US20150232712A1
US20150232712A1
US20150232712A1
2712A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2015/0232712 A1
Roth et al. (43) Pub. Date: Aug. 20, 2015
(54) ADHESIVE COMPOSITIONS (30) Foreign Application Priority Data
(71) Applicant: CELANESE EMULSIONS GMBH, Oct. 12, 2012 (EP) .................................. 12188427.4
Sulzbach (Taunus) (DE)
(72) Inventors: Meike Roth, Nackenheim (DE); Hans Publication Classification
Uwe Faust, Liederbach am Taunus (DE);
Rone
one M hmidt, Weil
Manneschmidt, Weilmunster (51) Int.
C09.Cl.I3/04 (2006.01)
(DE); Renate Steube, Trebur (DE); Sven C09. 29/04 (2006.01)
Dyhr, Frankfurt am Main (DE) CSK5/II (2006.01)
21) Appl. No.: 14/429,540 (52) U.S. Cl.
(21) Appl. No 9 CPC ................. C09J 131/04 (2013.01); C08K 5/11
(22) PCT Filed: Oct. 8, 2013 (2013.01); C09J 129/04 (2013.01)
(86). PCT No.: PCT/EP2013/OO3O14 (57) ABSTRACT
S371 (c)(1), An adhesive composition comprises an aqueous dispersion of
(2) Date: Mar. 19, 2015 a polymer comprising at least one vinyl ester of a carboxylic
O O acid having up to 20 carbon atoms; and a plasticizer compris
Related U.S. Application Data ing an ester of a polyol and a linear or branched aliphatic
(60) Provisional application No. 61/712,606, filed on Oct. monocarboxylic acid having 3 to 20 carbon atoms in the
11, 2012. molecule.
US 2015/02327 12 A1 Aug. 20, 2015
setting speed, tensile strength, and elongation. As a result, by ated organic acids, unsaturated silanes, glycidyl co-mono
using the present plasticizer, it is possible to reduce the plas mers, ureido co-monomers, co-monomers with crosslinkable
ticizer level in polyvinyl ester packaging adhesives by at least functions, crosslinking co-monomers and combinations
40% as compared to similar adhesives employing DIBP and thereof.
benzoate plasticizers. 0022 Suitable auxiliary co-monomers including unsatur
ated organic acids comprise ethylenically unsaturated car
Aqueous Polymer Dispersion boxylic acids and anhydrides and amides thereof, ethyleni
0012. The aqueous polymeric dispersion used in the pres cally unsaturated Sulfonic acids and salts thereof, and
ently disclosed adhesive composition is produced, generally ethylenically unsaturated phosphonic acids and salts thereof.
by emulsion polymerization, from a monomer composition 0023 For example, the auxiliary co-monomer may com
comprising, as a main monomer, at least one vinyl ester of a prise an ethylenically unsaturated C-C monocarboxylic
mono- or di-carboxylic acid having up to 20 carbon atoms. acid and/or an ethylenically unsaturated C-Cs dicarboxylic
Suitable vinyl esters include vinyl formate, vinyl acetate, acid, together with the anhydrides or amides thereof.
vinyl propionate, vinylbutyrate, vinyl isobutyrate, vinyl val Examples of suitable ethylenically unsaturated C-C mono
erate, vinyl-2-ethyl-hexanoate, vinyl isooctanoate, vinyl non carboxylic acids include acrylic acid, methacrylic acid and
ate, vinyl decanoate, vinyl pivalate, vinyl versatate, vinyl crotonic acid. Examples of suitable ethylenically unsaturated
laurate, vinyl Stearate, vinylbenzoate and mixtures thereof. In C-Cs dicarboxylic acids include maleic acid, fumaric acid,
one embodiment, the vinyl ester comprises vinyl acetate. itaconic acid and citraconic acid.
0013. In addition to vinyl esters, the monomer composi 0024 Examples of suitable ethylenically unsaturated sul
tion may comprise one or more additional main monomers fonic acids include those having 2-8 carbon atoms, such as
selected from C-Co-alkyl (meth)acrylates, vinyl-aromatic vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic
compounds having up to 20 carbons, ethylenically unsatur acid, 2-acryloyloxyethanesulfonic acid and 2-methacryloy
ated nitriles, vinyl halides, vinyl ethers of C-Co alcohols, loxyethanesulfonic acid, 2-acryloyloxy- and 3-methacryloy
C-C aliphatic hydrocarbons with 1 or 2 double bonds, and loxypropanesulfonic acid. Examples of suitable ethylenically
mixtures of these monomers. unsaturated phosphonic acids also include those having 2-8
0014 Preferred alkyl (meth)acrylates are C-Co-alkyl carbonatoms, such as vinylphosphonic acid and ethylenically
(meth)acrylates. Such as methyl methacrylate, methyl acry unsaturated polyethoxyalkyletherphosphates.
late, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acry 0025. In addition to or instead of said acids, it is also
late. Mixtures of alkyl (meth)acrylates can also be employed. possible to use the salts thereof, preferably the alkali metal or
0015 Suitable vinyl-aromatic compounds include vinyl ammonium salts thereof, particularly preferably the Sodium
toluene, C- and p-methylstyrene, C.-butylstyrene, 4-n-butyl salts thereof. Such as, for example, the Sodium salts of vinyl
styrene, 4-n-decyl-styrene and, preferably, styrene. Sulfonic acid and of 2-acrylamidopropanesulfonic acid.
0016 Examples of suitable nitriles include acrylonitrile 0026. Unsaturated silanes usful as auxiliary co-monomers
and methacrylonitrile. can generally correspond to the structural Formula I:
0017 Suitable vinyl halides include chloro-, fluoro- or
bromo-Substituted ethylenically unsaturated compounds,
such as vinyl chloride and vinylidene chloride. Formula I
00.18 Examples of vinyl ethers are vinyl methyl ether and
vinyl iso-butyl ether, with preference being given to vinyl
ethers of C-C alcohols.
0019. Examples of suitable C-C aliphatic hydrocarbons
with one olefinic double bond include ethene and propene,
whereas representative examples of C-Cs aliphatic hydro in which R denotes an organic radical olefinically unsaturated
carbons having two olefinic double bonds include butadiene, in the co-position and R. RandR which may be identical or
isoprene and chloroprene. different, denote the group —OZ, Z denoting hydrogen or
0020. In one embodiment, the present polymer dispersion primary or secondary alkyl or acyl radicals optionally Substi
is produced from a mixture of main monomers comprising tuted by alkoxy groups. Suitable unsaturated silane com
from 50 wt % to 99 wt % vinyl acetate and from 1 wt % to 40 pounds of the Formula I are preferably those in which the
wt % ethylene. radical R in the formula represents an ()-unsaturated alkenyl
0021. In addition to the main monomers discussed above, of 2 to 10 carbon atoms, particularly of 2 to 4 carbon atoms,
the aqueous polymerization mixture used to produce the oran ()-unsaturated carboxylic acid ester formed from unsat
present polymer dispersion may comprise up to 10% auxil urated carboxylic acids of up to 4 carbon atoms and alcohols
iary co-monomer(s) by weight based on the total weight of carrying the Si group of up to 6 carbon atoms. Suitable radi
monomers in the mixture. Such auxiliary co-monomers can cals R', R. Rare preferably the group —OZ, Z representing
be those which promote better film or coating performance by primary and/or secondary alkyl radicals of up to 10 carbon
the compositions herein or can provide films and coatings of atoms, preferably up to 4 carbon atoms, or alkyl radicals
desirable properties. Such desirable properties can include, substituted by alkoxy groups, preferably of up to 3 carbon
for example, enhanced adhesion to Surfaces or Substrates, atoms, or acyl radicals of up to 6 carbon atoms, preferably of
improved wet adhesion, and improved resistance to film or up to 3 carbon atoms, or hydrogen. Most preferred unsatur
coating cracking. The optional co-monomers useful for incor ated silane co-monomers are vinyl trialkoxy silanes.
poration into the emulsion copolymers of the compositions 0027. Examples of preferred silane compounds of the For
herein are those which contain at least one polymerizable mula I include Y-methacryloxypropyltris(2-methoxyethoxy)
double bond along with one or more additional functional silane, vinylmethoxysilane, vinyltriethoxysilane, vinyldi
moieties. Suitable auxiliary co-monomers include unsatur ethoxysilanol, vinylethoxysilanediol, allyltriethoxysilane,
US 2015/02327 12 A1 Aug. 20, 2015
vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltribu with polyvinyl alcohol. In one embodiment, also the emulsi
toxysilane, vinyltriacetoxysilane, trimethylglycolvinylsi fiers used contain no alkylphenolethoxylates (APEO).
lane, Y-methacryloxypropyltrimethylglycolsilane, Y-acrylox 0034 Examples of suitable nonionic emulsifiers include
ypropyltriethoxysilane and acyl, alkyl, oleyl, and alkylaryl ethoxylates. These products
Y-methacryloxypropyltrimethoxysilane. are commercially available, for example, under the name
0028. Glycidyl compounds can also be used as optional Genapolr, Lutensolr) or Emulan R. They include, for
auxiliary co-monomers to impart epoxy-functionality to the example, ethoxylated mono-, di-, and tri-alkylphenols (EO
emulsion copolymer. Examples of Suitable glycidyl optional degree: 3 to 50, alkyl Substituent radical: C to C) and also
co-monomers include glycidyl acrylate, glycidyl methacry ethoxylated fatty alcohols (EO degree: 3 to 80: alkyl radical:
late, allylglycidyl ether, and vinyl glycidyl ether. Cs to C), especially Co-C fatty alcohol (3-40) ethoxy
0029. Another type of optional co-monomer comprises lates, C-Cls oxo-process alcohol (3-40) ethoxylates, C
cyclic ureido co-monomers. Cyclic ureido co-monomers are Cs fatty alcohol (11-80) ethoxylates, Coxo-process alco
known to impart improved wet adhesion properties to films hol (3-40) ethoxylates, C oxo-process alcohol (3-40)
and coatings formed from copolymers containing these co ethoxylates, polyoxyethylenesorbitan monooleate with 20
monomers. Cyclic ureido compounds and their use as wet ethylene oxide groups, copolymers of ethylene oxide and
adhesion promoting co-monomers are disclosed in U.S. Pat. propylene oxide having a minimum ethylene oxide content of
Nos. 4,104,220; 4,111,877; 4,219,454; 4,319,032; 4,599,417 10 weight %, the polyethylene oxide (4-40) ethers of oleyl
and 5,208,285. The disclosures of all of these U.S. patents are alcohol, and the polyethene oxide (4-40) ethers of nonylphe
incorporated herein by reference in their entirety. nol. Particularly suitable are the polyethylene oxide (4-40)
0030. Another type of optional co-monomer comprises ethers of fatty alcohols, more particularly of oleyl alcohol,
co-monomers with crosslinkable functions such as N-methy Stearyl alcohol or C alkyl alcohols.
lolacrylamide, N-methylolmethacrylamide, N-methylolal 0035. The amount of nonionic emulsifiers used in prepar
lylcarbamate, N-methylolmaleimide, N-methylolmaleamic ing the presently disclosed dispersions is typically about 1%
acid, and the N-methylol amides of aromatic vinyl carboxylic to about 8 weight%, for example, about 1% to about 5 weight
acids, such as N-methylol-p-vinylbenzamide. N-ethanol %, or about 1% to about 4 weight%, based on the total main
(meth)acrylamide, N-propanol(meth)acrylamide, the N-me monomer quantity. Mixtures of nonionic emulsifiers can also
thylol esters or N-alkyl ethers or Mannich bases of N-methy be employed.
lol(meth)acrylamide O N-methylolallylcarbamate, 0036) Examples of suitable anionic emulsifiers include
acrylamidoglycolic acid and/or its salts, methyl acrylami Sodium, potassium, and ammonium salts of linear aliphatic
domethoxyacetate or N-(2,2-dimethoxy-1-hydroxyethyl) carboxylic acids of chain length C-Co. sodium hydroxy
acrylamide. octadecanesulfonate, Sodium, potassium, and ammonium
0031. A further group of co-monomers suitable for pre salts of hydroxy fatty acids of chain length C-C and their
paring the emulsion polymers used herein comprises Sulfonation and/or sulfation and/or acetylation products,
crosslinking monomers, such as co-monomers with polyeth alkyl Sulfates, including those in the form of triethanolamine
ylenic unsaturation, and hence with a crosslinking action. salts, alkyl (Co-Co) sulfonates, alkyl (Co-Co) arylsul
Examples include diallyl phthalate, diallyl maleate, triallyl fonates, and their Sulfonation products, lignoSulfonic acid
cyanurate, tetraallyloxyethane, divinylbenzene, butane-1,4- and its calcium, magnesium, sodium, and ammonium salts,
diol dimethacrylate, triethylene glycol dimethacrylate, divi resin acids, hydrogenated and dehydrogenated resin acids,
nyl adipate, allyl (meth)acrylate, vinyl crotonate, methyl and their alkali metal salts, dodecylated sodium diphenyl
enebisacrylamide, hexanediol diacrylate, pentaerythritol ether disulfonate, sodium lauryl sulfate, sulfated alkyl or aryl
diacrylate and trimethylolpropane triacrylate. ethoxylate with EO degree between 1 and 10, for example
ethoxylated sodium lauryl ether sulfate (EO degree 3) or a salt
Stabilization System of a bisester, for example, of a bis-C-C alkyl ester, of a
0032. Both during polymerization and thereafter, the poly Sulfonated dicarboxylic acid having 4 to 8 carbon atoms, or a
mer used to prepare the present adhesive composition is sta mixture of these salts, for example, Sulfonated salts of esters
bilized in the form of an aqueous dispersion or latex. The of Succinic acid, or salts. Such as alkali metal salts, of bis-Ca
dispersion therefore will be prepared in the presence of and Cs alkyl esters of Sulfonated Succinic acid, or phosphates of
will contain a stabilization system (i.e., stabilizer) which gen polyethoxylated alkanols or alkylphenols.
erally comprises one or more emulsifiers, in particular non 0037. The amount of anionic emulsifiers used can typi
ionic emulsifiers and/or anionic emulsifiers, and/or one or cally range from about 0.1% to about 3.0 weight %, for
more protective colloids. Mixtures of the different stabilizers example, from about 0.1% to about 2.0 weight %, or from
can also be employed. about 0.5% to about 1.5 weight %, based on the total main
0033. The amount of emulsifier employed will generally monomer quantity. Mixtures of anionic emulsifiers can also
beat least 0.5 weight %, based on the total quantity of main be employed.
co-monomers in the dispersion. Generally emulsifiers can be 0038 Along with, or instead of, emulsifiers, the presently
used in amounts up to about 8 weight %, based on the total disclosed aqueous dispersions can also comprise as part of the
quantity of main monomers in the dispersion. The weight stabilizer system a selected type of protective colloid based
ratio of nonionic to anionic emulsifiers may fluctuate within on cellulose ethers, polyvinyl alcohol, poly vinyl pyrolidone,
wide ranges, between 1:1 and 50:1 for example. Exemplary polyacrylic acid, maleic acid styrene copolymers or other
emulsifiers include nonionic emulsifiers having alkylene water soluble polymers. Suitable protective colloids used in
oxide groups and/or anionic emulsifiers having Sulfate, Sul the presently disclosed dispersions include water-soluble or
fonate, phosphate and/or phosphonate groups. Such emulsi water-dispersible polymeric modified natural Substances
fiers, if desired, can be used together with molecularly or based on cellulose ethers. Such cellulose ethers have a vis
dispersely water-soluble polymers, for example, together cosity, when tested as a 1 weight% aqueous in water at 25°C.,
US 2015/02327 12 A1 Aug. 20, 2015
of 5 to 5,000 mPas, for example, of 10 to about 1,500 mPas, ized in an aqueous medium under pressures up to 120 bar in
or 10 to 500 mPas. Mixtures of celluloses ethers may be used the presence of one or more initiators, at least one emulsifying
to achieve these viscosity values. Examples of suitable cellu agent and a protective colloid component. The aqueous reac
lose ether materials include methyl cellulose, hydroxyethyl tion mixture in the polymerization vessel can be maintained
cellulose, hydroxypropyl cellulose, hydroxypropyl methyl by a suitable buffering agent at a pH of about 2 to about 7.
cellulose, ethylhydroxyethyl cellulose, methylhydroxyethyl 0049. The manner of combining the several polymeriza
cellulose and combinations of these cellulose ethers. In one tion ingredients, i.e. emulsifiers, monomers, initiators, pro
embodiment, hydroxyethyl cellulose, which is commercially tective colloids, etc., can vary widely. Generally an aqueous
available under the tradename NatrosolTM, is used. medium containing at least some of the emulsifier(s) can be
0039 Hydrophobically modified cellulose ethers may initially formed in the polymerization vessel with the various
also be employed as the protective colloid in the presently other polymerization ingredients being added to the vessel
disclosed dispersions. Such materials comprise cellulose thereafter.
ethers which have been hydrophobically modified with long 0050 Monomers can be added to the polymerization ves
chain hydrocarbon groups to reduce their water solubility. sel continuously, incrementally or as a single charge addition
Hydrophobically modified cellulose ethers of this type are of the entire amounts of co-monomers to be used. Co-mono
those described, for example, in U.S. Pat. Nos. 4.228,277; mers can be employed as pure monomers or can be used in the
4.352,916 and 4,684,704; all of which patents are incorpo form of a pre-mixed emulsion. Ethylene as a co-monomer can
rated herein by reference. be pumped into the polymerization vessel and maintained
0040. The protective colloids can be used individually or under appropriate pressure therein.
in combination. In the case of combinations, the two or more 0051. It is also possible to start the emulsion polymeriza
colloids can each differ in their molecular weights or they can tion using a seed latex, for example in an amount from about
differ in their molecular weights and in their chemical com 0.5 to about 15 weight% of the dispersion.
position, such as the degree of hydrolysis, for example.
0041. In one embodiment, the protective colloid is poly 0052. As noted, the polymerization of the ethylenically
vinyl alcohol. Suitable polyvinyl alcohol has degrees of unsaturated monomers will generally take place in the pres
hydrolysis of from 60 to 100 mol% and viscosities of the 4% ence of at least one initiator for the free-radical polymeriza
aqueous solutions at 20°C. of 2-70 mPas, especially from 4 tion of these co-monomers. Any known initiator capable of
to 40 mPas. initiating free-radical, aqueous polymerization in het
0042. When protective colloids are used, the amount erophase systems can be used. These initiators may be per
thereof, based on the total amount of monomers used, is oxides, such as alkali metal and/or ammonium peroxodisul
typically from 0.1 to 5 parts by weight, for example, from 0.3 fates, organic hydroperoxides, more particularly water
to 5 parts by weight. soluble ones, or azo compounds, more particularly water
0043. In addition to the emulsifiers and/or protective col soluble azo compounds.
loids that are used during the emulsion polymerization, it is 0053 As polymerization initiators, it is also possible to
also possible to add further emulsifiers, protective colloids use what are called redox initiators. Examples thereof are
and/or other stabilizers after the polymerization. peroxodisulfates, tert-butyl hydroperoxide and/or hydrogen
peroxide in combination with reducing agents, such as with
Preparation of the Aqueous Polymer Dispersion Sulfur compounds, an example being the Sodium salt of
0044) Many of the aqueous polymer dispersions employed hydroxymethanesulfinic acid, Bruggolite R FF6 and FFT,
in the present adhesive are commercially available but, where Rongalit C, sodium Sulfite, sodium disulfite, sodium thiosul
necessary, can be prepared using conventional emulsion fate, and acetone-bisulfate adduct, or with ascorbic acid,
polymerization procedures. Such procedures are described, Sodium erythobate, tartaric acid, or with reducing Sugars.
for example, in U.S. Pat. No. 5,849,389, and in the Encyclo 0054 The amount of initiator or initiator combination
pedia of Polymer Science and Engineering, Vol. 8, p. 659 used in the process varies within what is usual for aqueous
(1987), the disclosures of both of these publications are incor polymerizations in heterophase systems. In general the
porated herein by reference in their entirety. amount of initiator used will not exceed 5 weight%, based on
0045. The polymerization may be carried out in any man the total amount of the co-monomers to be polymerized. The
ner known per se in one, two or more stages with different amount of initiators used, based on the total amount of the
monomer combinations, giving polymer dispersions having co-monomers to be polymerized, can be, for example, 0.05%
particles with homogeneous or heterogeneous, e.g., core shell to 2.0 weight%.
or hemispheres, morphology. Any reactor system Such as 0055. In this context, it is possible for the total amount of
batch, loop, continuous, cascade, etc., may be employed. initiator to be included in the initial charge to the reactor at the
0046. The polymerization temperature generally ranges beginning of the polymerization. Alternatively, a portion of
from 20° C. to 150° C., for example, from 50° C. to 120° C. the initiator may be included in the initial charge, and the
The polymerization generally takes place under pressure if remainder added after the polymerization has been initiated,
appropriate, for example, from 2 to 150 bar, or from 5 to 100 in one or more steps or continuously. The addition may be
bar. made separately or together with other components, such as
0047. The polymerization can be undertaken by batch, emulsifiers or monomer emulsions.
semi batch or continuous emulsions polymerization, i.e. by 0056. The molecular weight of the various polymers in the
processes in which all the monomer is added upfront or by presently disclosed dispersions can be adjusted by adding
monomer slow add processes. Small amounts of one or more molecular weight regulator
0048. In a typical polymerization procedure involving, for Substances. These regulators, as they are known, are generally
example, aqueous copolymer dispersions, monomers, such as used in an amount of up to 2 weight '%, based on the total
vinyl acetate, ethylene, and other monomers, can be polymer co-monomers to be polymerized. As regulators, it is possible
US 2015/02327 12 A1 Aug. 20, 2015
to use all of the substances known to the skilled artisan, for ylene glycol di-n-heptanoate, triethylene glycol di-2-ethyl
example, organic thio compounds, silanes, allyl alcohols, and butyrate, triethylene glycol di-n-heptanoate and tetraethylene
aldehydes. glycol di-2-ethylhexanoate.
0057 Following polymerization, the solids content of the 0064. In contrast to typical plasticizers employed in pack
resulting aqueous dispersions can be adjusted to the level aging applications (e.g., benzoate esters), which generally
desired by the addition of water or by the removal of water by must be present in concentrations of at least 10% by weight of
distillation. Generally, the desired level of polymeric solids vinyl ester polymer in order to achieve the right balance of
content after polymerization is from about 40 weight percent flexibility, bond strength, and minimum film formation tem
to about 70 weight percent based on the total weight of the perature required for use in packaging adhesives, the pres
polymer dispersion, for example, from about 45 weight per ently disclosed adhesive composition can comprise less than
cent to about 55 weight percent. 10%, for example 3 to 7%, of the plasticizer by weight of the
0058 Where appropriate, the presently disclosed aqueous polymer.
dispersions can also optionally comprise a wide variety of
conventional additives, such as fillers, pigments, and auxilia Adhesive Composition
ries including defoamers, Surfactants, dispersants, biocides, 0065. In addition to the aqueous polymer dispersion and
rheology modifiers, freeze-thaw additives, formaldehyde plasticizer described above, the adhesive composition can
Scavenger like urea, complexing agents like EDTA or thick include one or more conventional adjuvants, for example,
eners, which are typically used in the formulation of binders film-forming assistants, such as white spirit, Texanol R,
and/or adhesives. Such optional additives may be present in TxiB(R), butyl glycol, butyl diglycol, butyl dipropylene gly
the dispersion from the beginning of or during polymeriza col, and butyl tripropylene glycol; wetting agents, such as
tion or may be added to the dispersion post-polymerization. AMP 90R, TegoWet.280R, Fluowet PE(R); defoamers, such
as mineral oil defoamers or silicone defoamers: UV pro
Plasticizer tectants, such as Tinuvin 1130(R); agents for adjusting the pH:
preservatives; Subsequently added stabilizing polymers. Such
0059. In addition to the vinyl ester-based polymer disper as polyvinyl alcohol or additional cellulose ethers.
sion described above, the present adhesive includes a plasti 0066. The presently disclosed adhesive composition is
cizer comprising an ester of a polyol and a linear or branched particularly useful as a packaging adhesive. The packaging
aliphatic monocarboxylic having 3 to 20 carbon atoms, for adhesives market is one with ever evolving needs. Packaging
example, 5 to 10 carbonatoms. Suitable polyols can include, adhesives can be used with paper, board, film & foil, enve
for example, compounds of the general formula: lopes, book making, folded boxes, cigarettes, etc. The pres
ently disclosed adhesive composition can achieve good
wherein R' and R are independently hydrogen, an alkyl machining using a variety of application methods from rollers
radical having 1 to 5 carbonatoms, for example, methyl, ethyl to nozzles for effective application on even difficult sub
Strates.
or propyl, or a hydroxyalkyl radical having 1 to 5 carbon 0067. The invention will now be more particularly
atoms, for example, hydroxy-methyl radical; m is an integer described with reference to the following non-limiting
from 1 to 10, for example, 1 to 8 and in particular, 1, 2, 3 or 4: Examples.
and o is an integer from 2 to 15, for example, 2 to 8 and in 0068. In the Examples, the thickening ratio (THR) is the
particular, 2, 3, 4 or 5. ratio of the viscosities of the polyvinyl acetate-based disper
0060. In one embodiment, the presently disclosed ester of sion employed in each test before and after the addition of
a polyol can comprise, for example, 1,3-propandiol. 1,3-bu plasticizer into the dispersion. To determine the THR, 180 g
tanediol. 1,4-butanediol, neopentyl glycol, 2.2-dimethy of the dispersion and 20 g of the plasticizer are mixed without
lolbutan, trimethylol ethane, trimethylol propane, di-trim stirring in a 250 mL beaker. After stirring for 30 minutes, the
ethylolpropane, trimethylol butane, 2,2,4-trimethylpentane mixture and a blank sample of dispersion are stored for at
1,3-diol, 1.2-hexanediol, 1.6-hexanediol, pentaerythritol or least 24h in a climatic chamber or box at a constant tempera
dipentaerythritol or 3(4),8(9)-dihydroxy-methyl-tricyclo5. ture of 23° C. and a humidity of 50%. Afterwards, the viscos
2.1.0° decane. ity of each sample is measured with a Brookfield viscometer
0061. In one embodiment, the polyol can include, for and the THR is calculated as the ratio between the viscosity of
example, ethylene glycol, 1,2-propylene glycol and their oli the mixture and that of the blank sample.
gomers, particularly the etherdiols, di-, tri-, and tetra-ethyl 0069. The rheology index (RHI) is measured using a Rhe
ene glycol or dipropylene glycol, tripropylene glycol or tet ometer Physica Rheolab MC100 viscometer. After filling the
raethylene glycol. test cylinder at 23° C. with the adhesive, the shear rate is
0062) Exemplary carboxylic acids include, for example, accelerated from 0 to 1000s' over a period of 1 minute, held
are propionic acid, n-butyric acid, isobutyric acid, n-pen at this shear rate for 5 minutes and then decelerated back to 0
tanoic acid, 2-methylbutyric acid, 3-methyl butyric acid, s' over a period of 1 minute. Viscosity measurements are
2-methyl-pentanoic acid, n-hexanoic acid, 2-ethylbutyric taken at shear rates of 300 s' and 1000 s. The RHI is the
acid, n-heptanoic acid, 2-methyl-hexanoic acid, cyclohexan ratio of the viscosity at 300 s' and the viscosity at 1000 s.
ecarboxylic acid, 2-ethylhexanoic acid, n-nonanoic acid, 0070 The Fipago setting speed test is a combination of a
2-methyloctanoic acid, isononanoic acid, 3.5.5-trimethyl peel and a shear experiment. After fixing two GD-1 card
hexanoic acid, 2-propylheptanoic acid, 2-methylundecanoic boards in the Fipago tester with the rough side on top, 100 um
acid, isoundecane carboxylic acid, tricyclodecanecarboxylic wet film of adhesive is applied on a kraftpaper. After an open
acid and isotridecane carboxylic acid. time of 10 seconds, the paper is laminated by a roller on the
0063. In one embodiment, the plasticizer comprises at cardboard. After a predetermined close time, a pendulum
least one of triethylene glycol di-2-ethylhexanoate, tetraeth holding both substrates together is released and the force
US 2015/02327 12 A1 Aug. 20, 2015
necessary to separate the paper from the cardboard is mea With an applicator frame, a 1000 um thick, blister free, wet
Sured. The experiment is repeated several times with varying film of the adhesive is applied to a Hostaphan polyester foil.
closed times. At the end, the set speed is defined as the close After drying the film, the foil is stored for at least 24 hours in
time when the measured force exceeds 40 scale divisions on a climate-controlled chamber. With a stamping machine, 10
the tester. bone-shaped test specimens are then cut from the foil and
0071 Heat resistance of the adhesive is determined by each is secured at its ends to two brackets, one of which is
applying 0.5 cm wide and 75 um thick film of the adhesive to fixed and the other is movable away from the fixed bracket.
a first sheet of kraftpaper and then pressing a second sheet of The stretching force required to break each test specimen and
kraftpaper onto the first sheet using a weight of 600 grams, the elongation at break are then measured with the tensiom
afterwards allowing the adhesive to dry over night. On the eter.
next day, 3 samples are cut out of the bonded paper sheets in
order to conduct parallel determinations. Both ends of each Examples
sample are fixed in brackets; one bracket is connected to a
weight of 200 grams and the other is attached to the top of a (0073. A comparison of plasticizer WVC 3800 (also des
column. The column is moved into a drying chamber. After a ignated Mowiplus PL3000 a plasticizer composed mainly
period of 30 minutes at an initial temperature of 30°C. with of di-2-ethylhexanoic acid triethylene glycol ester available
out strain being applied to the adhesive bond, the column is from Celanese) and BenZoflexTM 2088 Plasticizer (available
moved upwards until the weight is 15-20 cm away from the from Eastman) with polyvinyl acetate-based dispersions,
bottom. After each additional 30 minutes, the temperature is specifically (RMowilith DHS S1 and (RMowilith LD 167
raised by 5° C. until the weight falls causing the sheets to (both available from Celanese Emulsions) was performed.
separate. The final temperature recorded before the weight The following properties were identified using WVC 3800 in
falls is defined as the heat resistance temperature. The median comparison to BenZoflexTM 2088:
of all three samples is the stated temperature.
0072 Measurements of elongation and tensile strength are 10074) a) Improved efficiency in lowering the Tg (glass
made according to DIN 53328 using a Zwick tensiometer. transition temperature):
TABLE 1.
Wt 9% plasticizer in WVC 3800 BenZoflex TM 2088 Wt 9% plasticizer in WVC 3800 BenZoflex TM 2088
(RMowilith DHSS1 T (- C.) T (C.) (RMowilith LD 167 T (- C.) T (C.)
O% 41 41 O% 42 42
196 28 39 196 38 39
3% 28 34 3% 31 35
59 22 28 59 22 29
79% 2O 22 79% 15 25
10% 18 18 10% 8 22
O% 1 1 O% 1 1
196 1.1 1.1 196 1.1 1
3% 1.3 1.2 3% 1.3 1.2
59 1.4 1.3 59 1.4 1.3
79% 1.9 1.5 79% 1.9 1.6
10% 3 1.7 10% 2.6 1.8
US 2015/02327 12 A1 Aug. 20, 2015
190 2O 30 190 5 15
3% 25 30 3% 5 10
59% 25 30 59% 5 10
79% 2O 25 79% 5 10
10% 2O 25 10% 5 10
I0081. As reflected in Tables 1-7, by using Plasticizer WVC tact), a 40% reduction in plasticizer can be achieved, while
3800 as opposed to BenZoflexTM 2088 Plasticizer (i.e., the lowering the T and MFFT. Furthermore, the elongation at a
standard plasticizer in packaging not intended for food con- level of 5% is improved, as well as the tensile strength, while
US 2015/02327 12 A1 Aug. 20, 2015
keeping the heat resistance and rheology the same. Thus, ethylhexanoate, tetraethylene glycol di-n-heptanoate, trieth
Plasticizer WVC 3800, which is classified as a SVOC (Super ylene glycol di-2-ethyl butyrate, triethylene glycol di-n-
low Volatile Organic Compound), makes a universal and far heptanoate, and tetraethylene glycol di-2-ethylhexanoate.
more cost effective plasticizer for packaging not intended to 7. The adhesive composition of claim 1, wherein the adhe
come into contact with food. Furthermore, it decreases the sive composition comprises up to 10% plasticizer by weight
risk of migration compounds in recycled paper and boards. of the polymer, preferably from 3 to 7% plasticizer by weight
0082 While various embodiments have been described, it of the polymer.
is to be understood that variations and modifications may be 8. The adhesive composition of claim 1, wherein the poly
resorted to as will be apparent to those skilled in the art. Such mer dispersion is produced by emulsion polymerization.
variations and modifications are to be considered within the
purview and Scope of the claims appended hereto. 9. The adhesive composition of claim 1, wherein the poly
1. An adhesive composition comprising an aqueous disper mer dispersion comprises a stabilizer, preferably a polyvinyl
alcohol stabilizer.
sion of a polymer produced from a monomer composition
comprising at least one vinyl ester of a carboxylic acid having 10. The adhesive composition of claim 1, wherein the at
up to 20 carbonatoms; and a plasticizer comprising an ester of least one vinyl ester is selected from the group consisting of
a polyol and an aliphatic monocarboxylic acid having 3 to 20 vinyl formate, vinyl acetate, vinyl propionate, vinylbutyrate,
carbon atoms. vinyl isobutyrate, vinyl Valerate, vinyl-2-ethyl-hexanoate,
2. The adhesive composition of claim 1, wherein the polyol vinyl isooctanoate, vinyl nonate, vinyl decanoate, vinyl piv
is selected from the group consisting of ethylene glycol, alate, vinyl versatate, and mixtures thereof.
1.2-propylene glycol, and oligomers thereof. 11. The adhesive composition of claim 1, wherein the at
3. The adhesive composition of claim 1, wherein the polyol least one vinyl ester comprises vinyl acetate.
is selected from the group consisting of di-, tri-, and tetra 12. The adhesive composition of claim 1, wherein the
ethylene glycol, dipropylene glycol, tripropylene glycol, and monomer composition further comprises one or more co
tetraethylene glycol. monomers selected from C-Co-alkyl (meth)acrylates,
4. The adhesive composition of claim 1, wherein the plas vinyl-aromatic compounds having up to 20 carbons, ethyl
ticizer comprises an ester of a polyol and an aliphatic car enically unsaturated nitriles, vinyl halides, vinyl ethers of
boxylic acid selected from the group consisting propionic C-Co alcohols, and C-Cs aliphatic hydrocarbons with 1 or
acid, n-butyric acid, isobutyric acid, n-pentanoic acid, 2-me 2 double bonds.
thylbutyric acid, 3-methylbutyric acid, 2-methyl-pentanoic 13. The adhesive composition of claim 1, wherein the
acid, n-hexanoic acid, 2-ethylbutyric acid, n-heptanoic acid, polymer comprises a vinyl ester-ethylene copolymer.
2-methyl-hexanoic acid, cyclohexanecarboxylic acid, 2-eth 14. The adhesive composition of claim 1, wherein the
ylhexanoic acid, n-nonanoic acid, 2-methyloctanoic acid, monomer composition further comprises one or more auxil
isononanoic acid, 3.5.5-trimethyl hexanoic acid, 2-propyl iary co-monomers selected from unsaturated organic acids
heptanoic acid, 2-methylundecanoic acid, isoundecane car comprise ethylenically unsaturated carboxylic acids and
boxylic acid, tricyclodecanecarboxylic acid, and isotridecane anhydrides and amides thereof, ethylenically unsaturated Sul
carboxylic acid. fonic acids and salts thereof, and ethylenically unsaturated
5. The adhesive composition of claim 1, wherein the plas phosphonic acids and salts thereof.
ticizer comprises an ester of a polyol and a substituted or 15. A packaging adhesive comprising the adhesive compo
unsubstituted hexanoic acid.
sition of claim 1.
6. The adhesive composition of claim 1, wherein the plas
ticizer comprises one or more of triethylene glycol di-2-
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