USOO781 6443B2

(12) United States Patent (10) Patent No.: US 7.816,443 B2

Wilson (45) Date of Patent: Oct. 19, 2010
(54) RUBBER COMPOSITIONS WITH ACTIVATED 5,674,932 A 10/1997 Agostini et al.
SULFUR CURE 6,384,117 B1 5/2002 Hergenrother et al.
6,620,871 B2 9/2003 Wilson, III
(75) Inventor: Thomas W Wilson, Taichung (TW) 6,790,889 B2 9/2004 Hergenrother et al.
6,984.450 B2 * 1/2006 Menting et al. ........ 428/402.21
(73) Assignee: NIKE, Inc., Beaverton, OR (US) FOREIGN PATENT DOCUMENTS
(*) Notice: Subject to any disclaimer, the term of this JP 48052679 11, 1971
patent is extended or adjusted under 35 JP 48052678 7/1973
U.S.C. 154(b) by 397 days. WO WO 2005/06O472 * 7/2005
WO WO 2005/06O472 A2 7/2005
(21) Appl. No.: 11/776,654 OTHER PUBLICATIONS
(22) Filed: Jul. 12, 2007 Heideman, Geert et al., “Various routes for reduction of zinc oxide
levels in rubber compounds'. Tire Technology International 2004,
(65) Prior Publication Data pp. 22-27.
US 2008/OO15286 A1 Jan. 17, 2008 * cited by examiner
Related U.S. Application Data Primary Examiner Robert D. Harlan
(74) Attorney, Agent, or Firm Harness, Dickey & Pierce
(60) Provisional application No. 60/830,824, filed on Jul. PLC
14, 2006.
(57) ABSTRACT
(51) Int. Cl.
COSL 9/02 (2006.01) Cured rubber compositions with reduced divalent metal lev
C08L 3/36 (2006.01) els and improved physical properties are prepared using
(52) U.S. Cl. ....................................... 524/525; 524/570 methods that limit or avoid a deleterious side reaction, and
(58) Field of Classification Search ................. 524/525, that make activator compounds available only during cure
524/570 and not earlier during mixing. Specifically, the presence of
See application file for complete search history. activator Soap (or of components that can form the activator
Soap in situ) and silica filler together is avoided or minimized
(56) References Cited in process steps where the temperature would tend to be
U.S. PATENT DOCUMENTS above 100° C. or 110°C. The use of ZnO for example can be
reduced by as much as 90-95% in a typical rubber compound.
4,607,074 A 8, 1986 Hazelton et al.
4,639,487 A 1, 1987 Hazelton et al. 22 Claims, 1 Drawing Sheet
U.S. Patent Oct. 19, 2010 US 7,816.443 B2

Rheometer Data as a Function of ZnO Concentration

----------
S
d
E A.
P

-8. T90 roller mill

-E-TS2 roller mill
A T90 Banbury
A Ts2 Banbury
O% 1% 2% 3%
ZnO
 US 7,816,443 B2
1. 2
RUBBER COMPOSITIONS WITH ACTIVATED microencapsulation of activator components such as ZnO, Zn
SULFUR CURE Stearate and/or Stearic acid. The microcapsules are stable to
temperatures up to 120° C. up to 130°C., up to 140°C., or up
CROSS REFERENCE TO RELATED to 150° C., allowing a microencapsulated component to be
APPLICATIONS present with the silica filler at those temperatures with
reduced chance of participating in the undesired side reac
This application claims the benefit of U.S. provisional tions. Then, upon cure at higher temperatures (above those at
application 60/830,824 filed on Jul. 14, 2006, the disclosure which the microcapsules are stable), the microcapsules
of which is incorporated by reference. release the activator component and cure is activated. Advan
10 tageously, control of the side reactions allows lower than
INTRODUCTION conventional levels of Zinc to be used. In an exemplary
embodiment, ZnO and fatty acid are used at approximately a
Zinc oxide (ZnO), as well as other divalent metal oxides stoichiometric level (one mole of ZnO to two moles of fatty
such as CaO and MgO is commonly referred to as an activator acid), which is a significantly lower level of Zinc than is
for the cure of rubber compounds containing accelerators, conventionally used.
15 More details and embodiments of the invention will be
especially those containing Sulfur. More precisely, one mol described below.
ecule of cationic component (e.g. ZnO) combines with two
molecules of a fatty acid such as stearic acid (C7HCOOH) BRIEF DESCRIPTION OF THE DRAWINGS
to form a salt or soap such as Zinc stearate (Zn(C7HCOO))
and water. The Soap (e.g., the Zinc Stearate) is believed to be
the activator for cure. FIG. 1 shows cure parameters for illustrative rubber com
During mixing and/or cure, the ZnO (or other cationic positions.
component) and fatty acid react to form the Soap, which
activates the Sulfur cure. In actual practice, a stoichiometric DESCRIPTION
excess of the cationic component to fatty acid is employed in
the rubber compounds to obtain sufficient activation. 25 In one embodiment, the invention provides a method of
The excess of cationic component such as ZnO in the cured curing a rubber composition by activating a Sulfur cure with a
rubber tends to weaken the physical properties of the cured rubber soluble salt or soap. The method involves a first mixing
rubber. Additionally, zinc tends to leach out of cured rubber wherein uncured rubber, filler and optionally other rubber
compositions over time, which could lead to concerns over additives are combined. The first mixing does not include
contamination since Zinc oxide is considered to be an eco 30 components of the Sulfur curing system and excludes the salt
toxin. itself and at least the cation component of the rubber soluble
In light of the situation, it would be desirable to provide salt. The first mixing is carried out attemperatures up to about
methods and compositions for curing rubber that have low 190° C., preferably between 100° C. and 180° C. and more
levels of zinc, yet which still give acceptable cure kinetics and preferably between 110° C. and 140°C. In a second mixing,
physical properties in the resulting cured articles. 35 the Sulfur curing components are added at a lower tempera
ture, along with any salt or salt component left out of the first
SUMMARY mixing. Typically, the temperature of the second mixing does
not exceed 110° C. and is preferably 100° C. or less. After the
Cured rubber compositions with reduced divalent metal second mixing, the rubber composition is cured by heating at
levels and improved physical properties are prepared using 40
a temperature of 130° C. or higher, preferably 150° C. or
methods that limit or avoid a deleterious side reaction, and higher. When the cure is activated by use of a zinc fatty acid
that make activator compounds available only during cure salt, the salt components comprise one or more of a cationic
and not earlier during mixing. Zinc compound (the cation component of the salt, which is
It has been found that Zinc soaps participate in a side normally the oxide ZnO) and an organic fatty acid, such as
reaction on the Surface of silica filler commonly used in carboxylic acids of 8 to 26 carbon atoms, while the salt itself
rubber compounds that depletes the available zinc (as ZnO), 45 is a Zinc salt or Soap of Such a fatty acid.
regenerates the Stearic acid that further consumes ZnO, and The salt or the cationic salt component is added in a sepa
lowers the physical properties of the resultant cured rubber rate step as noted above. For the reasons discussed herein, the
compound. Although the side reaction is most prominently new method of compounding permits the use of lower levels
observed with Zinc activator components, the issue can also of cation to provide activation of the cure. Again in an illus
arise when analogous calcium or magnesium activation is 50 trative embodiment, when the cation is zinc, the rubber com
used. position (after the second mixing and before cure) advanta
According to various embodiments, the side reaction is geously contains 2 phr or less offatty acid and 2 phr or less of
eliminated or Suppressed by changing the order of addition of Zinc compound. Alternatively, the rubber composition con
ingredients and precise process control. Thus, in one aspect, tains 2 phr or less of the zinc fatty acid salt.
the invention is based on exploitation of the situation that the 55 When it is said the first mixing excludes the salt itself or at
activator components such as ZnO, Zn soap, and/or fatty acid least the cationic component of the rubber soluble salt, it
need be present, in a chemically active sense, only during the means that the first mixing contains no cationic component at
cure, and are not needed, as activators, during the mixing. a level that would react with the filler to contaminate the filler
Specifically, the presence of activator soap (or of components and deplete the cation required for cure activation. In some
that can form the activator soap in situ) and silica filler 60
recipes, the activator component is a cationic fatty acid salt,
together is avoided or minimized in process steps where the also called a soap. Examples of salts include those of Zinc,
temperature would tend to be above 100° C. or 110° C.; the calcium, and magnesium. In other recipes, the activator is
methods also result in less time of contact between the acti formed in situ during mixing or curing from a cationic com
vator soap and the filler even at lower temperatures prior to ponent and an anionic component of the salt provided as
cure. The use of ZnO for example can be reduced by as much separate additives to the rubber composition. Typically, the
as 90-95% in a typical rubber compound. 65 anionic component is a fatty acid, while the cationic compo
In other embodiments, control of the process and physical nent is an oxide or other compound of the cation. Illustrative
properties of the resulting cured rubber is achieved by cationic components include ZnO, CaO, and MgO. Thus, to
 US 7,816,443 B2
3 4
further illustrate, the first mixing contains no Zinc, calcium, or the Zinc compound (or calcium or magnesium if used) is
magnesium salt of a fatty acid, and further contains no ZnO, released from the microcapsules. If zinc oxide is microencap
CaO, or MgO. The first mixing excludes at least the cationic Sulated, upon release it combines with the fatty acid to pro
component, and can exclude the anionic component (i.e. the duce a zinc soap that activates the sulfur cure of the rubber
fatty acid) as well. However, the first mixing can contain (i.e. 5 composition. Advantageously, the rubber composition con
not exclude) the anionic component of the activator Soap, as tains 2 phr or less of Zinc oxide or Zinc fatty acid salt. In
according to the present teachings the fatty acid does not react preferred embodiments, the compounds contain less than 1
with the filler in a deleterious way. phr, preferably less than 0.5 phr or less than 0.3 phr of zinc
In compositions and methods of the invention, a preferred oxide or Zinc Soap.
filler is silica and a preferred cationic component is ZnO. 10 In various embodiments, the rubber compounds contain
Further non-limiting description of the invention is given with less than 2 phr Zinc oxide along with Sufficient fatty acid to
respect to these additives. form a level of soap sufficient to give suitable cure kinetics. In
In exemplary embodiments, the first mixing is carried out preferred embodiments, the rubber compositions comprise
in a barrel type shear mixer such as a Banbury, while the 10 to 100, 30 to 60 phr, or 40 to 50 phr silica filler. In various
second mixing is carried out on a roller mill. In various embodiments, the wall materials are selected from waxes,
embodiments, Zinc oxide is left out of the first mixing and paraffins, polyethylene, ethylene vinyl acetate copolymers,
added for the first time during the second mixing along with and polyvinyl alcohols.
before, or following addition of the curative package. During Rubber formulations are usually expressed as parts per
the first mixing, at least the cation component of the rubber hundred parts of rubber (phr). To illustrate, a typical rubber
soluble salt is omitted. Advantageously, less than 2 phr Zinc formula may contain 100 parts of rubber, 45 phr filler, 5 phr
oxide is added in the second mixing. For example, in various ZnO, 1 phr Stearic acid, 2 phr Sulfur, and various other ingre
embodiments, the level of zinc oxide is from 0.1 to 1 phr. Low dients such as accelerators, retarders, process oil, antioxi
levels of fatty acid are also added. In a non-limiting embodi dants, and so forth. In Such a formula, the weight percent of a
ment, 0.05 to 0.5 phr zinc oxide and 0.1 to 1.5 phr fatty acid component such as ZnO is calculated as a fraction or percent
are added. of the total weight of the whole.
In preferred embodiments, the filler comprises a silica filler 25 The rubber compositions of the invention contain natural
in an amount such as 10 to 100 phr. In further non-limiting or synthetic rubber, or mixtures of rubbers, as well as con
embodiments, the compounds comprise 30 to 60 phr silica ventional rubber additives such as curing agents and accel
filler or 40 to 60 phr silica filler. erators. In various embodiments, the compositions of the
In a preferred embodiment, Zinc oxide and fatty acid are invention are moldable rubber compositions containing a rub
added to the rubber compound in a stoichiometric ratio of 30 ber resin, a curing agent composition, a filler, and a protected
approximately 1 mole Zinc oxide to 2 moles of fatty acid. In activator composition for the curing agent. In particular
further preferred embodiments, the Zinc oxide is microencap embodiments, the protected activator composition comprises
sulated in a wall material that withstands the temperature of microencapsulated metal oxide or a microencapsulated metal
mixing but that dissolves or ruptures at the temperature of the soap or salt of a fatty acid. The metals are selected from those
Subsequent cure. In various embodiments, the Zinc oxide is of group IIA and IIB of the periodic table, but are preferably
provided as particles having a diameter in the micrometer Zinc, calcium, or magnesium, especially as the oxides ZnO,
range. In other embodiments, Zinc oxide comprises at least CaO, and MgO. A preferred metal for the activator composi
Some particles of at least 100 nm or less. In a commercial tion is zinc.
embodiment, the Zinc oxide comprises having an average In general, any rubber that can be crosslinked by a sulfur
diameter of 75 nm.
40
cure may be used to make the compositions of the invention.
In another embodiment, the invention provides methods of Sulfur cured describes the Vulcanization process typical of
producing cured rubber compositions using a protected acti making rubber. Mixtures of rubbers may also be used.
vator composition for the curing agent. As before, the cure Examples of rubbers useful in the invention include, without
mechanism of the rubber compositions involves activation of limitation, natural rubber and modified natural rubbers such
the sulfur cure with the zinc salt of a fatty acid or zinc soap. as those based on polyisoprene.
Alternatively, calcium or magnesium salts are used to activate 45 Synthetic rubbers may also be used in the invention.
the cure. Combining uncured rubber, filler, and other rubber Examples include, without limitation, synthetic polyiso
additives exclusive of the Sulfur cure package in a first mixing prenes, polybutadienes, acrylonitrile butadiene rubber, Sty
step is carried out at a temperature of about 150° C. or less, for rene acrylonitrile butadiene rubber, polychloroprene rubber,
example in a Banbury mixer. In a second mixing, such as in a styrene-butadiene copolymer rubber, isoprene-isobutylene
roller mill, the sulfur curative is added to the product of the 50 copolymer rubber and its halogenated derivatives, ethylene
first mixing, preferably at a temperature of 110°C. or less. As propylene-diene copolymer rubbers such as ethylene-propy
an example of a protected activator composition, microen lene-cyclopentadiene terpolymer, ethylene-propylene-5-eth
capsulated Zinc oxide and/or microencapsulated Zinc fatty ylidene-norbornene terpolymer, and ethylene-propylene-1,4-
acid salt is added to either the first mixing, the second mixing, hexadiene terpolymer, butadiene-propylene copolymer
or to both. In a preferred embodiment, when the temperature 55
rubber, butadiene-ethylene copolymer rubber, butadiene-iso
of the first mixing is above 130°C., the protected activator or prene copolymer, polypentenamerand their mixtures. Ingen
microencapsulated Zn, Ca, or Mg compound is added only in eral. Such compounds are characterized by repeating olefinic
the second mixing. The microencapsulated Zinc compounds unsaturation in the backbone of the polymer, which generally
comprise the respective Zinc compounds (Zinc oxide and Zinc arises from the presence ofbutadiene or isoprene monomers
fatty salt or soap) and a wall material Surrounding the Zinc 60
in the polymer structure.
compound. The wall material is stable to a temperature Suf Conventional Sulfur based curing agents may be used in the
ficiently high that it does not release the Zinc compound compositions of the invention. Such curing agents are well
during the first or second mixing. In this way, Zinc is pre known in the art and include elemental sulfur, soluble,
vented from coming into contact with the silica filler until the insoluble and mixtures thereof, as well as a variety of organic
rubber composition is cured at a higher temperature. The Sulfide, disulfide and polysulfide compounds. Examples
method further comprises curing the resulting rubber compo 65 include, without limitation, Vulcanizing agents such as mor
sition by heating at a temperature above 120° C. or above pholine disulfide, 2-(4-morpholinodithio)benzothiazole, and
130° C., and preferably at 150° C. and above. Upon curing, thiuram compounds such as tetramethylthiuram disulfide, tet
 US 7,816,443 B2
5 6
raethylthiuram disulfide and dipentamethylenethiuram tetra In preferred embodiments, the preserved zinc is present in
Sulfide. The Vulcanizing agents may be used alone or in com the rubber compositions at a level of 1 mole of zinc for two
bination with each other. In a preferred embodiment, sulfur is moles of fatty acid. This ratio is referred to as "stoichiomet
used as the curing agent. ric' because it corresponds to formation of a soap with the
The rubber compositions of the invention also in general, fatty acid and the divalent zinc. Stoichiometric zinc to 1 phr
contain conventional accelerators. Such accelerators and co fatty acid is typically below 0.5 phr. Thus in various embodi
accelerators are known in the art and include without limita ments the invention provides for a greater than 90% reduction
tion, those based on dithiocarbamate, thiazole, amines, of the zinc level (i.e. from a typical level of 5 phr down to 0.5
guanidines, Xanthates, thioureas, thiurams, dithiophosphates, phr or less). In a representative embodiment, activation is
and Sulfenamides. Non-limiting examples of accelerators 10 provided by about 0.3 phr ZnO and 1 phr fatty acid, corre
include: zinc diisobutyldithiocarbamate, Zinc salt of 2-mer sponding to about a stoichiometric ratio. Once the amount of
captobenzothiazole, hexamethylenetetramine, 1,3-diphenyl Zn relative to the acid species is less than Stoichiometric, then
guanidine, Zinc isopropyl Xanthate, trimethylthiourea, tetra activation of the cure is inhibited, because the active species
benzyl thiuram disulfide, zinc-O-O-di-n-butylphospho (zinc salt) is present in even lower levels.
rodithioate, and N-t-butyl-2-benzothiazylsulfenamide. 15
Fillers are used in rubber compositions to enhance proper
ties, to save money, to facilitate processing, to improve physi
In various embodiments, the accelerator activators com cal properties or for other reasons. A variety of filler materials
prise metal complexes of fatty acids, which are referred to as are known. In various embodiments, the compositions com
'soaps'. Zinc Soaps include the soap, or salt, of a fatty acid prise a silica filler. Typical levels of silica filler include from
such as one having from 8 to 36 carbon atoms or 8 to 26 about 10 phr to 100 phr or higher. In various embodiments,
carbon atoms. In a non-limiting embodiment, the fatty acids the compositions contain 10-80, 30-70, 40-60, 50-60, or
have 10-24 carbon atoms. Non-limiting examples include 35-60 phr filler.
lauric acid, oleic acid, and Stearic acid. The fatty acids form a Zinc oxide suitable for rubber compounding is available in
Soap with Zinc by combining two moles offatty acid with one a variety of particle sizes. For example, nanoparticle ZnO
mole of zinc. (75% masterbatch) can be purchased from Cosmos Chemical
For activation, zinc soaps can be added directly to a rubber 25 and is reported to have a particle size of 75 nm. A standard
composition and can be encapsulated according to the meth ZnO (80% masterbatch) from Atman is reported to have a
ods described herein. Alternatively or in addition, individual particle size of 50 m. Zinc oxide powder, of any dispersible
compounds such as ZnO and a fatty acid can be blended into particle size, as opposed to a masterbatch, can also be used.
the curable rubber compositions. During high temperature Methods of the invention call for addition of various com
treatment such as in curing, the individual compounds react to 30 ponents in a first mixing and in a second mixing. The mixing
form the Soap in place. In either case, the Soap is believed to refers to operational steps and may or may not entail transfer
be the active species. The terms soap components, activator of the mixing compound from one vessel to another. For
components, salt components, and the like are used herein, example, a first mixing may take place in a mixer Such as a
unless the context dictates otherwise, to refer to any of ZnO or Banbury, while the second mixing takes place in a roller mill
other Zinc salt, to the Zinc soap itself, and to the fatty acid after removal from the Banbury. Alternatively, a first mixing
component. Adding Soap components then means adding any 35
and a second mixing may take place in the same mixing vessel
of those components to the rubber composition during com or device. An example would be combining a subset of the
pounding. total compounding ingredients in a device Such a roller mill
In various embodiments, the invention provides methods and adding components sequentially in first and Subsequent
and compositions that avoid contact of zinc, as the Zinc soap, mixings.
with silica filler prior to high temperature cure. The deleteri 40 The designation of “first and “second mixings also does
ous side reaction of zinc with silica filler is avoided as long as not necessarily imply that the steps so designated take place in
no or very little Zinc component is present along with the immediate succession one after the other. Rather, the termi
filler, or alternatively if any Zinc component present is pre nology allows for there to be intermediate steps where for
vented from interacting with the surface by virtue of its being example, other components are added.
encapsulated. If one of the three ingredients, ZnO, Znstearate 45 In various embodiments, the first mixing (where in one
or Stearic acid (the latter two as non-limiting examples of soap embodiment Zinc components are not included and in another
and fatty acid), is encapsulated, then the Zn is preserved and embodiment Zinc components are included only if they are
is available during cure. In preferred embodiments, the ZnO microencapsulated) is carried out at a relatively high tempera
or Zn Stearate is encapsulated. Stearic acid may be encapsu ture of about 130-150° C. These temperatures are typical of
lated, but since other adjunct chemicals may introduce traces 50 barrel type shear mixers such a Banbury mixer. In a Banbury
of Stearic acid as dispersants, it is preferable to encapsulate or similar mixer, rubbers and other components (normally
the ZnO or Zn stearate. excluding the cure components) are mixed with shear. The
Advantageously, because the methods provide for preser shearing generates heat, and heat can be added to facilitate
Vation of Zinc (i.e., the Zinc remains available to activate the mixing. The filler Such as silica is normally added at this
cure accelerators instead of being bound and decomposed on 55
Stage.
the silica filler surface), relatively lower amounts of zinc need The second mixing, in which low levels of zinc can be
to be added to the rubber compounds to provide a suitable or added along with the cure package, preferably takes places at
acceptable cure. To illustrate, in cases where typically 5 phr of a lower temperature, preferably below about 110°C., in part
ZnO would be used along with about 1 phr of fatty acid, the to avoid a premature curing. In various embodiments, the
level of ZnO can be reduced below 2 phrand even below 1 phr temperature is 100° C. or less. In a non-limiting example, the
60 second mixing takes place in a roller mill. The temperature of
without adversely affecting cured rubber properties. In fact,
physical properties appear to be enhanced. Although the the material in the roller can be controlled by cooling the
invention is not limited by theory, the enhancement is rollers, and is typically below the higher temperatures that
believed to be due to lower contamination of the filler surface occur in the Banbury mixer.
with Zinc, and a lowered quantity of the relatively large (com Other combinations of mixing devices are well known to
pared to the other additives and fillers) particles of ZnO in the 65 those of skill in the art and are suitable for carrying out the first
rubber compositions that act as points of stress concentration, and second mixing, as well as any other mixing steps required
which can lead to cracks and failure in the bulk materials to formulate and cure the rubber compounds.
 US 7,816,443 B2
7 8
Methods of microencapsulation are varied and partly stage of the reaction, one Stearic acid molecule is generated.
dependent on the material being encapsulated and the desired Provided there is more ZnO, another stearic acid molecule is
mode of releasing the encapsulated component. Since the liberated, and the Zn then binds to two Surface oxygenatoms.
desired result is to release the encapsulated component during The reaction scheme is more fully described below.
the cure cycle, the microcapsule must possess certain prop
erties. First, it must be able to withstand compounding at ZnO Consumption and Regeneration of Stearic Acid
elevated temperatures such as on a roller mill or, if desired, a
Banbury-type mixer. The microcapsules must possess Suffi Step 1. Zinc oxide reacts with 2 molecules of stearic acid to
cient strength to withstand the shear encountered in the mill produce Zinc Stearate and water.
ing without a significant number of them rupturing. Prefer 10
ably, the microcapsules rupture at a temperature so that the
Zinc activator is available during cure. In various embodi Step 2. Zinc Stearate reacts with hydroxyl groups on the
ments, the microcapsules rupture and release the encapsu
lated zinc at temperatures of 130+20° C., 130+10° C. or Surface of the silica particle to regenerate one Stearic acid
125+5°C. The microcapsule material should not adversely molecule.
15
affect the cure characteristics of the system nor cause any
unacceptable reduction in the final properties of the cured
rubber. In various embodiments, by microencapsulating the
activator, the curing kinetics are somewhat slower. Such is not
necessarily disadvantageous for manufacturing.
The wall material of the microcapsules is selected for good -SOH
compatibility with the constituents of the rubber mixtures.
Non-limiting examples include waxes, paraffins, polyethyl + Zn(CH3COO) --
ene (PE), ethylene-vinyl acetate copolymers, polyvinyl alco
hols (PVA), as well as mixtures of these. Other non-limiting
—lot
examples include calcium caseinate, calcium polypectate, 25
polyacrylic acid and derivatives, polycarbonates, polyethyl
ene oxide, polymethacrylate ester, polyorthoester, polyvinyl
acetate, polyvinylpyrrolidone and thermoplastic polymers. O
In various embodiments, Suitable coating materials also
include polymerizable compositions. Non-limiting examples 30 —to Zn(C17H35COO)
include liquid polyacrylate compositions that can contain a
catalyst system consisting of photoinitiator and thermal ini h + C17H3COOH
tiator, polymerizable mixtures of dihydropyridine, tetrazole
and a soluble ionic salt; polyurethanes; amorphous polyesters -kot
which optionally contain tertiary amine groups; mixtures of 35
polyamino compositions and derivatives of 2,4,6-triamino-1,
3,5-triazine with aldehydes; mixtures of polyethylene and
polyvinyl alcohols; aminoplast resins; and silicone polymers.
In some preferred embodiments, suitable wall materials
tend to melt in the temperature range which is important for Step 3. Further reaction with the silica hydroxyls can regen
rubber Vulcanization, i.e. between roughly 100 and 260° C. 40 erate the other Stearic acid; thus contaminating the silica
They preferably melt below 150° C. and preferably have a Surface.
melting point in the range from 120 to 140°C., in particular of
roughly 130° C. Preferably, the coating materials are rela
tively insoluble in rubber or in rubber mixtures prior to melt
ing, preferably up to temperatures of 120 to 140° C., in 45
O
particular up to about 130°C. In various embodiments, the
materials are soluble in rubber at higher temperatures, for Si
example above 120 or 130° C.
In a non-limiting embodiment, microencapsulation is car O
ried out by adding ZnO to a solution of polymeric wall mate 50 SO
/
rial in an alcoholic solution of a Group I-IV metal halide or
nitrate. To illustrate, 10 g of polyamide is dissolved in 190 g
saturated calcium chloride solution in methanol. 10 g of ZnO
is added to form a Suspension. The Suspension is added to one
liter of a 1:1 MeOH: water mixture and stirred for about 15
55
minutes to give ZnO microcapsules.
In another embodiment, powdered ZnO is combined in At large excesses of ZnO relative to Stearic acid, the reaction
about a 7:3 ratio with a polyethylene wax above its melting progresses to Step 3. At a slight excess or stoichiometric
point then passed in the melted State to a rotary table and deficit of stearic acid, the reaction stops at Step 2 when the
atomized in a cooling tower to provide microcapsules. ZnO is exhausted.
60
EXAMPLES The cessation of the above reaction scheme upon depletion
of ZnO (Zn stearate) has been shown via FTIR, where the
Example 1 species shown in the second part of reaction 2 is only resolved
via FTIR as the concentration of ZnO, and consequently Zn
As mentioned previously, the Zn is depleted in a side reac 65 Stearate, approaches Zero. This Suggests that the reaction to
tion. Zn Stearate is able to react with the hydroxyl groups on deplete Zn and regenerate Stearic acid (steps 2 and 3) is very
the surface of a filler, such as precipitated silica. At the first fast.
 US 7,816,443 B2
9 10
Example 2 For Example 3-1, all ingredients, except the curative pack
age, are combined in the Banbury. For Examples 3-2 through
Since in conventional compounding ZnO and Stearic acid 3-8, all ingredients except the curative package and the ZnO
are added in the initial mixing (Banbury) of the rubber com 80 are combined in a Banbury mixer at a temperature of 130°
ponents, they are present throughout the entire cycle from C. Then the components of the curative package and the ZnO
initial mixing to final cure. Furthermore, except for curing, are added in a roller mill at a temperature of about 70° C.
the initial mixing is where the rubber compound encounters Thereafter the compositions are cured at 150° C. for a total
the highest temperatures, often >130° C. time of T90+1 minutes.
By adding the activator components later in the process, for
example in a second mixing during addition of Sulfur and 10 For the results in Table 1, hardness is Shore A, 300%
accelerators, the total amount of ZnO required for cure is modulus and tensile strength are in units of kg/cm, elonga
reduced. Even without a reduction in ZnO, waiting until later tion is in percent, tear is in units of kg/cm, abrasion (Akron)
in the process improves the physical properties of the cured is in cc lost/3000 revolutions and density is in g/cm.
TABLE 1.
3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8

phr ZnO 6.25 6.25 2.5 O.625 O.313 O.156 O.0625 O

wt.% ZnO 2.94 2.94 1.2 O.3 O.15 O.O8 O.O3 O
hardness 68.5 70.5 72.5 71.5 74 66 68.5 66
300% mod. 48 55 57 S4 52 29 37 21
tensile 137 138 137 145 178 125 119 90
% elong. 616 S60 549 608 716 818 775 834
tear 52 58 60 64 71 8O 78 58
abrasion 0.249 O.231 O.167 O. 103 O.08 O.141 O.215 O.349
density 1155 1.141 1.13 1145 1.129 1.142 1119 1.1

rubber compound since the filler Surface is less contaminated. I claim:

Also, the cure accelerates as shown in FIG. 1. 30 1. A moldable rubber composition comprising: a rubber
As shown in FIG. 1, the cure time (T90) is reduced by 40 resin selected from the group consisting of natural rubber,
sec just by adding the ZnO on the roller mill (in a second synthetic rubber, and mixtures thereof; a curing agent com
mixing at 110° C. or less), instead of in the Banbury. Further position; a filler; and a microencapsulated activator compo
reductions in ZnO concentration (i.e., down from 5 phr-2.9 sition for said curing agent, wherein the activator composi
weight%) also cause the cure to progress more quickly until 35 tion comprises a metal oxide or a fatty acid soap, and wherein
the ZnO concentration approaches the Stoichiometric ratio the metal oxide if present is presentata level of 2 phr or less,
with stearic acid. As the ZnO level is further reduced below and the fatty acid soap if present is present at a level of 2 phr
the stoichiometric point, the cure slows down due to insuffi or less.
cient activation of the accelerator. 2. A moldable rubber composition according to claim 1,
40 wherein the metal oxide or fatty acid soap is present at a level
Example 3 of 1 phr or less.
3. A moldable rubber composition according to claim 2
The following data show how changes in ZnO concentra where the metal component of the metal oxide is selected
tion can have a dramatic effect on physical properties. The from groups IIA and IIB of the periodic table.
greatest percent change was in the abrasion resistance (mea 45 4. A moldable rubber composition according to claim 1
sured as cc of material lost), where a lower number is better. where the metal oxide is Zinc oxide or the fatty acid soap is a
In the compositions of Table 1, the following rubber addi Zinc Soap.
tives are used: 5. A moldable rubber composition according to claim 1
wherein the curing agent composition comprises elemental
50 Sulfur and accelerators.
Abbreviation Compound phr
6. A composition according to claim 1 wherein the filler is
silica filler.
IR Polyisoprene rubber 10 7. A composition according to claim 2 wherein the metal
NBR50.75 Acrylonitrile, butadiene rubber 10 oxide is CaO or MgO.
UBE-BR1SOL Polybutadiene rubber 8O 55
6ONS Homogenizing agent 3 8. A composition according to claim 6 wherein the com
175GR Filler (silica) 50 position comprises ZnO present at a level less than 1 phr.
ZnO-8O Zinc oxide, 80% varies 9. A composition according to claim 6 wherein the com
STAC Stearic acid 1
BHT Butylated hydroxytoluene 1 position comprises ZnO present at a level less than 0.5 phr.
1956 Okerin 1956 anti-blooming agent O.S 60
10. A moldable rubber composition comprising
PEG Polyethylene glycol 3 a) rubber selected from the group consisting of natural
RT1987 Rheinofit 1987 2
Curative Package rubber, synthetic rubber, and mixtures thereof;
b) a Sulfur curing agent composition;
SU135-75 Sulfur (crosslinker) 2.4 c) a silica filler; and
MBTS-75 2,2'-dithiobisbenzothiazole (accelerator) O.8
TBTZD-70 tetrabenzyl thiuramdisulfide (accelerator) O.26 65 d) a microencapsulated activator composition comprising
Z1nc,
wherein the composition comprises less than 2 phr ZnO.
 US 7,816,443 B2
11 12
11. A composition according to claim 10 comprising less d) a microencapsulated activator composition comprising
than 1 phr ZnO. Z1nc,
12. A composition according to claim 10 comprising less wherein the microencapsulated activator composition com
than or equal to 0.5 phr ZnO. prises wall material that melts at a temperature of from 120°
13. A composition according to claim 1 wherein the C. to 140° C.
microencapsulated activator composition comprises micro 17. A composition according to claim 16 comprising less
capsules that rupture and release encapsulated Zn at a tem than 2 phr ZnO.
perature of 130+20° C. 18. A composition according to claim 16 comprising less
14. A composition according to claim 10, wherein the than 1 phr ZnO.
microencapsulated activator composition comprises a wall 10 19. A composition according to claim 16 comprising less
material selected from the group consisting of waxes, paraf than or equal to 0.5 phr ZnO.
fins, polyethylene, ethylene vinyl acetate copolymers, and 20. A moldable rubber composition according to claim 4,
polyvinyl alcohol. wherein the fatty acid soap or Zinc oxide is present at a level
15. A composition according to claim 10 wherein the of 1 phr or less.
microencapsulated activator composition comprises a wall 15 21. A moldable rubber composition according to claim 4.
material with a melting point of 120° C. to 140°C. wherein the fatty acid soap or Zinc oxide is present at a level
16. A moldable rubber composition comprising of 0.5 phr or less.
a) rubber selected from the group consisting of natural 22. A moldable rubber composition according to claim 4.
rubber, synthetic rubber, and mixtures thereof; wherein the fatty acid soap or Zinc oxide is present at a level
b) sulfur curing agent composition; 20 of 0.3 phr or less.
c) 10 to 100 phr silica filler; and