CA1183989A - Vinyl resins containing non-extruding stable carboxylated polysiloxane - Google Patents

Abstract

Abstract Vinyl resin compositions are disclosed which possess improved lubricity, mold releasability, water repellency, abrasion resistance, gloss and/or processability. These improvements are obtained by mixing with the vinyl resin a minor portion of an organopolysiloxane which bears one or more acyloxyhydrocarbyl radicals bonded to silicon in the organopolysiloxane. Vinyl resins including those of the present invention may be used in molded products, cast products, laminates, films, fibers, bonding agents, rubber and paints.

Description

VINYL RESINS CONTAINING NON-EXI'RUDING
STAB LE CARBO~yL~TED POLYSILOXANE

Background of the Invention This invention relates to silicon-containing vinyl resin compositions. ~ore precisely, this invention concerns vinyl resin compositions which are comprised of an organopolysiloxane and which possess lubricity, mold releasability, water repellency, abrasion resistance, gloss and processability.

Vinyl resins have been used widely in molded products, cast products, laminates, films, fibersl bonding agents, rubbers and paints. Since properties such as lubricity, mold-releasability, water repellency, abrasion resistance, gloss, processability and mechanical strength are required in may cases, attempts have been made to improve these properties by compounding additives such as silicone oil, waxes, higher alcohols and metal soaps with the vinyl resin. In particular, the addition of silicone oil can remarkably improve lubricity and mold-releasability of a vinyl resin. However, silicone oil is poorly compatible with vinyl resins so that there is the drawback that many problems occur due to the separation and leakage of silicone oil from the resins. In order to overcome these problems, both silicone oil and silicone rubber were added together to thermoplastic resins in Kokai Japanese Patent No. Sho 50(1975)-121344. However, leakage o:E silicone oil could not be prevented sufficiently. In addition, there was a drawbac~
that the original characteristics of the thermoplastic resins were modified due to the addition of silicone rubber. In Japanese Patent No. Sho 52(1977)-6751, an organopolysiloxane having a -OCORl group directly bound to a silicon atom, where Rl represents substituted or unsubstituted monovalent hydrocarbon radicals, was added to vinyl chloride resins. In this case, since the -OCORl group is directly bound to the silicon atom, hydrolysis occurs easily and gelation, ~, '3 occurring due to the presence of moisture in the air, markedly impairs the lubricity and appearance of the vinyl chloride resin. In Japanese Patent Mo. Sho 53(1978)-44178, an organopolysiloxane having a carboxyl group bonded to silicon via a Si-C bond was compounded with thermoplastic materials. In this case, the system is quickly corroded, due to the presence of carboxyl groups, and the functions of the compound are impaired or disappear, due to the occurrence of a reaction with basic compounds.
srief Summary of the Invention It is an object of this invention to provide organopolysiloxane-containing vinyl resins which do not leak, i.e. do not exude organopolysiloxane. It is another object of this invention to provide improved vinyl resin which possess lubricity, mold-releasability, water-repellency, abrasion resistance, gloss and processability.
These objects, and others which will become apparent upon considering the following disclosure and appended claims, are obtained by mixing with a vinyl resin component an organopolysiloxane component which bears to least one silicon-bonded acyloxyhydrocarbyl radical.
Detailed Description of the Invention The present invention relates to a composition comprising (a) 100 parts by weight of a vinyl resin component and (b) from 0.01 to 20 parts by weight or an organopolysiloxane component having the formula A(R2SiO)m(RSio) SiR2A
R'OCR"
o wherein R denotes a substituted or unsubstituted monovalent hydrocarbon radical, R'denotes a divalent hydrocarbon radical, R" denotes an alkyl radical, A denotes an R radical or an R'OCOR" radical, m and n are each zero or a positive integer and the sum of _ ~ n has a value of from 1 to 2000, there being at least one R'OCOR" radical per molecule of or~anopolysiloxane.

- 3-~ -Vinyl resins used as component (a~ in this invention are well-known materials and include vinyl homopolymers, such as polyvinyl chloride, polyvinyl acetat, polyvinyl alcohol, polyvinyl acetal, polyvinyl formal, polyvinyl butyral, polyethylenes, polypropylenes, polyacrylo-nitriles, polyacrylates, polymethacrylates, polyvinylidene chloride, polyvinyl fluoride and other vinyl homopolymers;
vinyl copolymers, such as vinyl chloride/vinylidene chloride co~olymer, vinyl chloride/methyl acrylate copolymer, vinyl chloride/methyl methacrylate copolymer~ vinyl chloride/acrylonitrile copolymer, vinyl chlori~e/styrene copolylner, vinyl chloride/ethylene copolymer, styrene/acrylonitrile copolymer, methacrylate/acrylate co~olymer, acrylonitrile/butadiene copolymer, acrylonitrile/butadiene/styrene copolymer, vinyl acetate/vinyl chloride copolymer, vinyl acetate/~thylene copolymer, vinyl acetate/acrylic acid copolymer, vinyl acetate/acrylonitrile copolymer, vinyl acetate/acrylate copolymer, vinyl acetate/maleic acid copolymer, vinyl acetate/styrene copolymer, vinyl acetate/vinyl alcohol copolymer, vinyl acetate/vinyl chlori~e/vinyl alcohol copolymer, vinyl acetate/vinyl chloride/et~lylene co~olymer and other vinyl copolymers; rubbery elastomers, such as ethylene/propylene rubber, ethylene/propylene/diene rubber, butyl rubber, acrylic rubber, acrylonitrile/butadiene rub~er and chloroprene rubber and, copolymers of vinyl resins with resins other than vinyl resins. The vinyl resins used in this invention can also be mixtures of two or Inore types of the above vinyl resins. In particular, those which are most suitable ~long the vinyl resins mentioned above are polyvillyl acetate and its copolymers, polyacrylate and its co~ol~ners, and polymethacrylate and its copolymers. In the case of these ~referred copolymers the proportion of vinyl acetate or acrylate or methacrylate in the copolymer is at least 2 percent by wei~ht.
Component (a) can have any form, such as a solution, an emulsion, a paste, a latex, a powder or a solid form.
Oryanopolysiloxanes used as component (b) in the com~ositions of this invention are expressed by the formula A(R2SiO)m(Rsio)n~iR2A
R'OCR"

In this formula each R represents a substituted or unsubstituted monovalent hydrocarbon ra~ical, such as alkyl radicals such as methyl, ethyl, propyl, octyl and tridecyl; cycloaliphatic radicals, such as the cyclohexyl radical; alkenyl radicals, such as vinyl and dllyl radicals; aryl radicals, such as the phenyl radical, or said monovalent hydrocdrbon radicals in which hydroyen atoms are replaced with halo~en atoms or cyano radicals. It is nvt always necessary that all the R groups in a sin~le molecule are identical.
X' represents divalent hydrocarbon radicals, such as alkylene radicals r such as -CH2C~2-, -CH2CH2CH2-, -C~2(C~3)CH-~ -C~2C~(C~3)CH2- and -(CH2)4-, or alkylene arylene radicals, such as -(CH2~2-C6H4- or tCH2t4C~2-CH-CH2-C6Hs, R" represents an alkyl radical, such as methyl, et~yl, propyl, decyl and octadecyl. A
represents R or R'OC~R" radicals.
In the formula for colnyonent (b) m and n are 0 or inte;~ers of 1 or greater and m + n must be 1 to 200U. If m + n is 0, the effects on the lubricating aDility and mold-releasilly ability are poor, while if m + n exceeds ~00, the dispersibility of the component (b) in vinyl resins is reduced. Thus m + n preferably ranges from 10 to 1000. If n = 0 at least one A radical must be a X'OCOR" radical.

These organopolysiloxanes can impart lubricatiny ahility, mold-releasiny ability, water repellency, abrasion resistance and yloss to vinyl resins due to the presence of siloxane UllitS and also can impart affinity and compatibility with vinyl resins due to the presence of one or more acyloxyhydrocarbyl radicals o the formula R'OCOR" so that the transparency of vinyl resins is not impaired and the procesability is excellent. Therefore, leakage of oryanopolysiloxanes froln the vinyl resins does not occur. Since ~he R'OCOR" group is extremely stable, the various effects mentioned above are permanently maintained. In particular, in the cases when polyv nyl acetate and its copolymers, polyacrylate and its copolymers or polymethacrylate and its copolymers are used as vinyl resins, the compatibility and affinity with organopolysiloxanes haviny the R'OCO~" ~roup are extremely excellent.
Oryanopolysiloxane component (b) is well known and can be prepared by any one of several methods. U.S. Patent Nos. 2,550,205 issued ~pril 24, 1951 to John L. Speier; 2,691,032 issued October 5, 1954 to Leo H. Sommer; 2,770,633 issued November 13, 1956 to Leo H. Sommer; 2,891,980 issued June 23, 1959 to Alfred ~. Gilbert et al.; 2,90~,735 issued September 29, 1959 to John L. Speier and 21922t806 issued January 26, 1960 to Rokert R. Merker shcw hGw to pre~are oryanopolysiloxanes which are suitable as component (b) in the compositions of this invention.
In p,articular, an organopolysiloxane haviny the formula CH3{(CH3)2Sio}m{(cH3)t~)sio}nsi(c~3)~
can be reacted with o CH2=CHCH2OCCH3 in the presence of a platinum-containing catalyst to prepare an organopolysiloxane component (b) for ~he compositions of this invention haviny the formula CH3{(CH3)2Sio}m{(CH3)Si.O}nSi(CH3)3 ~2cH2cH2occH3 O.
The proportion of component (~) in the composition of this invention ranges from 0.01 to 20 ~arts by weiyht, preferably 0.1 to 10 parts by weight, base~ on 100 parts by weight of component (a).

..

The compositions of this invention can be pre~ared by simply mixing components (a) and (b) in any suitable manner. If a solvent is used, a solvent which is common to both components (a) and (b) is selected. If com~onent (a) is available in an emulslon form, component (b) is emulsified usiny emulsifiers, such as sulfates of hiyher alcohols, alkylbenzene sulfonates and polyhydroxyalkylene adducts of hiyher fatty acids, and then emulsified component (b) is added to emulsion (a). If component (a) is available in a solid form such as chips or pellets, component (b) can be added when the chips or pellets are molded, or the chips or pellets can be melted and then component (b) added directly to the melt. That is, component (b) can be added to com~onent (a) at any stage from the production process of component (a) to the final processing stage of the resin.
In addition to components (a) and (b), a variety of conventional additives can be compounded in the comyositions of this invention. Examples are as follows: dry silica, wet silica, magnesium silicate, alwninum silicate, calcium carbonate, clay, mica, talc, titaniwm oxide, aluminum oxide, magnesium oxide, red iron oxide, maynetic iron oxide, various metal ~owders, carbon black, asbestos, glass fiber, glass beads, phthalates, phosphates, netal soaps, silicone oil, silane coupling agents, resins, isocyanates, waxes, hiyher alcohols, organic tin fatty acid salts, thermoplastic resins other than vinyl resins; such as ~olyurethanes and polyasnides and polyesters, heat curable resins; such as melamine, phenol, urea, uran, xylene, alkyd, epoxy and silicone resins, natural rubbers and synthetic rubbers. In addition to these additives, the followiny known agents can be compounded in the compositions of this invention:
fillers, plasticizers, stabilizers, 1ame retardants, U.V. absorbents, lubricating agents, surfdctarlts, antistatics, antioxidants, antifungal agents, foaming agents, coloring agents and adilesiveness impartiny ayents.
The compositions of tshis invention can be used in all the uses of the conventional vinyl resins.
For example, the composltions can be used in molded products, cast products, laminates/ films, fibers, bondiny ageslts, rubbers and paints. When the compositions of this invention are used as molded products, the products exhibit excellent -12~

mold-releasiny ability and internal lubricatiny ability. When used as filins or resin plates, the products exhibit excellent transparency and non-blocking character. When used as paints, the paint film exhibits excellent gloss, smoothness and water repellency. If magnetic powders, carbon black or dyes are compounded with components (a) and (b) constituting the compositions of this invention, the ~roducts can be used as excellent magnetic toners. If binders or other a~ditives are compounded with the compositions constitutiny these maynetic toners, the products are suitable as maynetic paints for maynetic tapes and maynetic disks.
The followiny examples are disclosed to further illustrate, but not to limit, the present invention. All parts and percentayes are on a weiyht basis. Viscosities were measured at 25C.

Exam~le 1 The or~anopolysiloxanes that were used in this example, and their identifier syrnbols, are as ~ollows:
Or~anopolysiloxaneIdentifier CH3 ~3 CH3(SiO)350(sio)6si(c~3)3 A
c~3 CH2CH2c~2~1c~c~3 V

(150~ centistokes) Polydimethylsiloxane B
(1000 centistokes) Methylphenylpolysiloxane (1000 centistokes) Methyltridecylpolysiloxane D
(900 centistokes) 8~3 The vinyl resins that were used in this example, and their identifier symbols, are as follows:
Vinyl Resin Identifier Polyvinyl chloride (Sumilite SX-ll) PVC
(Sumimoto Chemical Industries, Ltd.) Vinyl chloride/5~ vinyl acetatePVC/PVA-5%
(Denka Vinyl M-70) (Denki Kayaku K.K.) ~-Vinyl chloride/10% vinyl acetate PVC/PVA-10 (Denka Vinyl M~-90 (Denki Ragaku K.K.3 ~thylene/28% vinyl acetate (Evalex) PE/PVA-28%
(Mitsui Polychemical Co., Ltd.) Polyethylene (Mirason 24H~ PE
(Mitsui Polychemical Co., Ltd.) Polypropylene (Noblen ~-501~ PP
(Sumimoto Chemical Industries Co., Ltd) Polymethylmethacrylate (Sumipex L~ PMMA
(S~nimoto Chemical Industries Co., Ltd.) *Trademark ., .

Two amounts (0.6 pa~ts and 1.5 parts) of each of the above-listed oryanopolysiloxanes were added to 10~ ~art portions of each of the above-listed vinyl resin.s to provide 56 compositions (14 of this invention and 42 comparison) which were cast as films haviny a thickness of 1.5 mm. Each film was examined macroscopically for leakaye before and after being heated at 70C for 7 days in a hot air circulation type oven. The results are sumrnarized in Table I.
The leakaye on the film surface was not found in the film prepared using Siloxane (A) specified in this invention and the film ~uality was excellent com~ared to those usiny the conventional silicone oils in the comparative examples. Especially when vinyl acetate resins, polymethacrylate resins, or polyacrylate resins were used as vinyl resins, the affinity and compatibility with Siloxane (A) were found to be particularly excellent. The reason for this seemed to be that these resins contain a group similar to the R'OCOR" yroup of the oryanopolysiloxane.

Based on the results mentioned above~ the compositions of this invention were expected to be useful in the fields using combillations of vinyl resins and silicone oils and in particular, in toners used for electrophotography and static printing, and magnet forming phase of the magnetic record ing med ia such as magnetic tapes and magnetic disks.
Exam~le 2 Organopolysiloxane (A) used in Example 1 was added in ~ proportion of 1 part based on 100 parts of emulsion for paints primarily consisting of polyvinyl acetate (clear) and the mixture was mixed at a rate of 3000 times/min. with a homogenizer for 30 minutes.
Subsequently, the composition was coated over an alurninum test panel ( 10U ITun x 100 rnm x O ~ 3 mm) to form a film with a thickness of about 100 llm and a transparent glossy f ilm w s ~orrned by drying . When an adhesive tape (Cellophane tal~e by Nichiban K.K.~ was adhered on the coated film surface under pressure and peeled ( this process was repeated f ive times), the peeling resistance was Eound to be extremely low and no abnorlnalities were found on the coated surface, indicating excellent non-blocking character. When the *Trademark ;.

aluminum test panel having the formed film was ~oiled in ~oiling water for one hour, transparency and gloss were not dissipated.
The same test as mentioned above was conducted in the cases using dimethylpolysiloxane (B) and methylphenylpolysiloxane ~C~ used in Example I as comparat~ve examples. Although ~oth gloss and the non-blocking character were found to he identical to those found in the case using organopolysiloxane (A), the coated film was found to ~e cloudy after the boiling water test.
Example 3 An organopolysiloxane (E) having a ~iscosity of 1200 centistokes and the following formula ~ CH3 ~ ~ 3 ~ CH3 CH3 ( SiO ) ~ SiO ) Si-CH3 ~ CH3 J 250 ~CH2~3ococ3H7J CH3 was added in a proportion of 0.6 parts and 1.5 parts to 100 parts of polyvinyl chloride or vinyl chloride/
vinyl acetate copolymer with a vinyl acetate content of 10% used in Example 1, and the same experiment as in Example 1 was conducted. Leakage of organopolysiloxane ~E~ on the film surface was not found in any cases.

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Claims (6)

Claims:

1. A composition comprising (a) 100 parts by weight of a vinyl resin component and (b) from 0.01 to 20 parts by weight of an organopolysiloxane component having the formula wherein R denotes a substituted or unsubstituted monovalent hydrocarbon radical, R' denotes a divalent hydrocarbon radical, R" denotes an alkyl radical, A denotes an R radical or an R'OCOR"
radical, m and n are each zero or a positive integer and the sum of m + n has a value of from 1 to 2000, there being at least one R'OCOR"
radical per molecule of organopolysiloxane.

2. The composition according to claim 1 wherein the vinyl resin component is a vinyl acetate resin.

3. The composition according to claim 1 wherein the vinyl resin component is an acrylate resin.

4. The composition according to claim 1 wherein the vinyl resin component is a methacrylate resin.

5. The composition according to claims 1, 2, or 3 wherein the organopolysiloxane component (b) has the formula

6. The compositon according to claims 1, 2, or 3 wherein the organopolysiloxane component (b) has the formula