JP2016044274A - Thermoplastic resin composition and molded body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having high flowability suitable for thin wall molding and excellent in surface impact resistance, shock resistance and flame resistance.SOLUTION: There is provided a thermoplastic resin composition containing (A) polycarbonate resin or polyester carbonate resin, (B) (co)polymer containing an aromatic vinyl monomer unit (b1) and (C) rubber containing graft copolymer obtained by graft polymerization of one or more kind of vinyl monomer with a rubber containing polyorganosiloxane. In the thermoplastic resin composition, the content of a component derived from the vinyl polymerizable group-containing silane compound in the polyorganosiloxane is 1 to 10 mass%, the content of the polyorganosiloxane in the rubber-containing graft copolymer (C) is 30 to 98 mass%, the content of a component derived from a polyfunctional vinyl monomer in the rubber-containing graft copolymer (C) is 0 mass% or more and less than 5 mass%, and volume average particle diameter of the rubber-containing graft copolymer (C) is 300 to 2,000 nm.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition having high fluidity suitable for thin-wall molding and excellent in surface impact resistance, impact resistance, and flame retardancy, and a molded product thereof.

  Polycarbonate resin (hereinafter sometimes referred to as PC resin) is used in various applications because of its excellent heat resistance, impact resistance, etc., but has a high molding processing temperature and poor fluidity. Has drawbacks.

  Therefore, polymer alloys made by blending PC resin with ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (styrene-acrylonitrile copolymer), etc. are used in office automation equipment such as copying machines, printers, facsimiles, personal computers, etc. It is widely used for materials in the electric and electronic fields such as mobile phones.

  These parts are thinned year by year for the purpose of miniaturization, weight reduction, high functionality, and the like. Therefore, recently, the resin material has high fluidity suitable for thin molding, mechanical properties such as impact resistance are good even in a thin and lightweight molded body, and flame retardancy. The heat resistance is required to be excellent.

  In order to meet these demands, for example, attempts have been made to improve by improving the blending ratio of ABS resin and AS resin. However, although high fluidity is obtained, inconveniences such as surface impact resistance, impact resistance, flame retardancy, and heat resistance decrease occur.

  In addition, butadiene-based copolymers such as ABS resin have unsaturated double bonds in the main chain, so the weather resistance, ozone resistance, and heat aging resistance are likely to decrease. Due to environmental influences, it tends to cause yellowing of the polymer material, loss of surface gloss, reduced impact resistance, and the like. Therefore, it is necessary to avoid the use of a butadiene-based copolymer or suppress the amount used as much as possible.

  Therefore, attempts have been made to improve the low-temperature impact resistance by blending a silicone-based material with the aforementioned polymer alloy. For example, Patent Document 1 proposes a flame retardant thermoplastic resin composition containing a graft copolymer containing 65 to 99% by weight of polyorganosiloxane. Patent Document 2 proposes a graft copolymer having a volume average particle size of 300 to 2000 nm and a polyorganosiloxane content of 70 to 98% by mass, which is blended in a thermoplastic resin. Patent Document 3 discloses a composite rubber-based graft containing a composite rubber component containing a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component, and a graft component containing an aromatic alkenyl compound and a vinyl cyanide compound. A composite rubber-based graft copolymer having a polyorganosiloxane rubber component in the composite rubber component of 20 to 80% by mass has been proposed.

JP 2000-17136 A International Publication No. 2013/162080 Pamphlet JP 2011-46843 A

  However, since the molded article obtained in Patent Document 1 has a small volume average particle diameter of the blended graft copolymer, the surface impact resistance and the strength development property at low temperature of the molded article reach a desired level. There are things that do not. Since the resin composition of Patent Document 2 has low fluidity, it is necessary to increase the molding processing temperature, which easily causes deterioration of the resin composition due to high temperature molding. The molded product obtained in Patent Document 3 is also described in which the blended graft copolymer has a large volume average particle diameter, but it contains a large amount of polyalkyl (meth) acrylate rubber component in the composite rubber. Therefore, the ductile-brittle transition (transition) temperature (DBTT) is high and insufficient, and the surface impact resistance is not satisfactory.

  An object of the present invention is to provide a thermoplastic resin composition having high fluidity suitable for thin-wall molding and having excellent surface impact resistance, impact resistance, and flame retardancy.

The problem is solved by the following [1] to [7].
[1]
Polycarbonate resin or polyester carbonate resin (A),
(Co) polymer (B) comprising an aromatic vinyl monomer unit (b1),
Rubber-containing graft copolymer (C) obtained by graft-polymerizing one or more vinyl monomers to rubber containing polyorganosiloxane
A thermoplastic resin composition comprising:
The content of the component derived from the vinyl-based polymerizable group-containing silane compound in the polyorganosiloxane is 1 to 10% by mass,
The content of the polyorganosiloxane in the rubber-containing graft copolymer (C) is 30 to 98% by mass,
The content of the component derived from the polyfunctional vinyl monomer in the rubber-containing graft copolymer (C) is 0% by mass or more and less than 5% by mass,
And the thermoplastic resin composition whose volume average particle diameter of this rubber-containing graft copolymer (C) is 300-2000 nm.
[2]
The thermoplastic resin composition according to the above [1], wherein the rubber containing polyorganosiloxane is a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate.
[3]
The thermoplastic resin composition according to [1] or [2], wherein the (co) polymer (B) is a (co) polymer containing a vinyl cyanide monomer unit.
[4]
The thermoplastic resin composition according to any one of [1] to [3], wherein the (co) polymer (B) is a (co) polymer not containing a butadiene monomer unit.
[5]
The rubber-containing graft copolymer (C) is 0 with respect to 100 parts by mass in total of 50 to 99 parts by mass of the polycarbonate resin or polyester carbonate resin (A) and 50 to 1 part by mass of the (co) polymer (B). The thermoplastic resin composition according to any one of [1] to [4], which is contained in an amount of 5 to 30 parts by mass.
[6]
1-30 mass parts of flame retardants (D) are further added with respect to 100 mass parts in total of 50-99 mass parts of said polycarbonate resin or polyester carbonate resin (A) and said (co) polymer (B). The thermoplastic resin composition according to any one of [1] to [5].
[7]
The molded object obtained by shape | molding the thermoplastic resin composition in any one of said [1]-[6].

  According to the present invention, it is possible to provide a thermoplastic resin composition having high fluidity suitable for thin-wall molding and excellent surface impact resistance and impact resistance. According to this invention, the thermoplastic resin composition excellent in the flame retardance can be given by adding a flame retardant (D) further.

In the present invention, “(meth) acrylate” means at least one of “acrylate” and “methacrylate”. The “(co) polymer” means at least one of “polymer” and “copolymer”.
Hereinafter, the present invention will be described in detail.

  The thermoplastic resin composition of the present invention contains a polycarbonate resin or a polyester carbonate resin (A), a (co) polymer (B), and a rubber-containing graft copolymer (C). Moreover, it is preferable to further contain a flame retardant (D).

[Polycarbonate resin or polyester carbonate resin (A)]
In the present invention, a polycarbonate resin or a polyester carbonate resin (A) is used as the thermoplastic resin.

  Examples of the polycarbonate resin include a polymer obtained by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. The PC resin may be either linear or branched. The PC resin may be either a homopolymer or a copolymer.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, and the like. 4,4-dihydroxydiphenyl is mentioned. These may be used alone or in combination of two or more. A compound in which one or more tetraalkylphosphonium sulfonates are bonded can also be used as the aromatic dihydroxy compound.

  In order to obtain a branched PC resin as the PC resin, a part of the aromatic dihydroxy compound described above may be substituted with a branching agent. Examples of the branching agent include the following. Phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6- Such as dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, etc. Polyhydroxy compounds; 3,3-bis (4-hydroxyaryl) oxindole (ie isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin and 5-bromoisatin. The usage-amount of a branching agent is 0.01-10 mol% normally with respect to an aromatic dihydroxy compound, Preferably it is 0.1-2 mol%.

  As the PC resin, a PC resin obtained from an aromatic dihydroxy compound containing bisphenol A is preferable in terms of heat resistance and flexibility. As the PC resin, a copolymer mainly composed of a PC resin such as a copolymer of a polycarbonate and a siloxane structure or a copolymer of an oligomer can be used. PC resin may be used individually by 1 type, and may use 2 or more types together.

The viscosity average molecular weight of the PC resin is preferably 16,000 to 30,000, more preferably 18,000 to 28,000. The viscosity average molecular weight of the PC resin is a value converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. When the viscosity average molecular weight is 30,000 or less, the melt fluidity of the resin composition tends to be good, and when it is 16,000 or more, the impact resistance of the molded article of the present invention is good. There is a tendency.
In order to adjust the molecular weight of the PC resin, for example, a part of the above-mentioned aromatic dihydroxy compound is mixed with m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, p- What is necessary is just to substitute with monovalent | monohydric aromatic hydroxy compounds, such as a long-chain alkyl substituted phenol.

  It does not specifically limit as a manufacturing method of PC resin, It can manufacture by the well-known phosgene method (interfacial polymerization method) and a melting method (transesterification method). Moreover, it is also possible to use an aromatic polycarbonate resin produced by a melting method and having a terminal OH group amount adjusted by adjusting the degree of pressure reduction during the reaction.

  Examples of the PC resin include the following. Product names Iupilon S-1000, Iupilon S-2000, Iupilon S-3000, Iupilon H-3000 or Iupilon H-4000 manufactured by Mitsubishi Engineering Plastics Co., Ltd., or product name Panlite L1250 manufactured by Teijin Chemicals Ltd., Bread Light L1225 or Panlite K1300. These shapes are usually pellets, but flaky PC resin may be used. For example, trade names Iupilon S-1000F, Iupilon S-2000F, Iupilon H-3000F, etc. manufactured by Mitsubishi Engineering Plastics Co., Ltd.

  Examples of the polyester carbonate resin include a polymer obtained from an aromatic dicarboxylic acid dihalide. The polyester carbonate may be either linear or branched, but is preferably linear polyester carbonate.

  Preferred aromatic dicarboxylic acid dihalides include, for example, diphthalic dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4′-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Among these, it is more preferable to use a mixture of diacid dichloride of isophthalic acid and terephthalic acid at a ratio of 1:20 to 20: 1. In the preparation of the polyester carbonate, a carbonic acid halide (preferably phosgene) can be used in combination as a bifunctional acid derivative.

In addition to the monophenols mentioned above, suitable chain terminators for preparing polyester carbonates are their chlorocarbonates and acid monochlorides of aromatic monocarboxylic acids (optionally C1-C22-alkyl groups or As well as aliphatic C2-C22-monocarboxylic acid chlorides, which may be substituted by halogen atoms).
The amount of chain terminator is based on the molar amount of diphenol in the case of phenol-based chain terminators and based on the molar amount of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride-based chain terminators. In some cases, the content is preferably 0.1 to 10 mol%.

  In preparing the polyester carbonate resin, one or more aromatic hydroxycarboxylic acids can be further used.

  The polycarbonate resin and the polyester carbonate resin may be used alone, or may be arbitrarily mixed and used.

[(Co) polymer (B) containing aromatic vinyl monomer (b1) unit]
In the present invention, the (co) polymer (B) is a (co) polymer containing an aromatic vinyl monomer (b1) unit. The (co) polymer (B) is a known monomer that is a raw material for the aromatic vinyl monomer (b1) unit and, if necessary, a vinyl monomer (b2) copolymerizable therewith. It is obtained by polymerizing by the method. Alternatively, a monomer as a raw material for the aromatic vinyl monomer (b1) unit, and a vinyl monomer (b2) copolymerizable therewith if necessary, a rubber polymer (however, polyorganosiloxane It is obtained by graft polymerization by a known method.
This component (B) contributes to the moldability (fluidity) improvement of a thermoplastic resin composition.

  Examples of the monomer that is a raw material for the aromatic vinyl monomer (b1) unit include the following. Styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene and vinylnaphthalene. These may be used alone or in combination of two or more. Among these, styrene and α-methylstyrene are preferable because the polymerization rate of the vinyl monomer (b2) is easily increased and the refractive index is close to that of the PC resin or the polyester carbonate resin (A).

  Examples of the vinyl monomer (b2) copolymerizable with the aromatic vinyl monomer (b1) include the following. Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; (meth) acrylic acid such as acrylic acid and methacrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate Alkyl (meth) acrylates such as 2-ethyl (meth) acrylate and 2-ethylhexyl methacrylate; α, β-unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; maleimide, N-methylmaleimide, N- Maleimide compounds such as ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide. These may be used alone or in combination of two or more. As the vinyl monomer (b2), it is preferable to use a vinyl cyanide monomer because heat resistance, mechanical strength, and chemical resistance can be imparted while maintaining transparency. In addition, when a vinyl cyanide monomer is used, the (co) polymer (B) has an aromatic ring and a polar group, so it is easy to control the compatibility with other resins by changing the composition ratio. It is preferable.

  The composition ratio of the aromatic vinyl monomer (b1) and the vinyl monomer (b2) is not particularly limited and is selected according to the application.

  As the rubbery polymer, other than rubber containing polyorganosiloxane can be used, and examples thereof include the following. Polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, diene rubbers such as butadiene-isoprene copolymers, ethylene- Random copolymer and block copolymer of propylene, copolymer of ethylene and alpha olefin, copolymer of ethylene-unsaturated carboxylic acid ester such as ethylene-methacrylate, ethylene-butyl acrylate, acrylate-butadiene Copolymers, for example, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene non-polymers such as ethylene-propylene-hexadiene copolymers, etc. Conjugated dienes Over polymers, butylene - Isoburen copolymers, chlorinated polyethylene. These may be used alone or in combination of two or more.

Specific examples of the (co) polymer (B) containing the aromatic vinyl monomer unit (b1) include styrene resin, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-N-phenylmaleimide copolymer Polymer, methyl methacrylate-styrene copolymer, methyl methacrylate-styrene-acrylonitrile copolymer, styrene-butadiene copolymer (SBR resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-ethylenepropylene -Styrene copolymer (AES resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile-acrylic elastomer-styrene copolymer (AAS resin), methyl methacrylate-butadiene-styrene copolymer Combined (MBS resin) It is below.
Styrene resin and AS resin are preferable. Since these do not contain butadiene units as constituents of (co) polymers, the molded products are subject to yellowing of the polymer material, loss of surface gloss, impact resistance due to the influence of the usage environment such as light and heat. It is preferable because it is difficult to cause a decrease or the like.
The upper limit of the weight average molecular weight (Mw) of the styrene resin and AS resin is preferably 200,000, more preferably 110,000, and the lower limit is preferably 30,000.

  There is no restriction | limiting in particular about the manufacturing method of (co) polymer (B), Normal well-known methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. It is also possible to blend separately (co) polymerized resins.

<Rubber-containing graft copolymer (C)>
In the present invention, the rubber-containing graft copolymer (C) is a copolymer obtained by graft polymerizing one or more vinyl monomers to rubber containing polyorganosiloxane.

[Rubber containing polyorganosiloxane]
The rubber containing polyorganosiloxane is preferably a polyorganosiloxane rubber or a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate. Composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate because the molded product obtained by molding has a good balance between impact strength (especially low temperature impact strength) and color development (pigment coloring). It is more preferable that

[Polyorganosiloxane]
A polyorganosiloxane is a polymer containing an organosiloxane unit as a constituent unit. The polyorganosiloxane rubber can be obtained by polymerizing “organosiloxane” and “vinyl-based polymerizable group-containing silane compound”, or an organosiloxane mixture containing components used as necessary. Examples of the components used as necessary include siloxane-based crosslinking agents and siloxane oligomers having terminal blocking groups.

  As the organosiloxane, either a chain organosiloxane or a cyclic organosiloxane can be used. Cyclic organosiloxane is preferred because it has high polymerization stability and a high polymerization rate. The cyclic organosiloxane is preferably a 3- to 7-membered ring, and examples thereof include the following. Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane and the like. These may be used alone or in combination of two or more. Among these, since it is easy to control the particle size distribution of rubber containing polyorganosiloxane, it is preferable that 60% by mass or more is octamethylcyclotetrasiloxane.

[Vinyl polymerizable group-containing silane compound]
A silane compound containing a vinyl polymerizable group is used as a siloxane graft crossing agent. The vinyl-based polymerizable group-containing silane compound has a siloxy group and a functional group copolymerizable with a vinyl monomer. By using a vinyl polymerizable group-containing silane compound, a polyorganosiloxane having a functional group copolymerizable with a vinyl monomer can be obtained. By using such a graft crossing agent, an alkyl (meth) acrylate component for composite rubber described later or a vinyl monomer can be grafted to the polyorganosiloxane by radical polymerization.

  Examples of the vinyl polymerizable group-containing silane compound include siloxane represented by the formula (1).

RSiR ¹ _n (OR ² ) _3-n (1)
In formula (1), R ¹ represents a methyl group, an ethyl group, a propyl group, or a phenyl group. R ² represents an organic group in the alkoxyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, and a phenyl group. n represents 0, 1 or 2. R represents any group represented by formulas (2) to (5).

^{_{CH 2 = C (R 3)}} -COO- (CH 2) p - (2)
_{^{CH 2 = C (R 4)}} -C 6 H 4 - (3)
CH ₂ = CH- (4)
HS- (CH ₂ ) _p − (5)
In these formulas, R ³ and R ⁴ each represent hydrogen or a methyl group, and p represents an integer of 1 to 6.

  A methacryloyloxyalkyl group can be mentioned as a functional group represented by Formula (2). Examples of the siloxane having this group include the following. β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyl Diethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and the like.

  As a functional group represented by Formula (3), a vinylphenyl group etc. can be mentioned, for example. Examples of the siloxane having this group include vinylphenylethyldimethoxysilane.

  Examples of the siloxane having a functional group represented by the formula (4) include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of the functional group represented by the formula (5) include a mercaptoalkyl group. Examples of the siloxane having this group include the following. γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, γ-mercaptopropylethoxydimethylsilane, γ-mercaptopropyltrimethoxysilane and the like.
Among these, a vinyl polymerizable group-containing silane compound having a functional group represented by the formulas (2), (4), and (5) is preferably used from the viewpoint of economy, and among these, the formula (2) is used. More preferred is a vinyl polymerizable group-containing silane compound having a functional group.

  These vinyl polymerizable group-containing silane compounds may be used alone or in combination of two or more. Content of a vinyl polymerizable group containing silane compound is 1-10 mass% in 100 mass% of organosiloxane mixtures, and it is preferable that it is 1-5 mass%. When the amount of the vinyl-based polymerizable group-containing silane compound is 1% by mass or more, the appearance of the resulting molded article is deteriorated and the surface impact resistance, impact resistance, and flame retardancy are excellent. When the amount of the vinyl polymerizable group-containing silane compound is 10% by mass or less, the resulting molded article has excellent impact resistance and flame retardancy.

  As the siloxane-based crosslinking agent, those having a siloxy group are preferable. By using a siloxane-based crosslinking agent, a polyorganosiloxane having a crosslinked structure can be obtained. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. Can be mentioned. Among these, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is more preferable. The content of the siloxane-based crosslinking agent is preferably 0 to 30% by mass in 100% by mass of the organosiloxane mixture, more preferably 0.1 to 30% by mass, and 0.1 to 10% by mass. Is more preferable, 0.1 to 5% by mass is particularly preferable, and 0.1 to 3% by mass is most preferable.

  The siloxane oligomer having a terminal blocking group means a siloxane oligomer having an alkyl group or the like at the terminal of the organosiloxane oligomer and stopping the polymerization of the polyorganosiloxane. Examples of the siloxane oligomer having a terminal blocking group include hexamethyldisiloxane, 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. And methoxytrimethylsilane.

[Production method of polyorganosiloxane rubber]
There is no restriction | limiting in particular as a manufacturing method of polyorganosiloxane rubber, For example, the following manufacturing methods are employable.
First, an emulsion is prepared by emulsifying an organosiloxane mixture containing an organosiloxane and a vinyl-based polymerizable group-containing silane compound, or a component further used as necessary, with an emulsifier and water, and then using an acid catalyst. And polymerize at high temperature. The acid is then neutralized with an alkaline substance to obtain a polyorganosiloxane rubber latex.

  In this production method, emulsion preparation methods include a method using a homomixer that makes fine particles by shearing force by high-speed rotation, a method that mixes by high-speed agitation using a homogenizer that makes fine particles by jet output from a high-pressure generator, etc. Is mentioned. Among these, a method using a homogenizer is a preferable method because the particle size distribution of the polyorganosiloxane rubber latex becomes narrow.

  As a method for mixing the acid catalyst during the polymerization, (1) a method in which an acid catalyst is added together with an organosiloxane mixture, an emulsifier and water and mixed, and (2) an acid catalyst aqueous solution is added to an emulsion of the organosiloxane mixture. Examples thereof include a method of adding all at once, and (3) a method in which an emulsion of an organosiloxane mixture is dropped into a high-temperature acid catalyst aqueous solution at a constant rate and mixed. Since the particle diameter of the polyorganosiloxane can be easily controlled, a method of collectively adding an acid catalyst aqueous solution to the emulsion of the organosiloxane mixture is preferable.

The polymerization temperature is preferably 30 to 100 ° C, more preferably 40 to 100 ° C. By setting the temperature within the above range, a latex of polyorganosiloxane rubber can be produced in a short time.
The polymerization time is preferably 2 to 15 hours, more preferably 5 to 10 hours.

  Furthermore, since the cross-linking reaction between silanols proceeds at a temperature of 30 ° C. or lower, in order to increase the cross-linking density of the polyorganosiloxane, after polymerization at a high temperature of 50 ° C. or higher, 5 at a temperature of 30 ° C. or lower. It can also be held for about 100 hours from time.

  The polymerization reaction of the organosiloxane mixture can be terminated by neutralizing the latex to pH 6-8 with an alkaline substance such as sodium hydroxide, potassium hydroxide, or aqueous ammonia solution.

  The emulsifier used in the production method is not particularly limited as long as the organosiloxane mixture can be emulsified, but an anionic emulsifier or a nonionic emulsifier is preferable. Examples of the anionic emulsifier include the following. Sodium alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl sulfate, polyoxyethylene alkyl sodium sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate.

Examples of nonionic emulsifiers include the following. Polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol.
These emulsifiers may be used individually by 1 type, and may use 2 or more types together.

  The amount of the emulsifier used is preferably 0.05 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the organosiloxane mixture. It is possible to adjust to a desired particle size depending on the amount of emulsifier used. When the amount of the emulsifier used is 0.05 parts by mass or more, the emulsion stability of the emulsion of the organosiloxane mixture becomes sufficient, and when the amount of the emulsifier used is 10 parts by mass or less, the graft copolymer caused by the emulsifier Coloring of the coalescence (C) and a decrease in the heat decomposability of the resin composition can be suppressed.

  Examples of the acid catalyst used for polymerization of the organosiloxane mixture 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 may be used individually by 1 type, and may use 2 or more types together. Among these, the use of mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid can narrow the particle size distribution of the polyorganosiloxane rubber latex, and further, molding caused by the emulsifier component in the polyorganosiloxane rubber latex. The appearance defect of the body can be reduced.

  The mass average particle diameter Dw of the polyorganosiloxane rubber latex is preferably 250 nm to 1000 nm. By setting the mass average particle diameter of the latex of the polyorganosiloxane rubber to 250 nm to 1000 nm, the volume average particle diameter of the rubber-containing graft copolymer (C) or the mass average particle of the latex of the rubber-containing graft copolymer (C) The diameter can be adjusted to 300 to 2000 nm.

The particle size distribution (mass average particle size Dw / number average particle size Dn) of the polyorganosiloxane rubber latex is preferably 1.0 to 1.7. By setting Dw / Dn to 1.0 to 1.7, a graft copolymer (C) having high color developability can be obtained.
In addition, the measuring method of the volume average particle diameter Dw and the number average particle diameter Dn of the latex of a polyorganosiloxane rubber and the latex of a graft copolymer (C) is mentioned later.

  An emulsifier may be added to the polyorganosiloxane rubber latex obtained by the above method, if necessary, for the purpose of improving mechanical stability. As the emulsifier, the same anionic emulsifier and nonionic emulsifier as those exemplified above are preferable.

[Composite rubber]
In the present invention, as the rubber containing polyorganosiloxane, a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate (hereinafter sometimes abbreviated as “composite rubber”) can be used. The composite rubber is a rubber containing the polyorganosiloxane and a polyalkyl (meth) acrylate having a glass transition temperature (Tg) represented by the following FOX formula of 0 ° C. or less.
1 / (273 + Tg) = Σ (wi / (273 + Tgi))
In the formula, Tg is the glass transition temperature (° C.) of the copolymer, wi is the mass fraction of monomer i, and Tgi is the glass transition temperature (° C.) of the homopolymer obtained by polymerizing monomer i. is there. The value of Tg of the homopolymer is a value described in POLYMER HANDBOOK Volume 1 (WILEY-INTERSCIENCE).
The composite rubber is preferably a rubber obtained by polymerizing an alkyl (meth) acrylate in the presence of a polyorganosiloxane rubber.

  The polyalkyl (meth) acrylate constituting the composite rubber can be obtained by polymerizing an alkyl (meth) acrylate component (hereinafter sometimes abbreviated as “(meth) acrylate component for composite rubber”). The (meth) acrylate component for composite rubber preferably contains “alkyl (meth) acrylate having a homopolymer Tg of 0 ° C. or lower” and “crosslinkable monomer”.

  Examples of the alkyl (meth) acrylate having a homopolymer Tg of 0 ° C. or lower include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, and the like. These may be used alone or in combination of two or more. Among these, n-butyl acrylate is particularly preferable in consideration of the impact resistance of the thermoplastic resin composition and the gloss of the molded product.

  Examples of the “crosslinkable monomer” include the following “polyfunctional vinyl monomers”. Allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triallyl trimellitate and the like. These may be used alone or in combination of two or more.

[Production method of composite rubber]
There is no restriction | limiting in particular as a manufacturing method of composite rubber, For example, although it can manufacture by an emulsion polymerization method, suspension polymerization method, and fine suspension polymerization method, it is preferable to use an emulsion polymerization method. In particular, the (meth) acrylate component for composite rubber is added to the latex of the polyorganosiloxane rubber, and the (meth) acrylate component for composite rubber is impregnated into the rubber particles, and then the (meth) acrylate component for composite rubber is emulsified. A method of polymerizing to obtain a composite rubber latex is particularly preferred.

  As a method of preparing a mixture of a polyorganosiloxane rubber latex and a composite rubber (meth) acrylate component, the alkyl (meth) acrylate and the polyfunctional vinyl monomer are added to the polyorganosiloxane rubber latex. A method is mentioned. Thus, the (meth) acrylate component for the composite rubber is impregnated in the particles of the polyorganosiloxane rubber, and then the temperature is raised and polymerization is performed by using a known radical polymerization initiator. In this production method, examples of the method of adding the (meth) acrylate component for composite rubber to the latex of the polyorganosiloxane rubber include a method of adding the whole amount at once, a method of adding dropwise at a constant rate. It is done.

  In producing the latex of the composite rubber, an emulsifier can be added in order to stabilize the latex and control the mass average particle size of the latex of the composite rubber. The emulsifier is not particularly limited, and an anionic emulsifier and a nonionic emulsifier are preferable.

  Examples of the anionic emulsifier include the following. Sodium alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl sulfate, polyoxyethylene alkyl sodium sulfate, polyoxyethylene nonyl phenyl ether sodium sulfate, sodium sarcosine, fatty acid potassium, fatty acid sodium, alkenyl succinate dipotassium, rosin acid soap, Polyoxyethylene alkyl sodium phosphate, polyoxyethylene alkyl calcium phosphate, etc.

  Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene tribenzyl phenyl ether. These emulsifiers may be used individually by 1 type, and may use 2 or more types together.

  Examples of the radical polymerization initiator used for the polymerization of the (meth) acrylate component for composite rubber include an azo initiator, a peroxide, and a redox initiator that is a combination of a peroxide and a reducing agent. These may be used alone or in combination of two or more. Among these, an azo initiator and a redox initiator are preferable from the viewpoint of suppressing outgassing of the resin composition.

  Examples of the azo initiator include the following. Oil-soluble azo initiators such as 2,2′-azobisisobutyronitrile and dimethyl 2,2′-azobis (2-methylpropionate); 4,4′-azobis (4-cyanovaleric acid) 2,2′-azobis [N- (2-carboxymethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis- (N, N′-dimethyleneisobutylamidine) dihydrochloride, 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and other water-soluble azo initiators. These may be used alone or in combination of two or more.

  Examples of peroxides include the following. Inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, succinic acid peroxide, t- Butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexanoate. These peroxides may be used alone or in combination of two or more.

When a peroxide is used as a redox initiator in combination with a reducing agent, the above peroxide, a reducing agent such as sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, dextrose, sorbose, inositol, and sulfuric acid It is preferable to use a combination of monoiron and ethylenediaminetetraacetic acid disodium salt.
These reducing agents may be used individually by 1 type, and may use 2 or more types together. In addition, when using sodium formaldehyde sulfoxylate as a reducing agent, it is preferable to suppress the usage-amount as much as possible from a viewpoint of suppressing the outgas of a resin composition.

  When using an azo initiator, the amount used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the composite rubber.

  When using a redox-type initiator, it is preferable that the usage-amount of a peroxide is 0.01-10 mass parts with respect to 100 mass parts of (meth) acrylate components for composite rubber. It is preferable that the usage-amount of a reducing agent is 0.01-1 mass part with respect to 100 mass parts of composite rubber.

  The ratio of polyorganosiloxane and polyalkyl (meth) acrylate in the composite rubber is preferably “31/69 to 99/1” mass%, and “39/61 to 94/6” mass%. It is more preferable. By setting the ratio of the ratio of polyorganosiloxane and polyalkyl (meth) acrylate to “31/69 to 99/1” mass%, the impact strength of the molded product obtained by molding becomes favorable, which is preferable.

[Graft copolymer (C)]
The graft copolymer (C) of the present invention can be obtained by graft polymerization of one or more vinyl monomers in the presence of rubber containing polyorganosiloxane. Therefore, in the graft copolymer (C) of the present invention, the graft portion is formed of a polymer of one or more vinyl monomers. Although the vinyl monomer will be described later, a “polyfunctional vinyl monomer” can be used as the vinyl monomer.

  The volume average particle diameter of the graft copolymer (C) is 300 to 2000 nm. The volume average particle diameter is preferably 300 to 1000 nm, more preferably 350 to 800 nm, and still more preferably 400 to 600 nm. When the volume average particle diameter of the graft copolymer (C) is 300 nm or more, the molded product obtained by blending the graft copolymer (C) with the thermoplastic resin has impact resistance (particularly low temperature impact resistance). And surface impact resistance is improved. In addition, when the volume average particle diameter of the graft copolymer (C) is 2000 nm or less, the molded product obtained by blending the graft copolymer (C) with the thermoplastic resin has color development properties and impact resistance (particularly low temperature). Impact resistance is improved and the surface appearance is improved.

  The content of “polyorganosiloxane” in 100% by mass of the graft copolymer (C) is 30 to 98% by mass. This content is preferably 30 to 94% by mass, and more preferably 45 to 94% by mass. When the content of polyorganosiloxane is 30% by mass or more, the flame retardancy, surface impact resistance, and impact strength at low temperature of the molded product are good, and when it is 98% by mass or less, the surface appearance of the molded product is good. preferable.

  The content of the “polyorganosiloxane rubber” in 100% by mass of the graft copolymer (C) is preferably 70 to 99% by mass, and more preferably 80 to 95% by mass. If the content of the rubber containing polyorganosiloxane is 70% by mass or more, the surface impact resistance and impact strength of the molded product at a low temperature are sufficient, and if it is 99% by mass or less, the surface appearance of the molded product is good. It is preferable.

  The content of the component derived from the polyfunctional vinyl monomer in 100% by mass of the graft copolymer (C) is 0% by mass or more and less than 5% by mass, more than 0% by mass and 4% by mass or less. Preferably, it is 0.1 to 3% by mass, more preferably 0.1 to 2% by mass. By making content of the component derived from a polyfunctional vinyl monomer into 0 mass% or more and less than 5 mass%, the molded object obtained shows high impact resistance and flame retardance.

  The particle size distribution (mass average particle size Dw / number average particle size Dn) of the latex of the graft copolymer (C) is preferably 1.0 to 2.0, and preferably 1.0 to 1.5. It is more preferable. When the particle size distribution (Dw / Dn) of the latex is 2.0 or less, the color developability (pigment colorability) of the molded product obtained from the thermoplastic resin composition is good. In addition, the measuring method of the mass average particle diameter Dw and the number average particle diameter Dn is mentioned later.

In the graft copolymer (C) of the present invention, the graft portion is formed by a polymer of one or more vinyl monomers, and the glass transition temperature of the polymer expressed by the above-mentioned FOX formula is 0 ° C. It is preferably 50 ° C. or higher. Although it does not specifically limit as a vinyl monomer used for graft polymerization, For example, the following are mentioned. Styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinylnaphthalene, vinylanthracene Aromatic vinyl monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 4-t -Butylphenyl (meth) acrylate, monobromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (Meth) acrylates such as (meth) acrylate, trichlorophenyl (meth) acrylate and naphthyl (meth) acrylate; carboxyl group-containing monomers such as (meth) acrylic acid and carboxyethyl (meth) acrylate; (meth) acrylonitrile Vinyl cyanide monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl ether monomers such as vinyl benzoate, vinyl acetate and vinyl butyrate; glycidyl (meth) acrylate and allyl glycidyl Vinyl monomers having a glycidyl group such as ether; olefins such as ethylene, propylene and butylene. These vinyl monomers may be used alone or in combination of two or more.
When using 2 or more types, a vinyl monomer mixture may contain a "polyfunctional vinyl monomer" as needed. Examples of the polyfunctional vinyl monomer include the following. Allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triallyl trimellitate. These may be used alone or in combination of two or more.

  Among these, when one or more kinds of vinyl monomers contain a (meth) acrylic acid ester such as methyl (meth) acrylate, the obtained graft copolymer (C) is a polycarbonate resin or a polyester carbonate resin (A). Excellent compatibility and dispersibility. When one or more vinyl monomers contain an aromatic vinyl monomer such as styrene, a molded product obtained by molding a thermoplastic resin composition is excellent in flame retardancy. Therefore, it is preferable to use these vinyl monomers alone or in combination.

  Various chain transfer agents and graft crossing agents for adjusting the molecular weight and graft ratio of the graft polymer can be added to the raw material used in the graft polymerization.

[Production Method of Graft Copolymer (C)]
Examples of the polymerization method for the graft portion include a method in which one or more vinyl monomers for graft polymerization are added to rubber latex containing polyorganosiloxane and polymerization is performed in one or more stages. When polymerizing in multiple stages, it is possible to polymerize by adding one or more vinyl monomers for graft polymerization separately or sequentially to a latex of rubber containing polyorganosiloxane rubber. preferable. Such a polymerization method has good polymerization stability and can stably obtain a latex of a graft copolymer (C) having a desired particle size and particle size distribution.

  In the polymerization of the graft part, an emulsifier can be added to the raw material as necessary. Examples of the emulsifier include the same emulsifiers as those used in the production of the composite rubber, and anionic emulsifiers and nonionic emulsifiers are preferable. As the usage-amount of an emulsifier, 0.1-10 mass parts is preferable with respect to 100 mass parts of vinyl monomers for graft polymerization, and 0.2-5 mass parts is more preferable.

  Examples of the polymerization initiator used for the polymerization of the graft portion include the same polymerization initiators used for producing the composite rubber, and azo initiators and redox initiators are preferable.

  When the powder of the graft copolymer (C) is recovered from the latex of the graft copolymer (C), either a spray drying method or a coagulation method can be used.

The spray-drying method is a method in which the latex of the graft copolymer (C) is sprayed in the form of fine droplets in a dryer, and dried by applying a heating gas for drying thereto. Examples of the method for generating fine droplets include a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type. The capacity of the dryer may be a small capacity as used in a laboratory or a large capacity as used industrially. The temperature of the heating gas for drying is preferably 200 ° C. or less, and more preferably 120 to 180 ° C.
The latexes of two or more graft copolymers (C) produced separately can also be spray dried together. Furthermore, in order to prevent blocking during spray drying and improve powder properties such as bulk specific gravity, an optional component such as silica may be added to the latex of the graft copolymer (C) and spray dried. it can.

  The coagulation method is a method in which the latex of the graft copolymer (C) is coagulated, and the graft copolymer (C) is separated, recovered, and dried. First, the graft copolymer (C) latex is put into hot water in which a coagulant is dissolved, salted out, and solidified to separate the graft copolymer. Next, the separated wet graft copolymer is dehydrated to recover the graft copolymer (C) having a reduced water content. The recovered graft copolymer is dried using a press dehydrator or a hot air dryer.

  Examples of the coagulant include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, and sodium nitrate, organic salts such as calcium acetate, and acids such as sulfuric acid, and calcium acetate is particularly preferable. These coagulants may be used alone or in combination of two or more. When a coagulant is used in combination, it is necessary to select a combination that does not form an insoluble salt in water. For example, the combined use of calcium acetate and sulfuric acid or a sodium salt thereof is not preferable because a calcium salt insoluble in water is formed.

  The above-mentioned coagulant is usually used as an aqueous solution. The concentration of the coagulant aqueous solution is preferably 0.1% by mass or more, particularly 1% by mass or more from the viewpoint of stably coagulating and recovering the graft copolymer (C). In addition, if the amount of the coagulant remaining in the recovered graft copolymer is large, the thermal decomposition resistance of the molded product is deteriorated, so the concentration of the coagulant aqueous solution is 20% by mass or less, particularly 15% by mass or less. It is preferable. Although the quantity of the coagulant aqueous solution with respect to latex is not specifically limited, It is preferable that it is 10 to 500 mass parts with respect to 100 mass parts of latex.

  The method of bringing the latex into contact with the coagulant aqueous solution is not particularly limited, but the following methods are usually mentioned. (1) A method in which a latex is continuously added to the aqueous solution of the coagulant while stirring and the solution is maintained for a certain period of time. The mixture containing the coagulated polymer and water is continuously withdrawn from the container. The temperature at which the latex is brought into contact with the coagulant aqueous solution is not particularly limited, but is preferably 30 ° C. or higher and 100 ° C. or lower. The contact time is not particularly limited.

  The coagulated graft copolymer (C) is washed with about 1 to 100 times by weight of water, and the wet graft copolymer (C) separated by filtration is obtained using a fluid dryer or a press dehydrator. Dried. What is necessary is just to determine a drying temperature and drying time suitably with Tg of the graft copolymer (C) obtained. In addition, it does not collect | recover the graft copolymer (C) discharged | emitted from the press dehydrator or the extruder, It sends directly to the extruder and molding machine which manufacture a resin composition, and mixes with a thermoplastic resin, and a molded object is obtained. It is also possible to obtain.

In the present invention, the graft copolymer (C) is preferably recovered using a coagulation method from the viewpoint of thermal decomposition resistance of a resin composition obtained by mixing with a thermoplastic resin.
In the powder of the graft copolymer (C) recovered in this way, when the vinyl monomer was graft-polymerized, it was polymerized without graft bonding to the rubber containing polyorganosiloxane (co). Polymers may be included.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention comprises a polycarbonate resin or a polyester carbonate resin (A), a (co) polymer (B) containing an aromatic vinyl monomer (b1) unit, and a rubber-containing graft copolymer (C ).

  As a compounding ratio ((A) / (B)) of the polycarbonate resin or the polyester carbonate resin (A) and the (co) polymer (B), it is preferably “50/50 to 99/1” parts by mass, “50/50 to 90/10” part by mass is more preferable, and “60/40 to 90/10” part by mass is further preferable. When the blending ratio is in the above range, the resulting resin composition has an excellent balance between fluidity and heat resistance.

  The blending amount of the graft copolymer (C) with respect to the polycarbonate resin or polyester carbonate resin (A) and (co) polymer (B) is 0.5 parts per 100 parts by mass in total of (A) and (B). It is preferably within the range of ˜30 parts by mass, more preferably within the range of 1 to 20 parts by mass, and even more preferably within the range of 3 to 15 parts by mass. When the content is 0.5 parts by mass or more, the obtained molded article is excellent in impact resistance. Moreover, it is excellent in fluidity | liquidity and the heat resistance of the molded object obtained as this content is 30 mass parts or less.

[Flame Retardant (D)]
A flame retardant (D) can be contained in the thermoplastic resin composition of the present invention as necessary. As a flame retardant (D), a well-known flame retardant can be used, for example, the following are mentioned. Halogen flame retardants comprising a combination of halogenated compounds such as halogenated bisphenol A, halogenated polycarbonate oligomers, brominated epoxy compounds, and flame retardant aids such as antimony oxide; organic salt flame retardants; phosphate ester flame retardants, Phosphorus flame retardants such as halogenated phosphoric acid ester flame retardants; sulfonic acid flame retardants such as metal salts of aromatic sulfonic acids and metal salts of perfluoroalkane sulfonic acids; branched phenyl silicone compounds and phenyl silicone resins Silicone flame retardants such as organopolysiloxanes.
Among these flame retardants (D), phosphorus-based flame retardants are preferred because they are non-halogen-based and the resulting molded articles are excellent in flame retardancy.

    Phosphorus flame retardants include red phosphorus, coated red phosphorus, polyphosphate compounds, phosphate ester compounds, phosphonate ester compounds, phosphite ester compounds, phosphinate ester compounds, phosphazene compounds Etc. Among these, phosphate ester compounds are preferable. Examples of phosphate ester compounds include the following. Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, isopropylphenyl diphosphate, tris (butoxyethyl) phosphate, trisisobutyl Phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate, 1,3 phenylene bis (diphenyl phosphate), 1,3 phenylene bis (di2,6 xylenyl phosphate), bisphenol A bis (diphenyl) Phosphate), resorcinol bisdiphenyl phosphate, diethylene ethyl ester Phosphate, dihydroxypropylene butyl ester phosphate, ethylene disodium ester phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butylphenyl) phosphate, tris (chloroethyl) phosphate, tris ( Dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, and the like. These may be used alone or in combination of two or more.

  As a compounding quantity of the said flame retardant (D), it is preferable to exist in the range of 1-30 mass parts with respect to a total of 100 mass parts of (A) and (B), and within the range of 5-20 mass parts. It is more preferable that

(Anti-drip agent)
Furthermore, it is effective and preferable to use a dripping inhibitor in combination with the flame retardant (D). Examples of the anti-dripping agent include fluorine resins such as polytetrafluoroethylene, silicone rubber, polycarbonate / diorganosiloxane copolymer, siloxane polyetherimide, and liquid crystal polymer. A fluororesin is preferable.
A well-known thing can be used as a fluororesin, what was synthesize | combined suitably may be used and a commercial item may be used. As a commercial item, the following are mentioned, for example. Polytetrafluoroethylene such as “Polyflon FA-500” (trade name, manufactured by Daikin Industries, Ltd.); SAN-modified polytetrafluoroethylene such as “BLENDEX B449” (trade name, manufactured by Galata Chemicals); Acrylic-modified polytetrafluoroethylene such as “3000”, “methabrene A-3750”, “methabrene A-3800” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). These fluororesins may be used alone or in combination of two or more.
Among these fluororesins, SAN-modified polytetrafluoroethylene and acrylic-modified polytetrafluoroethylene are excellent in dispersibility in the obtained molded product, and the molded product is excellent in mechanical properties, heat resistance, and flame retardancy. Acrylic modified polytetrafluoroethylene is preferable.

  The content of polytetrafluoroethylene in SAN-modified polytetrafluoroethylene or acrylic-modified polytetrafluoroethylene is preferably 10 to 80% by mass in 100% by mass of the fluororesin, and preferably 20 to 70% by mass. % Is more preferable. When the content is 10% by mass or more, the obtained molded article is excellent in flame retardancy. Further, when the content is 80% by mass or less, the resulting molded article is excellent in appearance.

  The blending amount of the anti-dripping agent is preferably 0.01 to 5 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of (A) and (B). More preferably, it is 0.3-2 mass parts. When the blending amount is 0.01 parts by mass or more, the obtained molded body is excellent in flame retardancy. Moreover, the original property of a thermoplastic resin is not impaired as this compounding quantity is 5 mass parts or less.

[Other additives]
The thermoplastic resin composition of the present invention may further contain, for example, the following components within a range that does not impair the original purpose. Reinforcing agents and fillers such as glass fiber, metal fiber, metal flake and carbon fiber; 2,6-di-butyl-4-methylphenol, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol Phenolic antioxidants such as tris (mixed, mono and dinylphenyl) phosphite, diphenyl isodecyl phosphite, etc .; dilauryl thiodipropionate, dimyristyl thiodipropionate di Sulfur-based antioxidants such as asterial thiodipropionate; benzotriazole-based UV absorbers such as 2-hydroxy-4-octoxybenzophenone and 2- (2-hydroxy-5-methylphenyl) benzotriazole; bis (2, 2,6,6) -tetramethyl-4-piperidinyl) and other light stabilizers; hydro Antistatic agents such as xylalkylamines and sulfonates; lubricants such as ethylenebisstearylamide and metal soaps, dyes and pigments. These may be used alone or in combination of two or more.

[Method for preparing resin composition]
Although the preparation method of the thermoplastic resin composition of this invention is not specifically limited, It is preferable to use a melt mixing method. Moreover, you may use a small amount of solvent as needed. For example, a polycarbonate resin or a polyester carbonate resin (A), a (co) polymer (B), a rubber-containing graft copolymer (C), and a flame retardant (D) and various additives as necessary, V-type It can be prepared by mixing and dispersing with a blender, a Henschel mixer or the like, and melt-kneading this mixture using a kneader such as an extruder, a Banbury mixer, a pressure kneader, or a roll. These components can be mixed batchwise or continuously, and the mixing order of the components is not particularly limited. The melt-kneaded product can be made into pellets and used for various moldings.

<Molded body>
Examples of the method for molding the thermoplastic resin composition of the present invention include molding methods used for molding ordinary thermoplastic resin compositions, such as injection molding, extrusion molding, blow molding, and calendar molding. .

  Since the molded article of the present invention has excellent impact resistance and surface impact resistance, and has excellent flame retardancy by adding a flame retardant (D), the automotive field, OA equipment field, home appliances It can be widely used industrially as various materials in the electric and electronic fields. More specifically, it can be used as a casing such as an electronic device, various parts, automobile structural members, automobile interior parts, and a light reflecting plate. More specifically, it can be used as an interior / exterior member of a personal computer casing, a mobile phone casing, a portable information terminal casing, a portable game machine casing, a printer, a copying machine, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
Prior to Examples, various evaluation methods and Production Examples 1 to 3 of polyorganosiloxane rubber latex will be described. In the following description, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
Each test piece for evaluation is formed by molding a resin composition (or its pellet) with a 100-t injection molding machine (SE-100DU manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. .

<1. Evaluation method>
(1) Solid content A latex of polyorganosiloxane rubber with a mass of ₁ is dried for 30 minutes with a hot air dryer at 180 ° C., and the mass w ₂ of the residue after drying is measured, and the solid content (%) is calculated by the following formula. To do.
Solid content [%] = w ₂ / w ₁ × 100 (6)

(2) Mass average particle size and particle size distribution (Dw / Dn)
A sample obtained by diluting “polyorganosiloxane rubber latex” with deionized water to a concentration of about 3% and using a CHDF2000 particle size distribution meter manufactured by MATEC, USA, is used. Dw / Dn) is measured.
The measurement is performed under the following standard conditions recommended by MATEC.
Cartridge: Capillary cartridge for particle separation (trade name; C-202)
Carrier liquid: Dedicated carrier liquid (trade name: 2XGR500)
Carrier liquid: almost neutral carrier flow rate: 1.4 ml / min Carrier liquid pressure: about 4,000 psi (2,600 kPa)
Measurement temperature: 35 ° C
Sample usage: 0.1 ml.
Further, as the standard particle size substance, 12 types of particles having a particle size of 40 to 800 nm in a monodisperse polystyrene having a known particle size manufactured by DUKE, USA are used.

(3) Volume average particle diameter
The volume average particle diameter of the graft copolymer is measured by the following method.
The latex of the graft copolymer is diluted with deionized water, and the median diameter in volume average is determined using a laser diffraction scattering particle size distribution analyzer (SALD-7100, manufactured by Shimadzu Corporation). The sample concentration of latex is appropriately adjusted so as to be within an appropriate range in the scattered light intensity monitor attached to the apparatus. The standard particle size substance is monodispersed polystyrene with a known particle size, and 12 types of particles having a particle size in the range of 20 to 800 nm are used.

(4) Charpy impact strength According to JIS K 7111, the test piece (length: 80.0 mm, width: 10.0 mm, thickness: 4 mm, with V notch) in the measurement environment temperature range of −50 ° C. to 23 ° C. Measure Charpy impact strength.

(5) DBTT (Ductility-brittle transition temperature)
The ductile-brittle transition temperature measured by notched Charpy impact measurement at different temperatures. Generally, when stress whitening is observed, it indicates a ductile fracture mode, and when stress whitening is not observed, it indicates a brittle fracture mode, but the Charpy impact strength is about 40 kJ / m ² as a boundary. Changes in the ductile-brittle fracture mode are easily observed. Therefore, here, for convenience, the temperature at which the Charpy impact strength is 40 kJ / m ² is DBTT. Measure and judge at -50 ° C to 10 ° C intervals.

(6) Surface impact strength A drop weight test was conducted in accordance with JIS K 7211 except that the impact was measured with a DuPont impact tester manufactured by Toyo Seiki Co., Ltd. and a load of 5 kg using a 1/2 inch hemispherical strike core. % Impact fracture height (cm) and 50% fracture energy (J) at that time are measured. The measurement environment temperature is 23 ° C., and the test piece has a shape of 100 mm × 50 mm × thickness 2 mm.

(7) Appearance near the gate (visual evaluation)
A flat plate of a test piece (length 100.0 mm, width 50.0 mm, thickness 2 mm) is molded, and visual evaluation of flow marks near the gate (patterns seen in the vicinity of the gate of the molded body) and surface roughness are visually observed. Observe and evaluate according to the following criteria.
++: No flow mark or rough surface is seen.
+: Flow marks and surface roughness are somewhat visible but not noticeable.
−: Flow marks and surface roughness are slightly noticeable.
-: Flow marks and surface roughness are conspicuous.

(8) Flame resistance
A UL-94V test is performed on a 1/16 inch test piece (length 127 mm, width 12.7 mm, thickness 1.6 mm).

<Production example>
[Production Example 1] Production of latex (S-1) of polyorganosiloxane rubber:
2 parts of tetraethoxysilane (TEOS), 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane (DSMA), and 96 parts of octamethylcyclotetrasiloxane (product name: TSF404) manufactured by Momentive Performance Materials Japan Co., Ltd. Were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution in which 1 part of sodium dodecylbenzenesulfonate (DBSNa) is dissolved in 150 parts of deionized water is added to the mixture, stirred at 10,000 rpm for 5 minutes with a homomixer, and then applied to a homogenizer at a pressure of 20 MPa. Passed twice to obtain a stable premixed emulsion.
The emulsion was then placed in a separable flask having a capacity of 5 liters equipped with a cooling condenser, and then the emulsion was heated to a temperature of 80 ° C. Then, 0.20 parts of sulfuric acid and 49.8 parts of deionized water were added. The mixture was continuously charged over 3 minutes. The polymerization reaction was carried out while maintaining the temperature heated to 80 ° C. for 6 hours, and then cooled to room temperature (25 ° C.), and the resulting reaction solution was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane rubber latex (S-1). The evaluation results of this latex are shown in Table 1.

[Production Example 2] Production of polyorganosiloxane rubber latex (S-2):
2 parts of TEOS, 0.5 part of DSMA, and 97.5 parts of cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, mixture of 3-6 membered cyclic organosiloxane) 100 parts of an organosiloxane mixture were obtained. An aqueous solution prepared by dissolving 0.68 parts each of sodium dodecylbenzenesulfonate (DBSNa) and dodecylbenzenesulfonate (DBSH) in 200 parts of deionized water was added to the mixture, and the mixture was added at 10,000 rpm with a homomixer. After stirring for a minute, the mixture was passed twice through a homogenizer at a pressure of 20 MPa to obtain a stable premixed emulsion.
Next, the emulsion was put in a separable flask having a capacity of 5 liters equipped with a cooling condenser, and then the emulsion was heated to a temperature of 85 ° C., and this temperature was maintained for 6 hours, followed by a polymerization reaction. 25 ° C.) and the resulting reaction was kept at room temperature for 12 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane rubber latex (S-2). The evaluation results of this latex are shown in Table 1.

[Production Example 3] Production of latex (S-3) of polyorganosiloxane rubber:
2 parts of TEOS, 0.5 parts of DSMA and 97.5 parts of octamethylcyclotetrasiloxane (product name: TSF404, manufactured by Momentive Performance Materials Japan Co., Ltd.) are mixed to prepare an organosiloxane mixture 100 Got a part. An aqueous solution in which 1 part of DBSNa is dissolved in 170 parts of deionized water is added to the above mixture, stirred for 5 minutes at 10,000 rpm with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa for stable premixing. An emulsion was obtained.
The emulsion was then placed in a 5 liter separable flask equipped with a cooling condenser, and then the emulsion was heated to a temperature of 80 ° C., and then 0.20 parts of sulfuric acid and 14.7 parts of deionized water. The mixture was continuously charged over 3 minutes. The polymerization reaction was carried out while maintaining the temperature heated to 80 ° C. for 6 hours, and then cooled to room temperature (25 ° C.), and the resulting reaction solution was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane rubber latex (S-3). The evaluation results of this latex are shown in Table 1.

[Example 1]
The polyorganosiloxane rubber latex (S-1) obtained in Production Example 1 was collected in a 79.7 part, 5 liter separable flask in terms of polymer, and 46 parts of deionized water was added and mixed. Next, a mixture of 10.0 parts of n-butyl acrylate (n-BA), 0.3 parts of allyl methacrylate (AMA) and 0.04 parts of cumene hydroperoxide (CHP) was added into the separable flask.

  The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the liquid temperature was raised to 50 ° C. When the liquid temperature reached 50 ° C., 0.001 part of ferrous sulfate (Fe), 0.003 part of ethylenediaminetetraacetic acid disodium salt (EDTA), and 0.18 part of sodium formaldehyde sulfoxylate (SFS) were removed. An aqueous solution dissolved in 4.2 parts of ionic water was added to initiate radical polymerization. In order to complete the polymerization of the acrylate component, a liquid temperature of 70 ° C. was maintained for 1 hour to obtain a composite rubber latex of polyorganosiloxane and poly n-butyl acrylate.

  While maintaining the latex temperature of the composite rubber at 70 ° C., a mixture of 9.5 parts of MMA, 0.5 part of n-BA and 0.1 part of CHP was added over 1.0 hour. The polymer was dropped into the polymer. After completion of dropping, the liquid temperature was maintained at 70 ° C. for 1 hour and then cooled to 25 ° C. to obtain a latex of polyorganosiloxane-containing graft copolymer (G-1). Table 2 shows the volume average particle diameter of the graft copolymer (G-1).

  Next, 500 parts of an aqueous solution having a calcium acetate concentration of 1% by mass is maintained at a temperature of 40 ° C., and while stirring, 300 parts of the latex of the graft copolymer (G-1) is gradually dropped into the solution and solidified. did. The obtained graft copolymer was filtered and dehydrated. Furthermore, after adding 10 times the amount of water to 100 parts of the graft copolymer, the mixture was washed for 10 minutes in a flask equipped with a stirrer, filtered and dehydrated. This operation was repeated twice, followed by drying to obtain a graft copolymer (G-1) powder. Table 2 shows the volume average particle diameter of the graft copolymer (G-1).

[Examples 2 and 3, Comparative Examples 1 to 3]
A polyorganosiloxane-containing graft copolymer (G-2, G-3, G) was prepared in the same manner as in Example 1 except that the types and amounts of the respective raw materials used in Example 1 were changed to the conditions shown in Table 2. '-1, G'-2 and G'-3) were produced, and the powder was obtained. Table 2 shows the volume average particle diameters of the obtained graft copolymers.

[Example 4]
The polyorganosiloxane rubber latex (S-1) obtained in Production Example 1 was collected in a separable flask having a volume of 5 liters and 90 parts in terms of polymer, and 46 parts of deionized water was added and mixed. A mixture of 0.5 parts AMA and 0.07 parts CHP was then added to the separable flask. The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the liquid temperature was raised to 50 ° C. An aqueous solution in which 0.001 part of ferrous sulfate (Fe), 0.003 part of EDTA, 0.18 part of SFS, and 4.2 part of deionized water are dissolved when the liquid temperature reaches 50 ° C. Was added to initiate radical polymerization. In order to complete the polymerization of the allyl methacrylate component, the liquid temperature of 70 ° C. was maintained for 1 hour. In this way, the first stage graft polymerization was performed. Then, 9 parts of MMA, 0.5 part of n-BA, and 0.1 part of CHP were added dropwise over 1.0 hour for polymerization. In this way, the second stage graft polymerization was performed. Subsequently, after maintaining the liquid temperature of 70 degreeC for 1 hour, it cooled to 25 degreeC and obtained latex of the polyorganosiloxane containing graft copolymer (G-4). Table 2 shows the volume average particle diameter of the graft copolymer (G-4). Thereafter, in the same manner as in Example 1, a powder of the graft copolymer (G-4) was obtained.

[Comparative Example 4]
A polyorganosiloxane-containing graft copolymer (G′-4) was produced in the same manner as in Example 4 except that the type and amount of each raw material used in Example 4 were changed to the conditions shown in Table 2. Furthermore, the powder was obtained. Table 2 shows the volume average particle diameters of the obtained graft copolymers.

Abbreviations in the table are as follows.
BA: n-butyl acrylate AMA: allyl methacrylate CHP: cumene hydroperoxide t-BH: t-butyl hydroperoxide CB: diisopropylbenzene hydroperoxide Fe: ferrous sulfate EDTA: ethylenediaminetetraacetic acid disodium salt SFS: sodium Formaldehyde sulfoxylate MMA: Methyl methacrylate

[Examples 5 to 10, Comparative Examples 5 to 11]
Polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon S-2000F, viscosity average molecular weight 22,000), AS resin (UMG-ABS Co., Ltd., trade name: AP-20, η _sp / c 0.61), ABS resin (manufactured by UMG-ABS Co., Ltd., trade name: R-50, rubber content 45%) and graft copolymers obtained in Examples 1 to 4 or Comparative Examples 1 to 4 ( G-1 to G-4, G′-1 to G′-4) powders were blended in the amounts shown in Table 3. The blend was melt-mixed at a cylinder temperature of 280 ° C. and a screw rotation speed of 150 rpm using a twin-screw extruder (L / D = 30) having a cylinder inner diameter of 30 mm to obtain a polycarbonate resin composition. Next, this polycarbonate resin composition was shaped into pellets.

  The obtained pellets were dried at 80 ° C. for 12 hours and then supplied to a 100-ton injection molding machine (trade name: SE-100DU, manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding was performed at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. Each test piece was obtained. Subsequently, Charpy impact strength measurement, surface impact strength measurement, and visual appearance evaluation were performed using each test piece, and the evaluation results shown in Table 3 were obtained. In the table, “NA” indicates that no data exists.

[Example 11, Comparative Examples 12 and 13]
Graft copolymer (G-1, G′-2) powder obtained in Example 1 or Comparative Example 2, aromatic phosphate ester flame retardant (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: PX-200), polytetrafluoroethylene-containing powder (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Metabrene A-3800), polycarbonate resin (Iupilon S-2000F), AS resin (AP-20) Were blended in the amounts shown in Table 4. Except for these, a polycarbonate resin composition and test pieces were obtained in the same manner as in Example 5. The UL-94V test was conducted and the evaluation results shown in Table 4 were obtained.

  The resin composition of Example 5 in which 5.2 parts of the graft copolymer (C) was blended was excellent in surface impact resistance as compared with the resin compositions of Comparative Examples 5 to 7. It also showed a low ductile-brittle transition temperature and excellent impact resistance. The resin compositions of Examples 6 to 8 containing 8.1 parts of the graft copolymer were excellent in surface impact resistance as compared with the resin composition of Comparative Example 8. It also showed a low ductile-brittle transition temperature and excellent impact resistance. The resin composition of Example 9 containing 11.1 parts of the graft copolymer (C) and Example 10 containing 11.1 parts in total of the graft copolymer (C) and the ABS resin (R-50), Compared to the resin compositions of Comparative Examples 9 and 10, it was found that the surface impact resistance, the ductile-brittle transition temperature (impact resistance) and the balance of appearance were excellent. The resin composition of Comparative Example 5 has a volume average particle diameter of the used graft copolymer (G′-1) smaller than 300 nm, and is derived from the vinyl polymerizable group-containing silane compound in the polyorganosiloxane (B1). Since the content of the component is less than 1% by mass, when the graft copolymer (C) is added in a low amount, the ductile-brittle transition temperature is high, the impact resistance is inferior, the surface impact resistance is slightly low, and the vicinity of the gate The appearance of was low. In the resin compositions of Comparative Examples 6, 8, and 10, since the content of the polyorganosiloxane in the graft copolymer (G′-2) used is less than 30% by mass, the ductile-brittle transition temperature is high and the impact resistance is high. The surface impact resistance was low. In the resin composition of Comparative Example 9, the content of the component derived from the vinyl-based polymerizable group-containing silane compound in the polyorganosiloxane (B1) of the used graft copolymer (G′-3) is from 1% by mass. The surface impact resistance was low because the amount was small, and the appearance near the gate was low. The resin composition of Comparative Example 7 contains the components derived from the polyfunctional vinyl monomer in the graft copolymer (C) (100% by mass) of the graft copolymer (G′-4) used. Is 5 mass% or more, the ductile-brittle transition temperature is high and the low-temperature impact resistance is low. Since the resin composition of Comparative Example 11 did not contain the graft copolymer (C), the surface impact resistance, ductility-brittle transition temperature, and impact resistance were low.

  It turned out that the resin composition of Example 11 which mix | blended 8.1 parts of graft copolymers (C) was excellent in the flame retardance compared with the resin composition of Comparative Examples 12-13. The resin composition of Comparative Example 12 had a low flame retardancy because the content of polyorganosiloxane in the used graft copolymer (G′-2) was less than 30% by mass. Since the resin composition of Comparative Example 13 did not contain the graft copolymer (C), the flame retardancy was low.

  The thermoplastic resin composition of the present invention exhibits high fluidity suitable for thin-wall molding, and is excellent in surface impact resistance, DBTT, impact resistance and flame retardancy. This resin composition is useful as a material in the fields of automobiles, OA equipment such as printers, and electric / electronic fields such as mobile phones.

Claims (12)

Polycarbonate resin or polyester carbonate resin (A),
(Co) polymer (B) comprising an aromatic vinyl monomer unit (b1),
Rubber-containing graft copolymer (C) obtained by graft-polymerizing one or more vinyl monomers to rubber containing polyorganosiloxane
A thermoplastic resin composition comprising:
The content of the component derived from the vinyl-based polymerizable group-containing silane compound in the polyorganosiloxane is 1 to 10% by mass,
The content of the polyorganosiloxane in the rubber-containing graft copolymer (C) is 30 to 98% by mass,
The content of the component derived from the polyfunctional vinyl monomer in the rubber-containing graft copolymer (C) is 0% by mass or more and less than 5% by mass,
And the thermoplastic resin composition whose volume average particle diameter of this rubber-containing graft copolymer (C) is 300-2000 nm. The thermoplastic resin composition according to claim 1, wherein the rubber containing polyorganosiloxane is a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate. The thermoplastic resin composition according to claim 1 or 2, wherein the (co) polymer (B) is a (co) polymer containing a vinyl cyanide monomer unit. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the (co) polymer (B) is a (co) polymer not containing a butadiene monomer unit. The rubber-containing graft copolymer (C) is 0 with respect to 100 parts by mass in total of 50 to 99 parts by mass of the polycarbonate resin or polyester carbonate resin (A) and 50 to 1 part by mass of the (co) polymer (B). The thermoplastic resin composition according to any one of claims 1 to 4, which comprises 5 to 30 parts by mass. 1-30 mass parts of flame retardants (D) are further added with respect to 100 mass parts in total of 50-99 mass parts of said polycarbonate resin or polyester carbonate resin (A) and said (co) polymer (B). The thermoplastic resin composition according to any one of claims 1 to 5. The molded object obtained by shape | molding the thermoplastic resin composition of any one of Claims 1-6. Polycarbonate resin or polyester carbonate resin (A)
(Co) polymer (B) containing aromatic vinyl monomer unit (b1)
Graft copolymer obtained by graft polymerization of vinyl monomer to rubber containing polyorganosiloxane (C)
A thermoplastic resin composition comprising:
A thermoplastic resin composition having a volume average particle diameter of 300 to 2000 nm of the graft copolymer (C). The thermoplastic resin composition according to claim 8, wherein the (co) polymer (B) contains a vinyl cyanide monomer unit. The thermoplastic resin composition according to claim 8 or 9, wherein the (co) polymer (B) does not contain a butadiene monomer unit. 1-30 mass parts of flame retardants (D) are further added to 100 mass parts of 50-99 mass parts of the polycarbonate resin or polyester carbonate resin (A) and 1-50 mass parts of the (co) polymer (B). The thermoplastic resin composition of any one of Claims 8-10 containing. The molded object obtained by shape | molding the thermoplastic resin composition of any one of Claims 8-11.