JPH09157482A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a polycarbonate resin and a graft copolymer having a specific composition, and useful for impact- resistant resins excellent in impact resistance and pigment colorability. SOLUTION: This composition comprises (A) a polycarbonate resin and (B) a graft copolymer produced by graft-polymerizing (iii) at least one kind of monomer selected from aromatic alkenyl compounds, methacrylic esters, etc., to a composite rubber comprising (i) a polyorganosiloxane having vinylic polymerizable functional groups, a gel content of 60-90wt.% and a swelling degree of 10-30 measured in a toluene solution and (ii) an alkyl (meth)acrylate rubber. Therein, the components (i) and (ii) are contained in amounts of 20-40wt.% and 60-80wt.%, respectively, in the component rubber of the components (i) and (ii), and the content of the component (iii) is 50-80wt.% based on the component B. The weight - average particle diameter of the component B is 0.10-0.20μm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an impact resistant resin which is excellent in impact resistance and pigment coloring property.

[0002]

2. Description of the Related Art Generally, when a resin material is used for industrial purposes, the appearance after molding, mechanical strength, and when used without painting, discoloration due to sunlight or rainfall, little deterioration of physical properties, so-called weather resistance is good. At the same time, the color developability and the pigment colorability when a colorant such as a pigment is mixed must be good.

In particular, in resin parts used in the vehicle field, it is necessary that the molding appearance, impact strength and pigment coloration are at a high level. Of these, the impact strength is generally A
It is evaluated by the Izod impact strength according to the STM D256 test method. For example, in order to determine whether it can be used as a material for automobile exteriors, in addition to the impact strength at room temperature, a low temperature atmosphere of -30 ° C or -40 ° C is used. Judged with impact strength. The Izod impact strength required in the low temperature atmosphere as a resin material for automobile exterior parts varies depending on each application, but in addition to the impact strength at room temperature, the resin material with high impact strength in the low temperature atmosphere is durable. It has high industrial value due to its high reliability of sex.

Further, the pigment coloring property required for a resin material used in the vehicle field is generally evaluated by its most representative color tone, that is, black coloring property, although it varies depending on the use and the desired hue. In this case, as an evaluation method, the lightness (L *) of a resin molded product to which a certain amount of a coloring agent such as carbon black is added is determined by hue / color difference analysis. A resin material having a smaller L * value has a higher pigment coloring property. It is judged to be excellent. Materials with a small L * value under the same coloring conditions can reduce the cost because the amount of colorant used when coloring various colors as industrial materials can be reduced, and resin materials can be added by adding colorants. Since the deterioration of the physical properties originally possessed by the is reduced, the industrial value is high.

Heretofore, as a method for dealing with such an application in which particularly high impact resistance and pigment coloring property are required, for example, a resin material having high impact resistance is provided with excellent weather resistance and pigment coloring property. A method of laminating materials, a method of coating, a method of coating, and the like are used, but these methods require complicated steps, resulting in high cost, and are not industrially preferable methods.

Polycarbonate resins are used in various industrial applications by taking advantage of their excellent impact resistance or heat resistance, but they have high molding processing temperature, poor fluidity, or impact strength. It has drawbacks such as large thickness dependence. Conventionally, as a method of improving the drawbacks of these polycarbonate resins, blending an ABS (acrylonitrile-butadiene-styrene) resin with the polycarbonate resin is disclosed in Japanese Patent Publication Nos. 38-15225 and Sho. No. 48-12170. However, in the method of blending the ABS resin with the polycarbonate resin, the resin composition obtained has good moldability and impact resistance, but has poor weather resistance, and the automobile exterior in an unpainted state. It cannot be used for materials. Further, as a method for improving the weather resistance of a polycarbonate resin-based resin composition and overcoming the drawbacks of the above polycarbonate resin, Japanese Patent Application Laid-Open No. 64-79257 discloses a polyorganosiloxane and a polyalkylsiloxane. It has been proposed to blend a composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer into a composite rubber composed of (meth) acrylate with a polycarbonate resin.

Further, as a method for improving the effect of the ABS resin as an impact resistance modifier, and particularly for improving the impact strength under a low temperature atmosphere, Japanese Patent Laid-Open No. 6-1897 discloses a polycarbonate resin. And / or copolyester card
A vinyl monomer is graft-polymerized on a resin matrix composed of a carbonyl-based resin and a SAN-based resin (styrene-acrylonitrile copolymer) to a ABS-based resin and a composite rubber containing a polyorganosiloxane and a polyalkyl acrylate. There has been proposed a method of using a resin composition comprising the composite rubber-based graft copolymer.

Further, JP-A-7-126510 discloses a composite rubber containing a polycarbonate resin, an ABS resin, a phosphoric acid ester, polytetrafluoroethylene, an inorganic filler and a polyorganosiloxane and a polyalkyl acrylate. A resin composition comprising a composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl monomer has been proposed.

Further, in Japanese Patent Application Laid-Open No. 7-133417, a composite rubber system obtained by graft-polymerizing a vinyl monomer onto a composite rubber containing a polycarbonate resin, a rubber-reinforced resin, a polyorganosiloxane and a polyalkyl acrylate. A resin composition composed of a graft copolymer and a halogen compound has been proposed.

Further, in Japanese Unexamined Patent Publication (Kokai) No. 6-157889, a composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer onto a composite rubber composed of polyorganosiloxane and polyacrylate, and a polycarbonate. As a method of improving the pigment colorability of the blended product with the resin, the number average particle diameter is 0.01 μm to 0.07 μm and 0.10 μm.
It has been proposed to use composite rubber-based graft copolymers in which the volume of the larger particles is 20% or less of the total particle volume.

[0011]

However, in Japanese Unexamined Patent Publication (Kokai) No. 64-79257, a vinyl compound is used for a composite rubber composed of polyorganosiloxane and polyalkyl (meth) acrylate having an average particle size of 0.08 to 0.6 μm. Regarding the graft copolymer obtained by graft polymerization of the monomer, although the ratio of the polyorganosiloxane to the polyalkyl (meth) acrylate and the amount of the graft component in the composite rubber for expressing the impact resistance are mentioned, Only the graft copolymer having a graft component content of 30% by weight is described in the examples, and the pigment coloring property of the resin composition containing these graft copolymers becomes poor. Cannot be used for applications that require a high degree of design.

Further, the resin composition described in Japanese Patent Application Laid-Open No. 6-1897 has poor weather resistance due to polybutadiene in the ABS resin. Further, there is no description about the pigment coloring property of the resin composition, and since the resin compositions shown in the examples are all poor in pigment coloring property, the excellent design originally possessed by the polycarbonate resin. However, it cannot be used for applications requiring a high degree of design, such as automobile exterior materials.

The resin composition described in JP-A-7-126510 contains a diene rubber component and therefore has poor weather resistance. Further, the object of the present invention is to provide a flame retardant resin material. And the impact resistance, and no specific method for improving the pigment coloring of the resin material is shown. Further, although the structure of the graft copolymer in which the vinyl monomer is graft-polymerized on the composite rubber composed of the polyorganosiloxane and the alkyl (meth) acrylate rubber constituting the resin composition is mentioned, The structure of the graft copolymer for improving the impact resistance and the pigment colorability is not shown, and the resin compositions shown in the examples have poor pigment colorability. It cannot be used for applications that require a high degree of design, such as materials for construction.

The invention of Japanese Patent Application Laid-Open No. 7-133417 relates to the flame retardancy and impact resistance of the resin composition, and a method for improving the pigment coloring property of the resin material will be specifically described. It has not been. Further, although the structure of the graft copolymer in which the vinyl monomer is graft-polymerized on the composite rubber composed of the polyorganosiloxane and the alkyl (meth) acrylate rubber constituting the resin composition is mentioned, The structure of the graft copolymer for improving the impact resistance and the pigment coloring property is not shown, and the resin compositions shown in Examples are all described in JP-A-64-79257. Only the examples using the graft copolymer produced according to the examples are described, and the pigment coloring property of the resin composition containing the graft copolymer produced by this method becomes poor, so that it is industrial. Low value.

On the other hand, in the method of using a graft copolymer in which the number average particle size is 0.01 to 0.07 μm and the particles larger than 0.10 μm are 20 volume% or less, proposed in JP-A-6-157889, -30 ℃ or-required for automobile exterior parts etc.
Due to its low impact resistance in a low temperature atmosphere of 40 ° C,
Its industrial utility value is low because it can be used for a limited number of purposes.

That is, conventionally, in a resin material having a matrix of a polycarbonate resin and a SAN resin, the thickness dependence of the impact resistance and the impact strength under a low temperature atmosphere without impairing the weather resistance and the pigment coloring property. Improve
For example, a material that can be used as a vehicle exterior material has not yet been found, and development of a technology satisfying this has been strongly desired.

[0017]

The present inventors have found that the polymer structure of polyorganosiloxane constituting the graft copolymer, the polymer composition of the graft copolymer, and the polycarbonate / SAN resin composition containing the same As a result of intensive studies on impact resistance and pigment coloring in a low temperature atmosphere, surprisingly, the crosslinking density of polyorganosiloxane and the amount of polyorganosiloxane, the amount of alkyl (meth) acrylate rubber in the composite rubber and the graft copolymer By producing by limiting the amount of the graft component in the coalescence and further the weight average particle diameter of the graft copolymer, a resin composition containing this graft copolymer has excellent impact resistance under a low temperature atmosphere which has never been obtained. The inventors have found that they exhibit pigment colorability and have reached the present invention.

That is, the gist of the present invention is that
A polycarbonate resin (A) and (b-1) a polyorganosiloxane having a vinyl polymerizable functional group, a gel content of 60 to 95% by weight, and a swelling degree of 10 to 30 measured in a toluene solvent; -2) At least one monomer selected from (b-3) an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester and a vinyl cyanide compound is grafted to a composite rubber composed of an alkyl (meth) acrylate rubber. 20-40% by weight of a polyorganosiloxane (b-1) in a composite rubber ((b-1) + (b-2)) which is a polymerized graft copolymer,
The alkyl (meth) acrylate rubber (b-2) is 60-
80% by weight, and the content of the graft component (b-3) based on the graft copolymer (B) is 50 to 80% by weight.
And the weight average particle diameter of the graft copolymer is 0.10.
A thermoplastic resin composition comprising the graft copolymer (B), characterized in that it is .about.0.20 .mu.m.

[0019]

DETAILED DESCRIPTION OF THE INVENTION As the polycarbonate resin (A) according to the present invention, a resin produced by a known method is used. That is, a transesterification reaction between a diester of carbonic acid obtained from a monofunctional aromatic or aliphatic hydroxy compound and a dihydroxy compound, an ester of a dihydroxy compound with itself or another dihydroxy compound with a bisalkyl or bisallyl carbonate. Examples include an exchange reaction, a reaction between a dihydroxy compound and phosgene in the presence of an oxygen binder, and a production method by a reaction between a dihydroxy compound and a bischlorocarbonate of the dihydroxy compound in the presence of an oxygen binder. Typically,
There is a production method in which bisphenol A is reacted with carbonyl chloride in the presence of an oxygen binder and a solvent.

The polyorganosiloxane (b-1) constituting the graft copolymer (B) according to the present invention is condensed by adding a crosslinking agent and a vinyl polymerizable functional group-containing siloxane which is a graft crossing agent to dimethylsiloxane. Can be manufactured.

The dimethylsiloxane may be a dimethylsiloxane having a 3- or more-membered ring, preferably a 3- to 6-membered ring. Specific examples include hexamethylcyclotrisiloxane, octamethyltetracyclosiloxane, decamethylpentacyclosiloxane, dodecamethylhexacyclosiloxane, and the like. These may be used alone or as a mixture of two or more.

The vinyl-polymerizable functional group-containing siloxane is not particularly limited as long as it has a vinyl-polymerizable functional group and can be bonded to dimethylsiloxane through a siloxane bond, but the reactivity with dimethylsiloxane is not limited. Considering the above, various alkoxysilane compounds having a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane,
Methacryloyloxy such as γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane. Examples thereof include siloxane, vinyl siloxane such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane, and mercaptosiloxane such as γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane.

These vinyl-polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more kinds. The amount of the siloxane-containing siloxane to be used depends on the impact resistance and Considering the molding appearance, the vinyl-polymerizable functional group-containing siloxane unit is preferably 0.2 to 3 mol%, more preferably 0.3 to 2 mol%, based on the siloxane unit of the polyorganosiloxane.
More preferably, it is 0.3 to 1 mol%.

The cross-linking agent is trifunctional or tetrafunctional.
Functional siloxane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane are used.

These cross-linking agents can be used alone or as a mixture of two or more kinds. The amount of the cross-linking agent used is such that the polyorganosiloxane has a gel content of 60 to 60.
95% by weight and a swelling degree measured in a toluene solvent of 10
It is necessary to adjust to the range of -30. When the gel content is less than 60% by weight, the resin composition containing the graft copolymer containing polyorganosiloxane has low impact resistance in a low temperature atmosphere, which is not preferable. If the degree of swelling is less than 10, the crosslink density of the polyorganosiloxane becomes high and the rubber elasticity is lost, and the impact resistance of the resin composition containing the graft copolymer containing this polyorganosiloxane at room temperature is high. Will be low. On the other hand, the degree of swelling is 3
When it exceeds 0, the impact resistance of the resin composition containing the graft copolymer containing polyorganosiloxane in a low temperature atmosphere becomes low. Considering both the impact resistance at room temperature and the impact resistance in a low temperature atmosphere, the swelling degree of the polyorganosiloxane is more preferably 10 to 20.

The swelling degree according to the present invention is a value which is measured by the following method and serves as an index of the crosslink density of the polyorganosiloxane. The prepared polyorganosiloxane latex is added to about 3 to 5 times the amount of isopropyl alcohol with stirring, and the emulsion is broken and coagulated to obtain a siloxane polymer. The polymer thus obtained is dried under reduced pressure at 80 ° C. for 10 hours. After drying, about 1 g of the polymer is precisely weighed, immersed in about 30 g of toluene, and left at 25 ° C. for 100 hours to swell the toluene in the polymer. Then, the residual toluene was separated and removed by decantation, and the balance was accurately weighed.
After drying under reduced pressure for a period of time, the absorbed toluene is removed by evaporation, and the sample is weighed again. The degree of swelling is calculated by the following equation.

Swelling degree = ((weight of swollen polymer) −
(Dry polymer weight) / (Dry polymer weight) As a method for producing the polyorganosiloxane according to the present invention,
A mixture of the above-mentioned dimethyl siloxane, vinyl-polymerizable functional group-containing siloxane, and cross-linking agent is emulsified with an emulsifier and water, and a homomixer that atomizes the latex by shearing force due to high-speed rotation, or atomization by the jet output from a high-pressure generator. After atomizing using a homogenizer etc.
Polymerization is carried out at a high temperature using an acid catalyst, and then the acid is neutralized with an alkaline substance.

The method of adding the acid catalyst used in the polymerization is as follows.
There are a method of mixing the siloxane mixture with the emulsifier and water, and a method of dropping the latex in which the siloxane mixture is atomized into a high-temperature acid aqueous solution at a constant speed.The method for controlling the particle diameter of the polyorganosiloxane is easy. Considering this, a method is preferred in which a latex in which the siloxane mixture is atomized is dropped at a constant rate into a high-temperature acid aqueous solution.

The emulsifier used in the production of polyorganosiloxane is preferably an anionic emulsifier, and an emulsifier selected from sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, etc. is used. Particularly, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

These emulsifiers are based on the siloxane mixture 10
It is used in the range of about 0.05 to 5 parts by weight with respect to 0 parts by weight. When the amount used is small, the dispersion state becomes unstable, and it becomes impossible to maintain the emulsified state with a fine particle size. On the other hand, if the amount is too large, coloring of the resin composition molded article caused by the emulsifier becomes excessively disadvantageous.

Examples of the acid catalyst used for the polymerization of polyorganosiloxane include 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 and nitric acid. . These acid catalysts are used alone or in combination of two or more. Among these, aliphatic-substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable, because it is also excellent in stabilizing the polyorganosiloxane latex. Further, the amount of the acid catalyst used for producing the polyorganosiloxane is not particularly limited, but considering the pigment coloring property and low temperature impact property of the resulting graft copolymer and the resin composition containing the same, The amount is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, still more preferably 1 to 3 parts by weight, based on 100 parts by weight of the siloxane mixture.

The polymerization temperature of the polyorganosiloxane is 5
The temperature is preferably 0 ° C or higher, more preferably 80 ° C or higher.

Further, after the polyorganosiloxane is polymerized at a high temperature, the polyorganosiloxane is allowed to stand at a temperature equal to or lower than the polymerization temperature, whereby the crosslinking reaction of the polyorganosiloxane proceeds, the gel content of the obtained polyorganosiloxane increases, and The degree of swelling in the toluene solvent decreases. The polymerization reaction and the crosslinking reaction can be stopped by cooling the reaction solution and then neutralizing the polymerization latex with an alkaline substance such as sodium hydroxide, sodium hydroxide, and sodium carbonate.

The time of the polymerization reaction is 2 hours or more, more preferably 5 hours or more when the acid catalyst is mixed with the siloxane mixture, the emulsifier and water to be finely divided and polymerized, and the siloxane is added to the aqueous solution of the acid catalyst. In the method of dropping the latex in which the mixture is atomized, it is preferable to keep the mixture for 1 hour or more after the dropping of the latex.

The time after which the latex after polymerization is left at a temperature not higher than the polymerization temperature is such that the polyorganosiloxane obtained has a gel content of 60 to 95% by weight and a swelling degree measured in a toluene solvent of 10 to 30. However, this standing time is appropriately selected depending on the amount of the crosslinking agent used.

The size of the polyorganosiloxane particles is
The weight average particle diameter of the graft copolymer using the polyorganosiloxane is not particularly limited as long as it is in the range of 0.10 μm to 0.20 μm, but the weight average particle diameter is preferably 0.05 to 0. It is in the range of 0.13 μm.

The polyorganosiloxane latex thus produced is impregnated with an alkyl (meth) acrylate component composed of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate, and then polymerized to form a composite rubber. Obtainable.

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 polyfunctional alkyl (meth) acrylates include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanate. Nurate and the like are included. The amount of the polyfunctional alkyl (meth) acrylate used is 0.1 to 20% by weight in the alkyl (meth) acrylate component, preferably 0.2 to.
1% by weight.

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

The composite rubber comprising the polyorganosiloxane and the alkyl (meth) acrylate rubber according to the present invention is
It can be produced by adding the above-mentioned alkyl (meth) acrylate component to the latex of the polyorganosiloxane 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 with the latex of the polyorganosiloxane component at once and a method of dropping it into the latex of the polyorganosiloxane component at a constant rate. Considering the impact resistance of the resulting resin composition containing the graft copolymer, a method of mixing the latex of the polyorganosiloxane component at once is preferable.

As the radical polymerization initiator used in the polymerization, a peroxide, an azo initiator or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox type initiator is preferable, and a sulfoxylate type initiator in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined is particularly preferable.

In the radical polymerization, an emulsifier can be added if necessary. As the emulsifier, nonionic, anionic and cationic emulsifiers are used. Considering the thermal stability when the obtained graft copolymer is blended with a polycarbonate resin-based matrix, a nonionic-anionic emulsifier is preferred, and sodium polyoxyethylene nonylphenyl ether sulfate is more preferred.

In the composite rubber comprising the polyorganosiloxane and the alkyl (meth) acrylate rubber according to the present invention, the amount of polyorganosiloxane is 20 to 40% by weight and the amount of alkyl (meth) acrylate rubber is 60 to 8.
0% by weight. If the amount of the polyorganosiloxane in the composite rubber is less than 20% by weight, the impact resistance of the resin composition containing the graft copolymer obtained in a low temperature atmosphere becomes low because the content of the polyorganosiloxane is small, and the weight ratio is 40% by weight. %, The resin composition containing the graft copolymer is poor in pigment coloring and has low industrial value. In consideration of both the impact resistance of the graft copolymer and the resin composition containing the same in a low temperature atmosphere and the pigment coloring property, the amount of the polyorganosiloxane in the composite rubber is preferably 22 to 35% by weight, The amount of alkyl (meth) acrylate rubber is 65-
78% by weight, more preferably 25 to 30% by weight of polyorganosiloxane and 70 to 75% by weight of alkyl (meth) acrylate rubber in the composite rubber.

The graft copolymer (B) constituting the resin composition according to the present invention is obtained by adding aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters and vinyl cyanide to the composite rubber produced by emulsion polymerization as described above. It can be produced by graft-polymerizing at least one monomer selected from compounds. Among the monomers used in the graft polymerization, the aromatic alkenyl compound is, for example, styrene, α-methylstyrene, vinyltoluene, etc., and the methacrylic acid ester is, for example, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, etc. Examples thereof include methyl acrylate, ethyl acrylate and butyl acrylate, and examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Among these, a mixture of styrene and acrylonitrile is preferable as the monomer used for graft polymerization in consideration of the thermal stability during molding of the resin composition containing the graft copolymer.

In the graft polymerization, at least one monomer selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters and vinyl cyanide compounds is added to the latex of the composite rubber, and the polymerization is carried out in a single step or in a multi-step manner by a radical polymerization technique. Polymerization can be carried out with
Considering impact resistance and pigment colorability of the resulting resin composition containing the graft copolymer, it is preferable to carry out the polymerization in two or more stages.

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

The amount of the graft component obtained by graft-polymerizing at least one monomer selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters and vinyl cyanide compounds in the graft copolymer according to the present invention is It is 50 to 80% by weight based on the total graft copolymer. When the content of the graft component is less than 50% by weight, the pigment composition of the resin composition containing the graft copolymer is poor in pigmentation. Further, in consideration of both impact resistance and pigment colorability of the resin composition containing the graft copolymer, it is selected from aromatic alkenyl compounds, methacrylic acid esters, acrylic acid esters and vinyl cyanide compounds in the graft copolymer. The amount of the graft component obtained by graft polymerization of at least one monomer is preferably 50 to 70% by weight, more preferably 50 to 70% by weight, based on the total graft copolymer.
60% by weight.

The weight average particle diameter of the graft copolymer (B) constituting the resin composition according to the present invention is 0.10 to 0.2.
0 μm, and if it is less than 0.10 μm, the impact resistance of the resin composition containing the graft copolymer in a low temperature atmosphere becomes low, and in the range exceeding 0.20 μm, the resin composition containing the graft copolymer. The pigment coloring property of the product is poor and the industrial value is low. Considering both the impact resistance of the resin composition containing the graft copolymer in a low temperature atmosphere and the pigment coloring property, the weight average particle diameter of the graft copolymer is 0.10 to 0.15.
More preferably, it is μm.

The graft copolymer according to the present invention is prepared by adding the graft copolymer latex produced as described above to hot water in which a metal salt such as calcium chloride, calcium acetate or aluminum sulfate is dissolved, and salting out and coagulating. By doing so, the graft copolymer can be separated and recovered. Of these, calcium salts such as calcium chloride and calcium acetate are particularly preferable as a coagulant to be used in consideration of the thermal stability when the obtained graft copolymer is blended with a polycarbonate resin matrix.

The thermoplastic resin composition comprising the polycarbonate resin (A) and the graft copolymer (B) of the present invention further comprises an aromatic alkenyl compound, a vinyl cyanide compound and a vinyl monomer copolymerizable therewith. A copolymer (C) obtained from at least one selected from the above can be blended.

The copolymer (C) according to the present invention is a copolymer obtained from at least one selected from aromatic alkenyl compounds, vinyl cyanide compounds and vinyl monomers copolymerizable with them. . Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, vinyltoluene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-terephthalate.
Shari-butyl styrene, ethyl styrene, vinyl naphthalene and the like are preferable, and styrene and α-methyl styrene are preferable. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.
Preferably it is acrylonitrile. As the copolymerizable vinyl monomer, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate,
Methacrylic acid esters such as glycidyl methacrylate,
Examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, maleimide compounds such as N-phenylmaleimide and N-methylmaleimide, and maleic anhydride.

Preferred examples of the copolymer (C) include a styrene-acrylonitrile copolymer (SAN resin) and a styrene-acrylonitrile-N-phenylmaleimide copolymer. As the method for producing the copolymer (C), generally known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization are used.

The amount of addition can be arbitrarily selected.

The resin composition according to the present invention is obtained by extrusion-molding the graft copolymer (B), the polycarbonate resin (A) and the copolymer (C) produced by the above-mentioned method with a usual kneading machine. Can be manufactured by. Examples of the molding machine used for kneading include an extruder, an injection molding machine, a blow molding machine, a calender molding machine, and an inflation molding machine.

Further, a dye, a pigment, a stabilizer, a reinforcing agent, a filler, a flame retardant and the like may be added to the resin composition containing the graft copolymer, if necessary.

[0056]

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

The weight average particle diameters of the polyorganosiloxane in the latex in the reference example and the graft copolymer in the example are DLS-700 manufactured by Otsuka Electronics Co., Ltd.
It was determined by a dynamic light scattering method using a mold.

The Izod impact strength in the examples and comparative examples is measured by the method according to ASTM D258. Especially, the Izod impact strength in a low temperature atmosphere is measured at -30 ° C. or -40 ° C. for 12 hours or more. The measurement was performed after leaving the Izod test piece to stand.

The surface hardness (Rockwell hardness) in the examples and comparative examples was measured by the method according to ASTM D785.

Further, the pigment coloring properties of the resin compositions in Examples and Comparative Examples were evaluated using an injection molding machine IS-100EN manufactured by Toshiba Machine Co., Ltd. 100 mm * 10.
It was performed by a hue measurement of a 0 mm * 3 mm plate in accordance with JIS Z8729.

Reference Example 1 Preparation of Polyorganosiloxane Latex L-1 96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane mixture. Got 300 ml of distilled water containing 0.67 parts of sodium dodecylbenzenesulfonate dissolved therein.
And 10,000 parts / min with a homomixer.
After stirring for 300 minutes, add 300 kg / cm ^{2 to the} homogenizer.
Once to obtain a stable premixed organosiloxane latex.

On the other hand, 2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device, and 2% by weight of dodecylbenzenesulfonic acid was added. An aqueous solution was prepared.

With this aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and the temperature was maintained and cooled for 1 hour after the completion of the addition. The reaction solution was left at room temperature for 48 hours, and then neutralized with an aqueous solution of sodium hydroxide.

The latex (L-
When 1) was dried at 170 ° C. for 30 minutes to obtain a solid content, it was 17.3%. The weight average particle diameter of the polyorganosiloxane in the latex was 0.08 μm. Also, the gel content of polyorganosiloxane is 8
The swelling degree measured in a 5% toluene solvent was 14.5.

Reference Example 2 Polyorganosiloxane L-
Preparation of 2 95 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 3 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based mixture. 300 ml of distilled water containing 0.67 parts of sodium dodecylbenzenesulfonate dissolved therein.
And 10,000 parts / min with a homomixer.
After stirring for 300 minutes, add 300 kg / cm ^{2 to the} homogenizer.
Once to obtain a stable premixed organosiloxane latex.

On the other hand, 2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device, and 2% by weight of dodecylbenzenesulfonic acid was added. An aqueous solution was prepared.

With the aqueous solution heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of the addition, the temperature was maintained for 1 hour and cooled. After the temperature of the reaction solution dropped to 40 ° C., the reaction solution was neutralized with a caustic soda aqueous solution.

The latex (L-
The solid content of 2) was 17.7%, and the weight average particle diameter of the polyorganosiloxane in the latex was 0.08 μm. Also, the gel content of polyorganosiloxane is 80
%, The swelling degree measured in a toluene solvent was 17.7.

Reference Example 3 Polyorganosiloxane L-
Preparation of 3 Latex (L-3) was prepared in the same manner as in Reference Example 1 except that the siloxane mixture in Reference Example 1 was changed to 98 parts of octamethyltetracyclosiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane. . The solid content of the obtained polyorganosiloxane latex was 17.5%, and the weight average particle diameter was 0.08 μm. The polyorganosiloxane was soluble in the toluene solvent, and no gel component was observed.

Reference Example 4 Polyorganosiloxane L-
Preparation of 4 Latex (L) was carried out in the same manner as in Reference Example 1 except that the siloxane-based mixture in Reference Example 1 was changed to 93 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane and 5 parts of ethyl orthosilicate. -4) was prepared. The solid content of the obtained polyorganosiloxane latex was 17.5%, and the weight average particle diameter was 0.08 μm. The gel content of the polyorganosiloxane was 95%, and the degree of swelling measured in a toluene solvent was 7.0. Reference Example 5 Production of Polyorganosiloxane L-5 In Reference Example 1, polyorganosiloxane latex (L-5 was prepared in the same manner as in Reference Example 1 except that the amount of dodecylbenzenesulfonic acid used was changed to 10 parts. ) Was prepared. The solid content of the obtained polyorganosiloxane latex is 17.5% by weight, and the weight average particle diameter is 0.05 μm.
Met. The gel content of the polyorganosiloxane was 10%, and the degree of swelling measured in a toluene solvent was 25.0.

Reference Example 6 Polyorganosiloxane L-
Preparation of 6 96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based mixture. To this was added 200 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate and 0.67 part of dodecylbenzenesulfonic acid were dissolved, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes. One pass at a pressure of ² cm ² resulted in a stable premixed organosiloxane latex. This organosiloxane latex was transferred into a reactor equipped with a condenser, a jacket heater and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and then cooled. The reaction solution was left at room temperature for 48 hours, and then neutralized with an aqueous solution of sodium hydroxide. The solid content of the obtained polyorganosiloxane latex (L-6) was 29.0%, and the weight average particle diameter was 0.19 μm. The gel content of the polyorganosiloxane was 95%, and the degree of swelling measured in a toluene solvent was 7.0.

Table 1 shows the preparation conditions and the results of the polyorganosiloxanes of Reference Examples 1 to 6 above.

[0073]

[Table 1]

Reference Example 7 Preparation of Graft Copolymer S-1 A polyorganosiloxane latex (reference example 1) was prepared in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer. L-1) 119.5 parts and sodium polyoxyethylene alkylphenyl ether sulfate (Emal NC-35 manufactured by Kao Co., Ltd.) 0.8 parts were collected and added with 203 parts of distilled water and mixed, and then n-butyl acrylate. 53.2 parts, allyl methacrylate 0.21 parts,
1,3-butylene glycol dimethacrylate 0.11
Parts and 0.13 parts of tertiary butyl hydroperoxide were added.

By passing a nitrogen stream through this reactor, the atmosphere was replaced with nitrogen, and the temperature was raised to 60.degree. When the internal liquid temperature reaches 60 ° C., ferrous sulfate 0.00
01 parts, ethylenediaminetetraacetic acid disodium salt 0.0
An aqueous solution obtained by dissolving 003 parts and 0.24 parts of Rongalit in 10 parts of distilled water was added to start radical polymerization. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component, thereby obtaining a composite rubber latex of polyorganosiloxane and butyl acrylate rubber.

After the liquid temperature inside the reactor dropped to 60 ° C.,
An aqueous solution prepared by dissolving 0.4 parts of Rongalit in 10 parts of distilled water was added, and then a mixed solution of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 parts of tert-butyl hydroperoxide was added for about 1 hour. It was dropped and polymerized. After holding for 1 hour after the completion of the dropwise addition, ferrous sulfate was added to a solution containing 0.1 mg of ferrous sulfate.
0002 parts, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalide in 10 parts of distilled water were added, and then 7.4 parts of acrylonitrile, 22.2 parts of styrene and tert-butylhydrogen were added. A mixture of 0.1 part of peroxide was added dropwise over about 40 minutes to carry out polymerization. After the completion of dropping, the mixture was maintained for 1 hour and then cooled to obtain a latex of a graft copolymer obtained by graft-polymerizing acrylonitrile and styrene onto a composite rubber composed of polyorganosiloxane and butyl acrylate rubber. The weight average particle diameter of the graft copolymer in the latex determined by the dynamic light scattering method was 0.13 μm.

Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% 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, washed and dried to obtain a graft copolymer (S-1).

Reference Example 8 Production of Graft Copolymer S-2 Using the polyorganosiloxane latex (L-2) obtained in Reference Example 2, the same composite rubber reaction and graft copolymerization as in Reference Example 7 were carried out. Polymer preparation was carried out. The weight average particle size of the graft copolymer in the obtained latex is
It was 0.13 μm.

Reference Example 9 Production of Graft Copolymer T-1 Using the polyorganosiloxane latex (L-3) obtained in Reference Example 3, the same composite rubber reaction and graft copolymerization as in Reference Example 7 were carried out. Polymer preparation was carried out. The weight average particle size of the graft copolymer in the obtained latex is
It was 0.13 μm.

Reference Example 10 Production of Graft Copolymer T-2 Using the polyorganosiloxane latex (L-4) obtained in Reference Example 4, the same composite rubber reaction and graft copolymerization as in Reference Example 7 were carried out. Polymer preparation was carried out. The weight average particle size of the graft copolymer in the obtained latex is
It was 0.13 μm.

Reference Example 11 Production of Graft Copolymer T-3 Using the polyorganosiloxane latex (L-5) obtained in Reference Example 5, the same composite rubber reaction and graft copolymerization as in Reference Example 7 were carried out. Polymer preparation was carried out. The weight average particle size of the graft copolymer in the obtained latex is
It was 0.08 μm.

Reference Example 12 Production of Graft Copolymer T-4 The polyorganosiloxane latex charged in the reactor in Reference Example 7 was changed to L-6 prepared in Reference Example 6, and further this polyorganosiloxane was used. Latex (L
-5) was added to 71.3 parts, and distilled water was added to 251.
A graft copolymer was produced in the same manner as in Reference Example 7 except that the amount was changed to 2 parts. The weight average particle diameter of the graft copolymer in the obtained latex was 0.25 μm.

Reference Example 13 Production of Graft Copolymer T-5 In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, the polyorganosiloxane latex obtained in Reference Example 1 ( 16 parts of L-1) and 0.8 parts of sodium polyoxyethylene alkylphenyl ether sulfate (Emal NC-35 manufactured by Kao Co., Ltd.) were collected and mixed with 163.4 parts of distilled water, and then n- Butyl acrylate 74.4 parts, allyl methacrylate 0.30
Part, 1,3-butylene glycol dimethacrylate 0.
A mixture of 15 parts and 0.19 parts of tertiary butyl hydroperoxide was added.

By passing a nitrogen stream through this reactor, the atmosphere was replaced with nitrogen, and the temperature was raised to 60.degree. When the internal liquid temperature reaches 60 ° C., ferrous sulfate 0.00
01 parts, ethylenediaminetetraacetic acid disodium salt 0.0
An aqueous solution obtained by dissolving 003 parts and 0.24 parts of Rongalit in 10 parts of distilled water was added to start radical polymerization. The liquid temperature rose to 82 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component, thereby obtaining a composite rubber latex of polyorganosiloxane and butyl acrylate rubber.

After the temperature of the liquid inside the reactor has dropped to 60 ° C.,
An aqueous solution prepared by dissolving 0.4 parts of Rongalit in 10 parts of distilled water was added, and then a mixed solution of 7.4 parts of acrylonitrile, 22.1 parts of styrene and 0.13 parts of tertiary butyl hydroperoxide was added for about 40 minutes. It was dropped and polymerized. After holding for 1 hour after completion of dropping, an aqueous solution prepared by dissolving 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalid in 10 parts of distilled water was added, and then acrylonitrile. A mixed solution of 3.7 parts, 11.1 parts of styrene and 0.1 part of tert-butyl hydroperoxide was added dropwise over about 10 minutes to carry out polymerization. After the completion of dropping, the mixture was maintained for 1 hour and then cooled to obtain a latex of a graft copolymer obtained by graft-polymerizing acrylonitrile and styrene onto a composite rubber composed of polyorganosiloxane and butyl acrylate rubber. The weight average particle diameter of the graft copolymer in the latex determined by the dynamic light scattering method is 0.11 μm.
Met.

Next, 150 parts of an aqueous solution in which 5% of calcium acetate was dissolved 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, washed and dried to obtain a graft copolymer (T-5).

Reference Example 14 Production of Graft Copolymer T-6 In Reference Example 7, the amount of polyorganosiloxane latex (L-1) charged in the reactor was 59.8 parts, and the amount of distilled water was 252. 6 parts of n-butyl acrylate in 3 parts
3.5 parts, 0.25 parts allyl methacrylate, 1,3
-0.13 parts of butylene glycol dimethacrylate and 0,3 parts of tertiary butyl hydroperoxide.
A graft copolymer (T-6) was produced in the same manner as in Reference Example 7 except that the amount was changed to 16 parts. The weight average particle size of the graft copolymer in the latex determined by the dynamic light scattering method was 0.15 μm.

Reference Example 15 Production of Graft Copolymer T-7 In Reference Example 7, the amount of polyorganosiloxane latex (L-1) charged into the reactor was 192.1 parts, and the amount of distilled water was 142 parts. .9 parts to 4 parts of n-butyl acrylate
0.6 parts, allyl methacrylate 0.16 parts, 1,3
-0.08 part of butylene glycol dimethacrylate and 0. 8 parts of tertiary butyl hydroperoxide.
A graft copolymer (T-7) was produced in the same manner as in Reference Example 7 except that the amount was changed to 10 parts. The weight average particle diameter of the graft copolymer in the latex determined by the dynamic light scattering method was 0.11 μm.

Table 2 shows the production conditions and results of the graft copolymers produced in Reference Examples 7 to 15 above.

[0090]

[Table 2]

(Examples 1 to 3 and Comparative Examples 1 to 7) In the examples and comparative examples, the following components were used. Component (A) (PC resin): Mitsubishi Engineering Plastics Co., Ltd.
Piron S2000F component (B) (composite rubber-based graft copolymer): Reference Example 7
~ 15 composite rubber-based copolymer component (C) (SAN resin): SAN-1: 70 parts styrene and acrylonitrile 3
0 part of the mixture was polymerized by the suspension polymerization method and the reduced viscosity (η _SP / C) measured in a dimethylformamide solution was 0.
SAN resin of 60 SAN-2: SAN resin (Styrac AS 709 manufactured by Asahi Kasei Co., Ltd.) The components (A), (B) and (C) described above were mixed at a ratio (weight ratio) shown in Table 3, Further, 0.3 parts of Adecastable C (manufactured by Asahi Denka Co., Ltd.) as a heat stabilizer, 0.4 parts of barium stearate as a release agent, 0.4 parts of EBS as a lubricant, and a black colorant. As
0.8 parts of Bonblack (CB-960: manufactured by Mitsubishi Chemical Corporation) were added and mixed, and the cylinder temperature was 260 ° C.
A twin-screw extruder set to 1 was used to form a pellet.
The pellets are then cylinder-set at 260 ° C,
Injection molding was performed at a mold temperature of 80 ° C. to obtain a test piece for evaluating physical properties and pigment coloring property. Table 3 shows the I * dot impact strength, the Rockwell hardness, and the L * value obtained from the hue measurement of each of the obtained test pieces.

[0092]

[Table 3]

From the examples and the comparative examples, the following facts became clear.

1) The resin compositions of Examples 1 to 3 show high Izod impact strength at room temperature and 20 kgcm / c even in a low temperature atmosphere of -30 ° C and -40 ° C.
It has a high impact strength of m or more and L * of a black colored plate.
It has a low value and simultaneously satisfies excellent pigment colorability.

2) Since the resin composition of Comparative Example 1 contains a graft copolymer using a polyorganosiloxane having no crosslinked structure as a composite rubber, it has an Izod impact strength at room temperature and a pigment coloring property. -30, although excellent in
Since the Izod impact strength in a low temperature atmosphere of ℃ and -40 ℃ is low, it cannot be used in applications requiring impact resistance in a high temperature atmosphere such as automobile exterior parts, which is not preferable.

3) The resin composition of Comparative Example 2 uses a graft copolymer containing a rigid polyorganosiloxane in the composite rubber, which has a high swelling degree of less than 10 measured in a toluene solvent and has a high crosslinking density. Therefore, the Izod impact strength under normal temperature and low temperature atmosphere is low, which is not preferable as an industrial material.

4) Since the resin composition of Comparative Example 3 contains the graft copolymer having a small average particle diameter of 0.08 μm, the Izod impact strength in a low temperature atmosphere is low, Not preferable.

5) Since the resin composition of Comparative Example 4 contains the graft copolymer having a large average particle size of 0.25 μm in weight average particle size, the black colored plate has a high L * value, for example, It cannot be used in applications where a high degree of pigment coloring is required, such as when the automobile exterior parts are used without painting.

6) Since the resin composition of Comparative Example 5 uses a graft copolymer having a small amount of the graft component of 30 parts, the pigment coloring property is poor.

7) The resin composition of Comparative Example 6 uses a graft copolymer having a polyorganosiloxane content of less than 20% in the composite rubber, so that although it is excellent in pigment coloration, it is -30 ° C and Since the Izod impact strength in a low temperature atmosphere such as -40 ° C is low, it cannot be used in applications requiring impact resistance in a high temperature atmosphere such as automobile exterior parts, which is not preferable.

8) Since the resin composition of Comparative Example 7 uses a graft copolymer having a polyorganosiloxane content in the composite rubber of more than 40%, the black colored plate has a high L * value, for example, in an automobile. It cannot be used for applications that require a high degree of pigment coloring, such as when the exterior parts are used without painting.

[0102]

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

1) The resin composition according to the present invention is excellent in impact resistance, particularly in impact resistance in a low temperature atmosphere, surface hardness and pigment colorability.

2) The balance between the Izod impact strength and the pigment coloring property, especially in a low temperature atmosphere, is known as a graft copolymer containing a composite rubber composed of a polyorganosiloxane and an acrylate rubber, a polycarbonate resin, and a SAN. This is a very high level that cannot be obtained with a resin composition composed of a base resin, and its utility value as various industrial materials, especially as materials for automobile exterior parts is extremely high.

Claims (2)

[Claims] 1. A polycarbonate resin (A) and (b-
1) It has a vinyl-polymerizable functional group and has a gel content of 60 to 9
5% by weight, swelling degree measured in toluene solvent is 10 to 3
A composite rubber composed of a polyorganosiloxane of 0 and an (b-2) alkyl (meth) acrylate rubber,
-3) A graft copolymer obtained by graft-polymerizing at least one monomer selected from an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester and a vinyl cyanide compound, which is a composite rubber ((b-1 ) +
(B-2)) contains 20 to 40% by weight of the polyorganosiloxane (b-1) and 60 to 80% by weight of the alkyl (meth) acrylate rubber (b-2), and the graft copolymer (B Content of the graft component (b-3) based on (4) is 50 to 80% by weight, and the weight average particle diameter of the graft copolymer is 0.10 to 0.20 μm. A thermoplastic resin composition comprising (B). 2. The thermoplastic resin composition according to claim 1, further comprising a copolymer (C) obtained from at least one selected from aromatic alkenyl compounds, vinyl cyanide compounds and vinyl monomers copolymerizable therewith. ) Is mixed with the thermoplastic resin composition.