JP2001059006A - Graft copolymer and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent low temperature impact property and pigmentation property. SOLUTION: This graft copolymer(A) is obtained by graft copolymerization of a composite rubber ((a-1)+(a-2)) comprising (a-1) an aryl group-containing polyorganosiloxane and (a-2) an alkyl (meth)acrylate rubber with at least one kind of monomers (a-3) selected from the group consisting of an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound. This thermoplastic resin composition contains the graft copolymer(A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent pigment coloring and impact resistance.

[0002]

2. Description of the Related Art Improving the impact resistance of a resin material is extremely useful in industrial applications, such as not only expanding the application of the material but also making it possible to cope with a thinner and larger molded product. The invention has been largely made by various methods.

[0003] Particularly, a resin material in which a rubber component having a low Tg or a low elastic modulus is dispersed in a resin matrix has been industrialized due to its excellent impact resistance.

Further, in order to improve the impact resistance of a resin material in which such a rubber component is dispersed, it has been proposed to use a polyorganosiloxane having a lower Tg and a lower elastic modulus as the rubber component as disclosed in Japanese Patent Application Laid-Open No. 60-252613. It is proposed in the gazette. However, in this method, a mat-like molded appearance defect derived from the polyorganosiloxane occurs, and when the particle size of the graft rubber is reduced to improve the molded appearance, the impact resistance is reduced, resulting in high impact resistance. The industrial value is low because good molding appearance cannot be achieved at the same time.

JP-A-63-69859 discloses that a vinyl monomer is graft-polymerized on a composite rubber comprising a polyorganosiloxane rubber and a poly (meth) acrylate rubber in order to improve the surface appearance of a resin molded product. Graft copolymers have been proposed.

However, JP-A-63-69859 discloses polyorganosiloxane and alkyl (meth)
Although it describes a method for improving the impact resistance and molding gloss of a resin composition containing a composite rubber-based graft copolymer composed of an acrylate rubber, for example, for pigmentation properties such as jet-blackness when blackened, No description is given, and a resin composition containing the graft copolymer produced by the method shown in the examples cannot obtain good pigment coloring properties.

Japanese Patent Application Laid-Open No. 5-279434 discloses a method for improving the pigment coloring of an impact-resistant resin.
Graft polymerization of a vinyl monomer onto a composite rubber composed of polyorganosiloxane and (meth) acrylate is carried out by graft polymerization in which particles having a number average particle diameter of 0.01 to 0.07 μm and larger than 0.10 μm are not more than 20% by volume. It has been proposed to use polymers.

However, in the method using a composite rubber-based graft copolymer having a number average particle diameter of 0.01 to 0.07 μm described in JP-A-5-279434, a pigment of a resin composition containing the graft copolymer is used. Although excellent in colorability and impact resistance in a normal temperature atmosphere, there is no description about the impact resistance in a low temperature atmosphere, and the resin composition containing the graft copolymer prepared by the method of the example has a low impact resistance in a low temperature atmosphere. It is difficult to use in applications requiring impact resistance in a low-temperature atmosphere, such as vehicle parts and building material parts, for example.

Further, Japanese Patent Application Laid-Open Nos. 8-041149, 8-199025, 8-239544
JP-A-8-283524 and JP-A-8-283524 each disclose the grafting of a vinyl monomer onto a composite rubber composed of polydimethylsiloxane and alkyl (meth) acrylate having a specific amount of a vinyl polymerizable functional group and a specific crosslinking structure. By specifying the amount of polydimethylsiloxane, the amount of alkyl (meth) acrylate, and the amount of the graft component in the composite rubber in the polymerized graft copolymer, the resin composition containing the same is excellent in impact resistance and pigment coloring property. Are described.

Further, Japanese Patent Application Laid-Open No. 11-199642 includes a graft copolymer in which the amount of a polyorganosiloxane in a composite rubber, the amount of an acetone-insoluble component in the graft copolymer and the reduced viscosity of the acetone-soluble component are specified. It is described that the resin composition has good pigment coloring properties, and the molded article has good gloss when molded at a relatively low molding temperature.

However, JP-A-8-041149, JP-A-8-199025, and JP-A-8-23
In the method using a graft copolymer having a relatively low polyorganosiloxane content described in JP-A-9544, JP-A-8-283524 and JP-A-11-199642, a pigment of a resin composition containing the graft copolymer is used. Although excellent in colorability and impact resistance in a normal temperature atmosphere, there is no description about the impact resistance in a low temperature atmosphere, and the resin composition containing the graft copolymer prepared by the method of the example has a low impact resistance in a low temperature atmosphere. For example, there is a limitation in use in vehicle parts, building material parts, and the like that require low impact resistance at low temperatures, for example, particularly requiring a high level of low-temperature impact characteristics.

Japanese Patent Application Laid-Open No. 9-157338 discloses that the weight average particle diameter of a specific amount of polyorganosiloxane having a specific gel content and a degree of toluene swelling is 0.10.
It is described that the resin composition containing the composite rubber-based graft copolymer having a size of from 0.2 μm to 0.20 μm has good pigment coloring properties and good low-temperature impact properties.

However, the balance between the pigment coloring property and the low-temperature impact property is determined by the weight average particle diameter of the graft copolymer, the content of the polyorganosiloxane in the composite rubber and the crosslinked structure of the polyorganosiloxane disclosed in JP-A-9-157338. In the method of keeping, it is difficult to further improve the pigmentation property or the low temperature impact property, for example, an automobile bumper,
It is difficult to use in applications that require higher pigment coloring and low-temperature impact properties, such as building material parts for cold districts, the average particle size of the graft copolymer, the polyorganosiloxane in the composite rubber There are limits to the design of composite rubber-based graft copolymers by controlling the content and the cross-linked structure of the polyorganosiloxane.

That is, conventionally, a graft copolymer containing a composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber and a resin composition containing the graft polymer simultaneously satisfy low-temperature impact characteristics and pigment coloring properties. No method has been found, and the development of a graft copolymer that satisfies these at a high level at the same time and can be used in particularly high-performance applications such as automotive bumpers and building material parts for cold districts has been developed. It was strongly desired.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition having excellent low-temperature impact characteristics and pigment coloring properties.

[0016]

Means for Solving the Problems The present inventors have studied the composition of the polyorganosiloxane constituting the graft copolymer and the impact resistance and pigment coloring of the resin composition containing the graft copolymer. Surprisingly, by using an aryl group-containing polyorganosiloxane, it is shown that a resin composition containing a graft copolymer containing the same as a constituent exhibits excellent low-temperature impact characteristics and pigment coloring properties which have not been achieved in the past. Heading, the present invention has been reached.

That is, the present invention provides a composite rubber ((a-1) comprising an aryl group-containing polyorganosiloxane (a-1) and an alkyl (meth) acrylate rubber (a-2).
+ (A-2)) includes at least one monomer (a-) selected from an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester, and a vinyl cyanide compound.
3) Graft copolymer (A) obtained by graft polymerization and a thermoplastic resin composition containing the same.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Graft copolymer (A) of the present invention
The aryl group-containing polyorganosiloxane (a)
-1) is a polyorganosiloxane containing a siloxane repeating unit having at least one aryl group on a silicon atom, wherein the aryl group includes a phenyl group, a naphthyl group, an alkyl nucleus-substituted phenyl group, an alkyl nucleus-substituted naphthyl group, and a halogen atom. Examples include a nucleus-substituted phenyl group and a halogen-nucleus-substituted naphthyl group.

The method for producing the aryl group-containing polyorganosiloxane (a-1) is not particularly limited. However, considering the ease of producing the graft copolymer (A), a hydroxyl group and an alkoxy group are added to the terminal. And a method comprising emulsifying and polymerizing a mixture comprising an aryl group-containing linear organosiloxane having a substituent selected from, an emulsifier, an acid catalyst, water and, if necessary, a vinyl polymerizable functional group-containing siloxane. .

The aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal is an organosiloxane having an aryl group on a silicon atom in at least one siloxane bond,
Further, it is an organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at both ends.

Specific examples of the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at a terminal include a linear polyorganosiloxane having the following structure.

[0022]

Embedded image

Embedded image Specific examples of the alkoxy group in the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal include a methoxy group, an ethoxy group, and an n-propylyloxy group.

Specific examples of the aryl group in the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal include a phenyl group, a naphthyl group, a phenyl group substituted with an alkyl nucleus, and an alkyl group. A nucleus-substituted naphthyl group, a halogen-nucleus-substituted phenyl group, a halogen-nucleus-substituted naphthyl group and the like can be mentioned.

Specific examples of the alkyl group optionally contained in the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal include a methyl group, an ethyl group, a normal butyl group, Examples include an isobutyl group, a normal propyl group, and an isopropyl group.

Further, specific examples of the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal include an organosiloxane having the following structure.

[0026]

Embedded image

Embedded image The viscosity of the aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the end is such that the particle size distribution and the molecular weight of the silicone in the obtained silicone latex can be easily controlled. In consideration of the viscosity, the viscosity measured at 25 ° C. is 0.01 to 1
0 Pa · s, more preferably,
The viscosity measured at 25 ° C. is 0.01 to 1 Pa · s,
More preferably, the viscosity measured at 25 ° C is 0.01 to
0.2 Pa · s. In particular, the viscosity measured at 25 ° C is 1
If it exceeds 0 Pa · s, poor dispersion of the polyorganosiloxane occurs during the production of silicone latex, and the stability of the latex tends to be poor.

An aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal is, for example, XF40- manufactured by Toshiba Silicone Co., Ltd.
B6197 (polymethylphenylmethoxysiloxane), YF3804 (polymethylphenylsiloxane)
And XF40-B6626 (polymethylphenylmethoxysiloxane) are commercially available.

As the emulsifier used for producing the aryl group-containing polyorganosiloxane (a-1), a usual anionic emulsifier or a nonionic emulsifier is used. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium lauryl sulfate, sodium sulfosuccinate, sodium polyoxyethylene alkyl phenyl ether sulfate, N-lauroyl sarcosine soda, dipotassium alkenyl succinate, rosin acid soap and olein. And the like. Among them, it is particularly preferable to use a sulfonate emulsifier such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate. As the nonionic emulsifier, polyoxyethylene nonylphenyl ether, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, and the like are used.

The amount of the emulsifier used is determined in consideration of the stability of the emulsified latex at the time of polymerization and the coloring at the time of molding the thermoplastic resin composition containing the graft copolymer (A). , Preferably in the range of 0.05 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the siloxane compound.
It is in the range of 2 parts by weight.

The acid catalyst used for producing the aryl group-containing polyorganosiloxane (a-1) includes sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid and aliphatic substituted naphthalenesulfonic acid, and Mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like. Among these, aliphatic substituted benzenesulfonic acid is preferred because of excellent stability of the emulsified latex during polymerization, and normal dodecylbenzenesulfonic acid is particularly preferred.

The vinyl polymerizable functional group-containing siloxane used for producing the aryl group-containing polyorganosiloxane (a-1) is composed of the obtained polyorganosiloxane (a-1) and an alkyl (meth) acrylate rubber (a-
It is a graft crossing agent component for complexing with 2).

The siloxane containing a vinyl polymerizable functional group is a siloxane containing a vinyl polymerizable functional group and capable of bonding to an organosiloxane through a siloxane bond. In consideration of the reactivity with the organosiloxane, the vinyl polymerizable functional group-containing siloxane is used. Various alkoxysilane compounds containing a group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane Methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane and γ-mercaptopropyl Dimethoxymethylsilane,
and mercaptosiloxanes such as γ-mercaptopropyltrimethoxysilane. In addition, these vinyl polymerizable functional group-containing siloxanes can be used as one kind or as a mixture of two or more kinds. In consideration of the impact resistance of the resin composition containing the graft copolymer (A), the preferred range of the amount of the siloxane containing a vinyl polymerizable functional group is based on the siloxane unit of the obtained polyorganosiloxane. The group-containing siloxane unit is 0.3
To 3 mol%, preferably 0.5 to 2 mol%, more preferably 0.5 to 1 mol%.

In the production of the aryl group-containing polyorganosiloxane (a-1), a cyclic diorganosiloxane compound can be used in combination as a siloxane component other than the aryl group-containing linear organosiloxane.
The cyclic diorganosiloxane used is, for example, an aryl group-containing linear organosiloxane in order to adjust the refractive index of the obtained silicone to a specific value or to control the aryl group content in the polyorganosiloxane (a-1). It is used together with.

As the cyclic diorganosiloxane to be used, a cyclic dialkylsiloxane having three or more membered rings is preferable in consideration of productivity at the time of polymerization of the polyorganosiloxane (a-1). Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or as a mixture of two or more.

By using a cyclic diorganosiloxane in combination with an aryl group-containing linear organosiloxane,
The molecular weight of the resulting polyorganosiloxane (a-1) can be increased, and the particle size of the polyorganosiloxane (a-1) in the latex can be easily controlled.

In addition to the above components, a siloxane-based crosslinking agent can be used as needed. As the siloxane-based crosslinking agent, trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetra-n-propyloxysilane Is used.

In the preparation of the polyorganosiloxane (a-1), an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal, an emulsifier, an acid catalyst, water and, if necessary, a cyclic organosiloxane. Methods for emulsifying a mixture of diorganosiloxane, siloxane containing a vinyl polymerizable functional group, and a siloxane-based crosslinking agent include mixing by high-speed stirring, mixing with a high-pressure emulsifying device such as a homogenizer, membrane emulsification using a porous membrane, and static emulsification. Although a method such as fluid mixing using a mixer may be mentioned, a method using a homogenizer is preferable in consideration of the ease of controlling the particle size distribution of siloxane in the latex.

The polymerization of the polyorganosiloxane (a-1) is carried out by heating the emulsion prepared by the above method. The heating temperature is preferably at least 50 ° C, more preferably at least 80 ° C. The heating time is at least 2 hours, more preferably at least 5 hours.

The termination of the polymerization can be carried out by cooling the reaction solution and neutralizing the latex with an alkaline substance such as caustic soda, potassium hydroxide, sodium carbonate and ammonia. Further, the time until the neutralization after cooling the heat-treated emulsion affects the molecular weight of the obtained silicone, and the longer the retention time until the neutralization, the higher the molecular weight tends to be. A preferred holding time until neutralization is 1 hour or more, and more preferably 10 hours or more.

As the polymerization method, an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at the terminal, an emulsifier, water and, if necessary, a cyclic diorganosiloxane, a vinyl polymerizable functional group After emulsifying the mixture of the contained siloxane and the siloxane-based cross-linking agent by the above-described method, the emulsion may be continuously dropped into an aqueous solution containing a heated acid catalyst to carry out polymerization. When polymerized by such a method, a polyorganosiloxane (a-1) latex having a smaller particle diameter can be prepared.

The aryl group content in the aryl group-containing polyorganosiloxane (a-1) constituting the graft copolymer (A) of the present invention is not particularly limited. Considering the pigment coloring property and the low-temperature impact property of the thermoplastic resin composition containing A), the content of the aryl group in the organo substituents bonded to all silicon atoms is 0.5 mol% to 50 mol%. Preferably, it is more preferably 5 mol% to 35 mol%.

The refractive index of the aryl group-containing polyorganosiloxane (a-1) constituting the graft copolymer (A) of the present invention is not particularly limited, but the refractive index of the thermoplastic resin (B) to be mixed is not limited. By approaching the refractive index, the pigment coloring property of the thermoplastic resin composition containing the graft copolymer (A) can be improved.

The aryl group-containing polyorganosiloxane (a-1) latex thus produced was impregnated with an alkyl (meth) acrylate component comprising an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate. By performing post-polymerization, a composite rubber ((a-1) + (a-2)) can be obtained.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Examples thereof include alkyl acrylates such as propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. The use of n-butyl acrylate is particularly preferable.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, Triallyl isocyanurate and the like can be mentioned. The amount of the polyfunctional alkyl (meth) acrylate used is 0.1 to 20% by weight, preferably 0.2 to 1% by weight in the alkyl (meth) acrylate component.

The alkyl (meth) acrylate and the polyfunctional alkyl (meth) acrylate are used alone or in combination of two or more.

The composite rubber ((a-1) + (a-) comprising the aryl group-containing polyorganosiloxane (a-1) and the alkyl (meth) acrylate rubber (a-2) according to the present invention.
2)) is an aryl group-containing polyorganosiloxane (a)
-1) It can be produced by adding the above-mentioned alkyl (meth) acrylate component to the latex of the component and polymerizing it by the action of a usual radical polymerization initiator. As a method of adding the alkyl (meth) acrylate, there are a method of mixing the poly (organosiloxane component) with the latex of the polyorganosiloxane component at a time and a method of dropping into the latex of the polyorganosiloxane component at a constant rate. In consideration of the impact resistance of the obtained graft copolymer and the resin composition containing the same, a method of mixing the latex of the polyorganosiloxane component at a time is preferable. As the radical polymerization initiator used for the polymerization, a peroxide, an azo-based initiator, or a redox-based initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferred,
Particularly, a sulfoxylate initiator obtained by combining sodium salt, longalide, and hydroperoxide with ferrous sulfate and ethylenediaminetetraacetic acid is preferable.

The composite rubber ((a-1) + (a-) comprising the aryl group-containing polyorganosiloxane (a-1) and the alkyl (meth) acrylate rubber (a-2) according to the present invention.
In 2)), the amounts of the aryl group-containing polyorganosiloxane (a-1) and the alkyl (meth) acrylate rubber (a-2) are not particularly limited, but the heat containing the graft copolymer (A) is not limited. Considering the pigment coloring property and the low-temperature impact property of the plastic resin composition, preferably, the aryl group-containing polyorganosiloxane (a-1) is 10 to 90% by weight, and the alkyl (meth) acrylate rubber (a-2) component is 90 to 10% by weight. %. When the amount of the aryl group-containing polyorganosiloxane (a-1) in the composite rubber is less than 10% by weight, the low-temperature impact characteristics of the thermoplastic resin composition containing the graft copolymer (A) because the content of the polyorganosiloxane is small. When the content exceeds 90% by weight, the pigment coloring property of the resin composition containing the graft copolymer (A) tends to decrease. Further, more preferable composite rubber ((a-1)
+ (A-2)), the amount of the aryl group-containing polyorganosiloxane (a-1) and the alkyl (meth) acrylate rubber (a-2) is 10 to 70%. % By weight, alkyl (meth)
The acrylate rubber (a-2) component is 30 to 90% by weight.

The graft copolymer (A) according to the present invention comprises:
As described above, the composite rubber ((a-1) + (a-2)) produced by emulsion polymerization contains at least one monomer selected from aromatic alkenyl compounds, methacrylic esters, acrylic esters and vinyl cyanide compounds. The product can be produced by graft polymerization (component (a-3)). Among the monomers used for the graft polymerization, aromatic alkenyl compounds include, for example, styrene, α-methylstyrene, and vinyl toluene, and methacrylic esters include, for example, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, and acrylate esters. Are, for example, methyl acrylate, ethyl acrylate, butyl acrylate and the like, and the vinyl cyanide compounds are, for example, acrylonitrile, methacrylonitrile and the like. Of these, the graft copolymer (A) is also preferably a mixture of styrene and acrylonitrile as a monomer used for graft polymerization in consideration of thermal stability.

In the graft polymerization, the composite rubber ((a-1) +
(A-2) an aromatic alkenyl compound in the latex,
One or two or more monomers selected from methacrylic acid esters, acrylic acid esters or vinyl cyanide compounds can be added, and the polymerization can be performed in one step or in multiple steps by a radical polymerization technique. In consideration of the impact resistance and pigment coloring of the resin composition containing A), it is preferable to carry out the polymerization in two or more stages.

In addition, various chain transfer agents for adjusting the molecular weight and the graft ratio of the graft polymer can be added to the monomers used in the graft polymerization.

A graft polymerization component obtained by graft polymerization of one or more monomers selected from aromatic alkenyl compounds, methacrylates, acrylates and vinyl cyanide compounds in the graft copolymer according to the present invention. The amount of (a-3) is not particularly limited, but in consideration of the pigment coloring property of the thermoplastic resin composition containing the graft copolymer (A), 50 to 80 with respect to all the graft copolymers. % By weight is preferred. 50 graft polymerization components
When the amount is less than 10% by weight, the pigment coloring property of the graft copolymer and the resin composition containing the same tends to decrease.
If the content is more than 10% by weight, the impact resistance tends to decrease because the amount of rubber decreases.

The weight average particle size of the graft copolymer (A) according to the present invention is not particularly limited, but the low-temperature impact characteristics and pigment coloring of the thermoplastic resin composition containing the graft copolymer (A) are not limited. 0.10-1.0μ considering the properties
m, more preferably 0.15 to 0.7 μm.

The graft copolymer (A) according to the present invention comprises
The graft copolymer latex produced as described above is poured into hot water in which a metal salt such as calcium chloride, calcium acetate or aluminum sulfate is dissolved, salted out and solidified to separate the graft copolymer (A). , Can be recovered.

The graft copolymer (A) can be kneaded alone or together with the thermoplastic resin (B) by a commonly known kneading apparatus to produce a thermoplastic resin composition.

The thermoplastic resin (B) is not particularly restricted but includes, for example, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylate-styrene copolymer ( ASA resin), acrylonitrile-ethylene-propylene-diene-styrene copolymer (AE
S resin), polycarbonate resin, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), polyolefin such as polyvinyl chloride, polyethylene, polypropylene, styrene-butadiene-styrene (SBS), styrene-butadiene (SB
R), hydrogenated SBS, styrene-based elastomers such as styrene-isoprene-styrene (SIS), various olefin-based elastomers, various polyester-based elastomers, polystyrene, methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene copolymer Coalescing (AS resin), polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymer, PPS resin, polyarylate, liquid crystal polyester resin, polyamide resin (nylon) and the like. Alternatively, two or more kinds can be used in combination.

The graft copolymer (A) is preferably blended in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin (B). More preferably, 1 to 10
A range of 0 parts by weight, particularly preferred is a range of 5 to 70 parts by weight.

The kneading method used in the production of the thermoplastic resin composition containing the graft copolymer (A) and the thermoplastic resin (B) of the present invention as constituents includes, for example, a thermoplastic resin in the form of powder, beads or pellets. A predetermined amount of (B) and the graft copolymer (A) are weighed and mixed, and the resulting mixture is melt-kneaded, or the like. For melt-kneading, an extruder or a kneader such as a Banbury mixer, a pressure kneader, or a roll may be used.

The thermoplastic resin composition containing the graft copolymer (A) of the present invention can be directly used as a raw material for producing a molded article. Further, a dye, a pigment, a stabilizer, a reinforcing agent, a filler, a flame-retardant auxiliary, and the like can be further blended as necessary.

Further, the thermoplastic resin composition containing the graft copolymer (A) of the present invention can be obtained by an injection molding method, an extrusion molding method,
The desired molded product is obtained by various molding methods such as a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method.

Examples of industrial applications of the thermoplastic resin composition containing the graft copolymer (A) of the present invention include various exterior / interior parts used for vehicle parts, especially unpainted, wall materials, window frames, etc. Home appliance parts such as building material parts, tableware, toys, vacuum cleaner housings, television housings, air conditioner housings,
Interior members, ship members, communication device housings, and the like are included.

Hereinafter, the present invention will be described with reference to examples. In Reference Examples, Examples and Comparative Examples, "parts" and "%" are "parts by weight" and "% by weight" unless otherwise specified.
Means

The weight average particle diameter of the polyorganosiloxane latex and the graft copolymer latex in Reference Examples, Examples and Comparative Examples was MATEC APPLIED SCIENC.
ES company submicron particle size distribution analyzer CHDF-2000
It measured using.

The weight-average molecular weight of the polyorganosiloxane in Reference Example was determined by precipitating and recovering a polyorganosiloxane latex in isopropyl alcohol, drying it in a vacuum at room temperature, and then dissolving the solution in tetrahydrofuran using GPC manufactured by WATERS. And measured from the retention time in terms of standard polystyrene.

The refractive index of the polyorganosiloxane in the reference example was determined by precipitating and recovering the polyorganosiloxane latex in isopropyl alcohol, drying it in a vacuum at room temperature, and measuring the refractive index using an Abbe refractometer manufactured by Shimadzu Corporation. The temperature was measured at ° C.

The phenyl content of the polyorganosiloxane in Reference Example was determined by precipitating and recovering a polyorganosiloxane latex in isopropyl alcohol, drying it in vacuo at room temperature, and then analyzing the NMR of a heavy acetone solution.
(GSX-400 manufactured by JEOL Ltd.) was measured to determine the molar amounts of the methyl group (M) and the phenyl group (P) bonded to the silicon atom, and the phenyl group content was determined by the following equation.

Phenyl content (mol%) = P / (P + M)
× 100 Measurement of the acetone-insoluble content in the graft copolymer in Examples and Comparative Examples was performed by placing about 2.5 g (weighed) of the graft copolymer and 80 ml of acetone in a flask equipped with a condenser and a heater. Extraction by heating at 65 ° C. for 3 hours using a centrifuge, and after cooling, the inner solution is treated with a centrifugal separator of Hitachi Koki Co., Ltd. at 15,000 rpm for 30 minutes to separate acetone-insoluble components. Then, the precipitate after removing the supernatant was dried, and its weight was measured and calculated by the following equation.

Acetone insoluble matter (% by weight) = (dry weight of precipitate after separation treatment) / (weight of graft copolymer before acetone extraction) × 100 Also, the acetone-soluble component in the graft copolymer in Examples and Comparative Examples was The measurement of the reduced viscosity is carried out by extracting the above-mentioned graft copolymer with an acetone solvent and then evaporating the acetone solvent in the supernatant obtained by separating the acetone-insoluble matter by centrifugation under reduced pressure to precipitate and recover acetone-soluble components. Then, the acetone-soluble component is added to the mixture.
The solution viscosity of a solution obtained by dissolving 2 g in 100 cc of N, N-dimethylformamide was measured using an automatic viscometer (SAN DENSHI
(Manufactured by Co., Ltd.) at 25 ° C., and the reduced viscosity of the acetone-soluble component was determined from the solvent viscosity measured under the same conditions.

The measurement of the Izod impact strength in Examples and Comparative Examples was carried out by a method in accordance with ASTM D258. In particular, the measurement of the Izod impact strength in a low-temperature atmosphere was carried out for at least 12 hours at -30 ° C. in an atmosphere. After standing, the measurement was performed.

The measurement of the surface hardness (Rockwell hardness) in Examples and Comparative Examples was performed by a method according to ASTM D785.

The evaluation of pigmentability of the resin compositions in Examples and Comparative Examples was 100 mm × 100 mm × 3.
Injection molding machine J85 manufactured by Japan Steel Works, Ltd.
-Performed by using ELII under the conditions of a cylinder set temperature of 230 ° C, a mold temperature of 60 ° C, and an injection speed of 50%, and a hue measurement (L * measurement) of the obtained molded plate according to JIS Z8729.

The glossiness of the resin compositions in Examples and Comparative Examples was determined by molding a 100 mm × 100 mm × 3 mm plate into an injection molding machine J85-ELII manufactured by Nippon Steel Works, Ltd.
Using a cylinder set temperature of 230 ° C and a mold temperature of 60
C. and an injection speed of 50%, and the measurement was performed using the obtained molded plate.

[0073]

EXAMPLES (Reference Example 1) Production of polyorganosiloxane latex (S-1) 98 parts of methoxydiphenyldimethylsiloxane terminated (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%) and γ-methacryloyloxypropyl Mix 2 parts of dimethoxymethylsilane,
100 parts of a siloxane mixture were obtained. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were added to the siloxane mixture, and the mixture was stirred.
After preliminarily stirring at 00 rpm, the mixture was stirred for 4 hours with a homogenizer.
The mixture was emulsified and dispersed by treating at a pressure of 0 MPa four times to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then left at 20 ° C. After 16 hours, the pH of this latex was adjusted with a 5% aqueous sodium hydroxide solution. After neutralization to 7.4, the polymerization was completed to obtain a polyorganosiloxane latex (S-1). The polyorganosiloxane latex (S-1) thus obtained had a solid content of 29% and a weight average particle size of 180 nm. The weight average molecular weight of the polyorganosiloxane in S-1 was 16,000, the phenyl content was 32 mol%, and the refractive index measured at 20 ° C. was 1.517. Table 1 shows the above results.

Reference Example 2 Preparation of polyorganosiloxane latex (S-2) 58.8 parts of methoxydiphenyldimethylsiloxane terminated (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%), octamethylcyclotetra Siloxane (TSF-40 manufactured by Toshiba Silicone Co., Ltd.)
4) 39.2 parts and γ-methacryloyloxypropyldimethoxymethylsilane 2 parts were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were added to the siloxane mixture, and the mixture was stirred.
After adding 00 parts and preliminarily stirring with a homomixer at 10,000 rpm, the mixture was emulsified and dispersed by treating it four times with a homogenizer at a pressure of 40 MPa to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then left at 20 ° C. After 16 hours, the pH of this latex was adjusted with a 5% aqueous sodium hydroxide solution. After neutralization to 7.4, the polymerization was completed to obtain a polyorganosiloxane latex (S-2). The polyorganosiloxane latex (S-2) thus obtained has a solid content of 29% and a weight average particle size of 130%.
nm. The weight average molecular weight of the polyorganosiloxane in S-2 was 110000, the phenyl content was 18 mol%, and the refractive index measured at 20 ° C. was 1.47.
It was 2. Table 1 shows the above results.

Reference Example 3 Production of Polyorganosiloxane Latex (S-3) 53.5 parts of methoxydiphenyldimethylsiloxane terminated (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%), octamethylcyclotetra Siloxane (TSF-40 manufactured by Toshiba Silicone Co., Ltd.)
4) 44.5 parts and γ-methacryloyloxypropyldimethoxymethylsilane 2 parts were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate was added to the siloxane mixture, and the mixture was stirred.
After preliminarily stirring at 00 rpm, the mixture was stirred for 4 hours with a homogenizer.
Emulsifying and dispersing by treating at a pressure of 0 MPa four times,
A premixed organosiloxane latex was obtained.

On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer.
A 0% dodecylbenzenesulfonic acid aqueous solution was prepared.

While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after completion of the addition, the temperature was maintained for 1 hour and the system was cooled. The reaction was left at 20 ° C. and after 16 hours the pH of this latex was neutralized to 7.4 with 5% aqueous sodium hydroxide,
The polymerization is completed and the polyorganosiloxane latex (S-
3) was obtained. The polyorganosiloxane latex (S-3) thus obtained had a solid content of 18% and a weight average particle size of 100 nm. The weight average molecular weight of the polyorganosiloxane in S-3 was 13,000.
0, the phenyl content was 13 mol%, and the refractive index measured at 20 ° C. was 1.451. Table 1 shows the above results.

(Reference Example 4) Production of polyorganosiloxane latex (T-1) Except that the amount of terminal methoxydiphenyldimethylsiloxane used in Reference Example 2 was changed to 0 parts and the amount of octamethylcyclotetrasiloxane was changed to 98 parts. Performs polymerization in the same manner and obtains a polyorganosiloxane latex (T-
1) was obtained. The polyorganosiloxane latex (T-1) thus obtained had a solid content of 29% and a weight average particle size of 130 nm. The weight average molecular weight of the polyorganosiloxane in T-1 was 220,000,
The phenyl content was 0 mol% and the refractive index measured at 20 ° C. was 1.407. Table 1 shows the above results.

(Reference Example 5) Production of polyorganosiloxane latex (T-2) Except that the amount of terminal methoxydiphenyldimethylsiloxane used in Reference Example 3 was changed to 0 parts and the amount of octamethylcyclotetrasiloxane was changed to 98 parts. Performs polymerization in the same manner and obtains a polyorganosiloxane latex (T-
2) was obtained. The polyorganosiloxane latex (T-2) thus obtained had a solid content of 18% and a weight average particle size of 80 nm. Further, the weight average molecular weight of the polyorganosiloxane in T-2 was 220,000, the phenyl content was 0 mol%, and the refractive index measured at 20 ° C. was 1.407. Table 1 shows the above results.

Example 1 Graft Copolymer (A-
Production of 1) 51.7 parts of the polyorganosiloxane latex (S-1) produced in Reference Example 1 and Emal NC-35 () were placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer. 0.2 parts of polyoxyethylene alkyl phenyl ether sulfate (manufactured by Kao Corporation) were collected, mixed with 133.3 parts of distilled water, and mixed with 35 parts of butyl acrylate and 0.2 parts of allyl methacrylate. , 1,
A mixture of 0.1 part of 3-butylene glycol dimethacrylate and 0.1 part of t-butyl hydroperoxide was added.

The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal liquid temperature reaches 60 ° C., ferrous sulfate 0.00
An aqueous solution in which 0075 parts, 0.000225 parts of ethylenediaminetetraacetic acid disodium salt and 0.2 parts of Rongalite were dissolved in 10 parts of distilled water was added, and radical polymerization was started. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for one hour to complete the polymerization of the acrylate component to obtain a latex of a composite rubber of polyorganosiloxane and butyl acrylate rubber.

After the liquid temperature inside the reactor has dropped to 70 ° C.,
An aqueous solution obtained by dissolving 0.25 parts of Rongalite in 10 parts of distilled water was added, and then a mixed solution of 2.5 parts of acrylonitrile, 7.5 parts of styrene and 0.05 part of t-butylhydroperoxide was added in 0.5 part. It was added dropwise over time to polymerize. After completion of the dropwise addition, the temperature of 60 ° C. was maintained for 1 hour, and then 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of Rongalite and Emar NC-35 (Kao Corporation Aqueous solution obtained by dissolving 0.2 part) in 10 parts of distilled water was added. Then, a mixed solution of 10 parts of acrylonitrile, 30 parts of styrene and 0.2 part of t-butylhydroperoxide was added to 1.3. It was added dropwise over time to polymerize. After the completion of the dropping, the temperature of 60 ° C. was maintained for 0.5 hour and then cooled. As described above, a polymerization latex of a graft copolymer (A-1) obtained by graft-polymerizing acrylonitrile and styrene on a composite rubber composed of polyorganosiloxane and butyl acrylate rubber was obtained.

The weight average particle diameter of the graft copolymer in A-1 was 280 nm.

Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 1% was heated to 60 ° C. and stirred. 100 parts of the latex of the graft copolymer was gradually dropped into this, and solidified. Next, the precipitate was separated and washed, and then washed with a centrifuge (H-130E, manufactured by Domestic Centrifuge Co., Ltd.).
A dehydration treatment was performed for 2 minutes at a condition of 800 rotations per second.

Then, the mixture was dried at 85 ° C. for 24 hours to obtain a powdery graft copolymer (A-1).

The acetone-insoluble content in the graft copolymer (A-1) was 73%, and the reduced viscosity of the acetone-soluble component was 0.69 dl / g.

Example 2 Graft Copolymer (A-
Preparation of 2) The polyorganosiloxane used in Example 1 was S
Polymerization was carried out in the same manner except for changing to -2, to obtain a latex of the graft copolymer (A-2).

The weight average particle diameter of the graft copolymer in A-2 was 230 nm.

The latex was coagulated in the same manner as in Example 1 and then dried to obtain a powdery graft copolymer (A-
2) was obtained.

The acetone-insoluble content in the graft copolymer (A-2) was 80%, and the reduced viscosity of the acetone-soluble component was 0.73 dl / g.

Example 3 Graft Copolymer (A-
Production of 3) Same as above except that the polyorganosiloxane used in Example 1 and the amount thereof were changed to S-3 and 83.3 parts, and the amount of distilled water initially charged was changed to 101.7 parts. And the graft copolymer (A-
The latex of 3) was obtained.

The weight average particle size of the graft copolymer in A-3 was 180 nm.

The latex was coagulated in the same manner as in Example 1 and then dried to obtain a powdery graft copolymer (A-
3) was obtained.

The acetone-insoluble content in the graft copolymer (A-3) was 80%, and the reduced viscosity of the acetone-soluble component was 0.68 dl / g.

Example 4 Graft Copolymer (A-
Preparation of 4) 166.7 parts of the polyorganosiloxane latex (S-3) manufactured in Reference Example 3 and Emal NC-35 (a) were placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, and a stirrer. 0.2 parts of polyoxyethylene alkyl phenyl ether sulfate (manufactured by Kao Corporation) were collected, 33.3 parts of distilled water was added and mixed, and then 20 parts of butyl acrylate and 0.1 part of allyl methacrylate were mixed. , 1,
A mixture of 0.05 parts of 3-butyleneglycol dimethacrylate and 0.1 parts of t-butyl hydroperoxide was added.

The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal liquid temperature reaches 60 ° C., ferrous sulfate 0.00
An aqueous solution in which 0075 parts, 0.000225 parts of ethylenediaminetetraacetic acid disodium salt and 0.2 parts of Rongalite were dissolved in 10 parts of distilled water was added, and radical polymerization was started. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for one hour to complete the polymerization of the acrylate component to obtain a latex of a composite rubber of polyorganosiloxane and butyl acrylate rubber.

After the temperature of the liquid inside the reactor has dropped to 70 ° C.,
An aqueous solution obtained by dissolving 0.25 parts of Rongalite in 10 parts of distilled water was added, and then a mixed solution of 2.5 parts of acrylonitrile, 7.5 parts of styrene and 0.05 part of t-butylhydroperoxide was added in 0.5 part. It was added dropwise over time to polymerize. After completion of the dropwise addition, the temperature of 60 ° C. was maintained for 1 hour, and then 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of Rongalite and Emar NC-35 (Kao Corporation Aqueous solution obtained by dissolving 0.2 part) in 10 parts of distilled water was added. Then, a mixed solution of 10 parts of acrylonitrile, 30 parts of styrene and 0.2 part of t-butylhydroperoxide was added to 1.3. It was added dropwise over time to polymerize. After the completion of the dropping, the temperature of 60 ° C. was maintained for 0.5 hour and then cooled. As described above, a polymerization latex of a graft copolymer (A-4) obtained by graft-polymerizing acrylonitrile and styrene on a composite rubber composed of polyorganosiloxane and butyl acrylate rubber was obtained.

The weight average particle diameter of the graft copolymer in A-4 was 150 nm.

The latex was coagulated in the same manner as in Example 1 and then dried to obtain a powdery graft copolymer (A-
4) was obtained.

The acetone-insoluble content in the graft copolymer (A-4) was 81%, and the reduced viscosity of the acetone-soluble component was 0.70 dl / g.

Comparative Example 1 Graft copolymer (P-
Preparation of 1) The polyorganosiloxane used in Example 1 was T
Polymerization was carried out in the same manner except for changing to -1, to obtain a latex of the graft copolymer (P-1).

The weight average particle size of the graft copolymer in P-1 was 240 nm.

The latex was coagulated in the same manner as in Example 1 and then dried to obtain a powdery graft copolymer (P-
1) was obtained.

The acetone-insoluble content in the graft copolymer (P-1) was 89%, and the reduced viscosity of the acetone-soluble component was 0.66 dl / g.

Comparative Example 2 Graft Copolymer (P-
Production of 2) The same procedure was carried out except that the polyorganosiloxane used in Example 1 and the amount thereof were changed to T-2 and 83.3 parts, and the amount of distilled water initially charged was changed to 101.7 parts. Polymerization by the method described above, and the graft copolymer (P-
The latex of 2) was obtained.

The weight average particle diameter of the graft copolymer in P-2 was 100 nm.

The latex was coagulated in the same manner as in Example 1 and then dried to obtain a powdery graft copolymer (P-
2) was obtained.

The acetone-insoluble content in the graft copolymer (P-2) was 88%, and the reduced viscosity of the acetone-soluble component was 0.61 dl / g.

The conditions and results of Examples 1-4 and Comparative Examples 1-2 are summarized in Table 2.

[Examples 5 to 8 and Comparative Examples 3 to 4] 48 parts of each of the graft copolymers (S-1 to 4 and T-1 to 2) produced in Examples 1 to 4 and Comparative Examples 1 and 2 52 parts of an acrylonitrile-styrene copolymer comprising 29% of an acrylonitrile component and 71% of a styrene component and having a reduced viscosity of 0.60 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution, Asahi Denka Co., Ltd. 0.3 parts of ADK STAB C, 0.3 parts of barium stearate, 0.4 parts of ethylenebisstearylamide and 0.8 parts of carbon black (# 960 manufactured by Mitsubishi Chemical Corporation) using a Henschel mixer. Mix and bring this mixture to 230 ° C
Was supplied to a heated degassing extruder and kneaded to obtain pellets.

The obtained pellets were heated at a cylinder temperature of 230.
A test piece was molded by an injection molding machine set at a temperature of 60 ° C. and a mold temperature of 60 ° C. The Izod impact strength and Rockwell hardness in a -30 ° C atmosphere were measured using the test pieces.

The obtained pellets were formed into a plate having dimensions of 100 mm × 100 mm × 3 mm by an injection molding machine set at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. The glossiness and L * value of the molded plate molded under these conditions were measured.

Table 3 shows the above measurement results.

[0114]

[Table 1]

[Table 2]

[Table 3] The following is clear from the examples and the comparative examples.

1) According to Examples 5 to 8, the resin composition containing a graft copolymer containing an aryl group-containing polyorganosiloxane as a constituent component has a high Izod impact strength under a high -30 atmosphere and a high molded plate gloss. And low forming plate L
A material having a low value and having both low-temperature impact characteristics and pigment coloring properties is highly useful as various industrial materials.

2) The resin composition of Comparative Example 3 containing a graft copolymer containing a polyorganosiloxane containing no aryl group as a component has an Izod impact strength under a high -30 atmosphere, but a molded plate L * Such a resin material having a high value and having poor pigment coloring properties is difficult to use for applications requiring high designability, and has low utility value as an industrial material.

3) The resin composition of Comparative Example 4 containing a graft copolymer containing a polyorganosiloxane containing no aryl group as a component shows a low molded plate L * value and has good pigment coloring properties. Resin materials having low Izod impact strength at −30 ° C. and low in low-temperature impact characteristics have limited utility in use, and thus have low utility value as industrial materials.

[0118]

As described above, the present invention has the following remarkable effects, and its industrial value is extremely large.

1) The thermoplastic resin composition containing the graft copolymer according to the present invention has excellent low-temperature impact properties and pigment coloring properties.

2) In particular, the balance cannot be attained by a resin composition containing a graft copolymer containing a composite rubber composed of a conventionally known polydimethylsiloxane and an alkyl (meth) acrylate rubber as a component. It has a very high level of value, and is extremely useful as a material for various industrial materials, particularly for vehicle parts and building material parts that require both design properties and low-temperature impact characteristics.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AA01X BB05W BG04W BN12W BN22W CP14W CP17 GL00 GN00 HA07 4J026 AA44 AA63 AB44 AC09 AC32 BA27 BA28 BA31 BB04 DA04 DB04 DB15 FA07 GA01 GA09

Claims (4)

[Claims] An aryl group-containing polyorganosiloxane (a-1) and an alkyl (meth) acrylate rubber (a-
2) composite rubber ((a-1) + (a-2))
To an aromatic alkenyl compound, methacrylic acid ester,
A graft copolymer (A) obtained by graft polymerization of at least one monomer (a-3) selected from an acrylate ester and a vinyl cyanide compound. 2. The graft copolymer (A) according to claim 1.
And a thermoplastic resin composition comprising: a thermoplastic resin (B). An aryl group-containing polyorganosiloxane (a-1) is produced by emulsion polymerization of a siloxane compound containing an aryl group-containing linear organosiloxane having a substituent selected from a hydroxyl group and an alkoxy group at a terminal. The graft copolymer according to claim 1, wherein 4. The aryl group-containing polyorganosiloxane (a-1) has an aryl group content of 5 mol% to 35 mol% based on the total number of organo substituents bonded to silicon atoms.
The graft copolymer according to claim 1, wherein