, the composition is a body or tives or preservation boosting ingredients are listed above .
face care composition such as face creams , neck creams, In a preferred embodiment, the skin -whitening composition
body lotions , body milks , face serums, blemish balm has a pH value from 1.0 to 8.0 , preferably from 2.0 to 7.0 ,
creams, hand creams , foot creams, body butters , lip creams, 10 even more preferably from 3.0 to 6.0 .
9

eye creams , after - sun lotions , make -up removing lotions or In at least one embodiment, the composition is a self
body mists , diaper creams or baby lotions . Optionally the tanning composition. Optionally the self -tanning composi
body or face care composition comprises from 0.1 wt % to tion comprises from 0.001 wt % to 40 wt % , preferably from
15 wt % , preferably from 0.5 wt % to 10 wt % , even more 0.05 wt % to 30 wt % , even more preferably from 0.1 wt %
preferably from 1.0 wt % to 5.0 wt % of at least one 15 to 20 wt % of at least one oily substance . Oily substances are
emulsifier, coemulsifier and / or solubilizer. Emulsifiers, listed above. Optionally the self -tanning composition com
coemulsifiers and / or solubilizers are listed above . Optionally prises from 0.01 wt % to 20 wt % , preferably from 0.1 wt
the body or face care composition comprises from 0.01 wt % to 10 wt % , even more preferably from 0.5 wt % to 5.0
% to 40 wt % , preferably from 0.05 wt % to 30 wt % , even wt % of at least one further auxiliary. Auxiliaries are listed
more preferably from 0.1 wt % to 20 wt % of at least one oily 20 above .
substance. Oily substances are listed above . Optionally the In at least one embodiment, the composition is aa cleansing
body or face care composition comprises from 0.01 wt % to composition such as body washes, face washes , micellar
20 wt % , preferably from 0.05 wt % to 10 wt % , even more waters or gels , body scrubs, face peeling, facial exfoliators ,
preferably from 0.1 wt % to 5.0 wt % of at least one wax . liquid soaps, bath additives, bubble baths, shower creams or
Waxes are listed above . Optionally the body or face care 25 milks , shower foams and face masks . Optionally the cleans
composition comprises from 0.01 wt % to 15 wt % , pref- ing composition comprises from 0.5 wt % to 25 wt % ,
erably from 0.1 wt % to 10 wt % , even more preferably from preferably from 1.0 wt % to 20 wt % , even more preferably
0.3 wt % to 5.0 wt % of at least one viscosity modifier or from 2.0 wt % to 15 wt % of at least one surfactant.
thickening and / or gelling agent. Viscosity modifiers or Surfactants are listed above . Optionally the cleansing com
thickening and /or gelling agents are listed above. Optionally 30 position comprises from 0.01 wt % to 15 wt % , preferably
the body or face care composition comprises from 0.001 wt from 0.1 wt % to 10 wt % , even more preferably from 0.5
% to 5.0 wt % , preferably from 0.05 wt % to 3.0 wt % , even wt % to 5.0 wt % of at least one viscosity modifier or
more preferably from 0.1 wt % 1.0 wt % of at least one thickening agent. Viscosity modifier or thickening agents are
skin conditioning agent. Skin conditioning agents are listed listed above . Optionally the cleansing composition com
above . Optionally the body or face care composition com- 35 prises from 0.01 wt % to 15 wt % , preferably from 0.05 wt
prises from 0.001 wt % to 10 wt % , preferably from 0.05 wt % to 10 wt % , even more preferably from 0.5 wt % to 5.0
% to 5.0 wt % , even more preferably from 0.1 wt % to 3.0 wt % of at least one particulate substance . Particulate
wt % , most preferably from 0.05 wt % to 1.0 wt % of at least substances are listed above . Optionally the cleansing com
one antioxidant. Antioxidants are listed above . Optionally position comprises from 0.001 wt % to 30 wt % , preferably
the body or face care composition comprises from 0.001 wt 40 from 0.05 wt % to 20 wt % , even more preferably from 0.1
% to 5.0 wt % , preferably from 0.01 wt % to 3.0 wt % , even wt % to 10 wt % of at least one oily substance. Oily
more preferably from 0.1 wt % to 2.0 wt % of at least one substances are listed above. Optionally the cleansing com
biogenic active substance . Optionally the body or face care position comprises from 0.05 wt % to 15 wt % , preferably
composition comprises from 0.01 wt % to 4.0 wt % , from 0.1 wt % to 10 wt % , even more preferably from 0.5
preferably from 0.1 wt % to 3.0 wt % , even more preferably 45 wt % to 5.0 wt % of at least one functional acid or / and an
from 0.4 wt % to 1.0 wt % of at least one preservative or active ingredient. Functional acids or / and an active ingre
preservation boosting ingredient. Preservatives or preserva- dients are listed above. Optionally the cleansing composi
tion boosting ingredients are listed above . Optionally the tion comprises from 0.001 wt % to 5.0 wt % , preferably from
body or face care composition comprises from 0.01 wt % to 0.05 wt % to 3.0 wt % , even more preferably from 0.1 wt %
3.0 wt % , preferably from 0.05 wt % to 2.0 wt % , even more 50 to 1.0 wt % ofat least one electrolyte . Electrolytes are listed
preferably from 0.1 wt % to 1.0 wt % of at least one perfume above . Optionally the cleansing composition comprises
or fragrance ingredient. Perfume or fragrance ingredients or from 0.01 wt % to 5.0 wt% , preferably from 0.1 wt % to 3.0
are listed above . Optionally the body or face care compo- wt % , even more preferably from 0.4 wt % to 1.0 wt % of
sition comprises from 0.01 wt % to 20 wt % , preferably from at least one preservative or preservation boosting ingredient .
0.1 wt % to 10 wt % , even more preferably from 0.5 wt % 55 Optionally the cleansing composition comprises from 0.01
to 5.0 wt % of at least one further auxiliary. Auxiliaries are wt % to 20 wt % , preferably from 0.1 wt % to 10 wt % , even
listed above . more preferably from 0.5 wt % to 5.0 wt % of at least one
In at least one embodiment, the composition is a skin- further auxiliary. Auxiliaries are listed above .
whitening composition . Optionally the skin -whitening com- In at least one embodiment, the composition is a sun care
position comprises from 0.1 wt % to 15 wt % , preferably 60 composition such as sun sprays, sun milks, sun lotions , sun
from 0.5 wt % to 10 wt % , even more preferably from 1.0 gels . Body and face care compositions with sun protection
wt % to 5.0 wt % of at least one emulsifier, coemulsifier agents and /or UV filters such as day creams, hand creams ,
and / or solubilizer. Emulsifiers, coemulsifiers and / or solubi- foundations, lip balms and face serums can also serve as sun
lizers are listed above . Optionally the skin -whitening com- care compositions. Optionally the sun care composition
position comprises from 0.01 wt % to 10 wt % , preferably 65 comprises from 0.1 wt % to 15 wt % , preferably from 0.5 wt
from 0.1 wt % to 7.5 wt % , even more preferably from 0.3 % to 10 wt % , even more preferably from 1.0 wt % to 5.0
wt % to 5.0 wt % of at least one viscosity modifier or wt % of at least one emulsifier, coemulsifier and / or solubi
 US 11,311,473 B2
39 40
lizer. Optionally the sun care composition comprises from % , even more preferably from 0.4 wt % to 1.0 wt % of at
0.001 wt % to 50 wt % , preferably from 0.05 wt % to 40 wt least one preservative or preservation boosting ingredient.
% , even more preferably from 0.1 wt % to 30 wt % of at least In at least one embodiment, the composition is aa bar soap
one oily substance . Oily substances are listed above . Option- or syndet composition . Optionally the bar soap or syndet
ally the sun care composition comprises from 0.001 wt % to 5 composition comprises from 1.0 wt % to 50 wt %, preferably
30 wt % , preferably from 0.05 wt % to 20 wt % , even more from 2.0 wt % to 30 wt % , even more preferably from 5.0
preferably from 0.1 wt % to 10 wt % , most preferably from wt % to 20 wt % of at least one surfactant. Surfactants are
listed above . Optionally the bar soap or syndet composition
0.05 wt % to 5.0 wt % of at least one sun protection agent
and / or UV filter. Sun protection agents and / or UV filters are 10 wt % to 15 from
comprises 0.01 wt % to 20 wt % , preferably from 0.05
listed above . Optionally the sun care composition comprises wt % of wt % , even more preferably from 0.5 wt % to 10
from 0.1 wt % to 10 wt % , preferably from 0.5 wt % to 7.5 substances atareleast one particulate substance . Particulate
listed above . Optionally the bar soap or
wt % , even more preferably from 1.0 wt % to 5.0 wt % of syndet composition comprises from 0.001 wt % to 5.0 wt % ,
at least one film former. Film formers are listed above . preferably from 0.05 wt % to 3.0 wt % , even more preferably
Optionally the sun care composition comprises from 0.01 wt 15 from 0.1 wt % to 1.0 wt % of at least one electrolyte .
% to 5.0 wt % , preferably from 0.1 wt % to 3. wt % , even Electrolytes are listed above . Optionally the bar soap or
more preferably from 0.4 wt % to 1.0 wt % of at least one syndet composition comprises from 0.01 wt % to 20 wt % ,
preservative or preservation boosting ingredient. Preserva preferably from 0.1 wt % to 10 wt % , even more preferably
tives or preservation boosting ingredients are listed above . from 0.5 wt % to 5.0 wt % of at least one further auxiliary.
Optionally the sun care composition comprises from 0.01 wt 20 Auxiliaries are listed above .
% to 20 wt % , preferably from 0.1 wt % to 10 wt % , even In at least one embodiment, the composition is aa deodor
more preferably from 0.5 wt % to 5.0 wt % of at least one izing and / or antiperspirant composition . In at least one
further auxiliary. Auxiliaries are listed above . embodiment, the composition is in the form of a cream , a
In at least one embodiment, the composition is a color roll- on , a solid , an aerosol or a gel . Optionally the deodor
cosmetic composition such as foundations, fluid Illumina- 25 izing and / or antiperspirant composition comprises from
tors , eye brow products, primers, conc
ncealers, blushes , bronz- 0.001 wt % to 10 wt % , or from 0.01 wt % to 9.0 wt % , or
ers , eye shadows, eye lash products, eye liners , face pow- from 0.05 wt % to 8.0 wt % , or from 0.1 wt % to 5.0 wt %
ders, lipsticks , lip glosses , lip balms or nail polishes . of at least one antiperspirant and /or deodorizing agent.
Optionally the color cosmetic composition comprises from Optionally the deodorizing and /or antiperspirant composi
0.01 wt % to 25 wt % , preferably from 0.1 wt % to 15 wt 30 tion comprises 0.01 wt % to 3.0 wt % , preferably from 0.05
% , even more preferably from 0.5 wt % to 10 wt % of at least wt % to 2.0 wt % , even more preferably from 0.1 wt % to
one dye or pigment. Dyes and pigments are listed above. 1.0 wt % of at least one perfume or fragrance ingredient.
Optionally the color cosmetic composition comprises from Perfume or fragrance ingredients or are listed above. Option
0.01 wt % to 15 wt % , preferably from 0.05 wt % to 10 wt ally the deodorizing and / or antiperspirant composition com
% , even more preferably from 0.5 wt % to 5.0 wt % of at 35 prises from 0.5 wt % to 60 wt % , preferably from 1.0 wt %
least one particulate substance . Optionally the color cos- to 50 wt % , even more preferably from 2.0 wt % to 40 wt
metic composition comprises from 0.001 wt % to 60 wt % , % of at least one propellant. Propellants are listed above .
preferably from 0.05 wt % to 50 wt % , even more preferably Optionally the deodorizing and / or antiperspirant composi
from 0.1 wt % to 40 wt % of at least one oily substance . Oily tion comprises from 0.01 wt % to 20 wt % , preferably from
substances are listed above . Optionally the color cosmetic 40 0.1 wt % to 10 wt % , even more preferably from 0.5 wt %
composition comprises from 0.001 wt % to 30 wt % , to 5.0 wt % of at least one further auxiliary. Auxiliaries are
preferably from 0.05 wt % to 20 wt % , even more preferably listed above .
from 0.1 wt % to 10 wt % of at least one wax . Waxes are In at least one embodiment, the composition is a depil
listed above . Optionally the color cosmetic composition ating composition.
comprises from 0.1 wt % to 15 wt % , preferably from 0.5 wt 45 In at least one embodiment, the composition is a shaving
% to 10 wt % , even more preferably from 1.0 wt % to 5.0 composition .
wt % of at least one emulsifier, coemulsifier and /or solubi- In at least one embodiment, the composition is a fragrance
lizer. Optionally the color cosmetics composition comprises composition.
from 0.01 wt % to 5.0 wt % , preferably from 0.1 wt % to 3.0 In at least one embodiment, the composition is a hand
wt % , even more preferably from 0.4 wt % to 1.0 wt % of 50 sanitizing composition.
at least one preservative or preservation boosting ingredient. In at least one embodiment, the cosmetic , dermatological
Preservatives or preservation boosting ingredients are listed or pharmaceutical composition is for use on hair and /or
above . Optionally the color cosmetic composition comprises scalp . In at least one embodiment, the composition is an
from 0.01 wt % to 20 wt % , preferably from 0.1 wt % to 10 emulsion or gel , preferably an oil - in -water ( o/w ) , cream gel ,
wt % , even more preferably from 0.5 wt % to 5.0 wt % of 55 hydro - alcoholic gel or hydrogel composition. In a preferred
at least one further auxiliary. Auxiliaries are listed above . embodiment, the hair care composition has a viscosity from
In at least one embodiment, the composition is a face 100 000 to 150 000 mPa.s , preferably from 1 000 to 100 000
toner . Optionally the face toner composition comprises from mPa · s , more preferably from 2000 to 50 000 mPa.s and very
0.001 wt % to 5.0 wt % , preferably from 0.05 wt % to 3.0 preferably from 5 000 to 30 000 mPa s ( 25 ° C. , Brookfield
wt % , even more preferably from 0.1 wt % to 1.0 wt % of 60 RVT, T - C spindle at 20 revolutions per minute ).
at least one skin conditioning agent. Skin conditioning In at least one embodiment, the composition is a shampoo
agents are listed above . Optionally the face toner composi- composition. Optionally the shampoo composition com
tion comprises from 0.01 wt % to 15 wt % , preferably from prises from 0.5 wt % to 30 wt % , preferably from 1.0 wt %
0.1 wt % to 10 wt % , even more preferably from 0.5 wt % to 15 wt % , even more preferably from 2.0 wt % to 10 wt
to 5.0 wt % of at least one viscosity modifier or thickening 65 % of at least one surfactant. Surfactants are listed above. In
agent. Optionally the face toner composition comprises from at least one embodiment, the surfactant is selected from the
0.01 wt % to 5.0 wt % , preferably from 0.1 wt % to 3.0 wt group consisting of sodium laureth sulfate, sodium lauryl
 US 11,311,473 B2
41 42
sulfate , ammonium lauryl sulfate , sodium lauroyl sarcosi- Biogenic active substances are listed above . In at least one
nate, sodium methyl cocoyl taurate, cocamidopropyl embodiment, the biogenic active substance is selected from
betaine, sodium cocoyl glutamate, lauryl glucoside, cocoyl the group aloe collagen hydrolysates, bisabolol, allantoin ,
methyl glucamide, and combinations thereof. Optionally the hydrolyzed wheat protein , hydrolyzed silk , hydrolyzed kera
shampoo composition comprises from 0.1 wt % to 10 wt % , 5 tin, amino acids and its derivatives, glycoproteins, and
preferably from 0.5 wt % to 7.5 wt % , even more preferably combinations thereof. Optionally the hair conditioning and /
from 1.0 wt % to 5.0 wt % of at least one cationic polymer.
Optionally the shampoo composition comprises from 0.1 wt or hair and / or scalp treatment composition comprises from
0.01 wt % to 5.0 wt % , preferably from 0.1 wt % to 3.0 wt
% to 15 wt % , preferably from 0.5 wt % to 10 wt % , even % , even more preferably from 0.4 wt % to 1.0 wt % of at
more preferably
pearlizing agent. from 1.0 wtthe% shampoo
Optionally to 5.0 wtcomposition
% of at leastcom
one 10 least one preservative or preservation boosting ingredient.
Preservatives or preservation boosting ingredients are listed
prises from 0.001 wt % to 5.0 wt % , preferably from 0.05 wt above . In at least one embodiment, the preservative or
% to 3.0 wt % , even more preferably from 0.1 wt % to 1.0 preservation boosting ingredient is selected from the group
wt % of at least one electrolyte. Optionally the shampoo consisting of sodium benzoate , methylparaben, phenoxy
composition comprises from 0.01 wt % to 15 wt % , pref- 15 ethanol, methylisothiazolinone, DMDM hydantoin , methyl
erably from 0.1 wt % to 10 wt % , even more preferably from chloroisothiazolinone, pyrithione, octopirox, and combina
0.5 wt % to 5.0 wt % of at least one viscosity modifier or tions thereof. Optionally the hair conditioning and / or hair
thickening agent. Viscosity modifier or thickening agents are and / or scalp treatment composition comprises from 0.01 wt
listed above . Optionally the shampoo composition com % to 20 wt % , preferably from 0.1 wt % to 10 wt % , even
prises from 0.01 wt % to 5.0 wt % , preferably from 0.1 wt 20 more preferably from 0.5 wt % to 5.0 wt % of at least one
% to 3.0 wt % , even more preferably from 0.4 wt % to 1.0 further auxiliary. Auxiliaries are listed above . In a preferred
wt % of at least one preservative or preservation boosting embodiment, the hair conditioning and / or hair and / or scalp
ingredient. Preservatives or preservation boosting ingredi
ents are listed above . Optionally the shampoo composition treatment
preferably
composition has a pH value from 2.0 to 8.0 ,
from 3.0 to 7.0 , even more preferably from 4.0 to
comprises from 0.01 wt % to 20 wt % , preferably from 0.1 25 6.0 .
wt % to 10 wt % , even more preferably from 0.5 wt % to 5.0 In at least one embodiment, the composition is a hair
wt % of at least one further auxiliary. Auxiliaries are listed styling composition such as mousses , gels , sprays and
above . In a preferred embodiment, the shampoo composition waxes . Optionally the hair styling composition comprises
has a pH value of from 2.0 to 8.0 , preferably from 3.0 to 7.0 , from 0.1 wt % to 10 wt % , preferably from 0.5 wt % to 7.5
even more preferably from 4.0 to 6.0 . 30
In at least one embodiment, the composition is a hair wt % , even more preferably from 1.0 wt % to 5.0 wt % of
conditioning and/or hair and /or scalp treatment composition at least one film former or hairstyling polymer. Film formers
such as leave - in and rinse -off conditioners, masks , lotions ,
and hairstyling polymers are listed above . In at least one
combing creams, detangling creams, anti - frizz liquids, hairembodiment, the film former is selected from the group
serums, scalp serums, color protection creams. Optionally 35 consisting of PVP, VP /VA copolymer, styrene / acrylates
the hair conditioning and / or hair and / or scalp treatment copolymer, acrylates copolymer, butyl ester of PVM /MA
composition comprises from 0.1 wt % to 15 wt % , preferably copolymer, hydroxyethylcellulose, chitosan , polyquater
from 0.5 wt % to 10 wt % , even more preferably from 1.0 nium - 10 , polypropylsilsesquioxane, polyurethane -64, and
wt % to 5.0 wt % of at least one emulsifier, coemulsifier combinations thereof. Optionally the hair styling composi
and / or solubilizer. Emulsifiers, coemulsifiers and / or solubi- 40
lizers are listed above . In at least one embodiment, the tion comprises from 0.1 wt % to 10 wt % , preferably from
emulsifier, coemulsifier and / or solubilizer is selected from 0.5 wt % to 7.5 wt % , even more preferably from 1.0 wt %
the group consisting of cetearyl alcohol , cetrimonium chlo- to 5.0 wt % of at least one cationic polymer. Cationic
ride , behentrimonium chloride, steartrimonium chloride, polymers are listed above. In at least one embodiment, the
cetyl alcohol , stearyl alcohol , stearic acid , isostearamidopro- 45 cationic polymer is selected from the group consisting of
pyl dimethylamine, and combinations thereof. Optionally polyquaternium - 10, guar hydroxypropyltrimonium chloride,
the hair conditioning and/or hair and /or scalp treatment polyquaternium - 7, polyquaternium - 6, and combinations
composition comprises from 0.01 wt % to 20 wt % , pref- thereof. Optionally the hair styling composition comprises
erably from 0.05 wt % to 10 wt % , even more preferably from 0.5 wt % to 60 wt % , preferably from 1.0 wt % to 50
from 0.1 wt % to 5.0 wt % of at least one oily substance . Oily 50 wt % , even more preferably from 2.0 wt % to 40 wt % of at
substances are listed above . In at least one embodiment, the least one propellant. Propellants are listed above . In at least
oily substance is selected from the group consisting of one embodiment, the propellant is selected from the group
dimethicone, squalene, amodimethicone, argan oil , jojoba
oil , cyclopentasiloxane, mineral oil , castor oil , shea butter, consisting of nitrogen , carbon dioxide , pentane , n -butane ,
and combinations thereof. Optionally the hair conditioning 55 iso -butane, propane, and combinations thereof. Optionally
and / or hair and / or scalp treatment composition comprises the hair styling composition comprises from 0.01 wt % to
from 0.1 wt % to 10 wt % , preferably from 0.5 wt % to 7.5 5.0 wt % , preferably from 0.1 wt % to 3.0 wt % , even more
wt % , even more preferably from 1.0 wt % to 5.0 wt % of preferably from 0.4 wt % to 1.0 wt % of at least one
at least one cationic polymer. Cationic polymers are listed preservative or preservation boosting ingredient. Preserva
above
selected. Infrom
at leastthe one
groupembodiment
consisting, the cationic polymer- 10is, 60 tives or preservation boosting ingredients are listed above.
of polyquaternium
guar hydroxypropyltrimonium chloride, polyquaternium - 7 , In at leastingredient
one embodiment, the preservative or preservation
polyquaternium - 6, and combinations thereof. Optionally the boosting
sodium benzoate ,
is selected from the group consisting of
methylparaben , Phenoxyethanol, methyl
hair conditioning and / or hair and / or scalp treatment com
position comprises from 0.001 wt % to 5.0 wt% , preferably 65 isothiazolinone, DMDM hydantoin , methylchloroisothiaz
from 0.01 wt % to 3.0 wt % , even more preferably from 0.1 olinone , pyrithione, octopirox , and combinations thereof.
wt % to 2.0 wt % of at least one biogenic active substance . Optionally the hair styling composition comprises from 0.01
 US 11,311,473 B2
43 44
wt % to 20 wt % , preferably from 0.1 wt % to 10.0 wt % , Example Embodiments of the Second Aspect
even more preferably from 0.5 wt % to 5.0 wt % of at least
one further auxiliary. Auxiliaries are listed above. In a In a preferred embodiment, the second aspect relates to a
preferred embodiment, the hair styling composition has a pH cosmetic , dermatological or pharmaceutical composition
value from 2.0 to 9.0 , preferably from 3.0 to 8.0 , even more
5 comprising:
preferably from 4.0 to 7.0 . (1 ) a polymer; and
( II ) a cosmetically acceptable component;
In at least one embodiment, the composition is a hair wherein the polymer is crosslinked or non -crosslinked,
coloring /hair bleaching composition. Optionally the hair 10
characterized in that the polymer comprises :
coloring /hair bleaching composition comprises from 0.5 wt ( a) from 90 mol- % to 99.9 mol- % , preferably from 95
% to 60 wt % , preferably from 1.0 wt % to 50 wt % , even mol- % to 99.5 mol- % of repeating units according to
more preferably from 2.0 wt % to 40 wt % of at least one Formula ( 1 ) wherein at least 10 wt .- % , preferably at
direct dye. Direct dyes are listed above . Optionally the hair least 20 wt .- % of the repeating units according to
coloring /hair bleaching composition comprises from 00.001 15 Formula ( 1 ) comprise from 28 wt .- % to 100 wt .- %
wt % to 5.0 wt % , preferably from 0.05 wt % to 3.0 wt % , bio -based carbon content, relative to the total mass of
even more preferably from 0.1 wt % to 1.0 wt % of at least carbon in the repeating unit according to Formula ( 1 ) ,
one oxidizing or reducing agent. Oxidizing or reducing measured according to standard ASTM D6866-12 ,
agents are listed above . In at least one embodiment, the hair Method B ;
coloring/hair bleaching composition comprises a primary 20
intermediate and a coupling agent. In at least one embodi
ment, the primary intermediate is selected from the group + CH2 -ÇR! +
(1 )
consisting of 2,4,5,6 -tetraaminopyrimidine , 4 -aminophenol,
4 -amino - 3 -methylphonol, 2,5 - diamino -toluene and 2-(2,5
diaminophenyl) ethanol, 2 -methoxymethyl - 1,4 -benzenedi- 25 1
A -0 et
amine , and combinations thereof. In at least one embodi R2
ment, the coupling agent is selected from the group
consisting of 5 -amino - 4 - chloro - o - cresol, 2,6 -diaminopyri
dine, 2,6 -dihydroxyethylaminotoluene, resorcinol, 2 -methyl wherein :
resorcinol , 4 - amino - 2 -methylphenol, and combinations 30 R and R2 are independently selected from H , methyl or
thereof. Optionally the hair coloring /hair bleaching compo ethyl; A is a linear or branched C -C12 - alkyl group ;
sition comprises from 0.1 wt % to 15 wt % , preferably from and Qt is H * , NH4+ , organic ammonium ions
0.5 wt % to 10 wt % , even more preferably from 1.0 wt % [NHRPROR ] * wherein R , RO , and Rindependently
to 5.0 wt % of at least one emulsifier, coemulsifier and / or of one another may be hydrogen, a linear or branched
solubilizer. Optionally the hair coloring/hair bleaching com 35 alkyl group having 1 to 22 carbon atoms , a linear or
position comprises from 0.001 wt % to 5.0 wt % , preferably branched, singularly or multiply unsaturated alkenyl
from 0.01 wt % to 3.0 wt % , even more preferably from 0.1 group having 2 to 22 carbon atoms, a C6 - C22 alky
wt % to 1.0 wt % of at least one alkalizing or pH adjusting lamidopropyl group , a linear mono -hydroxyalkyl
agent. Alkalizing or pH adjusting agents are listed above . group having 2 to carbon atoms or a linear or
40 branched dihydroxyalkyl group having 3 to carbon
Optionally the hair coloring /hair bleaching composition atoms , and where at least one of the radicals RS , R " ,
2

comprises from 0.01 wt % to 20 wt % , preferably from 0.1 and R7 is not hydrogen, or Q7 is Li + , Na+ , K+ , 12
wt % to 10.0 wt % , even more preferably from 0.5 wt % to Ca ++ , 1/2 Mg ++ , 1/2 Zn++ , 1/3 A1 +++ , or combinations
5.0 wt % of at least one further auxiliary. Auxiliaries are thereof;
listed above . In a preferred embodiment, the hair coloring / 45 (b ) optionally from 0.01 mol- % to 10 mol- % , preferably
hair bleaching composition has a pH value from 6.0 to 14.0 , from 0.01 mol- % to 5 mol- % of crosslinking or branch
preferably from 7.0 to 13.0 , even more preferably from 8.0 ing units, wherein the crosslinking or branching units
to 12.0 . result from the incorporation of a monomer comprising
In at least one embodiment, the cosmetic , dermatological 50 at least two olefinically unsaturated double bonds .
or pharmaceutical composition is for use on mucous mem 96 Inmol- at least one embodiment, the polymer comprises from
% to 99.7 mol- % , preferably from 97 mol- % to 99.5
branes. In at least one embodiment, the composition is an mol- % units ( a) and from 0.3 mol- % to 4 mol- % , preferably
emulsion , gel or paste, preferably an oil -in -water ( o / w ) , from 0.5 mol- % to 3 mol- % units (b ) . In at least one
cream gel or hydrogel composition . In a preferred embodi- embodiment, the polymer comprises units ( a) and (b ) , such
ment , the composition suitable for mucous membranes has 55 that the sum thereof is at least 99 mol- % , by total weight of
a viscosity from 100 000 to 300 000 mPa.s , preferably from the polymer .
1 000 to 200 000 mPa.s , more preferably from 2 000 to 100 cosmetic In a preferred embodiment, the second aspect relates to a
, dermatological or pharmaceutical composition
000 mPa.s and very preferably from 5 000 to 30 000 mPa.s comprising:
( 25 ° C. , Brookfield RVT, T - C spindle at 20 revolutions per 60 (I ) a polymer; and
minute ). ( II ) a cosmetically acceptable component ;
In at least one embodiment, the composition is a tooth wherein the polymer is crosslinked or non -crosslinked ,
paste composition . In at least one embodiment, the compo characterized in that the polymer comprises :
sition is a mouthwash composition . ( a) from 40 mol- % to 98 mol- % , preferably from 55
65 mol- % to 98 mol- % repeating units according to For
In at least one embodiment, the composition is a lubricant mula ( 1 ) wherein at least 10 wt .- % , preferably at least
composition . 20 wt .- % of the repeating units comprises from 28
 US 11,311,473 B2
45 46
wt .- % to 100 wt .- % bio -based carbon content, relative In a preferred embodiment, the second aspect relates to a
to the total mass of carbon in the repeating unit accord- cosmetic , dermatological or pharmaceutical composition
ing to Formula ( 1 ) , measured according to standard comprising:
ASTM D6866-12 , Method B ; (I ) a polymer ; and
5 ( II ) a cosmetically acceptable component;
wherein the polymer is crosslinked or non -crosslinked ,
characterized in that the polymer comprises :
( a) from 9.49 mol- % to 98 mol- % , preferably from 27.5
(1) 10
mol- % to 97.4 mol- % repeating units according to
CH2 - ÇR ! + Formula ( 1 ) wherein at least 10 wt .- % , preferably at
least 20 wt .- % of the repeating units according to
N - A - S -O - Q+ Formula ( 1 ) comprise from 28 wt .- % to 100 wt .- %
R2 bio -based carbon content, relative to the total mass of
15 carbon in the repeating unit according to Formula ( 1 ) ,
measured according to standard ASTM D6866-12 ,
Method B ;

wherein : 20 (
)
1
1
CH2 - CR +
CRF
Rand R are independently selected from H , methyl or
ethyl; A is aa linear or branched C - C12 - alkyl group ;
and Q + is H * , NH4+ , organic ammonium ions
[NHR?R?R]] * wherein R®, Rº , and R'independently
2

of one another may be hydrogen , a linear or branched 25

alkyl group having 1 to 22 carbon atoms, a linear or
branched , singularly or multiply unsaturated alkenyl wherein :
N - A
R2 + *

group having 2 to 22 carbon atoms, a C6 - C22 alky Rand R2 are independently selected from H , methyl or
lamidopropyl group , a linear mono -hydroxyalkyl ethyl; A is aa linear or branched C1-C12 - alkyl group ;
group having 2 to carbon atoms or a linear or 30
and Q * is H * , NH4+ , organic ammonium ions
branched dihydroxyalkyl group having 3 to carbon [ NHR RR ?] + wherein R , R " , and R7 independently
atoms , and where at least one of the radicals RS , R " , of one another may be hydrogen , a linear or branched
and R’ is not hydrogen, or Q + is Li + , Na + , K+ , 1/2 alkyl group having 1 to 22 carbon atoms , a linear or
Ca ++ , 1/2 Mg ++ , 1/2 Zn++ , 1/3 A1 +++ , or combinations 35
branched, singularly or multiply unsaturated alkenyl
thereof; group having 2 to 22 carbon atoms, a Co - C22 alky
6

( b ) optionally from 0.01 mol- % to 5 mol- % , preferably lamidopropyl group, a linear mono -hydroxyalkyl
from 0.01 mol- % to 3 mol- % crosslinking or branching group having 2 to carbon atoms or a linear or
units, wherein the crosslinking or branching units result branched dihydroxyalkyl group having 3 to carbon
from the incorporation of a monomer comprising at 40 atoms , and where at least one of the radicals RS , R " ,
least two olefinically unsaturated double bonds ; and R ? is not hydrogen , or Q + is Li + , Na+ , K+ , 1/2
Ca ++ , 12 Mg ++ , 1/2 Zn++ , 1/3 A1 +++ , or combinations
2
(c ) optionally from 0.99 mol- % to 59.99 mol- % , prefer thereof;
ably from 1.99 mol- % to 44.99 mol- % of repeating (b ) optionally from 0.01 mol- % to 5 mol- % , preferably
neutral structural units wherein at least 10 wt .- % , 45 from 0.01 mol- % to 4 mol- % crosslinking or branching
preferably at least 20 wt .- % of the neutral structural units, wherein the crosslinking or branching units result
units comprises from 0 wt .- % to 100 wt .- % bio -based from the incorporation of a monomer comprising at
carbon content, relative to the total mass of carbon in least two olefinically unsaturated double bonds ;
the repeating unit , measured according to standard ( c ) optionally from 0.01 mol- % to 88.52 mol % , prefer
ASTM D6866-12 , Method B. 50 ably from 0.05 mol- % to 72.4 mol- % of repeating
In at least one embodiment, the polymer comprises from neutral structural units , preferably wherein at least 10
45 mol- % to 97 mol- % , preferably from 65 mol- % to 96 wt .- % , preferably at least 20 wt .- % of the repeating
mol- % units ( a) , from 0.25 mol- % to 4 mol- % , preferably neutral structural units comprises from 0 wt .- % to 100
from 0.3 mol- % to 3 mol- % units (b ) , from 2 mol- % to 54.7 wt .- % bio - based carbon content, relative to the total
mol- % , preferably from 2.5 mol- % to 34.5 mol- % units ( C ) . 55 mass of carbon in the repeating neutral structural unit,
In at least one embodiment, the polymer comprises units ( a ) , measured according to standard ASTM D6866-12 ,
(b ) and ( c ) such that the sum thereof is at least 99 mol- % , by Method B ;
total weight of the polymer. ( d ) optionally from 1.98 mol- % to 20 mol- % , preferably
from 2.5 mol- % to 18 mol- % of repeating anionic
In at least one embodiment, the polymer comprises from 60 structural units, wherein the repeating anionic struc
70 mol- % to 98 mol- % , preferably from 73 mol- % to 96 tural units result from the incorporation of a monomer
mol- % units ( a) , from 0.6 mol- % to 2.5 mol- % , preferably comprising at least one carboxylate anion , and wherein
from 0.75 mol- % to 2 mol- % units ( b ), from 1.4 mol- % to the repeating anionic structural units are different from
54.7 mol- % , preferably from 2.5 mol- % to 34.5 mol- % units units ( a) and preferably wherein at least 10 wt .- % ,
( c ) . In at least one embodiment, the polymer comprises units 65 preferably at least 20 wt .- % of the repeating anionic
( a) , (b ) and (c ) such that the sum thereof is at least 99 mol- % , structural units comprise from 0 wt .- % to 100 wt .- %
by total weight of the polymer. bio -based carbon content, relative to the total mass of
 US 11,311,473 B2
47 48
carbon in the repeating anionic structural unit, mea- units, wherein the crosslinking or branching units result
sured according to standard ASTM D6866-12 , Method from the incorporation of a monomer comprising at
B; least two olefinically unsaturated double bonds ;
and wherein the polymer has a weight average molecular ( c ) optionally from 0.01 mol- % to 88.52 mol- % , prefer
weight of at least 700 g /mol, preferably from 700 g /mol to 5 ably from 0.05 mol- % to 72.4 mol- % of repeating
10 million g /mol. neutral structural units , preferably wherein at least 10
In at least one embodiment, the polymer comprises from wt .- % , preferably at least 20 wt .- % of the repeating
37 mol- % to 96.4 mol- % , preferably from 43 mol- % to 95.3 neutral structural units comprises from 0 wt .- % to 100
mol- % units (a ) , from 0.1 mol- % to 3 mol- % , preferably 10 wt .- % bio - based carbon content, relative to the total
from 0.2 mol- % to 2 mol- % units ( b ), from 0.1 mol % to mass of carbon in the repeating neutral structural unit,
59.3 mol- % , preferably from 0.5 mol- % to 52.8 mol- % units measured according to standard ASTM D6866-12 ,
( c ) , and from 3.5 mol- % to 16 mol- % , preferably from 4 Method B ;
mol- % to 14 mol- % units (d) . In at least one embodiment, ( d) optionally from 1.98 mol- % to 20 mol- % , preferably
the polymer comprises units (a ) , ( b ), (c ) and (d) such that the 15 from 2.5 mol- % to 18 mol- % of repeating anionic
sum thereof is at least 99 mol- % , by total weight of the structural units, wherein the repeating anionic struc
polymer. tural units result from the incorporation of a monomer
In at least one embodiment, the polymer comprises from comprising at least one carboxylate anion , and wherein
70 mol- % to 94.5 mol- % , units (a ) , from 0.35 mol- % to 1.5 the repeating anionic structural units are different from
mol- % , units ( b ), from 0.65 mol- % to 25.65 mol- % units ( c ) , 20 units ( a) and preferably wherein at least 10 wt .- % ,
and from 4.5 mol- % to 12 mol- % units ( d ). In at least one preferably at least 20 wt .- % of the repeating anionic
embodiment, the polymer comprises units (a ) , ( b ), ( c ) and structural units comprise from 0 wt .- % to 100 wt .- %
( d ) such that the sum thereof is at least 99 mol- % , by total bio -based carbon content, relative to the total mass of
weight of the polymer. carbon in the repeating anionic structural unit, mea
In a preferred embodiment, the second aspect relates to a 25 sured according to standard ASTM D6866-12 , Method
cosmetic , dermatological or pharmaceutical composition
comprising : ( e) optionally at least one optional unit .
(I) a polymer; and Third Aspect
( II ) a cosmetically acceptable component;
wherein the polymer is crosslinked or non - crosslinked , 30 formulatingaspect
A third
a
of the invention relates to a process of
cosmetic , dermatological or pharmaceutical
characterized in that the polymer consists of:
(a ) from 9.49 mol- % to 98 mol- % , preferably from 27.5 composition, wherein theincorporating
composition comprising
polymer is
a polymer into the
crosslinked or non
mol- % to 97.4 mol- % repeating units according to
Formula ( 1 ) wherein at least 10 wt .- % , preferably at crosslinked , characterized in that the polymer comprises at
least 20 wt .- % of the repeating units according to 35 least 9.49 mol- % of repeating units (a ) according to Formula
Formula ( 1 ) comprise from 28 wt .- % to 100 wt .- % ( 1 ) wherein at least 10 wt .- % , preferably at least 20 wt .- %
bio -based carbon content, relative to the total mass of of the repeating units (a ) according to Formula ( 1 ) comprise
carbon in the repeating unit according to Formula ( 1 ) , from 28 wt .- % to 100 wt .- % bio - based carbon content,
measured according to standard ASTM D6866-12 , relative to the total mass of carbon in the repeating unit
Method B ; 40 according to Formula ( 1 ) , measured according to standard
ASTM D6866-12 , Method B ;
(1)
+ CH2 — ÇR ! +
Hz-PR' +
+
(1 )
CH2– ÇR! +

+
45
'N et
R2
N - A - S 0 +
R2
wherein : 50
R and R ’ are independently selected from H , methyl or wherein :
ethyl; A is aa linear or branched C - C12 - alkyl group ; R ! and R2 are independently selected from H , methyl or
and Q * is H + , NH4* , organic ammonium ions ethyl; A is a linear or branched C ,-C12 - alkyl group; and Q
[NHR RØR ?] * wherein R " , RC , and R7 independently is H +, NH4+ , organic ammonium ions (NHR RÖR? +
2

of one another may be hydrogen , a linear orbranched 55 wherein R" , R" , and R independently of one another may be
alkyl group having 1 to 22 carbon atoms, a linear or hydrogen, a linear or branched alkyl group having 1 to 22
branched , singularly or multiply unsaturated alkenyl carbon atoms, a linear or branched , singularly or multiply
group having 2 to 22 carbon atoms, a C6 - C22 alky- unsaturated alkenyl group having 2 to 22 carbon atoms , a
lamidopropyl group , a linear mono -hydroxyalkyl C6 - C22 alkylamidopropyl group , a linear mono -hydroxyal
group having 2 to carbon atoms or a linear or 60 kyl group having 2 to carbon atoms or a linear or branched
branched dihydroxyalkyl group having 3 to carbon dihydroxyalkyl group having 3 to carbon atoms, and where
atoms , and where at least one of the radicals RS , R " , at least one of the radicals RS , R ' , and R7 is not hydrogen ,
2

and R7 is not hydrogen, or Q + is Li + , Na + , K+ , 1/2 or Q + is Li + , Na + , K+ , 1/2 Ca++ , 1/2 Mg ++ , 1/2 Zn++ , 11 A1 +++ ,
>

Ca ++ , 1/2 Mg ++ , 12 Zn++ , 1/3 A1 +++ , or combinations or combinations thereof.

thereof; 65 In at least one embodiment of the third aspect , the
( b ) optionally from 0.01 mol- % to 5 mol- % , preferably cosmetic, dermatological or pharmaceutical composition is
from 0.01 mol- % to 4 mol- % crosslinking or branching according to the second aspect .
 US 11,311,473 B2
49 50
In at least one embodiment of the third aspect , the
composition comprises a cosmetically acceptable compo (3 )
H CH3
nent. In at least one embodiment, the polymer is mixed with
the cosmetically acceptable component. In at least one 5 " SO3 xt
embodiment, the composition comprises a plurality of cos H3C
metically acceptable components .
Suitable cosmetically acceptable components are men
tioned in the second aspect—such cosmetically acceptable and wherein X + is a proton . In at least one embodiment, the
components are compatible and combinable with the third 10 compound is neutralised with a base prior to polymerisation.
aspect . In at least one embodiment ,the cosmetically accept- In at least one embodiment, the polymer has been neu
able component is selected from the group consisting of tralized following polymerization using a base . In at least
surfactants, auxiliaries, hair conditioning agents, hairstyling one embodiment, the repeating units according to Formula
polymers, and combinations thereof. Surfactants, auxilia- ( 1 ) have a degree of neutralisation of between 0 mol- % and
ries , hair conditioning agents and hairstyling polymers are 15 100 mol-% . In at least one embodiment, the repeating units
disclosed in the second aspect — such cosmetically accept- according to Formula ( 1 ) have a degree of neutralisation of
able components are compatible and combinable with the from 50.0 to 100 mol- % , preferably from 80 mol- % to 100
third aspect . mol- % , more preferably from 90.0 to 100 mol- % , even more
In at least one embodiment, the composition
? is selected preferably from 95.0 to 100 mol- % . Particular preference
from the group consisting of shampoo, body wash , facial 20 being given to a degree of neutralisation of more than 80
cleanser, face mask , bubble bath , intimate wash , bath oil , mol- % , more preferably more than 90 mol- % , even more
cleansing milk , micellar water, make - up remover , cleansing preferably more than 95 mol- % .
wipes , hair mask , perfume, liquid soap , shaving soap , shav In at least one embodiment, the polymer is substantially
ing foam , cleansing foam , day cream , anti-ageing cream , free of units not being those according to Formula ( 1 ) ,
body milk , body lotion, body mousse, face serum, eye 25 wherein
a cation . R Inandat Rleast
’ are one
H; Aembodiment
is _C (CH3,)2the— H_Cpolymer
; and Qis+ isa
cream , sunscreen lotion, sun cream , face cream , after -shave homopolymer.
lotion , pre - shaving cream , depilatory cream , skin -whitening In at least one embodiment, the polymer is a copolymer
gel , self -tanning cream , anti - acne gel , mascara , foundation, of units according to those according to Formula ( 1 ) ,
primer, concealer, blush , bronzer, blemish balm (bb ) cream , wherein R1 and R2 are H ; A is C ( CH3) 2 - H2C ; and Q * is
30
eyeliner, night cream , eye brow gel , highlighter, lip stain , a cation , and at least one further unit.
hand sanitizer, hair oil , nail varnish remover, conditioner, In at least one embodiment, the polymer is a rheology
hair styling gel , hair styling cream , anti- frizz serum , scalp modifier or a thickening agent, or is suitable for use therefor.
treatment, hair colorant, split end fluid , deodorant, antiper- Fourth Aspect
spirant, baby cream , insect repellent, hand cream , sunscreen 35 A fourth aspect relates to aa method for treating keratinous
gel , foot cream , exfoliator, body scrub , cellulite treatment, material, comprising applying the composition according to
bar soap , cuticle cream , lip balm , hair treatment, eye the second aspect to the keratinous material. In at least one
shadow , bath additive, body mist , eau de toilette, mouth- embodiment of the fourth aspect , the composition is a
wash , toothpaste, lubricating gel , moisturizer, serum , toner, cosmetic composition.
aqua sorbet, cream gel , styling mousse , dry shampoo, lip 40 In at least one embodiment, the keratinous material is
stick , lip gloss , hydro - alcoholic gel, body oil , shower milk , keratin fibres. In at least one embodiment, the keratinous
illuminator, lip crayon , hair spray , combing cream , and material is selected from human skin and / or human hair.
sunblock . In at least one embodiment of the fourth aspect , the
In at least one embodiment, the composition comprises at composition comprises a cosmetically acceptable compo
least 0.1 wt .- % , or at least 0.2 wt .- % , or at least 0.3 wt .- % , 45 nent. In at least one embodiment, the composition comprises
or at least 0.4 wt .- % , or at least 0.5 wt .- % , or at least 0.6 a plurality of cosmetically acceptable components.
wt .- % , or at least 0.7 wt .- % , or at least 0.8 wt .- % , or at least Suitable cosmetically acceptable components are men
0.9 wt .- % , or at least 1.0 wt .- % , or at least 1.1 wt .- % , or at tioned in the second aspect_cosmetically acceptable com
least 1.2 wt .- % , or at least 1.3 wt .- % , or at least 1.4 wt .- % , ponents are compatible and combinable with the fourth
or at least 1.5 wt .- % , or at least 1.6 wt .- % , or at least 1.5 50 aspect . In at least one embodiment, the cosmetically accept
wt .- % , or at least 1.6 wt .- % , or at least 1.7 wt .- % , or at least able component is selected from the group consisting of
1.8 wt .- % , or at least 1.9 wt .- % , or at least 2.0 wt .- % of the surfactants , auxiliaries , hair conditioning agents, hairstyling
polymer.
In at least one embodiment, the polymer is a crosslinked polymers, and combinations thereof. Surfactants, auxilia
or non - crosslinked homopolymer. In at least one embodi- 55 ries , hair conditioning agents and hairstyling polymers are
ment, the polymer is a crosslinked or non - crosslinked copo- disclosed in the second aspect- such cosmetically accept
lymer. Preferably the polymer is crosslinked . able components are compatible and combinable with the
In at least one embodiment, the polymer has a weight fourth aspect.
average molecular weight of at least 700 g /mol, preferably In at least one embodiment, the composition is selected
from 700 g /mol to 10 million g /mol. 60
from the group consisting of shampoo, body wash , facial
In at least one embodiment, the polymer is obtained by cleanser
polymerising at least one compound according to Formula cleansing, face mask, bubble bath , intimate wash , bath oil ,
( 3 ) , wherein the compound comprises from 28 wt .- % to 100 wipes , hairmilk , micellar water, make-up remover , cleansing
mask , perfume, liquid soap , shaving soap , shav
wt .- % , preferably from 40 wt .- % to 100 wt .- % , bio -based
carbon content, relative to the total mass of carbon in the 65 ing foam , cleansing foam , day cream , anti -ageing cream ,
compound, measured according to standard ASTM D6866- body milk , body lotion , body mousse , face serum , eye
12 , Method B ; cream , sunscreen lotion , sun cream , face cream , after - shave
 US 11,311,473 B2
51 52
lotion , pre -shaving cream , depilatory cream , skin -whitening Monomer
gel , self -tanning cream , anti - acne gel , mascara , foundation , International patent application PCT/EP2017/ 064977
primer, concealer, blush , bronzer, blemish balm (bb ) cream , ( claiming priority from European patent application
16175218.3 filed on 20 Jun . 2016 ) in the name of Clariant
eyeliner, night cream , eye brow gel , highlighter, lip stain , 5 International
hand sanitizer, hair oil , nail varnish remover, conditioner, herein by reference Ltd , the disclosure of which is incorporated
hair styling gel , hair styling cream , anti - frizz serum , scalp acryloyldimethyltaurate , discloses the synthesis of bio -based
treatment, hair colorant, split end fluid , deodorant, antiper for the polymer according , which can be used as a monomer
to the present invention .
spirant, baby cream , insect repellent, hand cream , sunscreen Isobutene Samples Used :
gel , foot cream , exfoliator, body scrub, cellulite treatment, 10 The composition of petroleum -based isobutene is differ
bar soap , cuticle cream , lip balm , hair treatment, eye ent from bio -based isobutene . Bio -based isobutene contains
shadow , bath additive , body mist , eau de toilette, mouth- exclusively contemporary carbon and hence has a different
wash , toothpaste, lubricating gel , moisturizer, serum , toner, distribution of carbon isotopes as compared to fossil, pet
aqua sorbet, cream gel , styling mousse , dry shampoo, lip 15 rochemical- based carbon . Fossil carbon was cut off from the
stick , lip gloss , hydro -alcoholic gel , body oil , shower milk , natural carbon equilibrium for millions of years and all the
illuminator, lip crayon , hair spray, combing cream , and tion natural 14C has already degraded, and hence the concentra
sunblock . of 14C is zero in fossil carbon sources . Contemporary
In at least one embodiment, the composition comprises at carbon , produced by living organisms is part of the atmo
least 0.1 wt.-% , or at least 0.2 wt .-%, or at least 0.3 wt.-% , 20 spheric carbon
beingisotope
created equilibrium . 14C orbyradiocarbon
the interactionis
or at least 0.4 wt .- % , or at least 0.5 wt .- % , or at least 0.6 constantly in the atmosphere
of cosmic rays with atmospheric nitrogen. The resulting
wt .- % , or at least 0.7 wt .- % , or at least 0.8 wt .- % , or at least radiocarbon combines with atmospheric oxygen to form
0.9 wt .- % , or at least 1.0 wt .- % , or at least 1.1 wt .- % , or at radioactive carbon dioxide , which is incorporated into plants
least
or at 1.2
leastwt1.5
1
.-%wt, or.- %at , least
or at1.3leastwt.-1.6%, wtor.-at%least
, or at1.4least
wt.-1.5%, 25 by photosynthesis; animals then acquire 14C by eating the
wt .- % , or at least 1.6 wt .- % , or at least 1.7 wt .- % , or at least plants. When the animal or plant dies , it stops exchanging
1.8 wt .- % , or at least 1.9 wt .- % , or at least 2.0 wt .- % of the carbon with its environment, and from that point onwards
polymer. the amount of 14C it contains begins to decrease as the 14C
undergoes radioactive decay. Therefore, in contemporary
or Innonat- crosslinked
least one embodiment, the. polymer
homopolymer In at leastis aonecrosslinked
embodi 30 carbon the concentration of 14C is in the order of 10-10 %.
Masao Kunioka recently described “ Measurement Methods
ment, the polymer is a crosslinked or non - crosslinked copo of Biobased Carbon Content for Biomass -based Chemicals
lymer. and Plastics ” in Radioisotopes, 62 , 901-925 (2013 ) .
In at least one embodiment, the polymer has a weight Interestingly enough , also the chemical composition of
average molecular weight of at least 700 g/mol, preferably 35 bio -based and petrochemical-based isobutene is different in
several aspects . Table 1 shows differences in the composi
from 700 g /mol to 10 million g /mol.
Fifth Aspect tion for the isobutene samples used in the present invention .
Petrochemical -based isobutene contains small amounts of
A fifth aspect relates to a product comprising the com petrochemical
position according to the second aspect . In at least one 40 and isobutane , by -products such as propane , propene , butane
but it does not contain any traces of metabolic
embodiment, the product comprises a receptacle comprising
the composition according to the second aspect. In at least products ( Type Petro , IB1 ) . In contrast to the petrochemical
one embodiment, the product comprises an opening for isobutene , the bio - based samples contain carbon dioxide and
small quantities of ethanol as metabolic products from the
dispensing the composition . In at least one embodiment, the microorganisms ( Type Bio , samples IB2 to 1B5 ) . The bio
opening is equipped with a closure . In at least one embodi- 45 based isobutene samples do not contain any propane, pro
ment, the receptacle comprises plastics . pene, butane or isobutane.
TABLE 1
Isobutene sample qualities used
Isobutene Isobutene N2 CO2 H2O ethanol propane Propene Isobutane n - butane
sample units type m /v % m /v % m /v % m /v % m /v % m /v % m /v % m /v % m /v %
IB1 Petro 99.873 ND ND 0.06 ND 0.0003 0.0018 0.0639 0.001
IB2 Bio 99.72 0.1 0.3 0.03 0.002 ND ND ND ND
IB3 Bio 92.07 3.2 4.7 0.03 0.005 ND ND ND ND
IB4 Bio 21.94 60 18 0.05 0.008 ND ND ND ND
IB5 Bio 97.7 2 0.26 0.03 0.002 ND ND ND ND

KEY : ND = not detected .

60
Sixth Aspect Compared with the quality of petrochemically acquired
A sixth aspect relates to kit comprising the product of the isobutene , the amount of impurities in the bio - based
fifth aspect and a further product or implement. isobutene are significantly higher and the composition is
EXAMPLES different. Especially IB4 contains only 21.94 % isobutene
65 and 18 % carbon dioxide . Surprisingly it was found that it
The examples which follow are intended to illustrate the was possible to synthesize ACDMT with high purity based
subject matter of the invention , without restricting it thereto . on the isobutene with high levels of impurities.
 US 11,311,473 B2
53 54
TABLE 2 The Monomer Comparative Examples MCompEx2 to
Acrylonitrile sample qualities used
MCompEx3 were carried out in the same way, but the sulfur
trioxide excess was increased . Please see Table 3 .
Acrylonitrile 4 -methoxy
sample H2O after phenol 5 Monomer Comparative Example 4 (MCompEx4 )
Units Type Acrylonitrile H2O as is drying Ppm ( See US2010/0274048 , which is Incorporated
AN1 Petro 99.2 0.41 19 43 Herein by Reference ) for a Continuous Process
AN2 Bio 99.1 0.53 21 56 with Conventional Petrochemical Raw Materials

Acrylonitrile > 99 % , from Sigma-Aldrich contains 35-45 pipeTwoandglassan reactors each provided with a stirrer, an inlet
10
outlet pipe
ppm monomethyl ether hydroquinone as inhibitor, contained Acrylonitrile and sulfuric acid were connected to each other.
were fed by peristaltic pumps
0.41 % water before drying. It was dried by adding 50 g into the first reactor. With a flow rate of 47.1 g /h sulfuric acid
molecular sieve 0.4 nm from Merck Millipore , Merck and 22.36 g / h 20% commercial fuming sulfuric acid and
KGaA . The residual water content of the acrylonitrile was 15 161.1 g / h dry acrylonitrile was pumped . The sulfuric acid
19 ppm , measured by Karl - Fischer titration ( DIN 51777 ) . was 97 % concentrated . The concentration of sulfur trioxide
The biologically acquired acrylonitrile was relatively similar in fuming sulfuric acid was chosen to compensate for the
in chemical composition as compared to the petrochemical water carried by the raw materials acrylonitrile and
one . The used acrylonitrile was obtained in two steps via isobutene . The temperature of the reaction mixture in the
oxidative decarboxylation of glutamic acid and subsequent 20 first reactor was kept at -10 +2.5° C. The average residence
decarbonylation elimination of 3 - cyanopropionic acid to time was 90 minutes . Sulfonic acid and acrylonitrile were
form acrylonitrile using the method described in Green reactor mixed and the mixed fluid thereof was fed into the second
Chemistry, 2011 , 13 , 807 . . The second react was a three neck 250 ml round
bottom reactor, modified with aa side neck to allow overflow
Monomer Comparative Example 1 (MCompExl ), 25 of the reactor to a beaker. It was connected with an overhead
Using Conventional Petrochemical Raw Materials stirrer, glass stirrer with PTFE stirrer blades and an intensive
in aa Batch Process condenser. In the second reactor, isobutylene gas ( IB1 ) was
blown sub surface with aa flow rate of 30.8 g / h into the mixed
The reactor was a 5 neck 250 ml round bottom flask , fluid to synthesize ACDMT . The reaction ( synthesis) was
equipped with an overhead agitator, thermocouple , sub 30 conducted continuously with an average residence time of
90 minutes at a temperature of 40 + 2.5 ° C. After 11 h
surface gas injection pipe , intensive condenser and dropping continuously conducted reaction a sample of the reaction
funnel with pressure compensation. The head of the con mixture was taken and analyzed .
denser was equipped with a dry tube containing 50 g of 4 The ACDMT slurry obtained in the above production was
Angstrom molecular sieve . A PTFE plate stirrer with preci- 35 suction - filtered using a glass filter to obtain a cake on the
sion glass joint seal was connected to the overhead stirrer. glass filter. Acrylonitrile of an amount (mass ) shown in
150 ml dry acrylonitrile was dosed to the reactor. Under Table 5 , relative to the mass of the cake was poured onto the
stirring at 150 rpm the acrylonitrile was cooled with aa bath cake. Suction filtering was conducted again to wash the cake
consisting of a mixture of 300 g ice and 100 g NaCl . As soon with acrylonitrile .
as the reactor temperature reaches -10 ° C. , 39.30 g of 100 % 40 The washed cake was dried for 360 minutes at a tem
sulfuric acid was slowly dosed . The temperature was kept in perature of 80 ° C. with a rotational evaporator at reduced
a range of -10 ° C. to -7.5 ° C. The time for dosing the pressure . A vacuum of 400 mbar was applied for 30 minutes.
sulfuric acid was 40 minutes . The liquid stayed clear. Then the pressure was ramped down to 10 mbar in 2 hours
Then the ice bath was removed and replaced by a water and maintained at 10 mbar until drying was completed .
bath at 21 ° C. Subsequently 9.9 L of isobutene was dosed at 45 The yield determined was related to the sample size
a rate of 10 L /h . The temperature was allowed to climb drawn. The ACDMT powder obtained was analyzed by
quickly, but controlled to be stable at 40 ° C. for the course HPLC to measure the concentrations of acrylonitrile (abbre
of the dosage . After approximately 35 min . , fine white viated as AN ), acrylamide ( abbreviated as AM) , tert.-buty
crystals started to precipitate . After dosage was completed lacrylamide ( abbreviated as tBAM ) , 2 -methyl- 2 -propenyl
the reaction mixture was stirred for one hour at 40 ° C. Then 50 1 - sulfonic acid ( abbreviated as IBSA) . The results of the
the reaction mixture was cooled under agitation for 30 min comparative experiment is shown in Table 6 .
to 20 ° C. The reaction mixture was a fine white suspension . Monomer Example 1
The solid was separated by vacuum filtration over glass fiber
filter, stirred with 50 g fresh acrylonitrile in a 250 ml 55 The reactor was a 5 neck 250 ml round bottom flask ,
Erlenmeyer - flask for 10 minutes using a magnetic stirrer, equipped with an overhead agitator, thermocouple, sub
PTFE coated stirrer bar and covered with a glass lid . The surface gas injection pipe , intensive condenser and dropping
solids of the suspension was removed again by vacuum funnel with pressure compensation . The head of the con
filtration over a glass fiber filter (Whatman Grade GF / D ) . denser was equipped with a dry tube containing 50 g of 4
The solid was dried for 4 hours in a laboratory rotation 60 Angstrom molecular sieve . A PTFE plate stirrer with preci
evaporator at a bath temperature of 60 ° C. , starting at a sion glass joint seal was connected to the overhead stirrer.
pressure of 300 mbar. After 30 minutes the pressure was 150 ml dry acrylonitrile was dosed to the reactor. Under
ramped down to 10 mbar in 3 h . stirring at 150 rpm the acrylonitrile was cooled with a bath
With a yield of 85 wt .- % ACDMT was isolated with a consisting of a mixture of 300 g ice and 100 g NaCl .
purity of 95.9 wt .- % . And 0.3 wt .- % acrylonitrile, 0.6 wt .- % 65 Alternatively the mixture could be cooled down with a
acrylamide, 2.9 wt .- % tert. butylacrylamide and 0.3 wt .- % combination of acetone and dry ice . As soon as the reactor
2 -methylprop - 2 -en - 1 -sulfonic acid were detected . temperature reaches -10 ° C. , 49.30 g 100% sulfuric acid
 US 11,311,473 B2
55 56
was slowly dosed . The access of sulfur trioxide was con- bio -based ACDMT. Surprisingly, the purity of the bio -based
trolled to compensate for the water content of the raw ACDMT is higher as compared to the monomer comparative
materials isobutene and acrylonitrile. The variation of the experiments 1 to 3. In particular the impurities t - BAM and
process conditions are documented in Table 3 .
The temperature was kept in a range of -10 ° C. to -7.50 5 IBSA were reduced . The potential side products IBSA and
C. The time for dosing the sulfuric acid was 40 minutes . The IBDSA act to moderate ( control) the molecular weight in the
liquid stays clear. radical polymerization . Hence a person skilled in the art
Then the ice bath was removed and replaced by a water would expect the molecular weight of a polymer in the
bath at 21 ° C. 9.9 L of bio -based isobutene was dosed at a presence of a larger amount of a moderator to be lower as
rate of 10 L / h . The temperature was kept allowed to climb 10 compared to one polymerized under the same conditions
quickly, but controlled to stay at 40 ° C. for the course of the with a lesser amount of moderator. As an IBDSA standard
dosage . After approximately 25 min . , fine white crystals was not available the amount of IBDSA was not quantified.
started to precipitate . After dosage was completed the reac A surprising advantage of the invention is that bio -based
tion mixture was stirred for one hour at 40 ° C. Then the
reaction mixture was cooled under agitation for 30 min . to 15 isobutene can be used in the ACDMT production process
20 ° C. The reaction mixture was a fine white suspension . with a lower quality as compared to petrochemically -manu
The solid was separated by vacuum filtration over glass fiber factured isobutene to produce an as good or better quality of
filter, stirred with 50 g fresh acrylonitrile in a 250 ml ACDMT.
Erlenmeyer - flask for 10 minutes using a magnetic stirrer, To test the bio - based content, three samples were inves
PTFE coated stirrer bar and covered with a glass lid . The 20 tigated
solids of the suspension was removed again by vacuum pExl wasaccording to ASTM D6866-12 , Method B. MCom
filtration over a glass fiber filter (Whatman Grade GF / D ) . rials . Therefore it is toconventional
made with
be
, petrochemical raw mate
expected that all carbon is fossil
The solid was dried for 4 hours in a laboratory rotation
evaporator at a bath temperature of 80 ° C. , starting at a carbon . Consequently no 14C should be found and the
pressure of 300 mbar, after 30 minutes the pressure was 25 bio -based carbon content should be zero . In this experiment,
ramped down to 10 mbar in 3 h . the investigation indeed returned aa bio - based carbon content
TABLE 3
Reaction conditions for batch reactions
Oleum
H2SO4 , 20% Flow
Experiment AN 100 % SO3 Isobutene rate T1 T2
Unit [g ] Material [g ] [ g] [ g] Material [ L / h ] [ ° C .] [ ° C.]
MCompEx1 150 AN1 49.3 0.0 28.1 IB1 10 -10 40
MCompEx2 150 AN1 49.1 0.10 28.1 IB1 10 -10 40
MCompEx3 150 AN1 48.9 0.2 28.1 IB1 10 -10 40
M1 150 AN1 49.2 0.08 28.1 IB2 10 -10 40
M2 150 AN1 49.2 0.09 30.5 IB3 11 -10 40
M3 150 AN1 48.6 0.56 128 IB4 23 -10 40
M4 150 AN1 49.2 0.08 28.8 IB5 10 -10 40
M5 50 AN2 16.4 0.03 9.6 IB5 10 -10 40

The results of the comparative experiments and the of 0 wt .- % . In Experiment 1 , a sample of bio - based
experiments describing the invention are summarized in 45 isobutene (IB2 ) was used . As four of the seven ACDMT
Table 4 . carbon atoms were replaced by bio - based carbon, in theory
The experiments demonstrate that the precipitation of 57 wt .- % bio -based carbon should be found . The experiment
ACDMT starts earlier with the bio - based isobutene as com delivers a bio -based carbon content of 55 wt .- % . The devia
pared to the petro -chemical produced isobutene. Also it was tion of the theoretical value can be explained by the impurity
found that the use of bio - based isobutene was suitable make of the material and the analytical error of 2 % of the method .
TABLE 4
Results of the examples using the batch process
Bio -based
Yield ACDMT AM AN t - BAM IBSA content

Experiment [g] [%] [wt .- % ] [wt .- % ] [wt.- % ] [wt .- % ] [wt .- % ] [wt .- % ]

MCompEx1 91.1 88 95.9 0.6 0.3 2.9 0.3 0
MCompEx2 93.5 90 97.1 0.3 0.3 2.1 0.2
MCompEx3 91.6 88.5 96.2 0.3 0.3 1.9 0.4 ND
M1 98.4 95 99.4 0.07 0.06 0.45 0.05 55
M2 98.2 95 98.9 0.08 0.09 0.51 0.03 ND
M3 97.3 94 98.2 0.1 0.09 0.49 0.06 56
M4 98.3 95 99.5 0.05 0.04 0.39 0.02 ND
M5 33.0 95.5 99.2 0.04 0.04 0.41 0.03 99

KEY: ND = not detected ; ACDMT = acryloyldimethyltaurate ; AM = acrylamide; AN = acrylonitrile; BAM =

tert . -butyl acrylamide; BSA = isobutene sulfonic acid .
 US 11,311,473 B2
57 58
The use of bio -based isobutene achieve high yields of of a polymer. When the temperature maximum is reached ,
ACDMT as well as high purities of ACDMT. Indeed , the use heat the reaction to a gentle reflux for two hours . Cool the
of bio - isobutene leads to a purer ACDMT as compared to reaction mixture to room temperature and dry the polymer
petrochemical ACDMT. suspension at 60 ° C. under a vacuum of 150 mbar.
Polymer
Polymerization experiments show especially that 5 ization Polymerization Process B1 : General Precipitation Polymer
Procedure in Tert .-Butanol/Dimethylketone Mixture
ACDMT samples with lower content of IBSA lead to higher Dose in a 1 - Liter Quickfit round bottom flask equipped
molecular weight polymers as compared to ACDMT
samples with higher IBSA content. with a refux condenser, sub surface gas inlet tubing, inner
Polymerization Process A1 : General Precipitation Polymer 10 temperature sensor and overhead agitator 200 g tert. - butanol
ization Procedure in Tert . -Butanol and 200 g dimethylketon with a water content of 3 wt .- % .
Dose in a 1 - Liter Quickfit round bottom flask equipped Charge 100 g bio - based ACDMT. Neutralize the ACDMT
with a refux condenser, sub surface gas inlet tubing, inner by charging 40.5 g sodium hydrogen carbonate. Keep the
temperature sensor and overhead agitator 400 g tert . -butanol temperature below 40 ° C. Dose 1.45 g TMPTA , as a
with a water content of 2.5 wt .- % . Charge 100 g bio -based 15 crosslinker and according to Polymer Table B1 . Inject
ACDMT. Neutralize the ACDMT to a pH of 7 to 8 by nitrogen subsurface for 1 h at agitation of 200 rpm . During
injection of gaseous ammonia above the surface . Keep the this time the temperature of the reaction mixture is raised
temperature below 40 ° C. Dose a 1.45 g TMPTA as a and stabilized to 60 ° C. with help of a water bath . Readjust
crosslinker according to Polymer Table A1 . Inject nitrogen the pH at 60 ° C. to a pH of 7 to 8. The reaction is initiated
subsurface for 1 h at agitation of 200 rpm . During this time 20 by the dosage of radical building compound, 1.3 g DLP.
the temperature of the reaction mixture is raised and stabi- After a few minutes the start of polymerization becomes
lized to 60 ° C. with help of aa water bath . Readjust the pH at obvious due to the rising temperature and the precipitation
60 ° C. to a pH of 7 to 8. The reaction is initiated by the of a polymer. When the temperature maximum is reached ,
dosage of radical building compound, 1.3 g DLP . heat the reaction to a gentle reflux for two hours . Cool the
After aa few minutes the start of polymerization becomes reaction mixture to room temperature and dry the polymer
obvious due to the rising temperature and the precipitation suspension at 60 ° C. under a vacuum of 150 mbar.
Polymer Table Al ) :
Polymers according to polymerization process A1:
Polymer
example ACDMT in ACDMT in Crosslinker Initiator
name g mol- % Name g mol- % Name g

A1 / 1 100.0 99.0 TMPTA 1.45 1.00 DLP 1.30

A1 /2 100.0 98.7 TMPTA 1.81 1.25 DLP 2.00
A1 /3 100.0 99.0 TMPTA 2.17 1.50 DLP 1.30
A1 / 4 100.0 97.1 TMPMTA 4.50 2.94 V -601 1.10
A1 / 5 100.0 98.5 TMPMTA 2.30 1.52 V -601 1.10
A1 / 6 100.0 98.0 TMPMTA 3.05 2.01 V - 601 1.10
A1 /7 100.0 99.0 PEG 600 DMA 2.80 1.01 V -601 1.10
A1 /8 100.0 98.5 PEG 600 DMA 4.25 1.52 DLP 2.00
A1 / 9 100.0 98.8 PEG 600 DMA 3.48 1.25 DLP 2.00
A1 / 10 100.0 97.0 GPTA 6.30 2.96 V -601 1.10
A1 / 11 100.0 98.0 GPTA 4.20 1.99 V - 601 1.10
A1 / 12 100.0 98.8 GPTA 2.60 1.24 V -601 1.10
A1 / 13 100.0 99.0 PEAS 2.50 1.00 V -601 1.10
A1 / 14 100.0 98.5 PEAS 3.80 1.52 V -601 1.10
A1 / 15 100.0 98.8 PEAS 3.10 1.24 V -601 1.10
ACDMT = acryloyldimethyltaurate, NVP == N -vinylpyrollidone, DMAAm = dimethylacrylamide, TMPTA
= trimethylolpropantriacrylate, TMPTA = trimethylolpropantriacrylate, TMPTMA = trimethylolpropant
rimethacrylate, GPTA = glycerinpropoxylate triacrylate, PEAS = pentaerythritoldiacrylate monostearate,
=

DLP = dilauryl peroxide , V -601 = dimethyl -2,2'-azobis (2 -methylpropionate ), PEG 600 DMA = polyethylene
=
glycol dimethacrylate ( 600 g /mol).

Polymer Table B1 ) :
Polymers according to polymerization process B1:
Polymer Neutralization
example ACDMT reagent Crosslinker Initiator
name g mol- % Name g Name g mol- % Name
B1 / 1 100.0 99.0 NaHCO3 40.5 TMPTA 1.45 1.00 DLP 1.30
B1 / 2 100.0 98.7 NaHCO3 40.5 TMPTA 1.81 1.25 DLP 2.00
B1 / 3 100.0 98.5 NaHCO3 40.5 TMPTA 2.17 1.50 DLP 2.00
B1 / 4 100.0 97.0 KHCO3 48 TMPTA 4.35 2.95 V -601 1.10
B1 / 5 100.0 97.0 LiHCO3 32.6 TMPTA 2.17 1.50 V -601 1.10
B1 / 6 100.0 99.0 NaHCO3 40.5 TMPMTA 1.50 1.00 V -601 1.10
B1 / 7 100.0 98.7 NaHCO3 40.5 TMPMTA 1.89 1.25 V -601 1.10
 US 11,311,473 B2
59 60
-continued
Polymer Table B1 ) :
Polymers according to polymerization process B1 :
Polymer Neutralization
example ACDMT reagent Crosslinker Initiator
name g mol- % Name g Name mol- % Name
B1 / 8 100.0 98.5 NaHCO3 40.5 TMPMTA 2.30 1.52 DLP 2.00
B1 / 9 100.0 98.5 KHCO3 48 TMPMTA 2.30 1.52 DLP 2.00
B1 / 10 100.0 98.5 LiHCO3 32.6 TMPMTA 2.30 1.52 DLP 2.00
B1 / 11 100.0 97.0 LiHCO3 32.6 PEG 600 DMA 8.50 3.00 DLP 2.00
B1 / 12 100.0 98.0 NaHCO3 40.5 PEG 600 DMA 5.60 2.00 DLP 2.00
B1 / 13 100.0 98.8 NaHCO3 40.5 PEG 600 DMA 3.48 1.25 DLP 2.00
B1 / 14 100.0 98.8 NaHCO3 40.5 PEG 600 DMA 3.48 1.25 DLP 2.00
B1 / 15 100.0 98.8 NaHCO3 40.5 GPTA 2.60 1.24 V - 601 1.10
B1 / 16 100.0 99.0 Na2CO3 25.5 GPTA 2.06 0.99 DLP 2.00
B1 / 17 100.0 98.5 NaHCO3 40.5 GPTA 3.15 1.50 V - 601 1.10
B1 / 18
B1 / 19
100.0
100.0
98.8 Na2CO3 25.5
40.5
GPTA
PEAS
2.60
7.60
1.24
2.99
V - 601
V - 601
1.10
1.10
97.0 NaHCO3
B1 / 20 100.0 98.5 NaHCO3 40.5 PEAS 3.75 1.50 V -601 1.10
ACDMT acryloyldimethyltaurate, NVP = N -vinylpyrollidone, DMAAM dimethylacrylamide, TMPTA =
=

trimethylolpropane triacrylate, TMPTA = trimethylolpropane triacrylate, TMPTMA = trimethylolpropane trimeth

=

acrylate , GPTA = glycerinpropoxylattriacrylate, PEAS = pentaerythritoldiacrylate monostearate, DLP = dilaurylp

=

eroxide , V - 601 = dimethyl 2,2 '- azobis ( 2 -methylpropionate ), PEG 600 DMA = polyethylene glycol dimethacrylate
(600 g /mol ).

Polymerization Process A2 : General Precipitation Polymer- 25 Polymerization Process B2 : General Precipitation Polymer
ization Procedure in Tert . -Butanol ization Procedure in Tert .-Butanol/Dimethylketone Mixture
Dose in a 1 - Liter Quickfit round bottom flask equipped Dose in a 1 - Liter Quickfit round bottom flask equipped
with a refux condenser, sub surface gas inlet tubing, inner with a refux condenser, sub surface gas inlet tubing, inner
temperature sensor and overhead agitator 400 g tert . - butanol temperature sensor and overhead agitator 200 g tert. - butanol
with a water content of 2.5 wt .- % . Charge 80 g bio -based 30 and 200 g dimethylketone with a water content of 3 wt .- % .
ACDMT. Neutralize the ACDMT to a pH of 7 to 8 by Charge 80 g bio -based ACDMT. Neutralize the ACDMT by
injection of gaseous ammonia above the surface . Keep the charging 32.8 g sodium hydrogen carbonate. Keep the
temperature below 40 ° C. Dose a 0.63 g TMPTA as a temperature below 40 ° C. Dose 1.27 g TMPTA , as a
crosslinker and 4.3 g NVP as a neutral monomer according crosslinker and a 0.44 g methyl acrylate as a neutral mono
to Polymer Table A2 . Inject nitrogen subsurface for 1 h at 35 mer according to Polymer Table B2 . Inject nitrogen subsur
agitation of 200 rpm . During this time the temperature of the face for 1 h at agitation of 200 rpm . During this time the
reaction mixture is raised and stabilized to 60 ° C. with help temperature of the reaction mixture is raised and stabilized
of a water bath . Readjust the pH at 60 ° C. to a pH of 7 to 8 . to 60 ° C. with help of a water bath . Readjust the pH at 60 °
The reaction is initiated by the dosage of radical building C. to a pH of 7 to 8. The reaction is initiated by the dosage
compound , 1 g DLP. 40 of radical building compound , 11 g DLP.
After aa few minutes the start of polymerization becomes After a few minutes the start of polymerization becomes
obvious due to the rising temperature and the precipitation obvious due to the rising temperature and the precipitation
of a polymer. When the temperature maximum is reached , of a polymer. When the temperature maximum is reached ,
heat the reaction to a gentle reflux for two hours . Cool the heat the reaction to a gentle reflux for two hours . Cool the
reaction mixture to room temperature and dry the polymer 45 reaction mixture to room temperature and dry the polymer
suspension at 60 ° C. under a vacuum of 150 mbar. suspension at 60 ° C. under a vacuum of 150 mbar.
Polymer Table A2 ) :
Polymers according to polymerization process A2:
Polymer
example ACDMT Neutral Monomer Crosslinker Initiator
name g /mol- % Name g /mol- % Name g mol- % Name g

A2 / 1 80.0 90.4 NVP 4.3 9.1 TMPTA 0.63 0.50 DLP 1.0
A2 / 2 80.0 89.8 NVP 4.3 9.0 TMPTA 1.59 1.25 V - 601 1.1
A2/3 80.0 89.1 NVP 4.3 8.9 TMPTA 2.57 2.00 DLP 1.0
A2 / 4 80.0 89.7 NVP 4.3 9.0 TMPMTA 1.66 1.25 V - 601 1.1
A2/5 80.0 89.7 NVP 4.3 9.0 PEAS 2.75 1.25 V -601 1.1
A2 / 6 80.0 93.7 NVP 2.3 5.0 GPTA 2.21 1.25 V -601 1.1
A2 / 7 80.0 96.0 NVP 1.1 2.5 PEAS 3.07 1.50 V -601 1.1
A2 / 8 80.0 91.0 NVP 3.55 7.5 PEAS 3.26 1.50 V -601 1.1
A2 / 9 70.0 82.3 NVP 6.85 15.0 PEG 600 DMA 6.20 2.65 DLP 1.0
A2 / 10 80.0 89.8 NVP 4.3 9.0 GPTA 2.30 1.25 V -601 1.1
A2/ 11 80.0 97.0 DMAAm 1.0 2.5 GPTA 0.85 0.50 V -601 1.0
A2 / 12 80.0 94.0 DMAAm 2.1 5.0 GPTA 1.75 1.00 V -601 1.0
A2 / 13 80.0 74.0 DMAAm 12.9 25.0 TMPTA 1.55 1.00 V -601 1.20
A2 / 14 80.0 74.0 DMAAm 12.9 25.0 PEG 600 DMA 2.98 1.00 V -601 1.20
 US 11,311,473 B2
61 62
-continued
Polymer Table A2 ) :
Polymers according to polymerization process A2:
Polymer
example ACDMT Neutral Monomer Crosslinker Initiator
name g /mol- % Name /mol- % Name mol- % Name g

A2 / 15 81.5 89.0 N - isopropylacrylamide 5.0 10.0 TMPMTA 1.36 1.00 V -601 1.00
A2 / 16 80.0 95.8 Behenylpolyethoxy-(25 ) 21.0 3.5 TMPTA 0.90 0.75 DLP 1.75
methacrylate
A2 / 17 80.0 95.3 Behenylpolyethoxy- (25 ) 21.0 3.5 TMPTA 1.50 1.25 DLP 1.75
methacrylate
A2 / 18 80.0 96.3 Behenylpolyethoxy- (25) 18.0 3.0 PEG 600 DMA 1.60 0.70 DLP 1.75
methacrylate
A2 / 19 80.0 91.5 Laurylpoly - ethoxy- (7 ) 20.1 8.5 TMPTA 0.01 0.01 DLP 3.60
methacrylate
A2 / 20 80.0 91.5 Laurylpoly - ethoxy-(7 ) 20.1 8.5 TMPTA 0.01 0.01 DLP 3.60
methacrylate
A2 / 21 80.0 91.5 Laurylpoly -ethoxy-(7) 20.1 8.5 TMPTA 0.01 0.01 DLP 3.60
methacrylate
A2 / 22 80.0 93.0 Stearylpoly - ethoxy-( 8 ) 19.5 7.0 TMPTA 0.01 0.01 DLP 3.90
methacrylate
A2 / 23 80.0 93.0 Stearylpoly -ethoxy- (8 ) 19.5 7.0 TMPTA 0.01 0.01 DLP 3.90
methacrylate
A2 / 24 80.0 93.0 Stearylpoly -ethoxy-(8 ) 19.5 7.0 TMPTA 0.01 0.01 DLP 3.90
methacrylate
ACDMT = acryloyldimethyltaurate, NVP N -vinylpyrollidone, DMAAm = dimethylacrylamide, TMPTA = trimethylolpropane triacrylate,
TMPTA = trimethylolpropane triacrylate, TMPTMA = trimethylolpropane trimethacrylate, GPTA = glycerinpropoxylate triacrylate, PEAS =
pentaerythritoldiacrylate monostearate, DLP = dilaurylperoxide, V -601 = dimethyl2,2' -azobis ( 2 -methylpropionate ), PEG 600 DMA == polyethylene
=
glycol dimethacrylate ( 600 g /mol ).

Polymer Table B2 ) :
Polymers according to polymerization process B2:
Polymer Neutralization Neutral
example ACDMT reagent Monomer Crosslinker Initiator

name /mol- % Name g Name g /mol- % Name mol- % Name g

B2 / 1 80.0 90.0 NaHCO3 32.8 NVP 4.3 9.0TMPTA 1.27 1.00 DLP 1.0
B2 / 2 80.0 89.5 NaHCO3 32.8 NVP 4.3 9.0TMPTA 1.92 1.50 V -601 1.1
B2 / 3 80.0 89.8 NaHCO3 32.8 NVP 4.3 9.0GPTA 2.30 1.25 DLP 1.0
B2 / 4 80.0 89.7 NaHCO3 32.8 NVP 4.3 9.0PEG 600 DMA 3.07 1.25 V - 601 1.1
B2 / 5 80.0 96.3 NaHCO3 32.8 NVP 1.1 2.5 GPTA 2.15 1.25 V - 601 1.1
B2 / 6 80.0 91.2 NaHCO3 32.8 NVP 3.55 7.5 GPTA 2.27 1.25 V - 601 1.1
B2/7 80.0 93.5 NaHCO3 32.8 NVP 2.3 5.0 PEAS 3.16 1.50 V -601 1.1
B2 / 8 80.0 87.5 NaHCO3 32.8 NVP 4.9 10.0 PEG 600 DMA 6.28 2.50 DLP 1.0
B2 / 9 70.0 77.5 NaHCO3 28.6 NVP 9.7 20.0 PEG 600 DMA 6.20 2.50 DLP 1.0
B2/ 10 80.0 89.8 NaHCO3 32.8 NVP 4.3 9.0 TMPTA 1.59 1.25 DLP 1.0
B2 / 11 80.0 54.4 NaHCO3 32.8 DMAAM 31.5 44.8 GPTA 2.27 0.75 V -601 1.0
B2 / 12 80.0 68.9 NaHCO3 32.8 DMAAM 16.6 29.9 GPTA 3.00 1.25 V - 601 1.0
B2 / 13 80.0 74.0 NaHCO3 32.8 DMAAm 12.9 25.0 TMPMTA 1.60 1.00 V -601 1.20
B2 / 14 81.5 89.0 NaHCO3 32.8 N - Isopropylacrylamide 5.0 10.0 TMPTA 1.31 1.00 V - 601 1.00
B2 / 15 81.5 89.0 NaHCO3 32.8 N - Isopropylacrylamide 5.0 10.0 PEG600 DMA 2.51 1.00 V - 601 1.00
B2 / 16 80.0 95.5 NaHCO3 32.8 Behenylpolyethoxy 21.0 3.5 TMPTA 1.20 1.00 DLP 1.75
( 25 ) -methacrylate
B2/ 17 80.0 96.3 NaHCO3 32.8 Behenylpolyethoxy 18.0 3.0 PEG600 DMA 1.60 0.70 DLP 1.75
( 25 ) -methacrylate
B2 / 18 80.0 96.3 NaHCO3 32.8 Behenylpolyethoxy 18.0 3.0 PEG600 DMA 1.60 0.70 DLP 1.75
( 25 ) -methacrylate
B2 / 19 80.0 91.5 NaHCO3 32.8 Laurylpoly -ethoxy-(7 ) 20.1 8.5 TMPTA 0.01 0.01 DLP 3.60
methacrylate
B2/20 80.0 91.5 NaHCO3 32.8 Laurylpoly -ethoxy-(7 ) 20.1 8.5 TMPTA 0.01 0.01 DLP 3.60
methacrylate
B2 / 21 80.0 91.5 NaHCO3 32.8 Laurylpoly -ethoxy-( 7) 20.1 8.5 TMPTA 0.01 0.01 DLP 3.60
methacrylate
B2 / 22 80.0 91.5 NaHCO3 32.8 Laurylpoly -ethoxy-(7 ) 20.1 8.5 TMPTA 0.01 0.01 DLP 3.60
methacrylate
B2 / 23 80.0 93.0 NaHCO3 32.8 Stearylpoly- ethoxy- (8 ) 19.5 7.0 TMPTA 0.01 0.01 DLP 3.90
methacrylate
 US 11,311,473 B2
63 64
-continued
Polymer Table B2 ) :
Polymers according to polymerization process B2:
Polymer Neutralization Neutral
example ACDMT reagent Monomer Crosslinker Initiator
name 1g /mol- % Name g Name lg /mol- % Name g mol- % Name
B2/ 24 80.0 93.0 NaHCO3 32.8 Stearylpoly- ethoxy- (8 ) 19.5 7.0 TMPTA 0.01 0.01 DLP 3.90
methacrylate
B2 / 25 80.0 93.0 NaHCO3 32.8 Stearylpoly- ethoxy- (8 ) 19.5 7.0 TMPTA 0.01 0.01 DLP 3.90
methacrylate
ACDMT = acryloyldimethyltaurate, NVP = N -vinylpyrollidone, DMAAm = dimethylacrylamide, TMPTA = trimethylolpropane triacrylate, TMPTA == trimethylolpropane
= =

triacrylate, TMPTMA = trimethylolpropane trimethacrylate, GPTA = glycerinpropoxylate triacrylate , PEAS = pentaerythritol diacrylate monostearate , DLP =
dilaurylperoxide, V -601 = dimethyl 2,2' - azobis ( 2 -methylpropionate ), PEG 600 DMA = polyethylene glycol dimethacrylate (600 g /mol ).

Polymerization Process A3 : General Precipitation Polymer- Polymerization Process B3 : General Precipitation Polymer
ization Procedure in Tert . -Butanol ization Procedure in Tert. -Butanol/Dimethylketone Mixture
Dose in a 1 - Liter Quickfit round bottom flask equipped Dose in a 1 - Liter Quickfit round bottom flask equipped
with a refux condenser, sub surface gas inlet tubing, inner
with a refux condenser, sub surface gas inlet tubing, inner 20 temperature sensor and overhead agitator 200 g tert .- butanol
temperature sensor and overhead agitator 400 g tert .-butanol and 200 g dimethylketone
with a water content of 3 wt .- % . Charge 69 bio -based Charge 90 g bio - based ACDMT with aa water content of 2.5 wt .- % .
ACDMT and 9.2 g carboxyethyl acrylate. Neutralize the acrylate. Neutralize the ACDMT and and 8.25 g carboxyethyl
ACDMT to a pH of 7 to 8 by injection of gaseous ammonia late by charging 41.3 g sodium hydrogen the carboxyethyl acry
carbonate . Keep
above the surface. Keep the temperature below 40° C. Dose 25 the temperature below 40° C. Dose 0.88 g GPTA, as a
0.93 g GPTA as a crosslinker and 3.71 g methyl acrylate as
a neutral monomer according to Polymer Table A3 . Inject crosslinker and aa 0.44 g methyl acrylate as a neutral mono
mer according to Polymer Table B3 . Inject nitrogen subsur
nitrogen subsurface for 1 h at agitation of 200 rpm . During face for 1 h at agitation of 200 rpm . During this time the
this time the temperature of the reaction mixture is raised 30 temperature of the reaction mixture is raised and stabilized
and stabilized to 60 ° C. with help of aa water bath . Readjust to 60 ° C. with help of a water bath . Readjust the pH at 60 °
the pH at 60 ° C. to a pH of 7 to 8. The reaction is initiated C. to a pH of 7 to 8. The reaction is initiated by the dosage
by the dosage of radical building compound, 1.1 g V -601 . of radical building compound, 1.1 g V --601.
After a few minutes the start of polymerization becomes After a few minutes the start of polymerization becomes
obvious due to the rising temperature and the precipitation 35 obvious due to the rising temperature and the precipitation
of a polymer. When the temperature maximum is reached , of a polymer. When the temperature maximum is reached ,
heat the reaction to a gentle reflux for two hours . Cool the heat the reaction to a gentle reflux for two hours. Cool the
reaction mixture to room temperature and dry the polymer reaction mixture to room temperature and dry the polymer
suspension at 60 ° C. under a vacuum of 150 mbar. suspension at 60 ° C. under a vacuum of 150 mbar.
Polymer Table A3 ) :
Polymers to polymerization process A3 :
Polymer
example ACDMT/ Anionic monomer Neutral Monomer Optional Unit Crosslinker Initiator
name Mol- % Name Mol- % Name Mol- % Name Mol- % Name Mol- % Name g
A3/ 1 75.3 Carboxyethy 14.5 Methyl acrylate 9.7 GPTA 0.49 V -601 1.10
acrylate
A3 / 2 66.8 Carboxyethy 18.0 DMAAm 14.7 PEAS 0.50 DLP 1.60
acrylate
A3 / 3 88.0 Carboxyethy 11.59 Methyl acrylate 0.01 GPTA 0.40 V - 601 1.10
acrylate
A3 / 4 83.3 Carboxyethy 10.5 Stearylpoly -ethoxy 6.2 TMPTA 0.01 DLP 1.80
acrylate oligo ( 8 ) -methacrylate
A3 / 5 89.4 Carboxyethy 10.0 Methyl acrylate 0.1 TMPMTA 0.50 V -601 1.10
acrylate oligo
A3 / 6 88.9 Carboxyethy 9.9 Methyl acrylate 0.1 PEG 600 DMA 1.01 V -601 1.10
acrylate oligo
A3 / 7 76.2 Methacrylic acid 2.6 DMAAm 20.7 GPTA 0.52 V - 601 1.40
A3 / 8 74.0 Methacrylic acid 5.0 DMAAm 20.1 GPTA 0.85 V - 601 1.50
A3 / 9 73.8 Methacrylic acid 5.0 DMAAm 20.1 PEAS 1.18 V - 601 1.50
A3 / 10 90.5 Methacrylic acid 5.4 Behenylpoly -ethoxy 3.3 TMPTA 0.75 DLP 1.75
( 25 ) -methacrylate
A3 / 11 84.6 Methacrylic acid 9.0 Stearylpoly -ethoxy 6.3 TMPTA 0.01 DLP 1.80
( 8 ) -methacrylate
A3/ 12 74.0 Methacrylic acid 5.0 DMAAm 20.1 GPTA 0.85 V -601 1.50
A3 / 13 90.5 Methacrylic acid 5.4 Behenylpoly -ethoxy 3.3 TMPTA 0.75 DLP 1.75
( 25 )-methacrylate
A3 / 14 86.0 Acrylic acid 6.0 Laurylpoly -ethoxy- (7 ) 8.0 PEAS 0.01 DLP 1.80
methacrylate
 US 11,311,473 B2
65 66
-continued
Polymer Table A3 ) :
Polymers to polymerization process A3:
Polymer
example ACDMT / Anionicmonomer Neutral Monomer Optional Unit Crosslinker Initiator
name Mol- % Name Mol- % Name /Mol- % Name /Mol- % Name Mol- % Name g
A3 / 15 93.4 Acrylic acid 6.0 Methyl acrylate 0.1 GPTA 0.45 V - 601 1.10
A3 / 16 93.1 Acrylic acid 6.0 Methyl acrylate 0.5 GPTA 0.45 V -601 1.10
A3 / 17 87.6 2 -ethylacrylic acid 11.5 Methyl acrylate 0.5 PEAS 0.42 V - 601 1.10
A3 / 18 94.4 Itaconic acid 5.0 Methyl acrylate 0.1 GPTA 0.46 V - 601 1.10
A3 / 19 91.0 Itaconic acid 1.0 Laurylpoly -ethoxy-( 7 ) 8.0 TMPTA 0.01 DLP 1.80
methacrylate
A3 / 20 94.0 Itaconic acid 5.0 Methyl acrylate 0.5 GPTA 0.46 V - 601 1.10
A3 /21 80 Carboxyethy 5 DMAAm 4.5 NVP 5 GPTA 0.5 V -601 1.10
acrylate
A3 / 22 74.25 Methacrylic acid 5 Laurylpoly - ethoxy-(7 ) 10 DMAAm 10 TMPTA 0.75 DLP 1.80
methacrylate
A3 / 23 85 Acrylic acid 5 DMAAm 4.5 NVP 5 PEAS 0.5 V - 601 1.10
A3 /24 89 2 -ethylacrylic acid 5 DMAAm 2.5 Methyl 2.5 TMPMTA 1 V -601 1.10
acrylate
A3 /25 88.5 Itaconic acid 5 DMAAm 1.5 NVP 3.5 PEG 600 DMA 1.5 V - 601 1.10
ACDMT = acryloyldimethyltaurate, NVP = N -vinylpyrollidone, DMAAm = dimethylacrylamide, TMPTA = trimethylolpropantriacrylate , TMPTA = trimethylolpropane triacrylate ,
= =

TMPTMA = trimethylolpropane trimethacrylate, GPTA = glycerinpropoxylate triacrylate , PEAS = pentaerythritoldiacrylate monostearate, DLP = dilaurylperoxide, V - 601 = dimethyl
2,2'-azobis (2 -methylpropionate ), PEG 600 DMA = polyethylene glycol dimethacrylate ( 600 g /mol).
=

Polymer Table B3 ) :
Polymers according to polymerization process B3:
Polymer
example ACDMT/ Anionic Monomer NaHCO3 Neutral Monomer Optional units Crosslinker Initiator
name Mol- % Name Mol- % Name Mol- % Name / Mol- % Name Name Mol- % Name
B3 / 1 87.1 Carboxyethy 11.5 41.3 Methyl acrylate 1.0 GPTA 0.41 V - 601 1.10
acrylate
B3 / 2 83.3 Carboxyethy 10.5 36.5 Stearylpoly -ethoxy-(8 ) 6.2 TMPTA 0.01 DLP 1.80
acrylate methacrylate
B3 / 3 83.0 Carboxyethy 9.0 35.9 Laurylpoly -ethoxy-(7 ) 8.0 - PEAS 0.01 DLP 1.80
acrylate methacrylate
B3/ 4 88.0 Carboxyethy 11.59 41.3 Methyl acrylate 0.01 - GPTA 0.40 V - 601 1.10
acrylate
B3 / 5 88.5 Carboxyethy 9.9 40.5 Methyl acrylate 0.1 — GPTA 1.50 V -601 1.10
acrylate oligo
B3 / 6 67 . Carboxyethy 8.5 36.5 DMAAm 23.1 GPTA 0.50 1.30
acrylate oligo
B3 /7 79.0 Methacrylic acid 10.2 50.3 DMAAM 10.1 PEAS 0.70 V -601 1.50
B3 / 8 74.0 Methacrylic acid 5.0 43.3 DMAAm 20.1 GPTA 0.85 V - 601 1.50
B3 / 9 90.9 Methacrylic acid 8.5 39.9 Methyl acrylate 0.1 GPTA 0.44 V -601 1.10
B3 / 10 89.0 Methacrylic acid 3.0 33.5 Laurylpoly -ethoxy-(7 ) 8.0 TMPTA 0.01 DLP 1.80
methacrylate
B3 / 11 74.0 Meth acrylic acid 5.0 43.3 DMAAm 20.1 GPTA 0.9 V - 601 1.50
B3 / 12 90.6 Meth acrylic acid 8.5 39.9 Methyl acrylate 0.5 GPTA 0.44 V - 601 1.10
B3 / 13 89.7 Acrylic acid 6.0 34.6 Behenylpoly -ethoxy-( 25 ) 3.3 TMPTA 1.02 DLP 1.75
methacrylate
B3 / 14 87.5 Acrylic acid 6.0 34.6 Stearylpoly - ethoxy-(8 ) 6.5 PEAS 0.01 DLP 1.80
methacrylate
B3 / 15 93.0 Acrylic acid 3.0 33.5 Behenylpoly -ethoxy-( 25 ) 3.3 - TMPTA 0.65 DLP 1.75
methacrylate
B3 / 16 90.4 2 -propylacrylic 9.0 40.1 Methyl acrylate 0.1 — GPTA 0.44 V -601 1.10
acid
B3 / 17 90 Carboxyethy 2 35.9 DMMAA 4.5 NVP 3 GPTA 0.5 DLP 1.75
acrylate
B3 / 18 85 Carboxyethy 7 35.9 Stearylpoly -ethoxy- (8 ) 3 NVP 4 TMPTA 1 V - 601 1.10
acrylate oligo methacrylate
B3 / 19 86.8 Acrylic acid 7 36.5 Laurylpoly - ethoxy- (7 ) 3 NVP 2.7 TMPTA 0.5 DLP 1.75
methacrylate
B3 / 20 86.8 Methacrylic 7 36.5 Behenylpoly - ethoxy- (25 ) 3.3 NVP 2.2 GPTA 0.7 V - 601 1.10
acid methacrylate
ACDMT = acryloyldimethyltaurate, NVP = N -vinylpyrollidone, DMAAm = dimethylacrylamide, TMPTA = trimethylolpropane triacrylate, TMPTA = trimethylolpropane triacrylate,
= = =

TMPTMA = trimethylolpropane trimethacrylate, GPTA = glycerinpropoxylate triacrylate , PEAS = pentaerythritoldiacrylate monostearate, DLP = dilaurylperoxide, V - 601 = dimethyl
=
2,2 '-azobis (2 -methylpropionate ), PEG 600 DMA = polyethylene glycol dimethacrylate ( 600 g /mol).
=
 US 11,311,473 B2
67 68
Polymerization Process X : Solution Homopolymer of After a few minutes the polymerization start becomes
ACDMT in Water. obvious by a raising temperature and the precipitation of a
In a 1 - L 5 - neck round bottom flask , equipped with an polymer. After the temperature maximum was reached the
overhead stirrer and an anchor type stirrer, a pH probe , reaction mixture was heated to a gentle reflux for two hours.
sub - surface nitrogen inlet, dropping funnel, intensive con- 5 Then the polymer was cooled to room temperature and dried
denser and a gas out let valve 450 g distilled water was filled . at 60 ° C. under a vacuum of 150 mbar.
50 g bio - based ACDMT ( the ACDMT generated in Mono- The resulting polymer powder was dissolved 0.5 % in
mer Example 1 ) was dissolved . The agitator was set to rotate water and the Fickenscher k - value was measured .
with 200 rpm . Cooling with a water bath at 20 ° C. the Drying Acrylonitrile
solution was neutralized with approximately 19 g 50 % 10 500 ml acrylonitrile 299 % , contained 35-45 ppm monom
sodium hydroxide solution to a pH value of 7 + 0.5 . After the ethyl ether hydroquinone as inhibitor from Sigma -Aldrich ,
neutralization the reaction mixture was heated to 50 ° contained 0.41 % water before drying. It was dried by adding
C.:0.5° C. temperature . During the heating phase nitrogen 50 g molecular sieve 0.4 nm from Merck Millipore, Merck
was purged through the solution with a flow rate of 60 l / h . KGaA . The residual water content of the acrylonitrile was
The temperature was stabilized and the nitrogen purge 15 19 ppm , measured by Karl- Fischer titration ( DIN 51777 ) .
continued for 60 minutes. After this 60 minutes the nitrogen Analytical Methods
was dosed above the liquid surface and the polymerization Determination of the Fickenscher k - Value :
was initiated by addition of 0.10 g 2,2'- azobis (2 -methylpro- This method was used to determine the k -value of certain
pionamidine )dihydrochloride ( V -50 by Wako Specialty polymers according to DIN EN ISO 1628-1 .
Chemicals ). 20 A k -value measurement was a way to indirectly analyze
10 minutes after the reaction was started the purge was the molecular weight / size of a polymer. A comparatively
reduced to 6 l/h . After the temperature maximum was higher K -value corresponds to a larger molecular weight/
reached the bath temperature was maintained at 50 ° C. for size as compared to a polymer with the same composition
one hour. Then the bath temperature was increased to 80 ° C. and made by the same process.
for 2 h , then cooled to room temperature. The Brookfield 25 By measuring the measuring the pass - through time of a
viscosity of the solution as was measured at 25 ° C. , 20 rpm , solvent ( tº) and the pass - through time of a polymer solution
using a spindle delivering a value of 20 to 80 % of the ( t“ ) through the capillary of an Ubbelhode viscometer the
maximum scale . relative viscosity was determined .
Also the Fickenscher k - Value was determined .
Polymerization Process Y : Homopolymer of ACDMT by 30
Precipitation Polymerization in Tert - Butanol Ic ??
Z= - +
In a 1 -Liter Quickfit round bottom flask equipped with a to 10
refux condenser, sub surface gas inlet tubing, inner tempera
ture sensor and overhead agitator 400 g tert. -butanol was From the relative viscosity z the k -value can be calculated
dosed . 100 g bio -based ACDMT was charged and was 35 according to
neutralized to a pH of 7 to 8 by injection of gaseous
ammonia above the surface . The temperature was kept
below 40 ° C. At agitation of 200 rpm nitrogen was inject 75 k2
subsurface for 1 h . During this time the temperature of the
reaction mixture was raised and stabilized to 60 ° C. with 40
help of a water bath . At 60 ° C. the pH was readjusted to a
lg z = 1 + 150 kXc
+ K/ XI
?

pH of 7 to 8. Then the reaction was initiated by the dosage In this case

of 1.0 g of 2,2'-azobis( isobutyronitrile ).
After a few minutes the polymerization start became
obvious by a raising temperature and the precipitation of a 45
polymer. After the temperature maximum was reached the 1.51 lg 2-1 1 + le+2+1.5 18lg 2]1.5 1g z
?
reaction mixture was heated to a gentle reflux for two hours. k=
150 + 300 c
Then the polymer was cooled to room temperature and dried k - value = 1000 k
at 60 ° C. under a vacuum of 150 mbar.
The resulting polymer powder was dissolved 0.5 % in 50
water and the Fickenscher k- value was measured . Here in it was defined :
Polymerization Process Z : Synthesis of a Co - Polymer of
ACDMT and Acrylamide by Precipitation Polymerisation in
Tert . - Butanol. nc
Tc
In a 1 - Liter Quickfit round bottom flask equipped with a 55 Z=
to no
refux condenser, sub surface gas inlet tubing, inner tempera
ture sensor and overhead agitator 400 g tert. -butanol was
dosed . 70 g bio - based ACDMT was charged. The ACDMT relative Viscosity,
was neutralized to a pH of 7 to 8 by injection of gaseous nc dynamic viscosity of the solution ,
ammonia above the surface . The temperature was kept 60 n . dynamic viscosity of the solvent and
below 40 ° C. , then 30 g of acrylamide was dissolved in the n c mass concentration of polymer in solution in in g/cm3
reaction mixture. At agitation of 200 rpm nitrogen was inject Alternatively the k -value can be evaluated from lists
subsurface for 1 h . during this time the temperature of the provided by the manufacturer of the equipment.
reaction mixture was raised and stabilized to 60 ° C. with After determination of the mass concentration of the
help of a water bath . At 60 ° C. the pH was readjusted to a 65 polymer solution by microwave drying with a CEM Smart
pH of 7 to 8. Then the reaction was initiated by the dosage 5 at 120 ° C. , 20 ml of a 0.5 % polymer solution was prepared.
of 1.0 g of 2,2 '- azobis ( isobutyronitrile ). 16 to 18 ml of the solution was measured in an Ubbelhode
 US 11,311,473 B2
69 70
capillary viscometer at 25 ° C. The Ubbelhode viscometer Example Composition 2 : Sun Milk SPF 15
was chose to have a pass - through time of 100 to 120 s . It was
measured in a Schott AVS viscometer, combined with a CT
1150 Thermostate and flow cooler CK 100 .
The IT unit calculated the k -value . 5 Ethylhexyl Stearate 7.00 %
Decyl Oleate 5.00 %
Brookfield Viscosity in 1 % Solution : Plantasens ® Natural Emulsifier HE 20 3.00 %
Brookfield viscosity was determined with a Brookfield ( Clariant)
viscometer model LV, RVT DV - II or LVT DV - II. Cetearyl Glucoside ( and ) Sorbitan Olivate
Dimethicone 2.00 %
In aa 600 ml beaker, 4 g dry polymer was dissolved in 394 10
Octocrylene 7.00 %
g distilled water. The solution was stirred for 2 h at 20 ° C. Butyl Methoxydibenzoylmethane
Ethylhexyl Salicylate
2.50 %
4.50 %
with a finger stirrer driven by an overhead agitator at 200 Water Ad 100 %
rpm . Then the polymer solution , free of entrapped air, was Glycerin 3.00 %
tempered for 16 h at 20 ° C. The spindle was chosen to Polymer X
Nipaguard® POM ( Clariant)
1.00 %
1.00 %
measure between 20 to 80 % of the scale at 20 rpm . 15 Phenoxyethanol (and) Piroctone Olamine
Brookfield Viscosity in Solution as is . ( and ) Methylparaben
Brookfield viscosity was determined with a Brookfield Citric Acid q.s.
viscometer model LV, RVT DV - II or LVT DV - II.
In a 600 ml beaker, the polymer solution , free of
entrapped air, was tempered for 2 h at 20 ° C. The spindle 20 Example Composition 3 : Liquid Soap
was chosen to measure between 20 to 80 % of the scale at 20
rpm .
Analytical procedure for determination of bio - based con
tent according to ASTM 6866-12 , Method B : Water Ad 100 %
The provided sample material did not undergo any pre 25 Glycerin 3.00 %
treatment procedure and was converted to graphite as was 1,2 -Propanediol 2.00 %
using the following procedure. Polymer X
Genapol ® LRO liquid ( Clariant)
2.00 %
20.00 %
Depending on the estimated amount of carbon content, Sodium Laureth Sulfate
typically a few milligram of sample material was being Genagen ® CAB 818 (Clariant) 4.00 %
combusted in an Elemental Analyzer ( EA) . The resulting gas 30 Cocamidopropyl Betaine
mixture was being cleaned and CO2 was automatically GlucoTain ® Clear ( Clariant)
Capryloyl/ Caproyl Methyl Glucamide
2.00 %
separated by the EA using the purge and trap technology. Nipaguard TM DMDMH (Clariant) 0.40 %
The remaining CO2 was transferred into a custom -made DMDM Hydantoin
graphitization system , converted into carbon ( graphite) cata Fragrance 0.20 %
lytically using H , and an iron - powder catalyst. 35
Sodium Cloride 0.50 %
The carbon - 14 determination of the graphite was per
formed at the Klaus - Tschira - Archaeomtrie - Center using an
accelerator mass - spectrometer ( AMS) of the type MICA Example Composition 4 : Effect Shower Gel
DAS ( developed at the ETH Zurich , Switzerland ).
40
Composition Examples
Genapol ® LRO liquid ( Clariant) 30.00 %
The following composition examples comprise the poly Sodium Laureth Sulfate
mer according to the present invention e.g. as Polymer X. Genagen ® CAB 818 ( Clariant)
Cocamidopropyl Betaine
6.00 %
Polymer X can relate to any of Polymers A1 / 1 to A1 / 15 , 45 Hostapon ® KCG ( Clariant) 5.00 %
B1 / 1 to B1 / 20 , A2 / 1 to A2/ 24 , B2 / 1 to B2/ 25 , A3 / 1 to A3 / 25
2
Sodium Cocoyl Glutamate
and to B3 / 1 to B3 / 20 ( see above Polymer Tables for their Water Ad 100 %
respective compositions ). Polymer X 1.40 %
Nipaguard ® DMDMH ( Clariant) 0.50 %
Example Composition 1 : After - Sun Cream Gel DMDM Hydantoin
50 Cirebelle 104 Blue 1.00 %
Sythetic Wax

Mineral Oil 3.00 %

Isopropyl Palmitate 3.00 % Example Composition 5 : Facial Cleanser
Cetearyl Isononanoate 3.00 % 55
Jojoba Oil 3.00 %
Walnut Oil 3.00 %
Tocopheryl Acetate 1.00 %
Polymer X 1.20 % Water Ad 100 %
Water ad 100 % Polymer X 1.80 %
Glycerin 3.00 % 60 Genapol ® LRO paste ( Clariant) 4.50 %
Allantoin ( Clariant) 0.20 % Sodium Laureth Sulfate
Nipaguard ® POM ( Clariant) 1.00 % Medialan ® LD (Clariant) 13.50 %
Phenoxyethanol, Methylparaben , Piroctone Sodium Lauroyl Sarcosinate
Olamine Genagen ® CAB 818 (Clariant) 3.00 %
Panthenol 1.00 % Cocamidopropyl Betaine
Collagen nativ 1 % 3.00 %
65
Citric Acid q.s.
Ethanol 1.50 % Benzoic Acid 0.50 %
 US 11,311,473 B2
71 72
Example Composition 6 : Mascara Example Composition 8 : O/W Foundation

Hydroxyethylcellulose 0.50 % 5 Water Ad 100 %

Polymer X 0.50 % Polymer X 1.00 %
1,2 -Propyleneglycol 1.00 % Magnesium Aluminium Silicate 1.00 %
Magnesium Aluminium Silicate 1.00 % Plantasens ® Natural Emulsifier HP10 4.50 %
Triethanolamine 99 % 1.50 % ( Clariant)
Water Ad 100 % 10 Sucrose Polystearate , Cetearyl Alcohol,
Stearic Acid 3.00 %
Olea Europaea (Olive ) Oil Unsaponifiables
SilCare ® Silicone 41 M15 ( Clariant) 1.00 %
SilCare ® Silicone 31M50 ( Clariant) 2.00 %
Caprylyl Methicone Caprylyl Trimethicone
SilCare ® Silicone 31M50 ( Clariant ) 2.00 %
XIAMETER ® PMX - 200 Silicone Fluid 100 CS 2.00 %
Caprylyl Trimethicone 15 Dimethicone
Tego ® Care 450 4.00 %
Polyglyceryl- 3 Methylglucose Distearate Caprylic / Capric Triglyceride 5.00 %
Polybutene . 2.00 % Plantasens ® Olive Wax S51 ( Clariant) 1.50 %
Beeswax 2.50 % Hydrogenated Vegetable Oil
Plantasens ® Olive Wax S51 ( Clariant) 2.50 % Chroma -Lite ® Black 0.10 %
Hydrogenated Olive Oil 20 Mica (and ) Bismuth Oxychloride ( and ) Iron
Microcrystalline Wax 3.50 % Oxides
Iron Oxides 10.0 % Chroma- Lite ® Red 0.40 %
Phenonip TM ME ( Clariant) 1.00 % Mica (and ) Bismuth Oxychloride ( and ) Iron
Phenoxyethanol, Methylparaben , Oxides
Ethylparaben 25 Chroma - Lite ® Yellow 1.20 %
Baycusan® C 1004 2.00 % Mica ( and ) Bismuth Oxychloride ( and ) Iron
Polyurethane - 35 Oxides
Titanium Dioxide 7.00 %

30
Dicaprylyl Carbonate 4.00 %
Butylene Glycol 3.00 %
Example Composition 7 : BB Cream SPF 15 Plantasens ® Natural Vitamin E ( Clariant) 1.00 %
Tocopherol
Orgasol ® 4000 EXD NAT COS Caresse 1.00 %
Water Ad 100 % 35 Nylon - 6 / 12
Glycerin 2.00 % Fragrance 0.20 %
Polymer X 1.00 % Nipaguard ® POB (Clariant) 0.80 %
Hostaphat ® KW 340 D ( Clariant) 3.00 %
Phenoxyethanol (and) Piroctone Olamine
Triceteareth - 4 Phosphate
Cetearyl Alcohol 2.00 % ( and ) Benzoic Acid
Octocrylene 7.00 % 40
Butyl Methoxydibenzoylmethane 2.50 %
Ethylhexyl Salicylate 4.50 %
Plantasens ® Olive LD (Clariant) 2.00 %
Hydrogenated Ethylhexyl Olivate ( and )
Hydrogenated Olive Oil Unsaponifiables
Example Composition 9 : Liquid Highlighter
12-15 Alkyl Benzoate 8.00 %
45
Plantasens ® Olive Squalane ( Clariant) 2.00 %
Squalane
Plantasens ® Shea Butter ( Clariant) 1.00 % Water Ad 100 %
Butyrospermum Parkii ( Shea) Butter Bentonite 1.00 %
XIAMETER ® PMX - 200 Silicone Fluid 200 CS 2.00 % Polymer X 1.00 %
Dimethicone Liquiwax TM PolyIPL 2.00 %
Chroma - Lite ® Black 0.05 % 50 Stearyl/PPG - 3 Myristyl Ether Dimer
Mica (and ) Bismuth Oxychloride ( and ) Iron Dilinoleate
Oxides Plantasens ® Olive Wax S51 ( Clariant) 2.00 %
Chroma - Lite ® Red 0.20 % Hydrogenated Olive Oil
Mica ( and ) Bismuth Oxychloride ( and ) Iron Stearic Acid 1.20 %
Oxides Isostearic Acid 0.90 %
Chroma - Lite ® Yellow 0.60 % 55 Water 5.00 %
Mica ( and ) Bismuth Oxychloride ( and) Iron Sodium Hydroxide 0.12 %
Oxides Orgasol ® 4000 EXD NAT COS Caresse 1.50 %
Titanium Dioxide 5.00 % Nylon - 6 / 12
Butylene Glycol 4.00 % Timiron ® Super Gold 2.50 %
Plantasens ® Natural Vitamin E (Clariant) 1.00 % Mica , Titanium Dioxide
Tocopherol 60 Xirona ® Indian Summer 2.50 %
Panthenol 0.50 % Silica ( and ) Iron Oxides
Sodium Hyaluronate 0.40 % Panthenol 0.50 %
Fragrance 0.20 % Cyclopentasiloxane 7.50 %
Nipaguard® POB (Clariant) 0.80 % Phenonip TM ME ( Clariant) 1.00 %
Phenoxyethanol ( and ) Piroctone Olamine Phenoxyethanol, Methylparaben ,
(and ) Benzoic Acid Ethylparaben
Citric Acid q.s. 65 Tocopheryl Acetate 1.00 %
 US 11,311,473 B2
73 74
Example Composition 10 : Lipstain -continued
Ethanol 5.00 %
Tocopheryl Acetate 1.00 %
Water Ad 100 % 5
Nipaguard® POM ( Clariant) 1.00 %
Glycerin 30.00 % Phenoxyethanol, Methylparaben , Piroctone
Polymer X 3.00 % Olamine
FD &C Red No. 40 0.15 %
CI16035
Emulsogen ® HCO 040 ( Clariant) 0.50 %
PEG- 40 Hydrogenated Castor Oil 10
Example Composition 14 : Body Lotion for Men
Phenonip TM ME ( Clariant) 1.00 %
Phenoxyethanol, Methylparaben ,
Ethylparaben
Flavour 0.20 %
Caprylic / Capric Triglyceride 3.50 %
Plantasens ® Olive LD ( Clariant) 3.00 %
15 Hydrogenated Ethylhexyl Olivate ( and )
Example Composition 11 : Eyeliner Gel Hydrogenated Olive Oil Unsaponifiables
Myristyl Myristate 2.50 %
Cetearyl Alcohol 2.00 %
Octyldodecanol 1.00 %
Glyceryl Stearate Citrate 1.50 %
Water Ad 100 % 20 Polymer X 1.20 %
Glycerin 1.00 % Water ad 100 %
Polymer X 2.00 % Glycerin 5.00 %
Phenonip TM ME ( Clariant) 1.00 % Ethanol 3.00 %
Phenoxyethanol, Methylparaben , Tocopheryl Acetate 1.00 %
Ethylparaben Aloe Barbadensis Leaf Juice 1.00 %
PVP 1.50 % 25
Nipaguard ® POM ( Clariant) 1.00 %
Water 10.00 % Phenoxyethanol, Methylparaben , Piroctone
Timiron ® Super Gold 12.00 % Olamine
Mica , C177891 , Titanium Dioxide Fragrance 0.20 %
Sodium Hydroxide q.s.

30
Example Composition 12 : After - Shave Balm Example Composition 15 : Anti - Ageing Cream Gel

Hostaphat ® KL 340 D ( Clariant) 2.00 %

Trilaureth - 4 Phosphate 35 Caprylic / Capric Triglyceride 5.00 %
Octopirox ® ( Clariant) 0.05 % Dicaprylyl Ether 5.00 %
Piroctone Olamine Cetearyl Alcohol 2.00 %
Plantasens ® Abyssinian Oil ( Clariant) 2.00 % Nipaguard ® POB (Clariant) 0.80 %
Crambe Abyssinica Seed Oil Phenoxyethanol ( and ) Piroctone Olamine
Isopropyl Isostearate 3.00 % ( and ) Benzoic Acid
Plantasens ® Inca Inchi Serum (Clariant) 1.00 % 40 Ubiquinone 0.10 %
Plukenetia Volubilis Seed Oil ( and ) Aristoflex ® HMB (Clariant) 0.40 %
Phytosterols ( and ) Olea Europaea (Olive ) Oil Ammonium Acryoyldimethyltaurate /
Unsaponifiables ( and ) Beeswax Beheneth - 25 Methacrylate Crosspolymer
Water Ad 100 % Polymer X 0.40 %
Polyglykol 400 ( Clariant ) 3.00 % Sodium Hyaluronate 0.30 %
PEG - 8 Water Ad 100 %
Allantoin 0.30 % 45 Tocopheryl Acetate 0.30 %
Polymer X 1.50 % Fragrance 0.30 %
Dimethicone 1.00 %
Citric Acid q.s.
Phenonip TM ME ( Clariant) 1.00 %
Phenoxyethanol, Methylparaben ,
Ethylparaben 50
Example Composition 16 : Light Day Cream

Example Composition 13 : Sprayable Body Milk Water

Polymer X
Ad 100 %
0.75 %
55 Glycerin 3.00 %
Plantasens ® Natural Emulsifier HE20 1.20 %
( Clariant)
Hostaphat ® KL 340 D ( Clariant) 1.00 % Cetearyl Glucoside , Sorbitan Olivate
Trilaureth - 4 Phosphate Aristoflex ® AVC ( Clariant) 0.10 %
Mineral Oil 8.00 % Ammonium Acryloyldimethyltaurate /VP
Isopropyl Palmitate 3.00 % 60 Copolymer
Cetearyl Alcohol 0.50 % Plantasens ® Abyssinian Oil ( Clariant) 3.00 %
Caprylic / Capric Triglyceride 2.00 % Crambe Abyssinica Seed Oil
Glyceryl Stearate 0.50 % Octyldodecanol 5.00 %
SilCare ® Silicone 41M15 (Clariant) 1.00 % Isodecyl Neopentanoate 3.00 %
Caprylyl Methicone Plantasens ® Natural Vitamin E ( Clariant) 0.50 %
Polymer X 1.00 % Tocopherol
Water ad 100 % 65 Nipaguard ® SCP ( Clariant) 1.00 %
Glycerin 5.00 % Phenoxyethanol ( and ) Sorbitan Caprylate
 US 11,311,473 B2
75 76
-continued Example Composition 20 : Nail Varnish Remover
Gel
Fragrance 0.30 %
Citric Acid q.s.
5
Water Ad 100 %
Ethanol 27.00 %
Example Composition 17 : Caring Night Cream Polyglykol ® 400 (Clariant)
PEG - 8
3.00 %
Glycerin 3.00 %
10 Aristoflex ® TAC (Clariant) 0.20 %
Ammonium Acryloyldimethyltaurate /
Water Ad 100 % Carboxyethyl Acrylate Crosspolymer
Glycerin 2.00 % Polymer X 1.00 %
Polymer X 1.00 % Ethyl Acetate 30.00 %
Hostaphat ® KW 340 D ( Clariant) 2.00 %
Triceteareth - 4 Phosphate 15
Plantasens ® Oat Serum ( Clariant) 3.00 %
Avena Sativa (Oat) Kernel Oil ( and ) Example Composition 21 : Skin -Whitening Gel
Phytosterols ( and ) Olea Europaea (Olive ) Oil
Unsaponifiables (and) Beeswax
Plantasens ® Shea Butter ( Clariant) 7.00 %
Butyrospermum Parkii ( Shea) Butter
Isopropyl Palmitate 5.00 % 20
Genapol ® T 250 (Clariant) 2.00 %
Macadamia Integrifolia Seed Oil 4.00 %
Ceteareth - 25
Cera Alba ( Beeswax) 3.00 %
Genapol ® DAT 100 ( Clariant) 1.10 %
Nipaguard ® SCP ( Clariant) 1.00 %
PEG- 150 Polyglyceryl- 2 Tristearate
Phenoxyethanol ( and ) Sorbitan Caprylate Water Ad 100 %
Fragrance 0.30 %
Ascorbic Acid 2- Glucoside 3.00 %
Sodium Hydroxide 0.10 % 25 Polymer X 1.50 %
Nipaguard TM DMDMH Plus ( Clariant) 2.00 %
DMDM Hydantoin
Example Composition 18 : Sprayable Hair Styling
Gel 30
Example Composition 22 : Self- Tanning Cream
Polymer X 0.90 %
Water Ad 100 % Hostaphat ® CC 100 ( Clariant) 1.00 %
Genapol ® LA- 230 ( Clariant) 4.00 % 35 Cetyl Phosphate
Laureth -23 Glyceryl Stearate 0.50 %
Diaformer ® Z- 632N ( Clariant) 4.50 % Cetearyl Alcohol 0.50 %
Acrylates /Stearyl Acrylate /Ethylamine Oxide Mineral Oil 8.00 %
Methacrylate Copolymer Isopropyl Palmitate 7.00 %
Dipropylene Glycol 1.00 % Tocopheryl Acetate 1.00 %
Polyglykol 400 0.50 % 40 SilCare ® Silicone 41M15 ( Clariant) 1.00 %
PEG- 8 Caprylyl Methicone
Nipaguard TM DMDMH (Clariant) 0.50 % Polymer X 2.00 %
DMDM Hydantoin Water ad 100 %
Panthenol 0.50 % Hostapon ® KCG ( Clariant) 0.50 %
Emulsogen ® HCO 040 ( Clariant ) 0.50 % Sodium Cocoyl Glutamate
PEG- 40 Hydrogenated Castor Oil 45 Glycerin 5.00 %
Fragrance 0.30 % Fragrance 0.20 %
Phenonip TM ME ( Clariant) 1.00 %
Phenoxyethanol, Methylparaben ,
Ethylparaben
Dihydroxyacetone 5.00 %
Example Composition 19 : Conditioning Shampoo 50 Water 8.00 %
Sodium Hydroxide q.s.

Water Ad 100 %
Polymer X 1.10 % Example Composition 23 : Make -Up Remover
Genapol ® LRO liquid ( Clariant) 30.00 % 55
Sodium Laureth Sulfate
Genagen ® CAB 818 (Clariant) 6.00 %
Cocamidopropyl Betaine
XIAMETER ® PMX - 200 Silicone Fluid 50 CS 0.25 % Water ad 100 %
Dimethicone Glycerin 3.00 %
Water 10.00 %
60 Polymer X 0.80 %
Jaguar ® C- 162 0.20 % Hostaphat ® KL 340 D ( Clariant) 3.00 %
Hydroxypropyl Guar ( and ) Hydroxypropyl Trilaureth - 4 Phosphate
Guar Hydroxypropyltrimonium Chloride Cetearyl Alcohol 1.50 %
Citric Acid q.s. Plantasens ® Olive LD (Clariant) 2.00 %
Water 4.00 % Hydrogenated Ethylhexyl Olivate ( and)
Sodium Benzoate 0.45 %
65
Hydrogenated Olive Oil Unsaponifiables
Sodium Chloride 0.50 % Isostearyl Isostearate 4.00 %
Isohexadecane 4.00 %
 US 11,311,473 B2
77 78
-continued -continued
Sodium Hydroxide q.s. Glucotain ® Care (Clariant) 2.00 %
Nipaguard ® SCP ( Clariant) 1.00 % Cocoyl Methyl Glucamide
Phenoxyethanol (and) Sorbitan Caprylate 5
Plantasens ® Grape Seed Serum (Clariant) 1.00 %
Fragrance 0.20 % Vegetable Oil ( and) Phytosterols ( and ) Olea
Europaea (Olive ) Oil Unsaponifiables
Plantasens ® Abyssinian Oil ( Clariant) 3.00 %
Crambe Abyssinica Seed Oil
Example Composition 24 : Insect Repellent Lotion Hostacerin ® SFO ( Clariant)
Sunflower Seed Oil Sorbitol Esters
2.00 %
10 Kaolin 4.00
Green Clay 4.00
Titanium Dioxide 2.00
Diethyl Toluamide 10.00 % Nipaguard ® POM (Clariant) 1.00
DEET Phenoxyethanol ( and ) Piroctone Olamine
Hostaphat ® KL 340 D ( Clariant) 1.00 %
( and ) Methylparaben
Trilaureth - 4 Phosphate 15 Sodium Acetate 0.10
Isohexadecan 5.00 %
Citric Acid q.s.
C12-15 Alkyl Benzoate 5.00 %
Cyclopentasiloxane 2.00 %
Polymer X 1.00 %
Water Ad 100 %
Ethanol 10.00 %
Fragrance 0.30 %
20 Example Composition 28 : Micellar Gel
Nipaguard ® POB ( Clariant) 0.80 %
Phenoxyethanol ( and ) Piroctone Olamine
(and) Benzoic Acid
Water ad 100 %
25 Polymer X 1.00 %
Glycerin ( 85 % ) 3.00 %
Example Composition 25 : Facial Toner GlucoTain ® Clear ( Clariant) 4.00 %
Capryloyl/Caproyl Methyl Glucamide
Propylene Glycol 2.00 %
Sodium Citrate 0.10 %
Water ad 100 % 30 Emulsogen ® HCO 40 ( Clariant ) 1.00 %
Glycerin 5.00 %
PEG- 40 Hydrogenated Castor Oil
Butylene Glycol 3.00 %
Nipaguard ® POM (Clariant) 1.00 %
Alcohol 5.00 %
Phenoxyethanol, Methylparaben, Piroctone
Olamine
Polymer X 0.20 % Citric Acid q.s.
Emulsogen ® HCO 040 ( Clariant ) 0.40 %
PEG- 40 Hydrogenated Castor Oil 35
Fragrance 0.30 %
Tocopheryl Acetate 0.50 %
Panthenol
Nipaguard ® SCP ( Clariant)
0.30%
1.00 %
Example Composition 29 : Lubricating Gel
Phenoxyethanol ( and ) Sorbitan Caprylate
Citric acid q.s. pH 5.5 40
Water ad 100 %
Polymer X 0.50 %
Example Composition 26 : Depilating Cream Glycerin ( 85 % )
Polyglycol 300
5.00 %
3.00 %
PEG- 6
45 Aloe Barbadensis Leaf Juice 0.30 %

Cetyl Alcohol 4.00 %

Ceteareth - 20 3.00 %
Cetearyl Alcohol 2.00 %
Caprylic / Capric Triglyceride
Mineral Oil
5.00 %
2.00 % 50
Example Composition 30 : Emulsion for Wet Wipes
Water ad 100 %
Tetrasodium EDTA 0.10 %
Polymer X 3.00 %
Potassium Hydroxide ( 50 % sol ) 2.00 % Emulsogen ® CCT Green ( Clariant) 2.50 %
Calcium Hydroxide 5.00 % Caprylic / Capric Triglyceride, Water, Lauryl
Potassium Thioglycolate 10.0 % 55 Glucoside , Glycerin , Sodium Lauroyl
Fragrance 0.30 % Lactylate , Glyceryl Stearate, Cetearyl
Tocopheryl Acetate 0.50 % Alcohol , Sodium Stearoyl Lactylate
Panthenol 0.30 % Isopropyl Stearate 5.00 %
Plantasens ® Abyssinian Oil ( Clariant) 0.50 %
Crambe Abyssinica Seed Oil
60 Tocopheryl Acetate 0.10 %
Example Composition 27 : Face Mask Fragrance 0.20 %
Water ad 100 %
Polymer X 0.10 %
Panthenol 0.10 %
Nipaguard ® SCE ( Clariant) 1.50 %
Water ad 100 %
65
Sorbitan Caprylate ( and ) Propanediol (and )
Polymer X 2.00 % Benzoic Acid
Glycerin ( 85 % ) 5.00 %
 US 11,311,473 B2
79 80
Example Composition 31 : Antiperspirant for Example Composition 35 : Hair Detangling Cream
Roll -Ons

5 Water ad 100 %
Hydroxyethyl cellulose 0.30 % Glycerin 3.00 %
Alcohol 25.0 % Polymer X 1.50 %
Water ad 100 % Hostacerin ® SFO ( Clariant) 2.00 %
Polymer X 0.50 % Sunflower Seed Oil Sorbitol Esters
Locron ® LIC (Clariant) 25.0 % Plantasens ® Sweet Almond Oil ( Clariant) 3.00 %
Aluminium Chlorodydrate 10 Prunus Amygdalus Dulcis ( Sweet Almond)
Propylene Glycol 2.00 % Oil
Panthenol 0.10 % Plantasens ® Avocado Oil (Clariant) 2.00 %
Emulsogen ® HCO 40 ( Clariant) 1.00 % Persea Gratissima ( Avocao ) Oil
PEG- 40 Hydrogenated Castor Oil Isopropyl Palmitate 5.00 %
Fragrance 0.30 % SilCare ® Silicone SEA ( Clariant) 0.80 %
Trideceth - 9 PG - Amodimethicone and
15 Trideceth - 12
Panthenol 0.50 %
Example Composition 32 : Shaving Gel Fragrance 0.30 %
Tocopheryl Acetate 0.30 %
Nipaguard ® SCE ( Clariant) 1.20 %
Sorbitan Caprylate , Propanediol, Benzoic
20 Acid
Water ad 100 %
Glycerin 5.00 %
Polymer X 1.50%
Genapol ® LT ( Clariant)
PEG- 150 Polyglyceryl- 2 Tristearate (and )
1.00 % Example Composition 36 : Effect Shower Gel
Laureth - 3 (and ) Dipropylene Glycol 25
Genagen ® SC 15 ( Clariant) 6.00 % pH = 5.0 , 510 mPa · s ( Brookfield RVDV - 1, 20 ° C. , 20 rpm ,
Sodium Laureth Sulfate ( and ) Cocamide S04 )
MEA (and) Aqua
Genagen ® CAB 818 (Clariant) 3.00 %
Cocamidopropyl Betaine Genapol ® LRO liquid (Clariant) 30.00 %
Sodium Hydroxide (50 % sol ) 0.50 %
30 Sodium Laureth Sulfate
Panthenol 0.10 %
Genagen ® CAB 818 ( Clariant) 6.00 %
Allantoin 0.20 % Cocamidopropyl Betaine
Polyglycol 300 ( Clariant) 0.50 % Hostapon ® KCG (Clariant) 5.00 %
PEG- 6 Sodium Cocoyl Glutamate
Phenonip ® ME ( Clariant) 0.90 % Water Ad 100 %
Phenoxyethanol, Methylparaben , Polymer - A1/ 2 1.40 %
Ethylparaben 35
( according to polymerization process A1 )
Fragrance 0.30 % Nipaguard ® DMDMH ( Clariant) 0.50 %
DMDM Hydantoin
Cirebelle 104 Blue 1.00 %
Sythetic Wax
Example Composition 33 : Hand Sanitizer 40

Example Composition 37 : O/ W Foundation

Water ad 100 %
Glycerin 2.00 % pH = 6.0 , 18650 mPa s (Brookfield RVDV - 1 , 20 ° C. , 20
Polymer X 0.50 %
45 rpm , S06 )
Ethanol 70.0 %
XIAMETER ® OFX - 5324 Fluid 6.00 %
PEG- 12 Dimethicone
Aloe Barbadensis Leaf Extract 0.30 % Water Ad 100 %
Polymer -A1/ 2 1.00 %
( according to polymerization process Al )
50 Magnesium Aluminium Silicate 1.00 %
Example Composition 34 : Hair Serum Plantasens ® Natural Emulsifier HP10
( Clariant)
4.50 %

Sucrose Polystearate , Cetearyl Alcohol ,

Olea Europaea (Olive ) Oil Unsaponifiables
SilCare ® Silicone 31 M50 (Clariant) 2.00 %
Water ad 100 % 55 Caprylyl Trimethicone
Glycerin 5.00 % XIAMETER ® PMX - 200 Silicone Fluid 100 CS 2.00 %
Propylene Glycol 3.00 % Dimethicone
Polymer X 2.00 % Caprylic / Capric Triglyceride 5.00 %
XIAMETER ® PMX -200 (50cs) 2.00 % Plantasens ® Olive Wax S51 ( Clariant) 1.50 %
Dimethicone Hydrogenated Vegetable Oil
XIAMETER ® PMX - 0245 3.00 % Chroma- Lite ® Black 0.10 %
Cyclopentasiloxane 60 Mica ( and ) Bismuth Oxychloride ( and ) Iron
Polysorbate - 20 Oxides
Sodium Hyaluronate 1.00 % Chroma - Lite ® Red 0.40 %
Nipaguard ® POM ( Clariant) 1.00 % Mica (and ) Bismuth Oxychloride ( and ) Iron
Phenoxyethanol ( and) Piroctone Olamine Oxides
( and ) Methylparaben Chroma- Lite ® Yellow 1.20 %
Fragrance 0.50 % 65 Mica ( and ) Bismuth Oxychloride ( and ) Iron
Oxides
 US 11,311,473 B2
81 82
-continued -continued
Titanium Dioxide 7.00 % Polymer -A1/ 2 0.50 %
Dicaprylyl Carbonate 4.00 % ( according to polymerization process A1 )
Butylene Glycol 3.00 %
5 Ethanol 70.0 %
Plantasens ® Natural Vitamin E ( Clariant) 1.00 % XIAMETER ® OFX - 5324 Fluid 6.00 %
Tocopherol PEG- 12 Dimethicone
Orgasol ® 4000 EXD NAT COS Caresse 1.00 %
Aloe Barbadensis Leaf Extract 0.30 %
Nylon -6 / 12
Fragrance 0.20 %
Nipaguard® POB (Clariant) 0.80 %
Phenoxyethanol ( and) Piroctone Olamine 10 Method of Use
(and ) Benzoic Acid
Example Methods of Use :
Example Composition 19 is applied to wet hair in an
Example Composition 38 : Anti -Ageing Cream Gel amount of about 2 ml per 2 gram of hair ( dry weight ). Tap
15 water is employed to create a lather and spread the compo
sition throughout the hair and scalp . The composition is
pH = 5.1 , 1580 mPa s (Brookfield RVDV - 1, 20 ° C. , 20 immediately
rpm , S04) rinsed from the hair. The hair may further be
conditioned .
Caprylic /Capric Triglyceride 5.00 % 20 Example Compositions 1 , 2 , 12 , 13 , 14 , 15 , 16 , 17 , 22 , 24 ,
Dicaprylyl Ether 5.00 % and 37 to 39 are applied to human skin and left on the skin
Cetearyl Alcohol 2.00 % to sink in, and the skin allowed to dry .
Nipaguard ® POB (Clariant) 0.80 %
Phenoxyethanol (and ) Piroctone Olamine
( and ) Benzoic Acid EXPERIMENTAL
Ubiquinone 0.10 % 25
Aristoflex ® HMB (Clariant) 0.40 %
Ammonium Acryoyldimethyltaurate / Experimental Example 1 : Polymers According to
Beheneth - 25 Methacrylate Crosspolymer Polymerization Process B1 : Viscosity Dependence
Polymer - A1/ 2 0.40 %
( according to polymerization process A1 ) on Polymer Concentration
Sodium Hyaluronate 0.30 % 30
Water Ad 100 %
Tocopheryl Acetate 0.30 % The following example comprises a polymer according to
Fragrance 0.30 % the present invention as Polymer B1 / 16 compared with
Polymer B1 / 16 # . Polymer B1 / 16 # being a comparative
35 example in that is the same as Polymer B1 / 16 but with
Example Composition 39 : Caring Night Cream common building blocks derived from petrochemicals.
See FIG . 1 : The viscosity measurements in dependence of
pH = 5.8 , 22450 mPa * s (Brookfield RVDV - 1 , 20 ° C. , 20 polymer concentration with Polymer B1 / 16 ( solid line ) and
rpm , S06 ) Polymer B1 / 16 # (broken line ) showed very similar results ,
40 therefore Polymer B1 / 16 and Polymer B1 / 16 # are inter
Water Ad 100 % changeable with one another.
Glycerin 2.00 %
Polymer -A1 / 2 1.00 %
( according to polymerization process A1 ) Experimental Example 2 : Polymers According to
Hostaphat ® KW 340 D (Clariant) 2.00 % 45 Polymerization Process B1 : Viscosity Dependence
Triceteareth - 4 Phosphate on pH
Plantasens ® Oat Serum (Clariant) 3.00 %
Avena Sativa (Oat ) Kernel Oil ( and )
Phytosterols ( and ) Olea Europaea (Olive ) Oil
Unsaponifiables (and) Beeswax The following example comprises a polymer according to
Plantasens ® Shea Butter ( Clariant) 7.00 % the present invention as Polymer B1 / 16 compared with
Butyrospermum Parkii ( Shea) Butter 50 Polymer B1/ 16 # . Polymer B1 / 16 # being a comparative
Isopropyl Palmitate 5.00 % example in that is the same as Polymer B1 / 16 but with
Macadamia Integrifolia Seed Oil 4.00 %
Cera Alba (Beeswax) 3.00 % common building blocks derived from petrochemicals.
Nipaguard ® SCP (Clariant) 1.00 % See FIG . 2 : The viscosity measurements and their depen
Phenoxyethanol ( and ) Sorbitan Caprylate
Fragrance 0.30 % 55 dence on pH with Polymer B1 / 16 and Polymer B1 / 16 #
Sodium Hydroxide 0.10 % showed very similar results , therefore Polymer B1 / 16 and
Polymer B1 / 16 # are interchangeable with one another.
Example Composition 40 : Hand Sanitizer 60
Experimental Example 3 : Polymers According to
Polymerization Process A3
pH = 5.4 , 30600 mPa * s ( Brookfield RVDV- 1, 20 ° C. , 20
rpm , S06) The following example comprises a polymer according to
the present invention as Polymer-A3 / 8 compared with Poly
Water ad 100 % 65 mer - A3 / 8 # . Polymer A3 / 8 # being a comparative example
Glycerin 2.00 % in that is the same as Polymer -A3 / 8 but with common
building blocks derived from petrochemicals.
 US 11,311,473 B2
83 84
Typical measurements of Polymer -A3/ 8 and Polymer- shaving soap , shaving foam , cleansing foam , day cream ,
A3 / 8 # showed very similar results ( Exp . Table 1 ) , therefore anti- ageing cream , body milk , body lotion, body mousse ,
Polymer -A3 / 8 and Polymer -A3 / 8 # are interchangeable with face serum , eye cream , sunscreen lotion , sun cream , face
one another. cream , after - shave lotion , pre - shaving cream , depilatory
5 cream , skin -whitening gel , self -tanning cream , anti- acne gel ,
mascara , foundation, primer, concealer, blush , bronzer,
Exp. Table 1 : Polymers according to polymerization process A3 . blemish balm ( bb ) cream , eyeliner, night cream , eye brow
Viscosity measurement: Brookfield RVDV - 1 , 20 ° C., 20 rpm . gel , highlighter, lip stain , hand sanitizer, hair oil , nail varnish
Polymer Viscosity /mPa : S pH remover , conditioner, hair styling gel , hair styling cream ,
10 anti - frizz serum , scalp treatment, hair colorant, split end
A3/8
A3 / 8 #
18000
19300
5.0
5.3
fluid , deodorant, antiperspirant, baby cream , insect repellent,
hand cream , sunscreen gel , foot cream , exfoliator, body
scrub , cellulite treatment, bar soap , cuticle cream , lip balm ,
hair treatment, eye shadow , bath additive, body mist , eau de
Experimental Example 4 : Polymers According to 15 toilette , mouthwash , toothpaste, lubricating gel , moisturizer,
Polymerization Process A1 : Viscosity Dependence serum , toner, aqua sorbet, cream gel , styling mousse , dry
on pH shampoo, lip stick , lip gloss , hydro - alcoholic gel , body oil ,
shower milk, illuminator, lip crayon , hair spray, combing
The following example comprises a polymer according to cream , and sunblock .
the present invention as Polymer A1 / 2 compared with Poly- 20 3. The method according to claim 1 , wherein the cos
mer A1 / 2 # . Polymer A1 / 2 # being a comparative example metic , dermatological or pharmaceutical composition fur
in that is the same as Polymer A1 /2 but with common ther comprises:
building blocks derived from petrochemicals. ( II ) at least one cosmetically acceptable component.
See FIG . 3 : The viscosity measurements and their depen- 4. The method according to claim 3 , wherein the at least
dence on pH with Polymer A1 /2 and Polymer A1 / 2 # showed 25 one cosmetically acceptable component is an auxiliary or
very similar results, therefore Polymer A1 / 2 and Polymer mixture of auxiliaries, selected from the group consisting of
A1 /2 # are interchangeable with one another. oily substances , waxes , emulsifiers, coemulsifiers , solubi
The invention claimed is : lizers , cationic polymers , film formers, superfatting agents ,
1. A method for thickening or modifying a rheology in a refatting agents, foam stabilizers , stabilizers, active biogenic
cosmetic, dermatological or pharmaceutical composition 30 substances,,preservatives, preservation boosting ingredients,
comprising the step of adding at least one polymer to the anti- fungal substance, anti - dandruff agents , dyes or pig
cosmetic, dermatological or pharmaceutical composition , ments, particulate substances, opacifiers, abrasives , absor
wherein the polymer is crosslinked, and comprises at least bents, anticaking agents, bulking agents, pearlizing agents,
9.49 mol % of repeating units (a ) according to Formula ( 1 ) direct dyes, perfumes or fragrances, carriers, solvents or
wherein at least 10 wt.- % of the repeating units according to 35 diluents, propellants, functional acids , active ingredients,
Formula ( 1 ) comprise from 28 wt .- % to 100 wt .- % bio -based skin -brightening agents, self- tanning agents, exfoliants,
carbon content, relative to the total mass of carbon in the enzymes , anti- acne agents, deodorants and anti -perspirants ,
repeating unit according to Formula ( 1 ) , measured according viscosity modifiers , thickening and gelling agents, pH
to standard ASTM D6866-12 , Method B ; adjusting agents, buffering agents, anti-oxidants, chelants ,
40 astringents, sunscreens, sun protection agents, UV filters,
skin conditioning agents, emollients , humectants, occlusive
( 1 ) agents, pediculocides, anti - foaming agents, flavouring
agents, electrolytes, oxidizing agents and reducing agents .
-CR '+
CH2 - CR !+

??
wherein :
R1 and R2 are H ;
N - A
R2
-O et
5. The method according to claim 1 , wherein the polymer
45 has a weight average molecular weight of at least 700 g/mol .
6. The method according to claim 3 , wherein the cos
metic , dermatological or pharmaceutical composition is an
emulsion or a gel.
7. The method according to claim 3 , wherein the cos
50 metic , dermatological or pharmaceutical composition has a
A is aa linear or branched C4 -alkyl group ; and Q * is NH4 * , viscosity from 100 000 to 200 000 mPa · s , (measured at 25 °
C. , Brookfield RVT, T - C spindle at 20 revolutions per
and
wherein the polymer of Formula ( 1 ) is crosslinked with minute ).
8. The method according to claim 3 , wherein the cos
trimethylolpropane triacrylate ( TMPTA ).
2. The method according to claim 1, wherein the cos- 55 metic,ordermatological or pharmaceutical composition is a
metic , dermatological or pharmaceutical composition com body face care composition , and wherein the body or face
position is selected from the group consisting of shampoo, care least
composition comprises from 0.1 wt % to 15 wt % of at
one emulsifier, coemulsifier and / or solubilizer, by total
body wash , facial cleanser, face mask , bubble bath , intimate
wash , bath oil , cleansing milk , micellar water, make - up weight of the composition .
remover , cleansing wipes , hair mask , perfume, liquid soap ,