JPWO2007029732A1 - Acrylic rubber composition, molded body, and parts for automobiles, electrical and electronic - Google Patents

Abstract

The present invention provides an acrylic rubber composition containing a polyorganosiloxane-containing graft copolymer having excellent powder properties, excellent mechanical properties, heat resistance and oil resistance, and having mold releasability during molding processing. To do. (A) Acrylic rubber and (B) an acrylic rubber composition containing a polyorganosiloxane-containing graft copolymer, wherein (B) component is a copolymer of (d1) polyorganosiloxane and a graft component, The graft component ((b-1) + (b-2) + (b-3) = 100%) is (b-1) 50 to 95% by weight of an aromatic vinyl monomer, (b− 2) Acrylic rubber composition, characterized in that it is 50 to 5% by weight of vinyl cyanide monomer, and (b-3) 0 to 30% by weight of vinyl monomer copolymerizable therewith, A molded article comprising the composition, and an automotive part and an electrical / electronic part comprising the molded article.

Description

  The present invention comprises an acrylic rubber composition containing a polyorganosiloxane-containing graft copolymer having excellent powder properties, excellent mechanical properties, heat resistance and oil resistance, and having mold releasability during molding processing, The present invention relates to a molded article made of a composition, and parts for automobiles / electrical / electronics comprising the molded article.

  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, since acrylic rubber is highly adhesive, there is a problem in releasability.

  Conventionally, as a method for improving the releasability, a method of blending a resin with a fatty acid or a metal salt thereof, a lubricant such as a wax or higher alcohol, or a release agent such as silicone oil has been generally used (for example, Non-Patent Document 1). However, lubricants are mainly used for injection molding to reduce friction between pellets and improve the thermal stability of the resin. In order to improve releasability, a large amount of lubricant must be blended. Furthermore, the molded product obtained from the blend has problems such as significant deterioration in mechanical properties, poor appearance due to the generation of decomposition gas when molded at high temperatures, and further the degradation of the mold release effect due to the decomposition of the compounding ingredients. there were. In addition, adding a large amount of lubricant causes a decrease in mechanical properties, so increasing the amount of filler (silica or carbon black) used to maintain mechanical properties exacerbates compression set, an important factor for heat resistance. There was also a problem. Further, when polyethylene wax and silicone oil are added in a large amount, the lubricity at the time of kneading is too high to be kneaded, and conversely, when a small amount is added, there is a problem that sufficient releasability cannot be obtained.

On the other hand, a composition obtained by adding a polyorganosiloxane-containing graft copolymer to acrylic rubber is known. (For example, refer to Patent Document 1). Conventionally, the graft component of such a polyorganosiloxane-containing graft copolymer generally has a composition close to that of the matrix resin from the viewpoint of compatibility and physical properties. The composition of acrylic rubber is most often ethyl acrylate. However, when the graft component of the polyorganosiloxane-containing graft copolymer has the same composition as or close to that of acrylic rubber, good powder cannot be obtained. When the powder characteristics of the polyorganosiloxane-containing graft copolymer are poor, there is a problem that workability is deteriorated when the acrylic rubber composition is produced.
Edited by Japan Rubber Association Rubber Industry Handbook <Fourth Edition> P311-P324, P577-P581 JP-A-2005-146263

  The present invention comprises an acrylic rubber composition containing a polyorganosiloxane-containing graft copolymer having excellent powder properties, excellent mechanical properties, heat resistance and oil resistance, and having mold releasability during molding processing, It aims at providing the molded object which consists of a composition, the components for motor vehicles containing the molded object, and the components for electric / electronics.

  As a result of intensive studies to solve the above problems, the present inventors have found that the graft component (B) polyorganosiloxane-containing graft copolymer having a specific composition is excellent in powder characteristics, and (A) It has been found that the compatibility with acrylic rubber is good. Furthermore, when (A) acrylic rubber is blended with a small amount of (B) a polyorganosiloxane-containing graft copolymer having a specific composition as a graft component, an acrylic rubber composition having both mechanical properties, heat resistance, oil resistance and releasability The present inventors have found that a product can be obtained, and have completed the present invention.

  That is, the first of the present invention is an acrylic rubber composition containing (A) acrylic rubber and (B) a polyorganosiloxane-containing graft copolymer, wherein (B) component is (d1) polyorganosiloxane and graft component. And the graft component ((b-1) + (b-2) + (b-3) = 100% by weight) is (b-1) an aromatic vinyl monomer. 50 to 95% by weight, (b-2) 50 to 5% by weight of vinyl cyanide monomer, and (b-3) 0 to 30% by weight of vinyl monomer copolymerizable therewith. And an acrylic rubber composition.

  A preferred embodiment is characterized in that the amount of the graft crossing agent used in (B) the polyorganosiloxane-containing graft copolymer is 0.01 to 2.0% by weight in 100% by weight of the polyorganosiloxane. And the acrylic rubber composition.

  According to a preferred embodiment, the acrylic rubber according to any one of the above, wherein (B) the polyorganosiloxane-containing graft copolymer comprises 95 to 50% by weight of polyorganosiloxane and 5 to 50% by weight of the graft component. Relates to the composition.

  In a preferred embodiment, the volume average particle diameter of (d1) polyorganosiloxane in (B) polyorganosiloxane-containing graft copolymer is 0.01 μm to 0.6 μm, as described above, It relates to an acrylic rubber composition.

  In a preferred embodiment, the particle size distribution of (d1) polyorganosiloxane in the polyorganosiloxane-containing graft copolymer (B) is 25% or less in terms of CV value (standard deviation / volume average particle size × 100). It is related with the acrylic rubber composition in any one of the above characterized.

  A preferred embodiment relates to the acrylic rubber composition according to any one of the above, wherein (A) the acrylic rubber contains 0.01 to 20% by weight of a crosslinkable monomer unit in the whole acrylic rubber. .

  A preferred embodiment according to any one of the above, wherein (A) 0.1 to 10 parts by weight of a polyorganosiloxane-containing graft copolymer is contained per 100 parts by weight of acrylic rubber. The present invention relates to an acrylic rubber composition.

  A preferred embodiment relates to the acrylic rubber composition according to any one of the above, wherein 0.005 to 10 parts by weight of (C) a vulcanizing agent is contained per 100 parts by weight of (A) acrylic rubber. .

  2nd of this invention is related with the molded object which consists of an acrylic rubber composition in any one of the said.

  3rd of this invention is related with the components for motor vehicles comprised including said molded object, and the components for electric / electronics.

  The polyorganosiloxane-containing graft copolymer in the present invention is excellent in powder characteristics, and the acrylic rubber composition in which the copolymer is blended with acrylic rubber is particularly excellent in mechanical properties, heat resistance, oil resistance and releasability. Since it is excellent, it can be suitably used for automotive parts and electrical / electronic parts.

  Below, the composition of this invention is demonstrated in detail. The polyorganosiloxane-containing graft copolymer in the present invention is excellent in powder characteristics, and an acrylic rubber composition obtained by blending the copolymer with acrylic rubber has mechanical properties, heat resistance, oil resistance, and release during molding. It is excellent in moldability.

<(A) Acrylic rubber>
A publicly known acrylic rubber (A) in the present invention can be used and is not particularly limited. For example, an alkyl acrylate having an alkyl group having 1 to 12 carbon atoms and an alkoxy having an alkoxyalkyl group having 2 to 8 carbon atoms. It is preferably an acrylate monomer unit having as a main component at least one selected from the group consisting of alkyl acrylates, and a small amount of hydroxyl groups, epoxy groups, carboxyl groups, reactive halogen groups, amides. Those obtained by copolymerizing unsaturated monomers having a crosslinkable group such as a group or an unsaturated group may be more preferably used.

  The content of the acrylate monomer unit 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 acrylate monomer unit, the mechanical properties and compression permanent properties of the acrylic rubber composition can be obtained by using in combination with a vulcanizing agent described later. Distortion can be particularly improved. As content of a crosslinkable monomer unit, it is preferable that it is 0.01 to 20 weight% in the whole acrylic rubber, and it is more preferable that it is 0.02 to 15 weight%. If the content of the crosslinkable monomer unit is less than 0.01% by weight, the physical properties after crosslinking may not be sufficiently improved. Conversely, if the content is more than 20% by weight, the crosslink density becomes too high and brittle. On the contrary, physical properties may be deteriorated.

  Specific examples of acrylate monomers include, for example, acrylate esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, and polyalkylene glycol acrylate. Examples thereof include, but are not limited to, acrylate monomers having an alkylalkoxy group such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and butoxyethyl acrylate.

  As the crosslinkable monomer, known crosslinkable components can be widely used. For example, the crosslinkability of a unit having an active halogen, a unit having an unsaturated double bond, a unit having an epoxy group, etc. It is preferable that it is a monomer copolymerizable with the said acrylate-type monomer containing a component.

  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, haloalkyl alkenyl esters, haloalkyl alkenyl ketones or haloacetoxyalkyl esters of acrylic acid, and haloacetyl group-containing unsaturated compounds. In the present invention, (meth) acryl means acryl and / or methacryl unless otherwise specified.

  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, vinylidene chloride, Etc. The method for producing the acrylic rubber is not particularly limited and may be polymerized by a known method.

<(B) Polyorganosiloxane-containing graft copolymer>
The (B) polyorganosiloxane-containing graft copolymer in the present invention will be described. (B) The polyorganosiloxane-containing graft copolymer is blended and dispersed in an acrylic rubber serving as a matrix resin of the composition according to the present invention, and has a property that makes it possible to exhibit releasability. Furthermore, various characteristics that can be expressed by polyorganosiloxane can be imparted.

  In the present invention, the (B) polyorganosiloxane-containing graft copolymer has a graft component of 5 to 50% by weight, preferably 15 to (d1) 95 to 50% by weight, preferably 85 to 70% by weight. Those consisting of ˜30% by weight are preferred. If the content of the polyorganosiloxane (d1) in the polyorganosiloxane-containing graft copolymer (B) is more than 95% by weight, the tensile properties tend to deteriorate, and conversely if it is less than 50% by weight, the release properties are insufficiently improved. It may become.

  The (d1) polyorganosiloxane is not particularly limited in its production method, and can be obtained by ordinary emulsion polymerization. For example, there is a method of emulsifying a mixture of organosiloxane, water, emulsifier and the like using a homogenizer and the like, and polymerizing the emulsion with an acid. The polymerization of the above (d1) polyorganosiloxane is based on the advantage that the particle size distribution of the resulting polyorganosiloxane in the latex state can be 25% or less in terms of CV value (standard deviation / volume average particle size × 100). It is preferred to utilize polymerization. When the (B) polyorganosiloxane-containing graft copolymer obtained by using seed polymerization is used in the composition of the present invention, the physical properties of the molded article, such as releasability and tensile properties, can be improved. .

  The seed polymer used for the seed polymerization is not limited to rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene rubber, and butadiene-acrylonitrile rubber, and includes, for example, butyl acrylate-styrene copolymer. There is no problem even with polymers such as styrene-acrylonitrile copolymer. A chain transfer agent may be used for the polymerization for forming the seed polymer.

  In the polymerization of (d1) polyorganosiloxane, a graft crossing agent and, if necessary, a crosslinking agent can be used. The amount of seed polymer used in 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). It is preferable to use an organosiloxane having a cyclic structure 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. These organosiloxanes can be used in combination of at least one or two or more.

  A graft crossing agent can be used for the polymerization of the (d1) polyorganosiloxane. Here, the graft crossing agent is (d1) a component for introducing a chemical bond into the polyorganosiloxane and a graft component described later.

  Examples of the graft crossing agent include p-vinylphenylmethyldimethoxysilane, p-vinylphenylethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, and 3- (p-vinylbenzoyloxy) propylmethyldimethoxy. Silane, p-vinylphenylmethyldimethoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, (meth) acryloxy Examples thereof include propylmethyldimethoxysilane, (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropyltriethoxysilane and the like. The proportion of the grafting agent used is preferably 0.01 to 2.0% by weight, based on polyorganosiloxane, that is, the total of the organosiloxane and the grafting agent is 100% by weight. More preferably, it is 0.03-1.0 weight%, More preferably, it is 0.05-0.5 weight%. If the amount of the grafting agent used is more than 2.0% by weight, the effect of improving the releasability may be reduced. Conversely, if the amount of the grafting agent used is less than 0.01% by weight, a large lump may be formed during solidification / heat treatment. May not be recovered as a resin powder, or the moldability of the final molded body obtained from the composition of the present invention may be reduced.

  In the production of (d1) polyorganosiloxane used in the present invention, a crosslinking agent capable of introducing a crosslinked structure into the polyorganosiloxane can be added as necessary. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, tetraethoxysilane, and 1,3-bis [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. These crosslinking agents can also be used in combination. 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 (d1) polyorganosiloxane is impaired, so that the mold releasability improving effect may be lowered.

  The volume average particle diameter of the latex (d1) polyorganosiloxane is preferably 0.01 to 0.6 μm, more preferably 0.08 to 0.4 μm. In some cases, it is difficult to stably obtain a polyorganosiloxane having a volume average particle diameter of less than 0.01 μm. On the other hand, when the volume average particle diameter exceeds 0.6 μm, the impact resistance of the final molded product obtained from the composition of the present invention is low. May decrease. On the other hand, the particle size distribution of (d1) polyorganosiloxane is preferably 25% or less in terms of CV value (standard deviation / volume average particle size × 100) from the viewpoint of suppressing deterioration of physical properties of the obtained molded product. % Or less is more preferable. (D1) Volume average particle diameter and standard deviation of polyorganosiloxane can be measured by a light scattering method using (d1) latex containing polyorganosiloxane particles using Microtrac UPA 150 (manufactured by Nikkiso Co., Ltd.). it can.

  The graft component in the (B) polyorganosiloxane-containing graft copolymer of the present invention is (b-1) an aromatic vinyl monomer, (b-2) a vinyl cyanide monomer, if necessary ( b-3) It is preferable to polymerize a vinyl monomer copolymerizable therewith.

  Specific examples of the (b-1) aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, p-butylstyrene, chlorostyrene, bromostyrene, and the like. These can be used in combination of at least one or two or more. (B-1) The aromatic vinyl monomer is preferably contained in the graft component (B) in an amount of 50 to 95% by weight, more preferably 65 to 95% by weight, particularly 75 to 90% by weight. It is more preferable.

  Specific examples of the (b-2) vinyl cyanide monomer include acrylonitrile and methacrylonitrile. These can be used in combination of at least one or two or more. (B-2) The amount of vinyl cyanide monomer is preferably contained in the graft component (B) in an amount of 50 to 5% by weight, more preferably 35 to 5% by weight, especially 25 to 10% by weight. More preferably. (B-2) If the amount of vinyl cyanide monomer exceeds 50% by weight, the polymerization conversion rate to the polymer tends to be difficult to increase, and conversely if less than 5% by weight, (B) containing polyorganosiloxane It tends to be difficult to obtain the graft copolymer in a powder state.

  Specific examples of the vinyl monomer copolymerizable with (b-3) above include (i) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, (Meth) acrylic acid ester monomers such as glycidyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, (ii) itacon Carboxyl group-containing vinyl monomers such as acid, (meth) acrylic acid, fumaric acid, maleic acid, (iii) maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N -Phenylmaleimide, N- (p-methylphenyl Such as maleimide-based monomers such as maleimide, and the like. These may be used alone or in combination of two or more. (B-3) The vinyl monomer copolymerizable with these may be contained in the graft component (B) in an amount of 0 to 30% by weight, further 2 to 20% by weight, particularly 3 to 15%. % By weight may be included. (B-3) If the vinyl monomer copolymerizable with these exceeds 30% by weight, mechanical properties tend to be lowered.

  Specific examples of the radical polymerization initiator used in the production of the (B) polyorganosiloxane-containing graft copolymer of the present invention include cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, and t-butyl peroxyisopropyl. Organic peroxides such as carbonate, inorganic peroxides such as potassium persulfate and ammonium persulfate, azo such as 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile Compound etc. are mentioned. This radical polymerization is carried out in a redox system such as ferrous sulfate-sodium formaldehyde sulfoxylate-disodium ethylenediaminetetraacetate, ferrous sulfate-glucose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate. The polymerization can be completed even at a low polymerization temperature.

  A method for separating the polymer from the polyorganosiloxane-containing graft copolymer latex (B) obtained by the 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 and heat treatment of the latex by addition, and separation, washing, dehydration, and drying of the obtained coagulated slurry. A spray drying method can also be used.

  The (B) polyorganosiloxane-containing graft copolymer of the present invention is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts per 100 parts by weight of the (A) acrylic rubber. Part by weight is more preferred. (B) If the amount of the polyorganosiloxane-containing graft copolymer exceeds 10 parts by weight, the mechanical properties and oil resistance tend to be reduced. Conversely, if the amount is less than 0.1 parts by weight, the release effect is improved. May not be seen.

<(C) Vulcanizing agent>
The (C) vulcanizing agent in the present invention is a component used for crosslinking (A) the crosslinkable monomer unit of the acrylic rubber as a base point to express better rubber elasticity. (C) The vulcanizing agent can be efficiently cross-linked by properly using depending on the type of cross-linkable unit of the acrylic rubber, and it becomes possible to obtain a cross-linked rubber excellent in compression set more easily. In the present invention, widely known vulcanizing agents can be used. For example, when the crosslinkable unit of acrylic rubber has an active halogen, polyamine carbamates, organic carboxylic acid ammonium salts, organic carboxylic acid alkali metal salts, sulfur compounds can be used, and the crosslinkable unit of acrylic rubber has an epoxy group. If it has, polyamine carbamates, organic carboxylic acid ammonium salts, dithiocarbamates, organic carboxylic acid alkali metal salts, sulfur compounds can be used, and the crosslinkable unit of acrylic rubber is a unit having an unsaturated double bond Sulfur, organic peroxides, and the like can be suitably used, but are not limited thereto.

  The addition amount of (C) vulcanizing agent in the present invention is preferably 0.005 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of (A) acrylic rubber. preferable. (C) If the addition amount of the vulcanizing agent is less than 0.005 parts by weight, the vulcanization may not proceed sufficiently and the effect of improving the physical properties may not be exhibited. When the amount is more than part by weight, physical properties may be deteriorated due to the influence of the remaining vulcanizing agent component.

<Composition>
In the acrylic rubber composition of the present invention, a lubricant or a thermoplastic resin can be blended in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of (A) acrylic rubber.

  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 ethylenebisstearamide, 4-fluoride Fluorine resin powders such as ethylene resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, silica, and the like can be mentioned, but are not limited thereto. These may be used alone or in combination of two or more. Of these, stearic acid, zinc stearate, calcium stearate, magnesium stearate, and stearyl amide are preferred from the viewpoint of low friction and processability on the resin surface.

  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 in appropriate amounts 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), octyldiphenylamine, 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-phenylene Diamine, 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 Diamines, diallylphenylenediamine mixtures, diallyl-p-phenylenediamine mixtures, N- (1-methylheptyl) -N-phenyl-p-phenylenediamine, amine-based antioxidants such as diphenylamine derivatives, 2-mercaptobenzimidazole (MBI) ) Imidazole antioxidants, phenol-based antioxidants such as 2,6-di-t-butyl-4-methylphenol, dithiocarbamate antioxidants 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-diamino-3,3′-diphenyl acrylate, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone-2-hydroxy-4-octoxybenzophenone, monoglycol sari Examples include tyrates, oxalic acid amides, 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 one having excellent affinity with (A) acrylic rubber or (B) polyorganosiloxane-containing graft copolymer. 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 can be suitably 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 (manufactured by ADEKA Corporation), and Sunsizer 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.) It is done.

  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 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 of (A) acrylic rubber, (B) polyorganosiloxane-containing graft copolymer, and filler, various graft polymers and block polymers may be added as compatibilizers.

  Examples of the compatibilizer include Kraton series (manufactured by Kraton Polymer Japan Co., Ltd.), Tuftec series (manufactured by Asahi Kasei Kogyo Co., Ltd.), Dynalon (manufactured by JSR Corp.), 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 Polyethylene Co., Ltd.), Bond First (manufactured by Sumitomo Chemical Industries, Ltd.) ), Admer (Mitsui Chemicals Co., Ltd.), Umex (Sanyo Chemical Industries Co., Ltd.), VMX (Mitsubishi Chemical Co., Ltd.), Modiper (Nippon Oils and Fats Co., Ltd.), Staphyroid (Gantz Kasei) And commercial products such as Reseda (manufactured by Toa Gosei Co., Ltd.). These can be appropriately selected and used according to the combination of (A) the polyorganosiloxane-containing graft copolymer used to supplement the physical properties of the acrylic rubber.

  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 the vulcanization temperature, a temperature of 120 ° C. or higher is usually suitable, preferably 140 to 200 ° C., and vulcanization is performed at this temperature for about 1 to 30 minutes. Further, if necessary, post-vulcanization can be performed at a temperature of about 140 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 (molded product) obtained from the acrylic rubber composition of the present invention can be widely used mainly for applications such as gaskets, packing, 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 in the automobile field and electrical / 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 can, 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 and gymnasium floors as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls 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 field, 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 extinguishing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for dredging 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 property evaluation method)
According to the method described in JIS K7113, measurement was performed using an autograph AG-10TB type manufactured by Shimadzu Corporation. Measurement was performed at n = 3, and the average values of strength (MPa) and elongation (%) when the test piece was broken 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.

(Hardness evaluation method)
Measurement was performed using a type A durometer in accordance with JIS K6253. Measurement was performed at n = 3, and three 2 mm-thick test pieces were used.

(Oil resistance evaluation method)
In accordance with ASTM D638, ASTM Oil No. 1 maintained at 150 ° C. 3 or No. The molded body of the composition was immersed in 1 for 72 hours, and the weight change rate (% by weight) was determined.

(Tensile property heat resistance evaluation method)
After holding a test piece of type 2 (1/3) in an oven at 175 ° C. × 72 hours and 150 ° C. × 168 hours, the tensile strength change rate (%) and the tensile strength were measured by the tensile property evaluation method described above. The rate of change in elongation (%) was determined.

(Compression set evaluation method)
In accordance with JIS K6262, a large test piece was compressed 25% using a compression device, held in an oven at 150 ° C. for 72 hours, and then removed from the compression device and allowed to stand at room temperature for 30 minutes, and then compression set (% )

Compression set (%) = (t ₀ −t ₂ ) / (t ₀ −t ₁ ) × 100
t ₀ : Original thickness of the test piece (mm)
t ₁ : Spacer thickness (mm)
t ₂ : Thickness (mm) after 30 minutes after removing the test piece from the compression device
(Hardness heat resistance evaluation method)
After holding the test piece in an oven at 150 ° C. for 168 hours, it was measured by the hardness evaluation method described above, and the change (point) from the standard state was obtained.

(Releasability evaluation method)
After kneading a predetermined amount of acrylic rubber under a predetermined condition using a plast mill, the ease of peeling from the chamber and the screw and the degree of adhesion of the acrylic rubber were evaluated according to the following criteria.
(Double-circle): Peeling off is very easy and there is no adhesion of acrylic rubber to a chamber and a screw.
○: Easy to peel off, and no acrylic rubber adheres to the chamber and screw.
(Triangle | delta): Peeling off is comparatively easy and there is almost no adhesion of acrylic rubber to a chamber and a screw.
X: It is difficult to peel off, and acrylic rubber adheres to the chamber and the screw.

(Thermogravimetric change evaluation method: TGA measurement)
It measured using the thermogravimetry apparatus TGA-50 by Shimadzu Corporation. The test was performed at a heating rate of 20 ° C./min in a nitrogen stream.

<Method for producing molded article for evaluation>
Using a kneader “DS1-5MHB-E” (manufactured by Moriyama Co., Ltd.), a predetermined amount of acrylic rubber, carbon black, lubricant and antioxidant (sample amount: 700 g, chamber set temperature: 50 ° C., Preheating time: None, front blade rotation speed: 20 rpm, rear blade rotation speed: 14.7 rpm, chamber volume: 1 L, kneading time: 8 minutes). Thereafter, the front blade speed was changed to 34 rpm and the rear blade speed was changed to 24.9 rpm, and kneaded for 4 minutes to obtain a lump sample. A predetermined amount of the massive sample thus obtained was subjected to predetermined conditions (sample amount: 45 g, chamber set temperature: 80 ° C., preheating time: none using a plastmill “MODEL20C200” (manufactured by Toyo Seiki Co., Ltd.). , Screw rotation: 25 rpm, blade: roller type R60B biaxial, chamber capacity: 60CC, mixer: ticker anti-abrasion roller mixer R60HT, kneading time: 1 minute). Further, polyorganosiloxane-containing graft copolymer particles were added and kneading was continued for 7 minutes. After kneading was stopped and the resin temperature was cooled to 70 ° C., 1.5 parts by weight of ammonium benzoate was added as a vulcanizing agent to 100 parts by weight of acrylic rubber, and kneaded for 8 minutes under predetermined conditions. A lump sample was obtained. The massive sample thus obtained was pressed for 35 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 2 MPa and cooled to 30 ° C. to obtain a sheet-like molded body having a thickness of 2 mm. Further, the sheet-shaped molded body was annealed at 170 ° C. for a predetermined time, and each evaluation shown in Table 2 and Table 3 was performed using the obtained sheet-shaped molded body.

<Production Example of Polyorganosiloxane-Containing Graft Copolymer>
(Production Example 1)
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% by weight aqueous sodium dodecylbenzenesulfonate 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 butyl acrylate 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 by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of disodium ethylenediaminetetraacetate (EDTA), first sulfuric acid sulfate 0.0025 part by weight of iron was added and stirred for 1 hour. A mixed solution of 90 parts by weight of butyl acrylate, 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, reflux cooling water, nitrogen blowing port, monomer addition port, and thermometer. Thereafter, 175 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.49 parts by weight (solid content) of 15% by weight aqueous sodium dodecylbenzenesulfonate, 98 parts by weight of octamethylcyclotetrasiloxane, A mixture of 0.196 parts by weight of methacryloxypropylmethyldimethoxysilane 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, 1.5 parts by weight (solid content) of a 10% by weight dodecylbenzenesulfonic acid aqueous 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 for 7 hours at 80 ° C., then cooled to 25 ° C. and allowed to stand for 18 hours. The polymerization conversion rate was 85%. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained. The resulting latex containing polyorganosiloxane particles had a volume average particle size of 0.17 μm and a CV value of 19%.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 230 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., 0.2 part by weight of sodium formaldehyde sulfoxylate (SFS), 0.008 part by weight of disodium ethylenediaminetetraacetate (EDTA) and 0.002 part by weight of ferrous sulfate were added, and then 15 parts by weight of styrene. A mixture of 5 parts by weight of acrylonitrile, 5 parts by weight of acrylonitrile and 0.1 part by weight of cumene hydroperoxide (solid content) is added dropwise over 1 hour. A combined latex was obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15% by weight, and then 4 parts by weight (solid content) of a 25% by weight calcium chloride aqueous solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 95 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-containing graft polymer powder.

(Production Example 2)
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, 200 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.49 parts by weight (solid content) of 15% by weight aqueous sodium dodecylbenzenesulfonate, 98 parts by weight of octamethylcyclotetrasiloxane, A mixture composed of 1.96 parts by weight of methacryloxypropylmethyldimethoxysilane 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, 1.5 parts by weight (solid content) of a 10% by weight dodecylbenzenesulfonic acid aqueous 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 for 7 hours at 80 ° C., then cooled to 25 ° C. and allowed to stand for 18 hours. The polymerization conversion rate was 85%. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained. The resulting latex containing polyorganosiloxane particles had a volume average particle size of 0.17 μm and a CV value of 20%.

  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 methyl methacrylate. A mixture of 20 parts by weight and 0.073 parts by weight of cumene hydroperoxide (solid content) was added dropwise over 1 hour, and after the addition was completed, the mixture was further stirred for 1 hour to obtain a polyorganosiloxane-containing graft polymer latex. Obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15% by weight, and then 4 parts by weight (solid content) of a 25% by weight calcium chloride aqueous solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 95 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-containing graft copolymer powder.

(Production Example 3)
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% by weight aqueous sodium dodecylbenzenesulfonate 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 butyl acrylate 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 by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of disodium ethylenediaminetetraacetate (EDTA), first sulfuric acid sulfate 0.0025 part by weight of iron was added and stirred for 1 hour. A mixed solution of 90 parts by weight of butyl acrylate, 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, reflux cooling water, nitrogen blowing port, monomer addition port, and thermometer. Thereafter, 175 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.49 parts by weight (solid content) of 15% by weight aqueous sodium dodecylbenzenesulfonate, 98 parts by weight of octamethylcyclotetrasiloxane, A mixture of 0.196 parts by weight of methacryloxypropylmethyldimethoxysilane 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, 1.5 parts by weight (solid content) of a 10% by weight dodecylbenzenesulfonic acid aqueous 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 for 7 hours at 80 ° C., then cooled to 25 ° C. and allowed to stand for 18 hours. The polymerization conversion rate was 85%. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained. The resulting latex containing polyorganosiloxane particles had a volume average particle size of 0.17 μm and a CV value of 19%.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 230 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., 0.2 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.008 parts by weight of ethylenediaminetetraacetate (EDTA) and 0.002 parts by weight of ferrous sulfate were added, and then 20 parts by weight of styrene. And a mixture of cumene hydroperoxide 0.1 parts by weight (solid content) was added dropwise over 1 hour, and after completion of the addition, the mixture was further stirred for 1 hour to obtain a latex of a polyorganosiloxane-containing graft polymer. .

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15% by weight, and then 4 parts by weight (solid content) of a 25% by weight calcium chloride aqueous solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 95 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-containing graft copolymer. However, since this polyorganosiloxane-containing graft copolymer was agglomerated, it did not become powder.

(Production Example 4)
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% by weight aqueous sodium dodecylbenzenesulfonate 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 butyl acrylate 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 by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of disodium ethylenediaminetetraacetate (EDTA), first sulfuric acid sulfate 0.0025 part by weight of iron was added and stirred for 1 hour. A mixed solution of 90 parts by weight of butyl acrylate, 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, reflux cooling water, nitrogen blowing port, monomer addition port, and thermometer. Thereafter, 175 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.49 parts by weight (solid content) of 15% by weight aqueous sodium dodecylbenzenesulfonate, 98 parts by weight of octamethylcyclotetrasiloxane, A mixture of 0.196 parts by weight of methacryloxypropylmethyldimethoxysilane 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, 1.5 parts by weight (solid content) of a 10% by weight dodecylbenzenesulfonic acid aqueous 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 for 7 hours at 80 ° C., then cooled to 25 ° C. and allowed to stand for 18 hours. The polymerization conversion rate was 85%. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained. The resulting latex containing polyorganosiloxane particles had a volume average particle size of 0.17 μm and a CV value of 19%.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 230 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, 0.2 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.008 parts by weight of disodium ethylenediaminetetraacetate (EDTA) and 0.002 parts by weight of ferrous sulfate were added, and then ethyl acrylate Add a mixture of 20 parts by weight and cumene hydroperoxide 0.1 part by weight (solid content) dropwise over 1 hour, and continue stirring for 1 hour after the addition is completed, to thereby obtain a polyorganosiloxane-containing graft polymer latex. Obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15% by weight, and then 4 parts by weight (solid content) of a 25% by weight calcium chloride aqueous solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 95 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-containing graft copolymer. However, since this polyorganosiloxane-containing graft copolymer was agglomerated, it did not become powder.

(Production Example 5)
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% by weight aqueous sodium dodecylbenzenesulfonate 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 butyl acrylate 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 by weight of sodium formaldehyde sulfoxylate (SFS), 0.01 parts by weight of disodium ethylenediaminetetraacetate (EDTA), first sulfuric acid sulfate 0.0025 part by weight of iron was added and stirred for 1 hour. A mixed solution of 90 parts by weight of butyl acrylate, 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, reflux cooling water, nitrogen blowing port, monomer addition port, and thermometer. Thereafter, 175 parts by weight of pure water (including the amount brought in from the latex containing the seed polymer), 0.49 parts by weight (solid content) of 15% by weight aqueous sodium dodecylbenzenesulfonate, 98 parts by weight of octamethylcyclotetrasiloxane, A mixture of 0.098 parts by weight of methacryloxypropylmethyldimethoxysilane 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, 1.5 parts by weight (solid content) of a 10% by weight dodecylbenzenesulfonic acid aqueous 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 for 7 hours at 80 ° C., then cooled to 25 ° C. and allowed to stand for 18 hours. The polymerization conversion rate was 85%. Thereafter, the pH was adjusted to 6.5 with sodium hydroxide to complete the polymerization, and a latex containing polyorganosiloxane particles was obtained. The resulting latex containing polyorganosiloxane particles had a volume average particle size of 0.17 μm and a CV value of 19%.

  Subsequently, in a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port and a thermometer, 230 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., 0.2 part by weight of sodium formaldehyde sulfoxylate (SFS), 0.008 part by weight of disodium ethylenediaminetetraacetate (EDTA) and 0.002 part by weight of ferrous sulfate were added, and then 15 parts by weight of styrene. A mixture of 5 parts by weight of acrylonitrile, 5 parts by weight of acrylonitrile and 0.1 part by weight of cumene hydroperoxide (solid content) is added dropwise over 1 hour. A combined latex was obtained.

  Subsequently, the latex was diluted with pure water to a solid content concentration of 15% by weight, and then 4 parts by weight (solid content) of a 25% by weight calcium chloride aqueous solution was added to obtain a coagulated slurry. The coagulated slurry was heated to 95 ° C., cooled to 50 ° C., dehydrated, and dried to obtain a polyorganosiloxane-containing graft polymer powder.

Example 1
100 parts by weight of acrylic rubber (made by Nippon Zeon, trade name AR31) and 5 parts by weight of the polyorganosiloxane-containing graft copolymer obtained in Production Example 1 and 1 part by weight of antioxidant (made by calcium Shiraishi, trade name Nowguard 445) In accordance with a predetermined method, 52.5 parts by weight of carbon black (Seast 3, manufactured by Tokai Carbon Co., Ltd.) as an inorganic filler, 1 part by weight of stearic acid, and 1.5 parts by weight of ammonium benzoate as a lubricant are added in accordance with a predetermined method. A massive sample was obtained using Toyo Seiki Co., Ltd. The lump sample thus obtained was used for evaluation of releasability and then 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, heat resistance, and oil resistance. Table 2 shows the releasability evaluation, and Table 3 shows the evaluation results of each characteristic.

(Example 2)
In the method described in Example 1, 1 part by weight of the polyorganosiloxane-containing graft copolymer obtained in Production Example 5 was used in place of the polyorganosiloxane-containing graft copolymer of Production Example 1, and the rest was the same. After performing the releasability evaluation, a sheet-like molded body for evaluation was prepared, and each characteristic was evaluated. Table 2 shows the releasability evaluation, and Table 3 shows the evaluation results of each characteristic.

(Example 3)
In Example 2, the polyorganosiloxane-containing graft copolymer obtained in Production Example 5 was used in an amount of 2 parts by weight, and after a release property evaluation was performed in the same manner, a sheet-like molded body for evaluation was prepared. Each characteristic was evaluated. Table 2 shows the releasability evaluation, and Table 3 shows the evaluation results of each characteristic.

(Reference Example 1)
In Example 1, 30 parts by weight of the polyorganosiloxane-containing graft copolymer obtained in Production Example 1 was used, and after a release property evaluation was performed in the same manner, a sheet-like molded body for evaluation was prepared. Each characteristic was evaluated. Table 2 shows the releasability evaluation, and Table 3 shows the evaluation results of each characteristic.

(Comparative Example 1)
In the method described in Example 1, the polyorganosiloxane-containing graft copolymer was not added, and after the release property evaluation was performed in the same manner, each characteristic was obtained using the obtained sheet-like molded product. evaluated. Table 2 shows the releasability evaluation, and Table 3 shows the evaluation results of each characteristic.

(Comparative Example 2)
In the method described in Example 1, 2.0 parts by weight of silicone oil (SH-200, manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of the polyorganosiloxane-containing graft copolymer, and the releasability was evaluated in the same manner. Went. The evaluation results are shown in Table 2.

(Comparative Example 3)
In Comparative Example 2, 1.5 parts by weight of silicone oil (SH-200, manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and after the release property evaluation was performed in the same manner, a sheet-like molded body for evaluation was created. Each characteristic was evaluated. Table 2 shows the releasability evaluation, and Table 3 shows the evaluation results of each characteristic.

(Comparative Example 4)
In the method described in Example 1, 1.5 parts by weight of polyethylene wax (Neowax LA05, manufactured by Yasuhara Chemical Co., Ltd.) was used instead of the polyorganosiloxane-containing graft copolymer. It was. The evaluation results are shown in Table 2.

(Comparative Example 5)
In Comparative Example 4, 0.7 parts by weight of polyethylene wax (Neowax LA05, manufactured by Yasuhara Chemical Co., Ltd.) was used, and after a release property evaluation was performed in the same manner, a sheet-like molded body for evaluation was prepared, and each characteristic was Evaluated. Table 2 shows the releasability evaluation, and Table 3 shows the evaluation results of each characteristic.

(Comparative Example 6)
In the method described in Example 1, kneading was performed in the same manner except that the polyorganosiloxane-containing graft copolymer obtained in Production Example 3 was used as the polyorganosiloxane-containing graft copolymer. Since the siloxane-containing graft copolymer was not a powder, it could not be kneaded and a molded product could not be obtained.

(Comparative Example 7)
In the method described in Example 1, kneading was carried out in the same manner except that the polyorganosiloxane-containing graft copolymer obtained in Production Example 4 was used as the polyorganosiloxane-containing graft copolymer. Since the siloxane-containing graft copolymer was not a powder, it could not be kneaded and a molded product could not be obtained.

  As is apparent from Table 1, the polyorganosiloxane-containing graft copolymer using styrene / acrylonitrile as the graft component was a powder, but the polyorganosiloxane-containing graft copolymer using styrene or ethyl acrylate as the graft component. The polymer was agglomerated and did not become powder.

  As is clear from Table 2, it is possible to improve the releasability by adding a polyorganosiloxane-containing graft copolymer. Silicone oil and polyethylene wax could not be added in an amount of 2.0 parts by weight or more and 1.5 parts by weight, respectively. When silicone oil and polyethylene wax were added in an amount of 1.5 parts by weight and 0.7 parts by weight, respectively, the effect of improving the releasability was small.

  As is clear from Table 3, it was possible to improve the releasability by adding the polyorganosiloxane-containing graft copolymer without reducing the tensile properties, heat resistance and oil resistance. Further, by adding 2 parts of the polyorganosiloxane-containing graft copolymer prepared in Production Example 5, it was possible to largely prevent curing deterioration due to heat.

  As is clear from Table 4, the polyorganosiloxane-containing graft copolymer using styrene and acrylonitrile (Production Example 1) is more than the polyorganosiloxane-containing graft copolymer using methyl methacrylate (Production Example 2). The thermogravimetric change rate was small and the powder characteristics were excellent.

Claims (11)

  (A) Acrylic rubber and (B) an acrylic rubber composition containing a polyorganosiloxane-containing graft copolymer, wherein (B) component is a copolymer of (d1) polyorganosiloxane and a graft component, The graft component ((b-1) + (b-2) + (b-3) = 100% by weight) is (b-1) 50 to 95% by weight of an aromatic vinyl monomer, (b -2) An acrylic rubber composition characterized in that it is 50 to 5% by weight of vinyl cyanide monomer and (b-3) 0 to 30% by weight of vinyl monomer copolymerizable therewith.   2. The graft crossing agent used in (B) polyorganosiloxane-containing graft copolymer is 0.01 to 2.0% by weight in 100% by weight of polyorganosiloxane. Acrylic rubber composition.   The acrylic rubber composition according to claim 1 or 2, wherein the (B) polyorganosiloxane-containing graft copolymer comprises 95 to 50% by weight of polyorganosiloxane and 5 to 50% by weight of the graft component.   4. The volume average particle diameter of (d1) polyorganosiloxane in the polyorganosiloxane-containing graft copolymer (B) is 0.01 μm to 0.6 μm. 5. Acrylic rubber composition.   (B) The particle size distribution of (d1) polyorganosiloxane in the polyorganosiloxane-containing graft copolymer is 25% or less in terms of CV value (standard deviation / volume average particle size × 100). Item 5. The acrylic rubber composition according to any one of Items 1 to 4.   The acrylic rubber composition according to any one of claims 1 to 5, wherein the acrylic rubber contains 0.01 to 20% by weight of a crosslinkable monomer unit in the whole acrylic rubber.   (A) 0.1-100 weight part of (B) polyorganosiloxane containing graft copolymer is contained with respect to 100 weight part of acrylic rubber, The one of Claim 1 thru | or 6 characterized by the above-mentioned. Acrylic rubber composition.   The acrylic rubber composition according to any one of claims 1 to 7, wherein 0.005 to 10 parts by weight of (C) a vulcanizing agent is contained with respect to 100 parts by weight of (A) acrylic rubber.   The molded object which consists of an acrylic rubber composition in any one of Claims 1 thru | or 8.   An automotive part comprising the molded body according to claim 9.   An electrical / electronic component comprising the molded body according to claim 9.