JP2005146263A - Acrylic rubber composition, molded product and automobile/electric/electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic rubber composition excellent in molding and processing characteristics, extremely excellent in mechanical properties, and having both low-temperature characteristics and oil resistance. <P>SOLUTION: The acrylic rubber composition is composed of (A) an acrylic rubber and (B) a polyorganosiloxane-based graft polymer, and is excellent in molding and processing characteristics, is extremely excellent in mechanical properties, and has both low-temperature characteristics and oil resistance. A molded product having a good appearance and good characteristics is obtained from the composition and the molded product is useful as automobile, electric, and electronic components. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an acrylic rubber composition comprising an acrylic rubber and a polyorganosiloxane-based graft polymer having excellent molding processability, very excellent mechanical properties, and having both low temperature characteristics and oil resistance.

  Acrylic rubber is a polymer mainly composed of acrylate ester, and is generally known as an elastomer material with excellent heat resistance and oil resistance. It is used as a molding material for sealing materials such as oil seals, O-rings and packings. in use. However, in general, acrylic rubber has a problem of embrittlement at a low temperature, and further improvement in low temperature characteristics has been desired (see Non-Patent Document 1).

  On the other hand, in order to improve low-temperature properties, acrylic rubber has also been developed with the addition of acrylic ester having a low glass transition temperature as a monomer component, but the effects of deteriorating various physical properties such as oil resistance and mechanical strength are ignored. However, further improvement measures are desired (see Non-Patent Document 1).

Furthermore, oil resistance and low temperature characteristics are generally opposite physical properties (see Patent Document 1), and it has been desired to develop an elastomer material that achieves both oil resistance and low temperature characteristics.
International Publication No. 02/064822 Pamphlet Development of automotive polymer materials, CMC Publishing, 1989, p219

  An object of the present invention is to develop a composition comprising an acrylic rubber and a polyorganosiloxane-based graft polymer having excellent molding processability, extremely excellent mechanical properties, and having both low temperature characteristics and oil resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found that an acrylic rubber composition comprising (A) an acrylic rubber and (B) a polyorganosiloxane-based graft polymer has low temperature characteristics and oil resistance. In addition, the present inventors have found that it has excellent properties and is excellent in molding processability such as mold releasability and mechanical properties, and has completed the present invention.

That is, this invention is based on the following structures.

The present invention relates to an acrylic elastomer composition comprising (A) an acrylic rubber and (B) a polyorganosiloxane graft polymer.

  A preferred embodiment relates to an acrylic rubber composition comprising (A) 50 to 98% by weight of an acrylic rubber and (B) 50 to 2% by weight of a polyorganosiloxane graft polymer.

  An acrylic rubber composition comprising (A) acrylic rubber and (B) a polyorganosiloxane graft polymer (Claim 1).

  The acrylic rubber composition according to claim 1, comprising (A) 50 to 98% by weight of an acrylic rubber and (B) 50 to 2% by weight of a polyorganosiloxane-based graft polymer.

  The acrylic rubber composition according to claim 1 or 2, wherein the acrylic rubber contains 0.01 to 20% by weight of a crosslinking monomer unit in the whole acrylic rubber (claim 3).

  The cross-linking agent is contained in an amount of 0.005 to 10 parts by weight with respect to a total of 100 parts by weight of the acrylic rubber and the (B) polyorganosiloxane-based graft polymer. The acrylic rubber composition according to claim 4.

  (B) The polyorganosiloxane graft polymer is a polyorganosiloxane graft polymer having a graft component content of 5 to 40% by weight and a polyorganosiloxane content of 95 to 60% by weight. The acrylic rubber composition according to any one of 1 to 4 (claim 5).

  (B) A polyorganosiloxane-based graft polymer having an alkyl methacrylate content of 5 to 99.5% by weight and an alkyl acrylate content of 95 to 0.5% by weight in the entire graft component of the polyorganosiloxane-based graft polymer. The acrylic rubber composition according to any one of claims 1 to 5, which is a coalescence (Claim 6).

  The rubber composition according to any one of claims 1 to 6, wherein the polyorganosiloxane graft polymer (B) is obtained by seed polymerization.

  The rubber composition according to any one of claims 1 to 7, wherein the polyorganosiloxane-based graft polymer (B) is polymerized using a mercapto group-containing compound as a graft crossing agent (claim 8).

  The rubber composition according to any one of claims 1 to 8, wherein the polyorganosiloxane-based graft polymer (B) is polymerized using a polyfunctional monomer (claim 9).

  (A) It contains 0.1 to 10 parts by weight of a lubricant, 0.1 to 100 parts by weight of an inorganic filler, and 0.1 to 100 parts by weight of a thermoplastic resin with respect to 100 parts by weight of acrylic rubber. The acrylic rubber composition according to any one of claims 1 to 9 (claim 10).

  The molded object which consists of an acrylic rubber composition of any one of Claim 1 to 10 (Claim 11).

  An automobile / electric / electronic component comprising the molded article of the acrylic rubber composition according to claim 11 (claim 12).

  The composition comprising the acrylic rubber and the polyorganosiloxane-based graft polymer in the present invention is particularly excellent in oil resistance, low-temperature characteristics, and mechanical characteristics, and therefore can be suitably used for automotive, electrical and electronic parts.

Below, the composition of this invention is demonstrated in detail. The acrylic rubber composition of the present invention is an acrylic rubber composition comprising (A) an acrylic rubber and (B) a polyorganosiloxane graft polymer.

<(A) Acrylic rubber>
The acrylic rubber (A) in the present invention is mainly composed of at least one selected from the group consisting of alkyl acrylates having an alkyl group having 1 to 4 carbon atoms and alkoxyalkyl acrylates having an alkoxyalkyl group having 2 to 8 carbon atoms. Acrylic ester monomer unit, preferably a small amount of an unsaturated monomer having a crosslinkable group such as a hydroxyl group, an epoxy group, a carboxyl group, a reactive halogen group, an amide group or an unsaturated group. A copolymer is used.

  The acrylic ester monomer unit content in the acrylic rubber is not particularly limited as long as it is 50% by weight or more. For example, when a crosslinkable monomer unit is contained as a unit other than the acrylic ester monomer unit, the mechanical strength and compression set are particularly improved by using in combination with a crosslinking agent described later. Can do. As content of a crosslinkable monomer unit, 0.01 to 20 weight% is preferable in the whole acrylic rubber, Furthermore, it is preferable that it is 0.02 to 15 weight%. When the content of the crosslinkable monomer unit is less than 0.01% by weight, the physical properties after crosslinking may not be sufficiently improved. When the content is more than 20% by weight, the crosslink density becomes too high and becomes brittle. In some cases, the physical properties may be lowered.

  Acrylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, polyalkylene glycol acrylate, and other acrylic acid ester monomers; methoxymethyl acrylate, Examples include, but are not limited to, acrylate monomers having an alkylalkoxy group such as methoxyethyl acrylate, ethoxyethyl acrylate, and butoxyethyl acrylate.

  As the crosslinkable monomer, known crosslinkable components can be widely used. For example, a crosslinkable component such as a unit having an active halogen, a unit having an unsaturated double bond, or a unit having an epoxy group. And a monomer copolymerizable with the acrylate monomer.

  More specifically, the monomer having active halogen includes (1) 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, vinyl benzyl chloride, (2) vinyl chloroacetate, allyl chloro. Addition reaction product of glycidyl compound such as acetate, (3) glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ester and monochloroacetic acid, or (4) alkenyl ester of α- or β-halogen substituted aliphatic monocarboxylic acid, (meta ) Halogen-containing monomers such as haloalkyl esters, haloalkylalkenyl esters, haloalkylalkenyl ketones or haloacetoxyalkyl esters of acrylic acid, and haloacetyl group-containing unsaturated compounds.

  Examples of the unit having an unsaturated double bond include conjugated diene monomers such as butadiene, isoprene and cyclopentadiene, unsaturated norbornene monomers such as ethylidene norbornene and vinylidene norbornene, and 2-butenyl (meth) acrylate. And alkenyl (meth) acrylates such as 3-methyl-2-butenyl (meth) acrylate, 3-methyl-2-pentyl (meth) acrylate, and 3-methyl-2-hexenyl (meth) acrylate. Examples of the unit having an epoxy group include allyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate.

  The acrylic rubber in the present invention contains a monomer unit that can be copolymerized with an acrylate monomer in addition to the above monomer units, as long as the effects of the present invention are not substantially inhibited. Also good. Specific examples thereof include vinyl monomers such as ethylene, propylene, acrylonitrile, vinyl acetate, styrene, α-methylstyrene, acrylamide, vinyl chloride, acrylic acid, methyl methacrylate, ethyl methacrylate, methacrylonitrile, and vinylidene chloride. Body, etc. The method for producing the acrylic rubber is not particularly limited and may be polymerized by a known method.

<(B) Polyorganosiloxane-based graft polymer>
The polyorganosiloxane graft polymer (B) in the present invention will be described. The polyorganosiloxane-based graft polymer is blended and dispersed in acrylic rubber which is the matrix resin of the present composition. Even when the temperature is not higher than the embrittlement temperature of the acrylic resin alone, which is a matrix resin, breakage due to embrittlement does not occur, and favorable low-temperature characteristics can be expressed. In addition, low temperature properties such as low temperature elastic recovery characteristics (TR characteristics) and low temperature torsion characteristics (Geman torsion characteristics) can be improved, and low temperature elastic recovery temperature and tensile permanent strain characteristics at low temperatures can be achieved. It is possible to improve. Furthermore, various properties that can be inherently exhibited by polyorganosiloxane (molding property such as mold releasability, slidability, flame retardancy, etc.) can be imparted.

  The composition of the polyorganosiloxane-based graft polymer (B) is not particularly limited, but 0 to 10% by weight of the monomer (d2) is polymerized in the presence of 60 to 95% by weight of the polyorganosiloxane (d1). Furthermore, a copolymer obtained by polymerizing 5 to 40% by weight of the vinyl monomer (d3) (100% by weight in total of (d1), (d2) and (d3)) is preferable. The monomer (d2) is composed of 50 to 100% by weight of a polyfunctional monomer (x) containing two or more polymerizable unsaturated bonds in the molecule, and other copolymerizable vinyl monomers ( y) A monomer composed of 0 to 50% by weight.

  Furthermore, the content of the graft component combining the monomer (d2) and the vinyl monomer (d3) is 5 to 40% by weight, the polyorganosiloxane content is 95 to 60% by weight, particularly 95 to 75% by weight. % Is preferred.

  The polyorganosiloxane (d1) used in the present invention is not particularly limited in its production method, and can be obtained by ordinary emulsion polymerization. However, seed polymerization is also used because of the advantage that the particle size distribution in the latex state can be narrowed. Can do. The seed polymer used for seed polymerization is not limited to rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene and butadiene-acrylonitrile rubber, but butyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, etc. There is no problem with the polymer. A chain transfer agent may be used for the polymerization of the seed polymer.

  In the production of polyorganosiloxane, the particle size distribution can be controlled to be small by using seeds, and when used in the composition of the present invention, the physical properties of the molded article, for example, low temperature characteristics and tensile characteristics can be improved. preferable. In the polymerization of the polyorganosiloxane (d1), a graft crossing agent and, if necessary, a crosslinking agent can be used. The amount of the seed polymer used in the seed polymerization is preferably 0.1 to 10% by weight based on the organosiloxane used.

The organosiloxane specifically used is represented by the general formula R _m SiO _{(4-m) / 2} (wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and m is an integer of 0 to 3). And has a linear, branched or cyclic structure, and an organosiloxane having a cyclic structure is preferred from the viewpoint of availability and cost. Examples of the substituted or unsubstituted monovalent hydrocarbon group of the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. it can.

  Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenylcyclotrisiloxane. In addition to cyclic compounds such as these, linear or branched organosiloxanes can be mentioned. At least one of these organosiloxanes can be used.

  Examples of the graft crossing agent that can be used in the present invention include p-vinylphenylmethyldimethoxysilane, p-vinylphenylethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzo Iroxy) propylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane , (Meth) acryloxypropylmethyldimethoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane, etc. And the like.

  The proportion of the grafting agent used is preferably 0.1 to 10% by weight based on the organosiloxane. If the amount of the grafting agent used is more than 10% by weight, the impact resistance of the final molded product may be lowered. If the amount of the grafting agent used is less than 0.1% by weight, a large lump is formed during solidification and heat treatment. A decent resin powder may not be obtained or the moldability of the final molded product may be reduced.

  In the synthesis of the polyorganosiloxane (d1) used in the present invention, a crosslinking agent can be added if necessary. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, tetraethoxysilane, 1,3bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,3-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [1- (dimethoxymethylsilyl) ethyl] benzene 1- [1- (dimethoxymethylsilyl) ethyl] -3- [2- (dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -4- [2-dimethoxymethylsilyl] And tetrafunctional cross-linking agents such as ethyl] benzene. At least one kind of these crosslinking agents can be used.

  The addition amount of the crosslinking agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organosiloxane. When the addition amount of the crosslinking agent is more than 10 parts by weight, the flexibility of the polyorganosiloxane (d1) is impaired, so that the impact resistance at low temperature of the rubber material obtained from the acrylic rubber composition may be lowered.

  The average particle diameter of the latex polyorganosiloxane (d1) is preferably 0.008 to 0.6 μm, and more preferably 0.08 to 0.4 μm. It is difficult to stably obtain those having an average particle diameter of less than 0.008 μm, and if it exceeds 0.6 μm, the impact resistance of the final molded product may be deteriorated.

  Specific examples of the polyfunctional monomer (x) include allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, divinylbenzene and the like. At least one of these can be used.

  Specific examples of the copolymerizable monomer (y) include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, and acrylic acid. Examples thereof include (meth) acrylic acid ester monomers such as ethyl, methyl methacrylate, ethyl methacrylate and butyl methacrylate, and vinyl monomers containing an epoxy group in the molecule such as glycidyl methacrylate. At least one of these can be used.

  The monomer (d2) composed of the monomer (y) copolymerizable with the polyfunctional monomer (x), particularly, contains the polysiloxane (d1) in the polyorganosiloxane-based graft polymer (B). When the amount is as high as 75% by weight or more, the graft polymer resin can be powdered.

  Further, as the graft crossing agent used for the component (d1), generally, a graft crossing agent that is insufficient in grafting efficiency at the time of graft polymerization of the vinyl monomer (d3) described below, specifically, for example, In the case of using a mercapto group-containing compound such as mercaptopropylmethyldimethoxysilane described in JP-A-60-252613, the use of the component (d2) contributes to the grafting of the vinyl monomer (d3). It is possible to greatly reduce the polymer component (free polymer component) that does not, and more efficient graft polymerization. Due to such effects, it is possible to effectively improve the physical properties of the molded article obtained from the rubber composition according to the present invention, for example, low temperature characteristics and tensile characteristics.

  As the monomer (d2), the polyfunctional monomer (x) is preferably 50 to 100% by weight, more preferably 90 to 100% by weight, and the copolymerizable monomer (y) is preferably 0 to 100% by weight. It is preferably 50% by weight, more preferably 0 to 10% by weight.

  The amount of the monomer (d2) used is preferably 0 to 10% by weight, more preferably 0.5 to 10% by weight in the polyorganosiloxane graft polymer (B). The more the amount used, the better the state of the powder, but if it exceeds 10% by weight, the low-temperature properties (especially impact resistance) of the final molded product may deteriorate.

  The vinyl monomer (d3) used in the present invention ensures compatibility between the polyorganosiloxane graft polymer (B) and the acrylic rubber (A), and makes the polyorganosiloxane graft polymer (B) uniform. It is a component used to disperse in.

  Specific examples of the monomer include the same monomers as the other copolymerizable monomer (y). Specifically, aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylic acid (Meth) acrylic acid ester monomers such as methyl, ethyl methacrylate and butyl methacrylate, vinyl monomers containing an epoxy group in the molecule such as glycidyl methacrylate, ethylenic unsaturation such as methacrylic acid and acrylic acid Examples thereof include carboxylic acids, and at least one of them can be used.

  Here, the vinyl monomer (d3) is selected so that the solubility parameter value of the polymer obtained by polymerizing the vinyl monomer (d3) is close to the solubility parameter value of the acrylic rubber as the matrix resin. It is preferable to do. By selecting the solubility parameter of the polymer obtained by polymerizing the vinyl monomer (d3) to be close to the solubility parameter of the acrylic rubber, the polyorganosiloxane graft in the acrylic rubber The dispersed state of the copolymer is excellent, and the low temperature characteristics of the molded product can be greatly improved.

  On the other hand, if the solubility parameter value is too large, the dispersion state of the polyorganosiloxane graft polymer is not excellent, and the polyorganosiloxane graft polymer once dispersed may be re-aggregated. It becomes difficult to impart excellent low temperature characteristics by the graft polymer.

  When (meth) acrylic acid ester monomers are used as the component (d3), the alkyl methacrylate content is 5 to 99.5% by weight, further 5 to 97% by weight, alkyl acrylate. The content is preferably 95 to 0.5% by weight, more preferably 95 to 3% by weight. When the alkyl methacrylate content is more than 99.5% by weight, the heat resistance may decrease due to thermal decomposability. Moreover, when heat resistance is requested | required, it is preferable to contain 0.5 to 10 weight% of methacrylic acid or acrylic acid in the whole graft component of a polyorganosiloxane type graft polymer.

  Specific examples of the radical initiator used in the production of the polyorganosiloxane (d1) of the present invention include organic peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, and t-butyl peroxyisopropyl carbonate. And inorganic peroxides such as potassium persulfate and ammonium persulfate, and azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile. Redox such as ferrous sulfate-sodium formaldehydesulfoxylate-ethylenediaminetetraacetic acid 2Na salt, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate When carried out in the system, the polymerization is completed even at a low polymerization temperature.

  The method for separating the polymer from the polyorganosiloxane graft copolymer (B) latex obtained by emulsion polymerization is not particularly limited. For example, a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate is added to the latex. Examples of the method include coagulation, separation, water washing, dehydration, and drying of the latex. A spray drying method can also be used.

  About content of an acrylic rubber (A) and a polyorganosiloxane type graft polymer (B), acrylic rubber (A) is 50 to 98 weight% in the whole acrylic rubber composition, polyorganosiloxane type graft polymer (B ) Is 50 to 2% by weight. If the content of the polyorganosiloxane-based graft polymer (B) is more than 50% by weight, the oil resistance may be lowered. If the content is less than 2% by weight, the low-temperature characteristics may be insufficiently improved.

<Crosslinking agent>
The cross-linking agent in the present invention is a component used to cross-link from the cross-linkable monomer unit of the acrylic rubber (A) as a base point to develop better rubber elasticity.

  The cross-linking agent can be efficiently cross-linked by properly using the cross-linking unit of the acrylic rubber, and a cross-linked rubber having excellent compression set can be obtained. In the present invention, a widely known crosslinking agent can be used. For example, when the crosslinking unit of the acrylic rubber has an active halogen, polyamine carbamates, organic carboxylic acid ammonium salts, organic carboxylic acid alkali metal salts, sulfur When the compound has an epoxy group, polyamine carbamates, organic carboxylic acid ammonium salts, dithiocarbamates, organic carboxylic acid alkali metal salts, sulfur compounds, and in the case of units having an unsaturated double bond, sulfur or organic Although a peroxide etc. can be used conveniently, it is not necessarily limited to these.

The addition amount of the crosslinking agent in the present invention is preferably 0.005 to 10 parts by weight with respect to 100 parts by weight of the total of the acrylic rubber and the polyorganosiloxane graft polymer (B), and more preferably 0.1 to 5 parts by weight. It is preferable that it is a weight part. If the amount added is less than 0.005 parts by weight, crosslinking may not proceed sufficiently and the effect of improving physical properties may not be exhibited. If the amount added is more than 10 parts by weight, physical properties may be lowered due to the influence of the remaining crosslinking agent component. There is.
<Composition>
In the acrylic rubber composition of the present invention, a lubricant, an inorganic filler, and a thermoplastic resin can be blended. With respect to the blending amount, (A) 0.1 to 10 parts by weight of a lubricant, 0.1 to 100 parts by weight of an inorganic filler, and 0.1 to 100 parts by weight of a thermoplastic resin are preferable with respect to 100 parts by weight of an acrylic rubber. It can be illustrated as

  Examples of the lubricant include fatty acids such as stearic acid and palmitic acid, fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate and sodium palmitate, polyethylene wax, polypropylene wax, and montanic acid wax. Waxes, low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene, polyorganosiloxanes such as dimethylpolysiloxane, octadecylamine, alkyl phosphates, fatty acid esters, amide-based lubricants such as ethylenebisstearylamide, 4-fluoride Fluorine resin powder such as ethylene resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, silica, etc. are mentioned, but it is not limited to these.These may be used alone or in combination of two or more. Of these, stearic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearyl amide are preferable from the viewpoint of low friction and processability on the resin surface.

  Examples of inorganic fillers include titanium oxide, zinc sulfide, zinc oxide, carbon black, calcium carbonate, calcium silicate, clay, kaolin, silica, mica powder, alumina, glass fiber, metal fiber, california titanate, asbestos. , Wollastonite, mica, talc, glass flake, milled fiber, metal powder, and the like, but are not limited thereto. These may be used alone or in combination. Among these, carbon black and titanium oxide are preferable from the viewpoint of high elastic modulus and silica and weather resistance and pigment.

  Examples of the thermoplastic resin include polyvinyl chloride resin, polyethylene resin, polypropylene resin, cyclic olefin copolymer resin, polymethyl methacrylate resin, polystyrene resin, polyphenylene ether resin, polycarbonate resin, polyester resin, Examples thereof include polyamide resins, polyacetal resins, polyphenylene sulfide resins, polysulfone resins, polyimide resins, polyetherimide resins, polyetherketone resins, polyetheretherketone resins, polyamideimide resins, and imidized polymethylmethacrylate resins. These may be used alone or in combination of two or more.

  The composition of the present invention further includes stabilizers (anti-aging agents, light stabilizers, UV absorbers, etc.), flexibility imparting agents, flame retardants, mold release agents, antistatic agents, antibacterial agents, depending on the required properties A mold agent or the like may be added. These additives may be appropriately selected and used according to the required physical properties, workability, and the like.

  Examples of stabilizers (anti-aging agent, light stabilizer, ultraviolet absorber, etc.) include, but are not limited to, the following compounds.

  Anti-aging agents include phenyl α-naphthylamine (PAN), octyl diphenylamine, N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-di-β-naphthyl-p-phenylenediamine ( DNPD), N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine (IPPN), N, N′-diallyl-p -Phenylenediamine, phenothiazine derivative, diallyl-p-phenylenediamine mixture, alkylated phenylenediamine, 4,4'-α, α-dimethylbenzyldiphenylamine, p, p-toluenesulfonylaminodiphenylamine, N-phenyl-N '-( 3-methacryloyloxy-2-hydropropyl) -p-pheny Diamine, diallylphenylenediamine mixture, diallyl-p-phenylenediamine mixture, N- (1-methylheptyl) -phenyl-p-phenylenediamine, amine-based antioxidants such as diphenylamine derivatives, 2-mercaptobenzimidazole (MBI) ) Imidazole anti-aging agents, phenolic anti-aging agents such as 2,6-di-t-butyl-4-methylphenol, phosphate anti-aging agents such as nickel diethyl-dithiocarbamate, triphenyl phosphite Secondary anti-aging agents such as

  Examples of light stabilizers and ultraviolet absorbers include 4-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, ethyl-2-cyano-3,3′-diphenyl. Acrylate, 2-ethylhexyl-2-diano-3,3′-diphenyl acrylate, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone-2-hydroxy-4-octoxybenzophenone, monoglycol salicy Rate, oxalic acid amide, 2,2 ′, 4,4′-tetrahydroxybenzophenone and the like. These stabilizers may be used alone or in combination of two or more.

  Examples of the flexibility-imparting agent include plasticizers, softeners, oligomers, oils (animal oil, vegetable oil, etc.) usually used in thermoplastic resins and rubbers, petroleum fractions (kerosene, light oil, heavy oil, naphtha, etc.). However, it is preferable to use those having excellent affinity with the acrylic rubber (A) and the polyorganosiloxane graft polymer (B). Among these, low-volatility plasticizers with low heat loss are adipic acid derivatives, phthalic acid derivatives, glutaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, polyester plasticizers, glycerin derivatives, epoxy derivatives polyester polymerized plastics. An agent, a polyether polymerization type plasticizer and the like are preferably used.

  Examples of the softener include process oils such as petroleum process oils such as paraffinic oils, naphthenic process oils, and aromatic process oils.

  Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, and phthalic acid. Phthalic acid derivatives such as diisononyl, ditridecyl phthalate, octyl decyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; tetrahydrophthal such as di- (2-ethylhexyl) tetrahydrophthalic acid Acid derivatives: dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, dioctyl adipate, isononyl adipate, diisodecyl adipate, dibutyl diglycol adipate, etc. Adipic acid derivatives; azelaic acid derivatives such as di-2-ethylhexyl azelate; sebacic acid derivatives such as dibutyl sebacate; dodecanedioic acid derivatives; maleic acid derivatives such as dibutyl maleate and di-2-ethylhexyl maleate; fumaric acid Fumaric acid derivatives such as dibutyl; p-oxybenzoic acid derivatives such as 2-ethylhexyl p-oxybenzoate; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitic acid; pyromellitic acid derivatives; citric acid derivatives such as acetyltributyl citrate Itaconic acid derivative; oleic acid derivative; ricinoleic acid derivative; stearic acid derivative; other fatty acid derivative; sulfonic acid derivative; phosphoric acid derivative; glutaric acid derivative; dibasic acid such as adipic acid, azelaic acid, phthalic acid and glycol Polyester plasticizers that are polymers with monohydric alcohol, etc., glycol derivatives, glycerin derivatives, paraffin derivatives such as chlorinated paraffins, epoxy derivatives polyester polymerized plasticizers, polyether polymerized plasticizers, ethylene carbonate, propylene Examples thereof include carbonate derivatives such as carbonate, benzenesulfonic acid derivatives such as N-butylbenzeneamide, and the like, but are not limited to these, such as those widely marketed as plasticizers for rubber or thermoplastic resins. Various plasticizers can be used.

  Commercially available plasticizers include Thiocol TP (manufactured by Morton), Adekasizer O-130P, C-79, UL-100, P-200, RS-735 (Asahi Denka Kogyo Co., Ltd.), Sunsosizer N-400 (manufactured by Shin Nippon Rika Co., Ltd.), BM-4 (manufactured by Daihachi Chemical Industry Co., Ltd.), EHPB (manufactured by Ueno Pharmaceutical Co., Ltd.), UP-1000 (manufactured by Toagosei Co., Ltd.), etc. Can be given.

  Examples of the oil include vegetable oils such as castor oil, cottonseed oil, sesame oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, tall oil, sesame oil, and camellia oil.

  Examples of other flexibility imparting agents include polybutene oil, spindle oil, machine oil, tricresyl phosphate, and the like.

  Examples of the agent include process oils such as petroleum process oils such as paraffinic oils, naphthenic process oils, and aromatic process oils.

  Examples of the flame retardant include, but are not limited to, triphenyl phosphate, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, and antimony trioxide. These flame retardants may be used alone or in combination of two or more.

  In order to improve the compatibility between the acrylic rubber (A) and the polyorganosiloxane-based graft polymer (B), various graft polymers and block polymers may be added as a compatibilizing agent.

  Examples of the compatibilizer include the Kraton series (manufactured by Shell Japan Co., Ltd.), the Tuftec series (manufactured by Asahi Kasei Kogyo Co., Ltd.), Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), and Epofriend (manufactured by Daicel Chemical Industries, Ltd.). ), Septon (manufactured by Kuraray Co., Ltd.), Nofaloy (manufactured by Nippon Oil & Fats Co., Ltd.), Lexpearl (manufactured by Nippon Polyolefin Co., Ltd.), Bond First (manufactured by Sumitomo Chemical Co., Ltd.), Bondine (Sumitomo Chemical Industries ( Co., Ltd.), Admer (Mitsui Chemicals Co., Ltd.), Umex (Sanyo Kasei Kogyo Co., Ltd.), VMX (Mitsubishi Chemical Co., Ltd.), Modiper (Nippon Yushi Co., Ltd.), Staphyroid (Takeda) Examples include commercial products such as Yakuhin Kogyo Co., Ltd. and Reeta (Toagosei Co., Ltd.). These can be appropriately selected and used in accordance with the combination of the polyorganosiloxane graft polymer (B) used to supplement the physical properties of the acrylic elastomer (A).

  The acrylic rubber composition in the present invention is easily produced by kneading a predetermined amount of each component in a mixer such as a Banbury mixer, a kneader, an intermixer, a two-roll roll, or a plast mill used for general rubber kneading. Is possible.

  The acrylic rubber composition thus obtained is molded into a shape according to the molding purpose by, for example, a molding method such as injection molding or hot press molding, and vulcanized as necessary to form a molded product. As a vulcanization temperature, a temperature of 120 ° C. or higher is usually suitable, and preferably 140 to 200 ° C. At this temperature, vulcanization is performed for about 1 to 60 minutes. Further, if necessary, post-vulcanization can be performed at a temperature of about 120 to 200 ° C. for about 1 to 48 hours to improve physical properties.

  The acrylic rubber composition of the present invention can be used as a molded product. Examples of the molding include arbitrary molding methods such as extrusion molding, compression molding, blow molding, calendar molding, vacuum molding, foam molding, and injection molding.

  The rubber material obtained from the present invention can be widely used mainly in applications such as gaskets, packings, sealing materials, vibration proofing, waterproofing, and exercise equipment. As these uses, for example, it is suitably used for automobiles, electricity, electronics, architecture, sporting goods, particularly automobiles, electricity, and electronic parts.

 For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts.

 As electrical and electronic parts, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like.

 In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like.

 In the sports field, it can be used for all-weather pavement materials, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. as ball for ball games.

 In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like.

 In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

Next, the composition of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
<Test method>
(Tensile properties (mechanical strength))
According to the method described in JIS K7113, measurement was performed using an autograph AG-10TB type manufactured by Shimadzu Corporation. The measurement was performed at n = 3, and the average values of strength (MPa) and elongation (%) when the test piece broke were adopted. A test piece having a shape of 2 (1/3) shape and a thickness of about 2 mm was used. The test was conducted at 23 ° C. and a test speed of 500 mm / min. In principle, the test piece was conditioned at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 48 hours or more before the test.

(Compression set)
In accordance with JIS K6301, the cylindrical formed body was held at 150 ° C. for 70 hours under the condition of a compression rate of 25%, and left at room temperature for 30 minutes. Then, the thickness of the molded body was measured, and the strain residual degree was calculated. It means that all of the distortion is recovered at a compression set of 0%, and no distortion is recovered at 100% of the compression set.

(Oil resistance)
In accordance with ASTM D638, ASTM Oil No. maintained at 150 ° C. The molded product of the composition was immersed in 3 for 72 hours, and the weight change rate (% by weight) was determined.

(Low temperature embrittlement)
In accordance with JIS K7216, a 2 mm thick molded product sheet was cut into 38 × 6 mm, and a low temperature embrittlement temperature measuring device “Standard Model S type (dry ice type)” (manufactured by Toyo Seiki Co., Ltd.) was used. The low temperature embrittlement temperature was measured using a methanol mixture as a refrigerant.

(Low temperature elastic recovery (TR characteristics) evaluation method)
In accordance with JIS K 6261, a predetermined test piece was cut out from a 2 mm thick sheet-like molded body of an acrylic rubber composition produced by a predetermined method, and the low-temperature elastic recovery characteristic (TR characteristic) at an elongation rate of 50% was measured. . Note that TR10 is the temperature at which 10% of the extension is recovered, TR30 is the temperature at which 30% of the displacement is recovered, TR50 is the temperature at which 50% of the displacement is recovered, and TR70 is 70% of the same. This shows the temperature at which the displacement was recovered.

(Releasability evaluation method)
Ease of taking out from the stainless plate after press molding according to a predetermined method was evaluated according to the following criteria. ○: Easy to take out, x: It was necessary to peel off with considerable force.

<Evaluation molded body preparation method, when no inorganic filler is added>
Predetermined amounts of acrylic rubber, polyorganosiloxane-based graft polymer particles, and antioxidant were used under the predetermined conditions (sample amount: 45 g, chamber set temperature: 23) using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.). Kneading was performed at 0 ° C., preheating time: none, screw rotation speed: 100 rpm, blade: roller type R60B2 shaft, chamber capacity: 60CC, mixer: ticker wear-resistant roller mixer R60HT, kneading time: 3 minutes. Further, 1.5 parts by weight of ammonium benzoate as a cross-linking agent was added to 100 parts by weight of acrylic rubber, and kneaded for 7 minutes under predetermined conditions (of which only the rotation speed was changed to 50 rpm). A sample was obtained. The lump sample thus obtained was pressed for 15 minutes under a predetermined condition (press temperature: 170 ° C., press pressure: 5 MPa) using a press machine “NSF-50” (manufactured by Shinto Metal Industry Co., Ltd.). Thereafter, it was press-molded according to 5 MPa and cooled to 30 ° C. to obtain a sheet-like molded body having a thickness of 2 mm. Further, the sheet-like molded body was annealed at 170 ° C. for a predetermined time, and each of the following evaluations was performed using the obtained sheet-like molded body.

<Evaluation molded body preparation method, inorganic filler added>
Predetermined amounts of acrylic rubber, inorganic filler, lubricant, and antioxidant using plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) (sample amount: 45 g, chamber set temperature: 23 ° C., preheating time) : None, Screw rotation speed: 50 rpm, Blade: Roller type R60B 2-axis, Chamber capacity: 60CC, Mixer: Ticker wear-resistant roller mixer R60HT, Kneading time: 5 minutes). Further, polyorganosiloxane-based graft polymer particles were added and kneading was continued for 3 minutes. After the kneading was stopped and the resin temperature was cooled to 60 ° C., 1.5 parts by weight of ammonium benzoate was added as a crosslinking agent to 100 parts by weight of acrylic rubber, and kneaded for 7 minutes under predetermined conditions. A sample of was obtained. The massive sample thus obtained was pressed for 30 minutes at a predetermined condition (press temperature: 170 ° C., press pressure: 5 MPa) using a press machine “NSF-50” (manufactured by Shinto Metal Industry Co., Ltd.). Thereafter, it was press-molded according to 5 MPa and cooled to 30 ° C. to obtain a sheet-like molded body having a thickness of 2 mm. Further, the sheet-like molded body was annealed at 170 ° C. for a predetermined time, and each of the following evaluations was performed using the obtained sheet-like molded body.

<Production Example of Polyorganosiloxane Graft Polymer>
(Production Example 1) [Synthesis of NM006]
In a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 400 parts by weight of water and 12 parts by weight (solid content) of 10% sodium dodecylbenzenesulfonate aqueous solution After mixing, the temperature was raised to 50 ° C., and after the liquid temperature reached 50 ° C., nitrogen substitution was performed. Thereafter, 10 parts by weight of BA and 3 parts by weight of t-dodecyl mercaptan were added. After 30 minutes, 0.01 parts by weight of paramentane hydroperoxide (solid content), 0.3 parts of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of disodium ethylenediaminetetraacetate (EDTA), ferrous sulfate 0.0025 part by weight was added and stirred for 1 hour. A mixed solution of 90 parts by weight of BA, 27 parts by weight of t-dodecyl mercaptan, and 0.09 parts by weight of paramentane hydroperoxide (solid content) was continuously added over 3 hours. Thereafter, post-polymerization was performed for 2 hours to obtain a latex containing a seed polymer.

  Next, 2 parts by weight (solid content) of the above seed polymer was charged into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port, and a thermometer. Subsequently, 300 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.5 parts by weight of 5% aqueous sodium dodecylbenzenesulfonate (solid content), 98 parts by weight of octamethylcyclotetrasiloxane, mercapto A mixture of 2 parts of propylmethyldimethoxysilane was stirred with a homomixer at 7000 rpm for 5 minutes to prepare a polyorganosiloxane-forming component emulsion, which was added all at once.

  Next, 1 part by weight (solid content) of a 10% aqueous solution of dodecylbenzenesulfonic acid was added, and the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 10 hours, then cooled to 25 ° C. and left for 20 hours. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer, 240 parts by weight of pure water (including the amount brought in from the latex containing organosiloxane particles), and 80 parts by weight (solid content) of the polyorganosiloxane particles were charged, and the temperature was raised to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.2 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of ethylenediaminetetraacetic acid (EDTA), and 0.0025 parts by weight of ferrous sulfate were added, and then allyl methacrylate A mixture of 1 part by weight and cumene hydroperoxide 0.01 part by weight (solid content) was added all at once, and stirring was continued at 40 ° C. for 1 hour. Thereafter, a mixture of 14 parts by weight of MMA, 6 parts by weight of BA, and 0.04 part by weight of cumene hydroperoxide (solid content) was added dropwise over 1.5 hours. After the addition was completed, stirring was continued for another hour. A latex of a polyorganosiloxane graft polymer was obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts by weight (solid content) of 25% aqueous calcium chloride solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 85 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft polymer powder.

(Production Example 2) [Synthesis of BTM002]
Next, 2 parts by weight (solid content) of the seed polymer prepared in Production Example 1 was charged into a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen blowing port, a monomer addition port, and a thermometer. Subsequently, 300 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.5 parts by weight of 5% aqueous sodium dodecylbenzenesulfonate (solid content), 98 parts by weight of octamethylcyclotetrasiloxane, methacrylate A mixture of 2 parts by weight of roxicypropylmethyldimethoxysilane was stirred with a homomixer at 7000 rpm for 5 minutes to prepare an emulsion of a polyorganosiloxane-forming component, which was added all at once.

  Next, 1 part by weight (solid content) of a 10% aqueous solution of dodecylbenzenesulfonic acid was added, and the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 10 hours, then cooled to 25 ° C. and left for 20 hours. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer, 240 parts by weight of pure water (including the amount brought in from the latex containing organosiloxane particles), and 80 parts by weight (solid content) of the polyorganosiloxane particles were charged, and the temperature was raised to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.2 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of disodium ethylenediaminetetraacetate (EDTA), and 0.0025 parts by weight of ferrous sulfate are added, and then 14 parts by weight of MMA. , 6 parts by weight of BA and 0.04 part by weight of cumene hydroperoxide (solid content) were added dropwise over 1.5 hours, and after completion of addition, the mixture was further stirred for 1 hour to thereby polyorganosiloxane-based graft A polymer latex was obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts by weight (solid content) of 25% aqueous calcium chloride solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 85 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft polymer powder.

(Production Example 3) [Synthesis of BTM048]
2 parts by weight (solid content) of the seed polymer prepared in Production Example 1 was charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. Subsequently, 300 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.5 parts by weight of 5% aqueous sodium dodecylbenzenesulfonate (solid content), 98 parts by weight of octamethylcyclotetrasiloxane, methacrylate A mixture of 3 parts by weight of roxicypropylmethyldimethoxysilane was stirred with a homomixer at 7000 rpm for 5 minutes to prepare an emulsion of a polyorganosiloxane-forming component, which was added all at once.

  Next, 1 part by weight (solid content) of a 10% aqueous solution of dodecylbenzenesulfonic acid was added, and the temperature was raised to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 10 hours, then cooled to 25 ° C. and left for 20 hours. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer, 240 parts by weight of pure water (including the amount brought in from the latex containing organosiloxane particles), and 80 parts by weight (solid content) of the polyorganosiloxane particles were charged, and the temperature was raised to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.2 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of disodium ethylenediaminetetraacetate (EDTA), and 0.0025 parts by weight of ferrous sulfate are added, and then 14 parts by weight of MMA. , 6 parts by weight of EA, and 0.04 part by weight of cumene hydroperoxide (solid content) were added dropwise over 1.5 hours. After completion of the addition, the mixture was further stirred for 1 hour to obtain a polyorganosiloxane graft. A polymer latex was obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts by weight (solid content) of 25% aqueous calcium chloride solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 85 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft polymer powder.

(Production Example 4) [Synthesis of TAM020]
2 parts by weight (solid content) of the seed polymer prepared in Production Example 1 was charged into a 5-neck flask equipped with a stirrer, reflux cooling water, nitrogen inlet, monomer addition port, and thermometer. Thereafter, 300 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.49 parts by weight of 15% aqueous sodium dodecylbenzenesulfonate (solid content), 98 parts by weight of octamethylcyclotetrasiloxane, mercapto A mixture composed of 2.94 parts by weight of propylmethyldimethoxysilane was stirred with a homomixer at 7000 rpm for 5 minutes to prepare an emulsion of a polyorganosiloxane-forming component and added all at once.

  Next, 1.5 parts by weight (solid content) of a 10% aqueous dodecylbenzenesulfonic acid solution was added, and then the system was heated to 80 ° C. under a nitrogen stream while stirring the system. After reaching 80 ° C., stirring was continued at 80 ° C. for 9 hours, then cooled to 25 ° C. and allowed to stand for 18 hours. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 340 parts by weight of pure water (including the amount brought in from the latex containing organosiloxane particles), and The polyorganosiloxane particles 80 parts by weight (solid content) were charged, and the system was heated to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.39 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.0048 parts by weight of disodium ethylenediaminetetraacetate (EDTA) and 0.0012 parts by weight of ferrous sulfate were added, and then allyl methacrylate A mixture of 3 parts by weight and cumene hydroperoxide 0.16 part by weight (solid content) was added, and stirring was continued at 40 ° C. for 1 hour. Thereafter, a mixture of 15 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate and 0.08 part by weight of cumene hydroperoxide (solid content) was added dropwise over 1 hour, and stirring was continued for 1 hour after the addition was completed. As a result, a latex of a polyorganosiloxane graft polymer was obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15%, and then 4 parts by weight (solid content) of 25% aqueous calcium chloride solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 75 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane graft polymer powder.

(Production Example 5) [Synthesis of TAM026]
In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 340 parts by weight of pure water (including the amount brought in from latex containing organosiloxane particles), and production example 80 parts by weight (solid content) of the polyorganosiloxane particles obtained in 4 were charged, and the system was heated to 40 ° C. under a nitrogen stream while stirring the system. After reaching 40 ° C., 0.39 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.0048 parts by weight of disodium ethylenediaminetetraacetate (EDTA) and 0.0012 parts by weight of ferrous sulfate were added, and then methyl methacrylate. A mixture of 15 parts by weight, 5 parts by weight of ethyl acrylate, and 0.08 part by weight of cumene hydroperoxide (solid content) was added dropwise over 1 hour, and after completion of addition, polyorganosiloxane was further continued for 1 hour. A latex of a graft polymer was obtained.

  Subsequently, after the latex was diluted with pure water to a solid content concentration of 15%, 4 parts by weight of 25% calcium chloride aqueous solution (solid content) was added and coagulated to form a large mass. After dehydration and drying, a polyorganosiloxane graft polymer was obtained, but it became a large lump and did not become a good powder.

(Example 1)
100 parts by weight of acrylic rubber (manufactured by Nippon Zeon, trade name AR42W), 35 parts by weight of the polyorganosiloxane-based graft polymer particles (NM006) obtained in Production Example 1, 1 part by weight of antioxidant (manufactured by Ciba Geigy, trade name Irga) Nox 1010) and 1.5 parts by weight of ammonium benzoate were obtained in accordance with a predetermined method using Plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) to obtain a lump sample. The lump sample thus obtained was press-molded according to a predetermined method to obtain a sheet-like molded body having a thickness of 2 mm. Further, the sheet-like molded body was annealed at 170 ° C. for 4 hours, and the obtained sheet-like molded body was used to measure the tensile properties, the low temperature embrittlement temperature, and the oil resistance. Moreover, the mold release property at the time of press molding was also evaluated. The results are shown in Table 1.

(Example 2)
In Example 1, the polyorganosiloxane-based graft polymer described in Production Example 2 (BTM002) was used, and thereafter, a sheet-like molded product for evaluation was prepared in the same manner, and each characteristic was evaluated. The results are shown in Table 1.

(Comparative Example 1)
In the method described in Example 1, a polyorganosiloxane-based graft polymer was not added, and a sheet-like molded product was prepared by the same method, and each characteristic was evaluated. The results are shown in Table 1.

(Example 3)
100 parts by weight of acrylic rubber (made by Nippon Zeon, trade name AR31), 45 parts by weight of the polyorganosiloxane-based graft polymer particles (BTM048) obtained in Production Example 3, 1 part by weight of antioxidant (made by Ciba Geigy, trade name Irga) Nox 1010) and 1.5 parts by weight of ammonium benzoate were obtained in accordance with a predetermined method using Plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.) to obtain a lump sample. The lump sample thus obtained was press-molded according to a predetermined method to obtain a sheet-like molded body having a thickness of 2 mm. Furthermore, the sheet-like molded body was annealed at 170 ° C. for 8 hours, and the obtained sheet-like molded body was used to measure tensile properties, low temperature embrittlement temperature, low temperature elastic recovery properties (TR characteristics), and oil resistance. . Moreover, the mold release property at the time of press molding was also evaluated. The results are shown in Table 2.

(Comparative Example 2)
In the method described in Example 3, a polyorganosiloxane-based graft polymer was not added, and a sheet-like molded product was prepared in the same manner, and each characteristic was evaluated. The results are shown in Table 2.

Example 4
100 parts by weight of acrylic rubber (manufactured by Nippon Zeon, trade name AR31) and 45 parts by weight of the polyorganosiloxane-based graft polymer particles (TAM020) obtained in Production Example 4, 1 part by weight of antioxidant (made by calcium Shiraishi, trade name) Nowguard 445), 50 parts by weight of carbon black (Seast 3, manufactured by Tokai Carbon) as an inorganic filler, 1 part by weight of stearic acid as a lubricant, 1 part by weight of GREC G8205 (manufactured by Dainippon Ink Co., Ltd.), and ammonium benzoate According to a predetermined method, 1.5 parts by weight of a lumped sample was obtained using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.). The lump sample thus obtained was press-molded according to a predetermined method to obtain a sheet-like molded body having a thickness of 2 mm. Furthermore, the sheet-like molded body was annealed at 170 ° C. for 8 hours, and the obtained sheet-like molded body was used to measure tensile properties, low temperature embrittlement temperature, low temperature elastic recovery properties (TR characteristics), and oil resistance. . The results are shown in Table 3.

(Comparative Example 3)
100 parts by weight of acrylic rubber (manufactured by Nippon Zeon, trade name AR31) and 45 parts by weight of the polyorganosiloxane graft polymer (TAM025) obtained in Production Example 5, 1 part by weight of antioxidant (made by calcium Shiraishi, trade name Noward) 445), carbon black (Seast 3, manufactured by Tokai Carbon Co., Ltd.) as an inorganic filler, stearic acid 1 part by weight as a lubricant, Grec G8205 (Dainippon Ink Co., Ltd.) 1 part by weight, and ammonium benzoate 1 When 5 parts by weight were kneaded according to a predetermined method using a plast mill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.), it was not possible to knead well and a good molded product could not be obtained. It was.

(Comparative Example 4)
In the method described in Example 4, a polyorganosiloxane-based graft polymer was not added, and a sheet-like molded product was prepared in the same manner, and each characteristic was evaluated. The results are shown in Table 3.

  As is apparent from the results of Table 1 (Example 1, Example 2, and Comparative Example 1), the low temperature characteristics can be greatly improved without greatly reducing the tensile characteristics and oil resistance. Furthermore, as can be seen from the results in Tables 2 and 3, in addition to the low temperature embrittlement temperature, the low temperature elastic recovery (TR characteristics, tensile permanent strain at low temperature) also includes tensile characteristics, oil resistance, compression set, etc. It is possible to improve without drastically reducing.

Claims (12)

An acrylic rubber composition comprising (A) an acrylic rubber and (B) a polyorganosiloxane-based graft polymer. 2. The acrylic rubber composition according to claim 1, comprising (A) 50 to 98% by weight of acrylic rubber and (B) 50 to 2% by weight of a polyorganosiloxane-based graft polymer. The acrylic rubber composition according to claim 1 or 2, wherein the acrylic rubber contains 0.01 to 20% by weight of a crosslinking monomer unit in the whole acrylic rubber. The cross-linking agent is contained in an amount of 0.005 to 10 parts by weight with respect to a total of 100 parts by weight of the acrylic rubber and the polyorganosiloxane graft polymer (B). The acrylic rubber composition as described. (B) The polyorganosiloxane graft polymer is a polyorganosiloxane graft polymer having a graft component content of 5 to 40% by weight and a polyorganosiloxane content of 95 to 60% by weight. The acrylic rubber composition according to any one of 1 to 4. (B) A polyorganosiloxane-based graft polymer having an alkyl methacrylate content of 5 to 99.5% by weight and an alkyl acrylate content of 95 to 0.5% by weight in the entire graft component of the polyorganosiloxane-based graft polymer. The acrylic rubber composition according to any one of claims 1 to 5, wherein the acrylic rubber composition is a coalescence. The rubber composition according to any one of claims 1 to 6, wherein the polyorganosiloxane graft polymer (B) is obtained by seed polymerization. The rubber composition according to any one of claims 1 to 7, wherein the polyorganosiloxane-based graft polymer (B) is polymerized using a mercapto group-containing compound as a graft crossing agent. 9. The rubber composition according to claim 1, wherein the polyorganosiloxane graft polymer (B) is polymerized using a polyfunctional monomer. (A) It contains 0.1 to 10 parts by weight of a lubricant, 0.1 to 100 parts by weight of an inorganic filler, and 0.1 to 100 parts by weight of a thermoplastic resin with respect to 100 parts by weight of acrylic rubber. The acrylic rubber composition according to any one of claims 1 to 9. The molded object which consists of an acrylic rubber composition of any one of Claim 1 to 10. An automotive / electrical / electronic component comprising a molded article of the acrylic rubber composition according to claim 11.