JP2000186105A - Composite rubber, composite rubber-containing graft polymer particle and thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite rubber-containing graft copolymer particle comprising an acrylic rubber having highly modifying effect on impact resistance and a silicone rubber and a thermoplastic resin composition having excellent impact resistance/weather resistance/processability. SOLUTION: This composite rubber-containing graft copolymer particle is obtained by subjecting a vinyl-based monomer to graft polymerization onto (C) a composite rubber particle composed of (A) an acrylic rubber and (B) a silicone rubber in which 2-50 wt.% of 100 wt.% of the whole constituent monomer units forming (A) the acrylic rubber is a unit derived from an acrylic acid alkyl ester monomer containing an 8-12C alkyl group. This thermoplastic resin composition comprises the graft copolymer particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite rubber comprising an acrylic rubber and a silicone rubber, a graft copolymer particle using the composite rubber, and a thermoplastic resin composition having excellent impact resistance and weather resistance.

[0002]

2. Description of the Related Art Improving impact resistance by blending a graft copolymer particle containing a rubber component with a thermoplastic resin is known.
It has been widely used conventionally. It is said that the use of a rubber component having as low a glass transition temperature (hereinafter abbreviated as Tg) as the rubber component is advantageous for the development of impact resistance. In fact, a resin containing a graft copolymer containing a polybutadiene rubber component having a Tg of about -80 ° C, such as a resin containing a graft copolymer containing a polybutyl acrylate rubber component having a Tg of about -50 ° C, for example, Acrylonitrile / butadiene / styrene copolymer (ABS resin) has better impact resistance.

[0003] In terms of low Tg of rubber, polyorganosiloxane (hereinafter also referred to as silicone), for example, polydimethylsiloxane rubber has a Tg of about -120 ° C, so that a graft copolymer containing a silicone rubber component is used. If the particles can be used, they are expected to exhibit higher impact strength than those containing a polybutadiene rubber component. Therefore, studies have been made to use silicone rubber or composite rubber-based graft copolymer particles containing silicone rubber.

For example, Japanese Patent Application Laid-Open No. 62-280210 discloses a graft copolymer particle obtained by graft-polymerizing a vinyl monomer onto a composite rubber comprising a core of crosslinked silicone rubber particles and a shell of crosslinked acrylic rubber. It is described for use.

JP-A-64-6012 discloses a composite rubber comprising a core of crosslinked acrylic rubber particles and a shell of crosslinked silicone rubber, wherein graft copolymer particles obtained by graft polymerization of a vinyl monomer are used. It is described about that.

Further, Japanese Patent Application Laid-Open Nos. 4-100812, 1-279954, 1-190
No. 746 discloses a graft copolymer obtained by graft-polymerizing a vinyl monomer onto a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled so that they cannot be separated from each other. The use of particles is described.

[0007] WO 97/10283 describes the use of graft copolymer particles obtained by graft-polymerizing a vinyl monomer onto a composite rubber obtained by grafting crosslinked silicone onto crosslinked acrylic rubber particles.

[0008]

However, although the specification of the above publication mentions that various (meth) acrylic esters can be used as a monomer for forming an acrylic rubber, it is substantially the case. Describes only the use of butyl acrylate ("substantially" indicates that it contains a small amount of a crosslinking agent or a graft-crosslinking agent). That is, conventionally, only a graft copolymer of a composite rubber composed of silicone rubber and butyl acrylate rubber has been known. Even if the graft copolymer is used as an impact modifier, the impact resistance is still not satisfactory, and the development of an impact modifier for expressing higher impact resistance is an issue. Met.

[0009]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that 100% by weight of all monomer units of acrylic rubber which is a component of composite rubber particles.
When the unit derived from the acrylic acid alkyl ester monomer having 8 to 12 carbon atoms in the alkyl group is 2 to 50% by weight, a composite rubber having excellent impact resistance is obtained, and The inventors have found that the use of composite rubber-based graft copolymer particles obtained from the composite rubber has good weather resistance and is effective in improving impact resistance, and has completed the present invention.

The present invention relates to a composite rubber particle (C) comprising an acrylic rubber (A) and a silicone rubber (B), wherein all the constituent monomer units forming the acrylic rubber (A) are 100% ( 2% to 50% by weight (hereinafter the same) of the composite rubber particles (Claim 1), wherein the unit is derived from an alkyl acrylate monomer having 8 to 12 carbon atoms. ) Is acrylic rubber (A) 10
~ 99% and silicone rubber (B) 90 ~ 1% (however,
2. The composite rubber particles according to claim 1, wherein the total amount of (A) and (B) is 100%. (Claim 2) The acrylic rubber (A) has (a-1) an alkyl group having carbon number of an alkyl group. 8-12 alkyl acrylate monomers 2-5
0%, (a-2) selected from the group consisting of alkyl acrylate monomers having 1 to 7 carbon atoms in the alkyl group and alkyl methacrylate monomers having 4 to 12 carbon atoms in the alkyl group. At least one monomer 97.8-
29%, (a-3) 0.2 to 6% of a polyfunctional monomer containing two or more vinyl polymerizable groups in the molecule, (a-4) reactivity with the vinyl polymerizable group in the molecule 0 to 5% of a monomer having a silyl group and 0 to 10% of (a-5) and other copolymerizable monomers (provided that the total amount of (a-1) to (a-5) is 100 % Of the composite rubber particles (claim 3) and the silicone rubber (B) according to claim 1 or 2 obtained by copolymerizing an acrylic rubber-forming component consisting of (b-1) an organosiloxane. 9%, (b-2) 0 to 15% of a polyfunctional silane compound and (b-3) 0 to 15% of a silane compound having a vinyl polymerizable group or a mercapto group
3. A silicone rubber-forming component comprising the components (b-2) and (b-3) which are not simultaneously 0 and one of them is 0.1% or more.
Or the composite rubber particles according to claim 3 (claim 4), composite rubber-containing graft copolymer particles obtained by graft-polymerizing a vinyl monomer onto the composite rubber particles (C) according to claim 1 (claim 5), The composite rubber-containing graft copolymer particles (claim 6) according to claim 5, wherein 95 to 5% of the vinyl monomer is graft-polymerized to 5 to 95% of the composite rubber particles (C). At least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, vinyl halide monomers, (meth) acrylic acid, and (meth) acrylate monomers 6. The composite rubber-containing graft copolymer particles according to claim 5, which is a monomer of (5), and the graft copolymer particles 1 to 15 according to claim 5, 6, or 7.
A thermoplastic resin composition comprising 0 parts (parts by weight, hereinafter the same) and 100 parts of a thermoplastic resin (Claim 8), wherein the thermoplastic resin is a polyvinyl chloride resin, a polystyrene resin, a styrene-acrylonitrile copolymer resin, Acrylonitrile-N-phenylmaleimide copolymer resin, α-methylstyrene-acrylonitrile copolymer resin, polymethyl methacrylate resin, methyl methacrylate-styrene copolymer resin, polycarbonate resin, polyamide resin, polyester resin, polyphenylene ether-polystyrene composite resin The thermoplastic resin composition according to claim 8, which is at least one resin selected from the group consisting of, ABS resin, AAS resin and AES resin.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The composite rubber particles (C) of the present invention are:
A composite rubber particle (C) comprising an acrylic rubber (A) and a silicone rubber (B), wherein 2 to 50% of 100% of all constituent monomer units forming the acrylic rubber (A) are alkyl groups. Is a unit derived from an alkyl acrylate monomer having 8 to 12 carbon atoms.

In the present specification, the vinyl system is a concept including a polymerizable C ＝ C bond such as vinyl and vinylidene, and includes a C ＝ C bond included in a conjugated diene system.

That is, the composite rubber particles (C) of the present invention
Is characterized in that a specific amount of a specific monomer unit is present in a constituent monomer unit in an acrylic rubber as a constituent component.

When the composite rubber particles (C) are used as the rubber source of the impact modifier, the constituent monomer units of the acrylic rubber are composed of only the butyl acrylate units except for the crosslinking agent and the graft crosslinking agent. Composite rubber particles (conventional)
Develops high impact resistance as compared with the case of using.

Specific examples of the composite rubber particles (C) include a composite rubber having a chemical bond between a butyl acrylate-2-ethylhexyl acrylate copolymer rubber and a dimethylsiloxane polymer rubber; A composite rubber in which a 2-ethylhexyl acrylate copolymer rubber and a dimethylsiloxane polymer rubber are entangled with each other, a chemical bond between a butyl acrylate-2-ethylhexyl acrylate copolymer rubber and a dimethylsiloxane polymer rubber, and Composite rubber that coexists without entanglement, composite rubber having a chemical bond between butyl acrylate-octyl acrylate copolymer rubber and dimethylsiloxane polymer rubber, butyl acrylate-octyl acrylate copolymer rubber A composite rubber in which dimethylsiloxane polymer rubber is intertwined with each other, Butyl acrylic acid - such as composite rubber octyl acrylate copolymer rubber and the dimethyl siloxane polymer rubber coexist without even entanglement of mutual chemical bond. Among these, a composite rubber comprising a butyl acrylate-2-ethylhexyl acrylate copolymer rubber and dimethylsiloxane rubber is preferable because of its impact resistance and advantageous properties.

The ratio of the acrylic rubber (A) and the silicone rubber (B) forming the composite rubber particles (C) is such that the ratio of the acrylic rubber (A) / the silicone rubber (B) is 99/1 to 1
The ratio is preferably 0/90, more preferably 95/5 to 50/50, in view of the impact resistance.

The average particle diameter of the composite rubber particles (C) is from 0.01 to 1.1 μm, preferably from 0.03 to 1 μm, from the viewpoint of the development of impact resistance.

Solvent-insoluble content of the composite rubber particles (C) (gel content: weight fraction of toluene-insoluble content when a sample made of rubber particles is immersed in toluene for 24 hours at room temperature and centrifuged at 12,000 rpm for 1 hour) ) Is 70% or more, and preferably 80% or more from the viewpoint of the development of impact resistance. The upper limit is 100%.

The alkyl group in the constituent monomer units forming the acrylic rubber (A) has 8 to 12 carbon atoms.
The ratio of the unit derived from the alkyl acrylate monomer is 2 to 50%, but the preferable ratio is 5 to 30% from the viewpoint of the development of impact resistance, and more preferably 5 to 2%.
More preferably, it is 0%.

The acrylic rubber (A) includes (a-1) an alkyl acrylate monomer having an alkyl group having 8 to 12 carbon atoms (hereinafter also referred to as monomer (a-1)), (a)
-2) Acrylic acid alkyl ester monomer having 1 to 7 carbon atoms in the alkyl group and 4 to 12 carbon atoms in the alkyl group
At least one monomer selected from the group consisting of methacrylic acid alkyl ester monomers (hereinafter referred to as monomer (a-
2a), (a-3) a polyfunctional monomer containing two or more vinyl polymerizable groups in the molecule (hereinafter referred to as monomer (a-
3a), (a-4) a monomer having a vinyl polymerizable group and a reactive silyl group in the molecule (hereinafter referred to as monomer (a
-4)) and (a-5) other copolymerizable monomers (hereinafter also referred to as monomer (a-5)). a) is copolymerized.

The monomer (a-1) forms a part of the main skeleton of the acrylic rubber (A) and is a component for expressing the features of the present invention. Specific examples thereof include, for example, 2-ethylhexyl acrylate, octyl acrylate,
8 carbon atoms such as nonyl acrylate and lauryl acrylate
It is an acrylic acid alkyl ester having from 12 to 12 alkyl groups. These monomers (a-1) may be used alone or in combination of two or more. Among these,
2-Ethylhexyl acrylate is preferred from the viewpoint of low Tg of the obtained polymer and economy.

The monomer (a-2) is a monomer (a)
It is a component for forming the main skeleton of the acrylic rubber (A) by copolymerization with -1). Specific examples thereof include alkyl acrylates having an alkyl group having 1 to 7 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and 2-ethylhexyl methacrylate and lauryl methacrylate. Examples thereof include alkyl methacrylates having an alkyl group having 4 to 12 carbon atoms. These monomers (a-2)
May be used alone or in combination of two or more. Among them, butyl acrylate is preferred from the viewpoint of low Tg of the obtained polymer and economy.

The monomer (a-3) introduces a cross-linking into the acrylic rubber (A) to form a network structure, exhibit rubber elasticity, and also acts as a graft crossing agent. It is also a component for providing a graft active site of a vinyl monomer used when obtaining the composite rubber-containing graft copolymer particles of the present invention. Specific examples thereof include allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene and the like. These monomers (a
-3) may be used alone or in combination of two or more. Among these, allyl methacrylate, diallyl phthalate, triallyl cyanurate, and triallyl isocyanurate are particularly preferable in terms of good crosslinking efficiency and graft efficiency.

The monomer (a-4) is copolymerized with the monomer (a-1) or the like by a vinyl polymerizable group of the monomer to form a copolymer. A reactive silyl group is introduced into a side chain or terminal of the polymer. The reactive silyl group becomes a graft active site of the silicone rubber-forming component (b) when the later-described silicone rubber-forming component (b) is polymerized in the presence of acrylic rubber particles. Therefore, when the silicone rubber-forming component (b) is polymerized in the presence of acrylic rubber particles, it is preferable to use the monomer (a-4) from the viewpoint of exhibiting impact resistance.

Specific examples of the monomer (a-4) include, for example, those represented by the following general formula (1):

[0026]

Embedded image (Wherein, R ¹ is a hydrogen atom, a methyl group, and R ² is a C 1-6
Wherein X is an alkoxy group having 1 to 6 carbon atoms, a is 0, 1 or 2, and p is a number of 1 to 6), a general formula (2):

[0027]

Embedded image (Wherein R ² , X, a, and p are the same as those in the general formula (1)), a general formula (3):

[0028]

Embedded image (Wherein R ² , X and a are the same as those in the general formula (1)), a general formula (4):

[0029]

Embedded image (Wherein, R ² , X and a are the same as in the general formula (1), and R ³ is a divalent hydrocarbon group having 1 to 6 carbon atoms).

Specific examples of R ^{2 in} the general formulas (1) to (4) include, for example, an alkyl group such as a methyl group, an ethyl group and a propyl group, and a phenyl group. Examples thereof include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Further, specific examples of R ^{3 in} the general formula (4) include a methylene group, an ethylene group, a propylene group, and a butylene group.

Specific examples of the monomer represented by the general formula (1) include, for example, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane. Methacryloyloxypropyldimethylmethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyldiethoxymethylsilane, γ-methacryloyloxypropyltripropoxysilane, γ
-Methacryloyloxypropyldipropoxymethylsilane and the like, specific examples of the monomer represented by the general formula (2) include, for example, p-vinylphenyldimethoxymethylsilane, p-vinylphenyltrimethoxysilane,
Specific examples of the monomer represented by the general formula (3) include -vinylphenyltriethoxysilane, p-vinylphenyldiethoxymethylsilane and the like, for example, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane,
Specific examples of the monomer represented by the general formula (4) such as vinyltrimethoxysilane and vinyltriethoxysilane include, for example, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allyltrimethoxysilane,
Allyltriethoxysilane and the like can be mentioned. Among them, the monomers represented by the general formulas (1) and (2) are preferable from the viewpoint of economy and reactivity.

The monomer (a-5) is an acrylic rubber (A)
It is a component for adjusting the refractive index and affinity for silicone rubber. Specific examples thereof include, for example, methacrylic acid such as methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, hydroxylethyl methacrylate, benzyl methacrylate, and trimethylsilylpropyl methacrylate; Methacrylate esters other than the monomer (a-1)); aromatic vinyl monomers such as styrene and α-methylstyrene; and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Monomer (a-5) may be used alone,
More than one species may be used in combination.

The proportion of the monomers (a-1) to (a-5) used for producing the acrylic rubber (A) is as follows:
1) 2-50%, monomer (a-2) 97.8-29
%, The monomer (a-3) is 0.2 to 6%, and the monomer (a-
4) is 0 to 5% and the monomer (a-5) is 0 to 10%, and it is preferable to adjust the total amount thereof to 100%. Further, when the monomer (a-1) is 5 to 30
%, The monomer (a-2) is 94.5 to 56%, and the monomer (a
-3) is preferably 0.5 to 5%, the monomer (a-4) is 0 to 4%, and the monomer (a-5) is preferably 0 to 5%. -1) is 5 to 20% and the monomer (a-
2) 94.5-71%, monomer (a-3) 0.5-71%
3%, 0 to 3% of the monomer (a-4) and the monomer (a-
More preferably, 5) is 0 to 3%.

Here, when the amount of the monomer (a-1) is too small or too large, the high impact resistance characteristic of the present invention is not exhibited in both cases.
Preferably 5% or more, 50% or less, preferably 30%
% Or less, more preferably 20% or less.

If the amount of the monomer (a-2) is too small, the impact resistance becomes low, so that it is at least 29%, preferably at least 56%, more preferably at least 71%,
When the amount of the monomer (a-2) is too large, the other monomers (a-1), (a-3) and (a-
Since the amounts of 4) and (a-5) are too small, the effect of using these monomers is not exhibited.
8% or less, preferably 94.5% or less.

If the amount of the monomer (a-3) is too small, the crosslinking density of the acrylic rubber (A) is too low and the impact resistance is reduced. 5
% Or more, and when the amount of the monomer (a-3) is too large, the crosslink density becomes too high and the impact resistance is reduced, so that it is 6% or less, preferably 5% or less. ,
It is more preferably at most 3%.

The monomer (a-4) is an optional component,
The use of 0.2% or more is preferred in terms of the development of impact resistance. However, if the use amount is too large, a reactive silyl group is grafted during polymerization of the silicone rubber-forming component (b) under acidity described below. In addition to acting as a point, the degree of self-condensation increases, and the crosslink density of the rubber becomes too high, resulting in a decrease in impact resistance. Therefore, the amount used is 6% or less, preferably 5% or less, and more preferably 3% or less.

The monomer (a-5) is also an optional component. However, in order to appropriately adjust the refractive index and impact resistance of the obtained composite rubber particles, 10% or less, preferably 5% or less, More preferably, it is 3% or less. The lower limit is 0%.

The acrylic rubber (A) can be obtained by polymerizing the acrylic rubber-forming component (a) comprising the monomers (a-1) to (a-5). In addition,
It is preferable that the proportion of each monomer be the above-mentioned proportion in terms of the development of impact resistance.

As the polymerization method, a usual emulsion polymerization method can be used. The emulsifier used in the emulsion polymerization method is not particularly limited, and examples thereof include sodium oleate, sodium rosinate, sodium palmitate, alkylbenzenesulfonic acid, sodium alkylbenzenesulfonic acid, alkylsulfonic acid, sodium alkylsulfonic acid, and (di)
Examples thereof include sodium alkyl sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfonate, and sodium alkyl sulfate. The amount of the emulsifier used is not particularly limited, and the desired acrylic rubber (A)
May be appropriately adjusted according to the particle size of the particles.

The radical polymerization initiator and, if necessary, the chain transfer agent used in the emulsion polymerization method may be those used in ordinary emulsion polymerization, and are not particularly limited.

Specific examples of the radical polymerization initiator include cumene hydroperoxide, t-butyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butyl peroxide, lauroyl peroxide, and persulfate. Peroxides such as potassium, 2,2′-azobisisobutyronitrile,
An azo compound such as 2,2'-azobis-2,4-dimethylvaleronitrile is exemplified. Of these, peroxides are particularly preferred because of their high reactivity.

When the above peroxide is used, ferrous sulfate /
A mixture such as glucose / sodium pyrophosphate, ferrous sulfate / dextrose / sodium pyrophosphate, or ferrous sulfate / sodium formaldehyde sulfoxylate / ethylenediamine acetate can be used in combination as a reducing agent. The combined use of a reducing agent is particularly preferred because the polymerization temperature can be lowered.

The amount of these radical polymerization initiators used is
Usually, 0.005 to 10 parts, preferably 0.01 to 10 parts, per 100 parts of the acrylic rubber-forming component (a) used.
5 parts, more preferably 0.03 to 2 parts.

If the amount of the radical polymerization initiator is too small, the polymerization rate tends to be low, and the production efficiency tends to be poor. If the amount is too large, the molecular weight of the acrylic rubber (A) is low. However, the impact resistance tends to decrease.

Specific examples of the chain transfer agent include t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan and the like. In addition, when a rubber having a reactive silyl group is used, an acrylic rubber (A) having a reactive silyl group at a molecular chain terminal can be produced.

The chain transfer agent having a reactive silyl group includes, for example, a compound represented by the following general formula (5):

[0048]

Embedded image (Wherein R ² , X and a are the same as those in the general formula (1), and R ⁴ is a divalent hydrocarbon group having 1 to 18 carbon atoms).

Specific examples of R ^{4 in} the general formula (5) include a methylene group, an ethylene group, a propylene group and a butylene group.

Specific examples of the chain transfer agent represented by the general formula (5) include, for example, mercaptopropyltrimethoxysilane, mercaptopropyldimethoxymethylsilane and the like.

The chain transfer agent is an optional component. When used, the amount of the chain transfer agent is 0.001 to 5 parts based on 100 parts of the acrylic rubber-forming component (a) from the viewpoint of the development of impact resistance. Is preferred.

On the other hand, the silicone rubber (B) is (b-
1) Organosiloxane (hereinafter also referred to as organosiloxane (b-1)), (b-2) Polyfunctional silane compound (hereinafter also referred to as compound (b-2)) and (b-3)
It is obtained by copolymerizing a silicone rubber-forming component (hereinafter, also referred to as silicone rubber-forming component (b)) composed of a silane compound having a vinyl polymerizable group (hereinafter, also referred to as compound (b-3)).

The silicone rubber-forming component (b) comprises the above-mentioned compound (b-2) and the above-mentioned compound (b-3) using the above-mentioned organosiloxane (b-1) as a main raw material to form a silicone rubber (B). It is a component that does.

The organosiloxane (b-1) is a component for constituting the main skeleton of the silicone rubber (B), and specific examples thereof include linear or branched ones. From the viewpoint of applicability and economy of the emulsion polymerization system, cyclic siloxane is preferred. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane having a 6 to 12 membered ring. These may be used alone or in combination of two or more.

The compound (b-2) is copolymerized with the organosiloxane (b-1) to form a silicone rubber (B).
It acts as a cross-linking agent to introduce a cross-linking therein, and is a component for expressing rubber elasticity. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, triethoxymethylsilane, and triethoxyethylsilane. .

The compound (b-3) functions as a graft crossing agent and is a component for providing a graft active site of the vinyl monomer (c) described later. Further, it is a component which can form a cross-linking by a radical reaction between the graft active points by the radical polymerization initiator and can be used as a cross-linking agent. Even when cross-linking is performed by a radical reaction, grafting is possible because a part of the graft active site remains. Specific examples of the compound (b-3) include the same as the monomer (a-3) or a silane compound having a mercapto group in the molecule represented by the general formula (5). When the silane compound is of the trialkoxysilane type, the compound (b)
-2), it can be used as a grafting / crosslinking agent. In addition, cyclic siloxanes having a vinyl polymerizable group in the molecule, such as tetravinyltetramethylcyclotetrasiloxane and tetramethacryloyloxypropyltetramethylcyclotetrasiloxane, can also be used.

The proportions of the above-mentioned (b-1) to (b-3) used as the silicone rubber-forming component (b) are as follows: the organosiloxane (b-1) is 70 to 99.9%, and the compound (b)
-2) is 0 to 15%, and the compound (a-3) is 0 to 15% ((b-2) and (b-3) are not simultaneously 0%, and either one is 0.1%). %), And the total amount thereof is adjusted to be 100%. Further, the organosiloxane (b-1) is 80 to 99.8%, the compound (b-2) is 0.1 to 10%, and the compound is 0.1 to 10%.
And more preferably 90 to 99% of the organosiloxane (b-1) and 0.5 to 0.5% of the compound (b-2).
More preferably, the content of the compound is 0.5 to 5%, and the content of the compound is 0.5 to 5%.

When the amount of the organosiloxane (b-1) is too small, the obtained silicone rubber tends to have less flexibility and other properties.
0% or more, preferably 80% or more, more preferably 9% or more.
0% or more. In addition, the organosiloxane (b-
If the amount of 1) is too large, the other compound (b)
Since the amounts of (b-2) and (b-3) are too small, the effect of using these compounds is not exhibited.
9% or less, preferably 99.8% or less, more preferably 99% or less.

When neither the compound (b-2) nor the compound (b-3) is used, the impact resistance tends to decrease, and the content of either one is 0.1% or more, preferably 0.1% or more. 1% or more, more preferably both are used at 0.5% or more. If too much of each compound is used, the properties such as the flexibility of the silicone rubber are hardly exhibited, and it is less than 15%, preferably 10%.
Or less, more preferably 5% or less.

The polymerization of the silicone rubber-forming component (b)
A method in which the silicone rubber-forming component (b) is emulsified and dispersed in water by mechanical shearing in the presence of an emulsifier, and then heated and polymerized in an acidic state can be employed.

In this case, the emulsifier used at the time of producing the above-mentioned acrylic rubber (A) can be used.

The mechanical shearing can be obtained by using a high-speed stirrer such as a homomixer or a special disperser such as a high-pressure homogenizer or an ultrasonic disperser.

The acidic state may be determined by adding an inorganic acid such as sulfuric acid or hydrochloric acid, an alkylbenzenesulfonic acid, an alkylsulfonic acid,
It is preferably obtained by adding an organic acid such as trifluoroacetic acid, and the pH is preferably adjusted to 1.0 to 3 from the viewpoint that the production equipment is not corroded and an appropriate polymerization rate can be obtained. More preferably, it is adjusted to 2.5.

The heating for the polymerization is preferably from 60 to 120 ° C. from the viewpoint that an appropriate polymerization rate can be obtained, and from 70 to 10 ° C.
0 ° C. is more preferred.

In an acidic state, the Si—O—Si bond forming the skeleton of the silicone rubber is in an equilibrium state of cleavage and formation, and this equilibrium changes with temperature.
To stabilize the silicone rubber chain, it is preferable to neutralize by adding an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or sodium carbonate. Moreover,
In the equilibrium, a polymer having a high molecular weight or a high degree of crosslinking is more likely to be produced depending on the production side as the temperature becomes lower. After performing the above, it is preferable to neutralize after cooling to room temperature or less and holding for about 5 to 100 hours.

The composite rubber particles (C) comprising the acrylic rubber (A) and the silicone rubber (B) include, for example, (1) an acrylic rubber obtained by copolymerizing the acrylic rubber-forming component (a). Composite rubber particles (hereinafter also referred to as composite rubber particles (C1)) obtained by copolymerizing the silicone rubber-forming component (b) in the presence of the rubber particles,
(2) The acrylic rubber-forming component (a) is divided into an acrylic rubber-forming component (a-I) and an acrylic rubber-forming component (a-II). A rubber particle is prepared, a silicone rubber-forming component (b) is polymerized in the presence of the rubber particle, and a composite rubber particle obtained by copolymerizing an acrylic rubber-forming component (a-II) (hereinafter referred to as a composite rubber particle (C2 ), (3) an acrylic rubber-forming component (a) in the presence of silicone rubber particles obtained by copolymerizing the silicone rubber-forming component (b).
(Hereinafter, also referred to as composite rubber particles (C3)).

Among these, the composite rubber particles (C1) and (C2) of (1) and (2) have a narrow particle size distribution, and are composed of particles composed of only silicone rubber or particles composed of only acrylic rubber. This is preferable in that there is almost no by-product.

The composite rubber particles (C1) can be produced, for example, as follows.

The monomer (a-1) and the monomer (a-
2) An acrylic rubber obtained by emulsion-copolymerizing an acrylic rubber-forming component (a) comprising a monomer (a-3), a monomer (a-4) and a monomer (a-5) ( A) The silicone rubber-forming component (b) can be obtained by emulsion copolymerization in the presence of particles.

The average particle size of the acrylic rubber (A) can be controlled using ordinary emulsion polymerization techniques such as increasing or decreasing the amount of the emulsifier used, and from the viewpoint of the development of impact resistance, the average particle size can be adjusted to 0.01 to 0.01%.
Particles having a particle size of 1 μm, preferably in the range of 0.03 to 0.8 μm are used.

The gel content contained in the acrylic rubber (A) particles (weight fraction of toluene-insoluble content when a sample composed of rubber particles is immersed in toluene at room temperature for 24 hours and centrifuged at 12,000 rpm for 1 hour) is 70. % Or more, more preferably 80% or more from the viewpoint of impact resistance. The upper limit is 100%.

The acrylic rubber (A) particles obtained as described above include the monomer (a-1) and the monomer (a).
-2), the monomer (a-3), the monomer (a-4)
And a monomer (a-5) copolymerizable with these monomers
(Of course, when the monomer (a-4) and the monomer (a-5) are not used, they are not included.) It is generally considered that they are randomly copolymerized. The monomer (a-
It is considered to have a structure crosslinked by a part of the reactive group present in 2). Further, not all of the vinyl-based polymerizable groups of the monomer (a-2) are not consumed in the polymerization but remain partially and exist as graft points of the vinyl-based monomer described later. When the monomer (a-4) is used, a part of the reactive group present in the monomer (a-4) exists as a graft active site of the silicone rubber-forming component (b). It is considered to have a structure cross-linked by a part of the functional group.

By polymerizing the silicone rubber-forming component (b) in the presence of such an emulsion of acrylic rubber (A) particles, composite rubber particles (C1) are produced.

When the silicone rubber-forming component (b) is polymerized in the presence of the acrylic rubber (A) particles, for example, the organosiloxane (b-1), the compound (b-2) and the compound (b-3) are polymerized. The mixed solution is added all at once to the emulsion of the acrylic rubber (A) particles, and then an inorganic acid such as sulfuric acid or hydrochloric acid or an organic acid such as alkylbenzene sulfonic acid or trifluoroacetic acid is added to the system to adjust the pH to 3 or less, and then the pH is adjusted to 60 or less. It can be carried out by heating to at least ℃. In addition, after adding the mixed solution composed of (b-1) to (b-3) at once, the pH may be lowered after stirring for a certain period of time. Acrylic rubber with reduced pH (A)
It can also be carried out by sequentially adding the silicone rubber forming component (b) to the emulsion containing the particles.

In the case of the batch addition or the sequential addition,
The silicone rubber-forming component (b) can be used as it is or as an emulsion by mixing with water and the emulsifier, but it is preferable to use a method of adding the emulsion in the form of an emulsion from the viewpoint of polymerization rate.

The use ratio of the silicone rubber-forming component (b) to the acrylic rubber-forming component (a) ((b) /
(A)) is 30/70 to 90/10, and 50/5
0 to 90/10 is more preferable, and 60/40 to 90/1.
0 is particularly preferred. If the usage ratio of the silicone rubber-forming component (b) is too small, the polymerization conversion rate will be extremely low, and a large amount of unreacted silicone rubber-forming component (b) will remain, and the production efficiency tends to decrease. If it is too large, the amount of silicone rubber in the obtained composite rubber particles becomes too large, and the impact resistance tends to decrease.

As described above, the silicone rubber in the composite rubber particles is in an equilibrium state in which the Si—O—Si bond is cleaved and formed under an acidic condition. Therefore, an aqueous alkali solution is added to stabilize the silicone rubber chain. It is preferable to neutralize with.

The silicone rubber (B) formed in the course of the polymerization of the silicone rubber-forming component (b) is the same as the organosiloxane (b-1), the compound (b-2) and the compound (b).
-3) is usually a random copolymer (of course, when only one of the compound (b-2) and the compound (b-3) is used, the other is not included). In addition,
When the monomer (a-3) is used during the production of the acrylic rubber (A), a chemical bond is formed between the reactive silyl group present in the side chain of the acrylic rubber (A) and the silicone rubber (B). Is generated, and when the compound (b-3) is used, it is considered that the silicone rubber (B) has a network structure.

The average particle size of the composite rubber particles (C1) is from 0.01 to 1.1 μm, preferably from 0.03 to 1 μm, in view of the development of impact resistance.

The gel content of the composite rubber particles (C1) is at least 70%, and preferably at least 80% in view of the development of impact resistance.

The composite rubber particles (C1) thus obtained
It is desirable that the silicone rubber content is 30 to 90%, preferably 50 to 90%, and more preferably 60 to 90%. When the content of the silicone rubber is less than 30%, the residual ratio of the unreacted silicone rubber-forming component (b) increases, which is not preferable in terms of the development of impact resistance and the production efficiency. When the silicone rubber content exceeds 90%, the impact resistance tends to decrease.

The form of the composite rubber particles (C1) tends to take the form of particles in which silicone rubber is finely dispersed in acrylic rubber particles or (and) the form of particles composed of an acrylic rubber core and a silicone rubber shell.

In the case of the composite rubber particles (C1), it is difficult to obtain those having a low silicone rubber content at a high conversion. This is because, as described above, when the usage ratio ((b) / (a)) of the silicone rubber forming component (b) to the acrylic rubber forming component (a) is smaller than 30/70, the polymerization conversion of the silicone rubber forming component (b) is performed. This is because the rate is remarkably reduced, and the production efficiency is extremely deteriorated. The composite rubber particles (C2) have solved this problem.

The composite rubber particles (C2) were prepared by dividing the acrylic rubber-forming component (a) into an acrylic rubber-forming component (a-I) and an acrylic rubber-forming component (a-II). I) is copolymerized to prepare acrylic rubber (hereinafter also referred to as acrylic rubber (AI)) particles, and in the presence thereof, the silicone rubber-forming component (b) is polymerized using an amount that does not decrease the conversion. In order to further control the silicone rubber content, an acrylic rubber forming component (a
-II) (the acrylic rubber formed from the acrylic rubber-forming component (a-II) is hereinafter also referred to as acrylic rubber (AII)).

The acrylic rubber-forming component (a) was combined with the acrylic rubber-forming component (a-I) and the acrylic rubber-forming component (a-I).
As the ratio to be divided into I), the acrylic rubber forming component (a)
The acrylic rubber-forming component (a-II) is polymerized to a polymer obtained by polymerizing the ratio ((b) / (a-I)) of the silicone rubber-forming component (b) to -I) at 30/70 to 99/1. There is no particular limitation as long as the silicone rubber content is in the range of 1 to 50%.

The monomer (a) constituting the acrylic rubber-forming component (a-I) and the acrylic rubber-forming component (a-II)
-1) to the monomer (a-5), the acrylic rubber-forming component (a-I) and the acrylic rubber-forming component (a) may be used in the acrylic rubber-forming component (a) as long as the above-mentioned usage ratio is used.
-II).

The monomer (a-3) in the acrylic rubber forming component (a-I) is
-II) acts as a graft point between the vinyl monomer (c).

The monomer (a-4) mainly provides an active site with the silicone rubber-forming component (b). However, when the monomer (a-4) is used in the acrylic rubber-forming component (a-II), Is preferred because the acrylic rubber (AII) has an affinity for the silicone rubber (B).

The polymerization of the acrylic rubber-forming component (a-I) and the silicone rubber-forming component (b) can be carried out by emulsion polymerization as in the case of the composite rubber particles (C1). The polymerization of the acrylic rubber-forming component (a-II) in the presence of the emulsion of the obtained composite rubber particles can also be carried out by emulsion polymerization.

The acrylic rubber (AII) formed from the acrylic rubber-forming component (a-II) comprises a monomer (a-1),
Monomer (a-2), monomer (a-3), monomer (a-
4) and the monomer (a-5) are usually those obtained by random copolymerization (of course, when the monomer (a-4) and the monomer (a-5) are not used, they are Not included), a part of which is grafted to a vinyl polymerizable group derived from the monomer (a-3) in the acrylic rubber (AI) particles, and a compound ( b
When -3) is used, it is considered that the vinyl polymerizable group or the mercapto group derived from the compound (b-3) is also grafted.

The average particle size of the composite rubber particles (C2) obtained as described above is preferably from 0.01 to 1.1 μm, more preferably from 0.03 to 1 μm from the viewpoint of the development of impact resistance. It is.

The gel content of the composite rubber particles (C2) is preferably 70% or more, and more preferably 80% or more from the viewpoint of exhibiting impact resistance.

It is desirable that the composite rubber particles (C2) have a silicone rubber content of 1 to 50%, preferably 1 to 45%. 1% silicone rubber content
When the value is less than the above, the effect of using the silicone rubber is not obtained, and the degree of impact resistance tends to be low. When the silicone rubber content exceeds 50%, the composite rubber particles (C1) are preferable from the viewpoint of production efficiency.

Further, the form of the composite rubber particles (C2) tends to take a particle form in which silicone rubber is finely dispersed in acrylic rubber particles.

Next, the composite rubber particles (C3) will be described. The composite rubber particles (C3) are produced, for example, as follows.

Emulsion copolymerization of the silicone rubber-forming component (b) is carried out, and the acrylic rubber-forming component (a) is emulsion-copolymerized in the presence of the obtained silicone rubber (B) particles.

Emulsion polymerization of the silicone rubber-forming component (b) can be carried out using a known method described in, for example, US Pat. Nos. 2,891,920 and 3,294,725.

For example, the silicone rubber-forming component (b) can be emulsified and dispersed in water by mechanical shearing in the presence of an emulsifier and polymerized in an acidic state. In this method, when emulsified droplets having a size of several μm or more are prepared by mechanical shearing, the average particle size of the silicone rubber particles obtained after the polymerization is 0.02% depending on the amount of the emulsifier used.
It can be controlled in the range of 0.4 μm. Further, when emulsified droplets of 0.2 to 0.5 μm are prepared by mechanical shearing, the average particle size of the silicone rubber particles obtained after the polymerization can be substantially the same as the particle size of the droplets. In addition,
In order to obtain silicone rubber particles having an average particle diameter of about 0.2 to 0.5 μm, the latter method is preferable in that a particle having a narrow particle diameter distribution can be obtained.

When producing silicone rubber particles having a size of 0.1 μm or less, it is preferable to carry out polymerization in multiple stages. For example, several μm obtained by emulsifying the silicone rubber-forming component (b), water and an emulsifier by mechanical shearing.
Emulsion polymerization of 1 to 50% of the emulsion composed of the above emulsified droplets is first performed in an acidic state, and the remaining emulsion is additionally polymerized in the presence of the obtained silicone rubber particles. The silicone rubber particles thus obtained have an average particle size of 0.1 μm or less and a standard deviation of the particle size distribution of 50% or less.

Emulsified droplets of several μm or more can be prepared by using a high-speed stirrer such as a homomixer.
The 0.5 μm emulsified droplet can be prepared by using a special disperser such as a high-pressure homogenizer or an ultrasonic disperser.

The acidic state is preferably adjusted to pH 1.0 to 3 by adding an inorganic acid or an organic acid as described above.

The polymerization temperature during the polymerization of the silicone rubber-forming component (b) is 60 to 120 ° C. as described above,
C. to 100.degree. C. is preferred because the polymerization rate is moderate. As described above, in order to obtain a polymer having a high molecular weight or a high degree of crosslinking, the polymerization of the silicone rubber-forming component (b) is carried out at 60 ° C. or more, and then cooled to about room temperature to obtain 5-10%.
It is preferable to neutralize after holding for about 0 hours.

The silicone rubber (B) particles include, for example,
When formed from the organosiloxane (b-1) and the compound (b-2), they usually have a network structure which is randomly copolymerized and crosslinked. When formed from the organosiloxane (b-1) and the compound (b-3), they become a linear silicone rubber having a vinyl polymerizable group by random copolymerization. In this case, by reacting a part of vinyl polymerizable groups with a radical polymerization initiator, it is possible to obtain a polymer having a network structure and a vinyl polymerizable group. Further, when formed from the organosiloxane (b-1), the compound (b-2), and the compound (b-3), the compound has a network structure and a vinyl polymerizable group.

The average particle size of the silicone rubber (B) particles is 0.02 to 0.5 μm, preferably 0.1 to 0.5 μm.
03 to 0.4 μm. It tends to be difficult to produce those having an average particle diameter of less than 0.02 μm or more than 0.5 μm by emulsion polymerization of the silicone rubber-forming component (b).

The gel content of the silicone rubber (B) particles is from 0 to 100%, more preferably from 0 to 40%, or from 60% to 100% from the viewpoint of the development of impact resistance.

Acrylic rubber-forming component (a) in the presence of the emulsion of neutralized silicone rubber (B) particles
The composite rubber particles (C3) are produced by carrying out the emulsion polymerization of

The amount of the acrylic rubber-forming component (a) used is
1 to 90% of silicone rubber (B) particles, further 1 to 5
10-99 so that the total amount becomes 100% for 0%
%, More preferably 50 to 99%, in view of the development of impact resistance.

The structure of the composite rubber particles (C3) thus obtained is, for example, such that the silicone rubber (B) having a cross-linking bond derived from the compound (b-2) is different from the compound (b-3) present in the chain. It is chemically bonded to the acrylic rubber (A) via a vinyl polymerizable group or a mercapto group derived from the polymer, and further has a structure in which a crosslinked network of silicone rubber and a crosslinked network of acrylic rubber are entangled. Conceivable. Of course, if the compound (b-2) is not used, there is no cross-linking derived from the compound (b-2) in the silicone rubber (B).

The average particle size of the composite rubber particles (C3) is from 0.02 to 1.1 μm, preferably from 0.03 to 1 μm, in view of the development of impact resistance.

The gel content of the composite rubber particles (C3) is at least 70%, more preferably at least 80%, in view of the development of impact resistance.

The composite rubber particles (D3) preferably have a silicone rubber content of 1 to 90%, more preferably 1 to 50%. If the silicone rubber content is too low or too high, the degree of impact resistance tends to be low. In addition, the form of the composite rubber particles is as follows.
Shell, particle form of acrylic rubber as second shell, particle form of silicone rubber as core and acrylic rubber as shell, and / or particle form of acrylic rubber dispersed in silicone rubber in island form Tend to take.

By graft-polymerizing the vinyl monomer (c) to the composite rubber particles (C) produced as described above, the silicone rubber portion and / or the acrylic rubber portion of the composite rubber particles are added to the composite rubber particles. Composite rubber-containing graft copolymer particles (hereinafter, also referred to as graft copolymer particles) to which a polymer of a vinyl monomer is grafted are produced.

The vinyl monomer (c) is used to increase the compatibility of the obtained graft copolymer particles with the thermoplastic resin to be blended and to uniformly disperse the graft copolymer particles in the thermoplastic resin. What is used.

The average particle size of the graft copolymer particles is preferably at least 0.03 μm, more preferably at least 0.06 μm, and at most 1.2 μm, more preferably 1 μm.
m or less is preferable. If it is too small or too large, the impact resistance tends to decrease. Further, the gel content of the graft copolymer particles is preferably at least 70%, more preferably at least 80%. When the gel content is less than 70%, the impact resistance tends to decrease.

Specific examples of the vinyl monomer (c) include aromatic vinyl monomers such as styrene, α-methylstyrene and paramethylstyrene, and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Monomer, vinyl chloride, vinyl halide monomers such as vinylidene chloride, and methacrylic acid such as methacrylic acid, methyl methacrylate and ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate, and esters thereof. Examples include methacrylic acid monomers, acrylic acid monomers such as acrylic acid such as acrylic acid, methyl acrylate, butyl acrylate, glycidyl acrylate, and hydroxyethyl acrylate, and esters thereof. These may be used alone,
Two or more kinds may be used in combination.

The amount of the vinyl monomer (c) used is such that the total amount is 100% with respect to the composite rubber particles (C), preferably 5 to 95%, more preferably 10 to 90%. Preferably 5-95%, more preferably 10-9
0%. If the amount of the vinyl monomer is too large, the content of the rubber component tends to be too small to exhibit sufficient impact resistance, and if the amount is too small, the monomer to be grafted is too small. Is small, and when blended with a thermoplastic resin, the compatibility with the thermoplastic resin which is a matrix resin becomes poor, and the impact resistance also tends to decrease.

The graft polymerization can be carried out by using a usual emulsion polymerization method. As the radical polymerization initiator and the chain transfer agent used for the polymerization, the same ones that can be used in the production of the acrylic rubber (A) can be used. When an emulsifier is further used, those which can be used in the production of the acrylic rubber (A) can be used.

A preferred form of the graft polymerization is a method in which a mixture of a vinyl monomer (c) and a radical polymerization initiator is dropped into an emulsion of the composite rubber particles (C) to carry out polymerization.

In the polymerization of the vinyl monomer (c) in the presence of the emulsion of the composite rubber particles (C), the portion corresponding to the branch of the graft copolymer (here, the vinyl monomer (c) The polymer) does not graft on the trunk component (here, the composite rubber particles), but also polymerizes solely with the branch component alone, so-called free polymer, which is obtained as a by-product, and is obtained as a mixture of the graft copolymer and the free polymer. In the present invention, both are collectively referred to as a graft copolymer.

The graft copolymer particles after polymerization may be used by separating the polymer from the emulsion when blended with the thermoplastic resin, or may be used as an emulsion. Examples of the method for separating the polymer include a conventional method, for example, a method of adding a metal salt such as calcium chloride, magnesium chloride, or magnesium sulfate to the emulsion to coagulate, separate, wash, dehydrate, and dry the emulsion. Also, a spray drying method can be used.

The thus-obtained graft copolymer particles (separated polymer or as emulsion) are blended with various thermoplastic resins to obtain a thermoplastic resin composition having improved impact resistance. Is manufactured.

Specific examples of the thermoplastic resin include polyvinyl chloride resin, polystyrene resin, styrene-acrylonitrile copolymer resin, styrene-acrylonitrile-
N-phenylmaleimide copolymer resin, α-methylstyrene-acrylonitrile copolymer resin, polymethyl methacrylate resin, methyl methacrylate-styrene copolymer resin,
Examples include a polycarbonate resin, a polyamide resin, a polyester resin such as polyethylene terephthalate and polybutylene terephthalate, a polyphenylene ether-polystyrene composite resin, an ABS resin, an AAS resin, and an AES resin.

The amount of the graft copolymer particles to be added to 100 parts of the thermoplastic resin is from 1 to 150 parts, preferably from 3 to 120 parts in view of the balance of physical properties.
If the addition amount is too small, the impact resistance of the thermoplastic resin will not be sufficiently improved, and if it is too large, it will be difficult to maintain properties such as rigidity and surface hardness of the thermoplastic resin.

The powder of the graft copolymer particles from which the polymer has been separated from the emulsion and the thermoplastic resin are mixed by a Henschel mixer, ribbon blender or the like, and then melt-kneaded by a roll, extruder, kneader or the like. Can be performed.

At this time, commonly used compounding agents, ie, plasticizer, stabilizer, lubricant, ultraviolet absorber, antioxidant,
Flame retardants, pigments, glass fibers, fillers, polymer processing aids,
A polymer lubricant or the like can be blended.

When the thermoplastic resin is produced by an emulsion polymerization method, both the emulsion of the thermoplastic resin and the emulsion of the graft copolymer particles are blended in an emulsion state and then co-coagulated. It is also possible to obtain a thermoplastic resin composition.

The molding method of the obtained thermoplastic resin composition includes molding methods used for molding ordinary thermoplastic resin compositions, such as injection molding method, extrusion molding method, blow molding method, calender molding method and the like. Can be applied.

The obtained molded product is superior in both impact resistance and weather resistance as compared with a product using a conventional impact modifier.

[0129]

EXAMPLES The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The measurements and tests in the following Examples and Comparative Examples were performed as follows.

[Polymerization conversion rate] a) Composite rubber particles (C-1, C-1 ') Acrylic rubber forming component (a): An emulsion of the solid component (A) was dried in a hot air drier at 120 ° C. for 1 hour. The amount of the solid component (A) was calculated by the following formula.

Polymerization conversion (%) = ｛(solid component (A)
Amount) / (Acrylic rubber forming component (a) amount)｝ × 1
[0092] Silicone rubber-forming component (b): An emulsion containing solid component (A) and solid component (B) (solid component (A + B)) is dried in the same manner as in the case of the acrylic rubber-forming component (a) to form a solid. The amount of the component (A + B) was determined and calculated based on the following equation.

Polymerization conversion (%) = ｛(solid component (A +
B) Amount-solid component (A) amount / (prepared silicone rubber forming component (b) amount) ｂ × 100 b) Composite rubber particles (C-2 to C-4, C-2 ′ to C-)
3 ') Acrylic rubber-forming component (a-I): An emulsion containing solid component (AI) is dried in the same manner as in the case of the acrylic rubber-forming component (a) to determine the amount of solid component (AI). It calculated based on the formula of.

Polymerization conversion (%) = ｛(solid component (A
I) Amount) / (Feed acrylic rubber forming component (a-I))
Amount)｝ × 100 Silicone rubber forming component (b): An emulsion containing solid component (AI) and solid component (B) (solid component (AI + B)) was prepared in the same manner as in the case of the acrylic rubber forming component (a). After drying, the amount of the solid component (AI + B) is determined,
It was calculated based on the following equation.

Polymerization conversion (%) = ｛(solid component (AI +
B) Amount-solid component (AI) amount) / (charged silicone rubber forming component (b) amount)｝ × 100 acrylic rubber forming component (a-II): solid component (A)
E) An emulsion containing the solid component (B) and the solid component (AII) (solid component (AI + B + AII)) is dried in the same manner as in the case of the acrylic rubber-forming component (a) to reduce the amount of the solid component (AI + B + AII). It was calculated based on the following equation.

Polymerization conversion (%) = ｛(solid component (AI
+ B + AII) amount-solid component (AI + B) amount / (prepared acrylic rubber forming component (a-II) amount)｝ × 100 c) Composite rubber particles (C-5, C-4 ′) Silicone rubber forming component (b) : The emulsion containing the solid component (B) was dried in the same manner as in the case of the acrylic rubber-forming component (a) to determine the amount of the solid component (B), which was calculated based on the following equation.

Polymerization conversion (%) = (solid component (B)
Amount) / (Amount of charged silicone rubber forming component (b))｝ ×
100 Acrylic rubber forming component (a): An emulsion containing solid component (A) and solid component (B) (solid component (A + B)) is dried and solidified in the same manner as in the case of the acrylic rubber forming component (a). The amount of the component (A + B) was determined and calculated based on the following equation.

Polymerization conversion (%) = ｛(solid component (A +
B) Amount-solid component (B) amount / (prepared acrylic rubber forming component (a) amount)｝ × 100 d) Graft copolymer particles vinyl monomer (c): solid component (A + B) or solid component (AI + B + AII) and solid component (c) (solid component (A + B + c) or solid component (AI + B +
AII + c)) is dried in the same manner as the acrylic rubber-forming component (a) to dry the solid component (A +
B + c) or the amount of the solid component (AI + B + AII + c) was calculated based on the following equation.

Polymerization conversion (%) = ｛(solid component (A + B)
+ C) (or the amount of solid components (AI + B + AII + c))
-Solid component (A + B) amount (or solid component (AI + B +
AII) Amount)) / (Amount of vinyl monomer (c) charged)｝ × 100 [Silicone rubber content] It was calculated from the amounts of charged components and the polymerization conversion of each component based on the following formula. A) Composite rubber particles (C-1, C-1 ′) Silicone rubber content (%) = ｛(Prepared silicone rubber forming component (b) amount × silicone rubber forming component (b))
/ (Polymerization conversion rate of silicone rubber-forming component (b) × polymerization conversion rate of silicone rubber-forming component (b)) + (polymerization conversion of acrylic rubber-forming component (a) × acrylic rubber-forming component (a)) Rate)]｝ × 100 b) Composite rubber particles (C-2 to C-4, C-2 ′ to C-
3 ′) Silicone rubber content (%) = ｛(amount of charged silicone rubber-forming component (b) × polymerization conversion of silicone rubber-forming component (b)) / [(amount of charged silicone rubber-forming component (b) × amount of silicone rubber) (Polymerization conversion rate of component (b)) + (Acrylic rubber forming component (a-I) × polymerization conversion rate of acrylic rubber forming component (a-I)) + (Acrylic rubber forming component (a-II) × Polymerization conversion of acrylic rubber-forming component (a-II))} × 100 c) Composite rubber particles (C-5, C-4 ′) Silicone rubber content (%) = ｛(charged silicone rubber-forming component (b) ) Amount x silicone rubber forming component (b)
/ ((Amount of charged silicone rubber-forming component (b)) × (polymerization conversion of silicone rubber-forming component (b)) + (polymerization of charged acrylic rubber-forming component (a) × acrylic rubber-forming component (a)) (Conversion rate)]｝ × 100 [Gel content] The sample was immersed in toluene at room temperature for 24 hours, centrifuged at 12,000 rpm for 60 minutes, and the weight fraction (%) of the toluene-insoluble portion in the sample was measured. [Average particle diameter] As a measuring device, PACIFIC SCIENTIFI
The volume average particle diameter (μm) was measured by a dynamic light scattering method using NICOMP MODEL370 particle diameter analyzer manufactured by C). [Izod strength] 2 according to ASTM D-256
Measured at 3 ° C. and 0 ° C. with a notched イ ン チ inch bar. [Drop weight strength] 150 mm x 1 manufactured by injection molding
A plate-shaped compact of 00 mm × 2 mm was evaluated by half-break energy (weight drop × height) at 23 ° C. (kg
M). [Workability] Using a FAS100B injection molding machine manufactured by FANUC CORPORATION, cylinder temperature 250 ° C., injection pressure 135
At 0 kgf / cm ² , the flow length of the resin in a spiral mold having a thickness of 3 mm was measured.

Example 1 (1) Production of Composite Rubber-Containing Graft Copolymer Particles (D-1) A five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, and thermometer was used. The components described below were charged.

Ingredient Amount Amount (parts) Pure water 225 Sodium dodecylbenzenesulfonate (SDBS) 0.04 Then, the temperature was raised to 40 ° C. while replacing the system with nitrogen gas. And 10% of a solution obtained by adding 0.07 part of cumene hydroperoxide (CHP) to 50 parts of the acrylic rubber-forming component (a) having the ratio shown in (1).

After stirring for 5 minutes, 5 parts of pure water, 0.13 of sodium formaldehyde sulfoxylate (SFS)
, 0.001 part of ferrous sulfate and 0.004 part of disodium ethylenediaminetetraacetate (EDTA) were added to initiate polymerization, followed by stirring for 1 hour. Pure water 25
Parts, an aqueous solution consisting of 0.68 parts of SDBS was added, and the rest of the acrylic rubber-forming component (a) was added dropwise over 3 hours. After the addition was completed, stirring was further continued for 1 hour to terminate the polymerization, and the acrylic rubber ( A) Particles were obtained. Table 1 shows the polymerization conversion of the acrylic rubber-forming component (a) and the average particle size of the acrylic rubber particles.

Separately, 50 parts of a silicone rubber raw material (silicone rubber-forming component (b)) containing the siloxane and silane compounds shown in Table 1 in the proportions shown in Table 1 were mixed with 90 parts of pure water.
And a mixture consisting of 0.5 part of SDBS and 0.5 part of SDBS were stirred with a homomixer at 10,000 rpm for 5 minutes to prepare an emulsion.

The emulsion of the silicone rubber raw material was added all at once to the emulsion of the acrylic rubber (A) particles. After the temperature of the system was raised to 90 ° C. over about 50 minutes, an aqueous solution consisting of 18 parts of pure water and 2 parts of dodecylbenzenesulfonic acid (DBSA) was added to make the system acidic to pH 1.3. After reacting at 90 ° C. for 6 hours, the mixture is cooled to 25 ° C., maintained for 20 hours, and adjusted to pH 8.
2 to terminate the polymerization to obtain an emulsion of composite rubber particles (C-1). . Table 1 shows the polymerization conversion of the silicone rubber raw material, the average particle diameter of the obtained composite rubber particle emulsion, the gel content of the composite rubber, and the silicone rubber content.

Next, graft polymerization was carried out using the obtained emulsion of composite rubber particles. In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, the amount of components (parts) pure water 230 The composite rubber particles (C-1) (solid content) 80 SFS A mixed solution consisting of 0.2 ferrous sulfate 0.002 EDTA 0.008 was charged at once.

Next, a mixture of the following components was added at 45 ° C. for 2 hours.
The mixture was added dropwise over a period of time, and stirring was continued for 30 minutes after the completion of the addition to terminate the polymerization.

Table 2 shows the polymerization conversion of methyl methacrylate (MMA) 20 CHP 0.05 MMA, the average particle size of the graft copolymer particles, and the gel content of the graft copolymer particles. .

Next, 2 parts of calcium chloride was added to the emulsion for coagulation, followed by dehydration and drying to obtain powder of composite rubber-containing graft copolymer particles (D-1). (2) Preparation of Vinyl Chloride Resin Composition The following components were kneaded with a hot roll adjusted to 180 ° C. for 5 minutes, and then compression molded at 190 ° C. for 15 minutes to produce an Izod test piece.

Component Amount Amount (parts) Vinyl chloride resin 100 Graft copolymer particles (D-1) 7 Tin stabilizer 2.5 Lubricant 0.5 Filler 3.0 Polymer processing aid 2 Vinyl chloride Resin manufactured by Kanegafuchi Chemical Industry Co., Ltd .: Kanevinyl S1008, tin-based stabilizer manufactured by Nitto Kasei Co., Ltd .:
N-2000E, lubricant used by Hoechst: Hoechst-Wachs E
E), filler: R-650, manufactured by Sakai Chemical Co., Ltd .; polymer processing aid: Kaneace PA-20, manufactured by Kaneka Chemical Industry Co., Ltd.
Was used.

Using the obtained test pieces, Izod strength was measured at 23 ° C. and 0 ° C. The same test was performed on test pieces exposed for 1000 hours with a sunshine weather ometer. Table 2 shows the results.

Comparative Example 1 As Comparative Example 1, the acrylic rubber (A ′) was prepared in the same manner as in Example 1 except that the constituent monomers of the acrylic rubber-forming component (a) of Example 1 and the proportions thereof were shown in Table 1. ) Particles and composite rubber particles (C-1 ′) were prepared. Table 1 shows the results.
Further, graft copolymer particles (D-1 ′) were prepared in the same manner as in Example 1 using the composite rubber particles (C-1 ′), and were prepared from the vinyl chloride resin composition in the same manner as in Example 1. An Izod test piece was prepared and tested. Table 2 shows the results.

The abbreviations of the components in Table 1 represent the following substances. BA: butyl acrylate 2-EHA: 2-ethylhexyl acrylate AlMA: allyl methacrylate DSMA: γ-methacryloyloxypropyldimethoxymethylsilane D4: octamethylsictotetrasiloxane TEOS: tetraethoxysilane

[0153]

[Table 1]

[0154]

[Table 2] From the results shown in Table 2, when the composite rubber of the present invention in which a part of BA of the constituent monomer unit of the acrylic rubber was replaced with the 2-EHA monomer unit was used, the constituent unit amount of the acrylic rubber was It can be seen that the impact resistance and the weather resistance are superior to the case where the conventional composite rubber whose body unit consists essentially of only BA is used.

Examples 2 to 4 (1) Composite rubber-containing graft copolymer particles (D-2 to D
Preparation of -4) The components described below were charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer.

Component Amount Amount (parts) Pure water 33 SDBS 0.12 Then, the temperature was raised to 40 ° C. while replacing the system with nitrogen gas, and the acrylic containing the monomers shown in Table 3 in the proportions shown in Table 1 15% of a solution obtained by adding 0.01 part of CHP to 5 parts of the rubber-forming component (a-I) was added all at once.

After stirring for 5 minutes, 1.7 parts of pure water, SFS
0.02 parts, ferrous sulfate 0.0003 parts, EDTA
An aqueous solution consisting of 0.001 parts was added to start the polymerization, followed by stirring for 1 hour. Thereafter, the remainder of the acrylic rubber-forming component (a-I) was added dropwise over 15 minutes, and after the addition was completed, stirring was continued for 1 hour to terminate the polymerization to obtain an emulsion of acrylic rubber (AI) particles. Table 3 shows the polymerization conversion of the acrylic rubber-forming component (a-I).

Separately, 10 parts of a silicone rubber raw material (silicone rubber-forming component (b)) containing the siloxane and silane compounds shown in Table 3 in the proportions shown in Table 3 were mixed with pure water 13 parts.
And a mixture of 0.1 parts of SDBS were stirred with a homomixer at 10,000 rpm for 5 minutes to prepare an emulsion.

The silicone rubber raw material emulsion was added all at once to the acrylic rubber (AI) particle emulsion. After the temperature of the system was raised to 85 ° C. over about 50 minutes, an aqueous solution consisting of 3 parts of pure water and 0.3 parts of DBSA was added,
The system was acidified to pH 1.4. After reacting at 85 ° C. for 5 hours, the mixture was cooled to 25 ° C. and maintained for 20 hours, and the pH was returned to 8.1 with an aqueous sodium hydroxide solution to terminate the polymerization. Table 3 shows the polymerization conversion of the silicone rubber raw material.

Further, 180 parts of pure water, SFS 0.15
Parts, ferrous sulfate 0.001 part, and EDTA 0.004 part were charged at a time, and at 40 ° C., the monomers shown in Table 3 were in the proportions shown in Table 3, and the acrylic rubber forming component (a-II) 85
Of CHP was added dropwise over 5 hours, and after the addition was completed, stirring was continued for 30 minutes to terminate polymerization, and emulsion of composite rubber particles (C-2 to C-4) was added. I got Table 3 shows the polymerization conversion of the acrylic rubber-forming component (a-II), the average particle diameter of the obtained composite rubber particles (C-2 to C-4), the gel content, and the silicone rubber content.

Next, the obtained composite rubber particles (C-2 to
Graft polymerization was carried out in the same manner as in Example 1 using C-4) to obtain graft copolymer particles (D-2 to D-4).
Was prepared. Table 4 shows the MMA polymerization conversion, the average particle size of the graft copolymer particles, and the gel content.

(2) Preparation of Vinyl Chloride Resin Composition In the formulation shown in (2) of Example 1, the graft copolymer particles (D-1) were replaced with the graft copolymer particles (D-2 to D-2).
Instead of -5), a test piece was prepared in the same manner as in Example 1 except that the number of parts was changed to 10 parts, and the Izod strength was set to 23.
Measured in ° C. Table 4 shows the results.

Comparative Examples 2-3 As Comparative Example 2, the ratios of 2-EHA in the acrylic rubber-forming components (a-I) and (a-II) were as shown in Table 3, except that the proportions of Examples 2 to 3 were as shown in Table 3. In the same manner as in No. 4, composite rubber particles (C-2 ′) were prepared. Table 3 shows the results. Further, Examples 2 to 4 were performed using composite rubber particles (C-2 ′).
Graft copolymer particles (D-2 ′) were prepared in the same manner as in Example 2, and an Izod specimen made of the vinyl chloride resin composition was prepared and tested in the same manner as in Examples 2 to 4. Table 4 shows the results.

As Comparative Example 3, composites were prepared in the same manner as in Examples 2 to 4, except that the proportion of 2-EHA in the acrylic rubber-forming components (a-I) and (a-II) was as shown in Table 3. Rubber particles (C-3 ′) were prepared. Table 3 shows the results. Furthermore, using the composite rubber particles (C-3 ′), in the same manner as in Examples 2 to 4, the graft copolymer particles (D-
3 ′) was prepared, and an Izod test piece composed of a vinyl chloride resin composition was prepared and tested in the same manner as in Examples 2 to 4. Table 4 shows the results.

The MPrDMS in Table 3 represents mercaptopropyldimethoxymethylsilane.

[0166]

[Table 3]

[0167]

[Table 4] From the results shown in Table 4, the graft copolymer particles containing the composite rubber particles produced by using 2-EHA as the modifier for the acrylic rubber as the modifier for the vinyl chloride resin in the range of 2 to 50% were obtained. It can be seen that a higher impact resistance is exhibited as compared with the graft copolymer particles containing the composite rubber particles manufactured using the amount of 2-EHA outside the range of 2 to 50%.

Example 5 (1) Production of Graft Copolymer Particles Containing Composite Rubber (D-5) Silicone rubber raw material (silicone rubber-forming component (b))
The mixture of the following components
After stirring for 5 minutes at rpm, pressure 300 kgf / cm
The emulsion was prepared by passing twice through a high-pressure homogenizer set at 2.

Component Amount Amount (parts) Pure water 47.7 SDBS 0.13 D4 25 DSMA 0.4 The obtained emulsion was equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. Were charged all at once in a 5-neck flask. After the temperature of the system was raised to 90 ° C. over about 50 minutes, an aqueous solution consisting of 2.3 parts of pure water and 0.25 part of DBSA was added to acidify the system to pH 1.8. 5 at 90 ° C
After reacting for an hour, the mixture was cooled to 25 ° C. and maintained for 20 hours, and the pH was returned to 8.3 with an aqueous sodium hydroxide solution to complete the polymerization. The polymerization conversion of the silicone rubber raw material is 8
8%. The average particle size was 0.27 μm.

Next, 184 parts of pure water and 0.22 part of sodium oleate were added, and the temperature was raised to 60 ° C. The following acrylic rubber-forming component (a) was added all at once and stirred for 30 minutes, then 5 parts of pure water, 0.2 parts of SFS, and 0.1 part of ferrous sulfate.
An aqueous solution consisting of 002 parts and 0.008 parts of EDTA was added all at once to initiate polymerization.

Component Amount Amount (parts) BA 62.3 2-EHA 12 AlMA 0.7 t-butyl hydroperoxide 0.13 Stir for 2 hours to terminate polymerization, and composite rubber particles (C-5)
An emulsion containing At this time, the polymerization conversion of the acrylic rubber-forming component (a) was 99%. The average particle diameter of the obtained composite rubber particles (C-5) was 0.34.
μm, the gel content was 94% and the silicone rubber content was 22%.

Next, the obtained composite rubber particles (C-5)
Was used for graft polymerization. The components described below were collectively charged into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer.

Component Amount Amount (parts) Pure water 230 Composite rubber particles (C-5) (solid content) 60 Sodium rosinate 0.34 SFS 0.2 Ferrous sulfate 0.002 EDTA 0.008 Was added dropwise over 4 hours at 60 ° C., and after the addition was completed, stirring was continued for 1 hour to terminate the polymerization.

Component Amount Amount (parts) Styrene (ST) 30 Acrylonitrile (AN) 10 t-Dodecylmercaptan (t-DM) 0.01 CHP 0.1 The polymerization conversion of AN-ST was 99%. The average particle diameter of the graft copolymer particles (D-5) is 0.41 μm.
Met. The gel content was 93%. (2) Preparation of AN-ST copolymer resin composition An emulsion of AN-ST copolymer was prepared. The following components were collectively charged into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen gas injection port, a monomer addition port, and a thermometer.

Component Amount Amount (parts) Pure water 200 Dioctyl sodium sulfosuccinate 1.0 SFS 0.4 Ferrous sulfate 0.0025 EDTA 0.01 Next, the system was replaced with nitrogen gas and 65 with stirring. ° C
After reaching 65 ° C., the following monomer mixture was added dropwise over 6 hours. Also, 0.5 part of sodium dioctyl sulfosuccinate was added at the first hour of polymerization and 0.5 part at the third hour.
Part added. After the addition, stirring was continued for 1 hour to terminate the polymerization, and an emulsion of the AN-ST copolymer was obtained.

Component Amount Amount (parts) ST 70 AN 30 CHP 0.2 At this time, the polymerization conversion of the monomer mixture was 99%.

This AN-ST copolymer emulsion and the emulsion of the graft copolymer particles (D-5) obtained in (1) were mixed so that the amount of the composite rubber became 20% in terms of solid content. And a composite rubber AN-ST resin (Si / A
c-AN-ST resin). Then
The solidified slurry was dehydrated and dried to obtain Si / Ac-AN-ST resin powder.

Then, the obtained Si / Ac-AN-ST
To 100 parts of the resin powder, 0.2 part of a phenolic stabilizer (AO-20 manufactured by Asahi Denka Kogyo Co., Ltd.) and 0.5 part of ethylenebisstearyl amide were blended, and a single screw extruder (Tabata Kikai) The mixture was melt-kneaded with HW-40-28 manufactured by K.K. to produce pellets. The pellets were set at a cylinder temperature of 240 ° C. using an FAS100B injection molding machine manufactured by FANUC CORPORATION to prepare Izod test pieces and plate-like molded bodies. Izod strength and falling weight strength were evaluated. In addition, workability was evaluated using the pellets. Table 5 shows the results
Shown in

Comparative Example 4 Comparative Example 4 was carried out in the same manner as in Example 5 except that the amount of BA was 74.3 parts without using 2-EHA in the acrylic rubber-forming component of Example 5. Particle size 0.3
An emulsion of composite rubber particles (C-4 ′) having a thickness of 5 μm, a gel content of 95%, and a silicone rubber content of 22% was obtained. An emulsion of composite rubber-containing graft copolymer particles (D-4 ') was obtained in the same manner as in Example 5, except that the composite rubber particles (C-4') were used. The average particle size is 0.
40 μm, the gel content was 93%.

An Si / Ac-AN-ST resin was prepared in the same manner as in Example 5, (2) except that the obtained emulsion of the graft copolymer (D-4 ') was used. Also,
A test piece and a plate-like molded body were prepared in the same manner as in (5) of Example 5, and the Izod strength, the falling weight strength, and the workability were evaluated. Table 5 shows the results.

[0181]

[Table 5] From the results in Table 5, it can be seen that 2-EH
Si / Ac-A containing composite rubber produced using A
It can be seen that the N-ST resin not only exhibits high impact resistance but also has excellent workability as compared with the Si / Ac-AN-ST resin containing the composite rubber manufactured without using 2-EHA. . Examples 6 to 7 As Example 6, 30 parts of the graft copolymer particles (D-1) obtained in Example 1 were mixed with 100 parts of polyethylene terephthalate (manufactured by Kanebo KK: EFG-85A). , Single screw extruder (HW-40-2 manufactured by Tabata Machine Co., Ltd.)
The mixture was melt-kneaded in 8) to produce pellets. The pellets were set at a cylinder temperature of 250 ° C. using an FAS100B injection molding machine manufactured by FANUC CORPORATION to prepare Izod test pieces, and the Izod strength was evaluated at 23 ° C. Table 6 shows the results.

Example 7 As Example 7, 25 parts of the graft copolymer particles (D-1) of Example 1 and 100 parts of polycarbonate (NOVAREX 7025PJ, manufactured by Mitsubishi Chemical Corporation) were mixed. An Izod test piece was prepared as described above, and the Izod strength was evaluated at 23 ° C. Table 6 shows the results
Shown in

Comparative Examples 5 to 6 As Comparative Example 5, the graft copolymer particles (D
-1) instead of the graft copolymer particles of Comparative Example 1 (D
Except for using -1 ′), a test piece was prepared in the same manner as in Example 6, and the Izod strength was evaluated at 23 ° C. Table 6 shows the results.

As Comparative Example 6, the graft copolymer particles (D-1 ') of Comparative Example 1 were used instead of the graft copolymer particles (D-1) used in Example 7. A test piece was prepared in the same manner as in Example 7, and the Izod strength was evaluated at 23 ° C. Table 6 shows the results.

[0185]

[Table 6] From the results in Table 6, it was found that 2-EHA was used as an acrylic rubber-forming component as a modifier for various engineering plastics.
In the case of using the graft copolymer particles containing the composite rubber produced by using the above-mentioned method, a higher resistance is obtained as compared with the case of using the graft copolymer particles containing the composite rubber produced without using 2-EHA. It can be seen that impact properties are exhibited.

[0186]

According to the present invention, in a composite rubber comprising an acrylic rubber and a silicone rubber, 2 to 50% of all the constituent monomer units forming the acrylic rubber have an alkyl group having 8 to 8 carbon atoms. By using a composite rubber produced so as to be composed of units derived from an alkyl acrylate monomer of No. 12, a graft copolymer particle which is an impact modifier of a thermoplastic resin can be obtained. A thermoplastic resin composition comprising a blend of a copolymer particle and a thermoplastic resin is superior in impact resistance, weather resistance and processability as compared with a conventional composite rubber.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AA001 BC001 BC061 BC091 BD001 BG051 BG061 BN071 BN121 BN151 BN222 CF061 CG011 CH071 CL001 4J011 AA05 PA69 PA99 PB40 4J026 AA45 AB44 AC15 AC18 AC32 BA30 BA04 DA06 FA04 GA01 GA09 4J100 AB16R AG69R AG70R AJ02T AL03Q AL03T AL04P AL04Q AL05P AL05Q AL08T AL09T AL10T AL62R AL74R AP16S BA15S BA15T BA77S BC43S BC43T BC73R CA06 DA36 DA52

Claims (9)

[Claims] 1. A composite rubber particle comprising an acrylic rubber (A) and a silicone rubber (B), and 100% by weight of all constituent monomer units forming the acrylic rubber (A)
Composite rubber particles (C) in which 2 to 50% by weight of the above are units derived from an alkyl acrylate monomer having 8 to 12 carbon atoms in the alkyl group. 2. The composite rubber particles (C) are composed of 10 to 99% by weight of an acrylic rubber (A) and 90 to 90% of a silicone rubber (B).
1% by weight (however, the total amount of (A) and (B) is 100
% By weight). 3. The acrylic rubber (A) comprises (a-1) 2 to 50% by weight of an alkyl acrylate monomer having 8 to 12 carbon atoms in an alkyl group, and (a-2) carbon number in an alkyl group. At least one monomer selected from the group consisting of alkyl acrylate monomers having 1 to 7 alkyl methacrylate monomers having 4 to 12 carbon atoms in the alkyl group, and 97.8 to 29 wt. %, (A-3) a polyfunctional monomer containing two or more vinyl polymerizable groups in the molecule, 0.2 to 0.2%
6% by weight, (a-4) 0 to 5% by weight of a monomer having a vinyl polymerizable group and a reactive silyl group in the molecule, and (a-
5) An acrylic rubber-forming component comprising 0 to 10% by weight of the other copolymerizable monomer (the total amount of (a-1) to (a-5) is 100% by weight) is copolymerized. The composite rubber particles according to claim 1 or 2, wherein 4. The silicone rubber (B) comprises (b-1) 70 to 99.9% by weight of an organosiloxane, (b-2) 0 to 15% by weight of a polyfunctional silane compound, and (b-3) a vinyl-based polymer. A silane compound having a functional group or a mercapto group in an amount of 0 to 15% by weight (the components (b-2) and (b-3) do not become 0 at the same time and one of them is 0.1% by weight or more). 4. The composite rubber particles according to claim 1, 2 or 3, obtained by copolymerizing a silicone rubber-forming component. 5. Composite rubber-containing graft copolymer particles obtained by graft-polymerizing a vinyl monomer onto the composite rubber particles (C) according to claim 1. 6. The composite rubber particles (C) in an amount of 5 to 95% by weight,
The composite rubber-containing graft copolymer particles according to claim 5, wherein 95 to 5% by weight of the vinyl monomer is graft-polymerized. 7. The vinyl monomer is an aromatic vinyl monomer, a vinyl cyanide monomer, a halogenated vinyl monomer,
The composite rubber-containing graft copolymer particles according to claim 5, wherein the graft copolymer particles are at least one monomer selected from the group consisting of (meth) acrylic acid and (meth) acrylate monomers. 8. A thermoplastic resin composition comprising 1 to 150 parts by weight of the graft copolymer particles according to claim 5 and 100 parts by weight of a thermoplastic resin. 9. The thermoplastic resin is a polyvinyl chloride resin,
Polystyrene resin, styrene-acrylonitrile copolymer resin, styrene-acrylonitrile-N-phenylmaleimide copolymer resin, α-methylstyrene-acrylonitrile copolymer resin, polymethyl methacrylate resin, methyl methacrylate-styrene copolymer resin, polycarbonate resin, Polyamide resin, polyester resin, polyphenylene ether-polystyrene composite resin, ABS resin, A
The thermoplastic resin composition according to claim 8, which is at least one resin selected from the group consisting of an AS resin and an AES resin.