TW201506048A - Graft copolymer containing polyorganosiloxane, resin composition, molded product, slidability-improving agent and sliding member - Google Patents

Abstract

A graft copolymer (GF2) containing a gum is formed by graft polymerizing a composite gum and one or more vinyl monomer, wherein the composite gum contains a polyorganosiloxane (B1) and a polyalkyl(meth)acrylate (B2). The content of a component derived from a silane compound containing a vinyl polymerizable group in the polyorganosiloxane (B1) ranges from 1 mass% to 10 mass%. The volume average particle diameter of the graft copolymer containing the gum ranges from 300 nm to 2000 nm. The content of the polyorganosiloxane (B1) in the graft copolymer containing the gum ranges from 70 mass% to 98 mass%. An acetone soluble element ranges from 5.0 mass% to 30.0 mass%.

Description

Polyorganotoxime graft copolymer, resin composition, formed body, slidability improver, and sliding member

The present invention relates to a graft copolymer containing polyorganosiloxane, which improves the impact resistance of a thermoplastic resin, and provides high flame retardancy, slidability, and color development in a molded body obtained from a thermoplastic resin. Sex (pigment coloring) appears. Further, the present invention relates to a thermoplastic resin composition having high flame retardancy, slidability, and color rendering property (pigment coloring property) containing the graft copolymer, and a molded article thereof.

Further, the present invention relates to a slidability improver comprising a polyorganosiloxane-containing graft copolymer excellent in slidability, color rendering property (pigment coloring property), and impact strength, and the slidability improver A thermoplastic resin composition and a sliding member obtained by molding the thermoplastic resin composition.

A thermoplastic resin composition excellent in flame retardancy and excellent mechanical properties. There is a large demand in the market such as the electronics field, and high performance is required. In particular, polycarbonate resin is used as a general engineering plastic, transparency, impact resistance, Excellent heat resistance, dimensional stability, etc., because of its excellent characteristics, it is used in the field of office automation (OA), automotive, mobile phones, etc. in the automotive field, printers, etc. The materials in the electronic field are widely used in the industry. Among them, in parts such as personal computer exterior parts, high flame retardancy or impact resistance is required. In these parts, in order to satisfy such safety requirements, high flame retardancy equivalent to UL94V-0 or V-1 is required.

In addition, recently, in order to reduce the size, weight, and functionality, the parts have been thinned year by year. Therefore, in a molded article which is thinner and lighter, a resin material having excellent mechanical properties such as sufficient impact resistance and excellent in flame retardancy and heat resistance is required.

Therefore, in order to improve the flame retardancy of a thermoplastic resin, in particular, a polycarbonate resin, there has been previously been a method of blending a halogen-based flame retardant or a phosphorus-based flame retardant. However, a thermoplastic resin composition containing a halogen-based flame retardant containing chlorine or bromine has a problem that a corrosive gas is generated during combustion, and it is desirable to use a flame retardant containing no such halogen.

Further, in the case of using a thermoplastic resin composition in which a phosphorus-based flame retardant is excessively formulated, there is a possibility that the phosphorus-based flame retardant oozes out of the product at the time of disposal, causing environmental pollution. Therefore, a thermoplastic resin composition which is used as much as possible to reduce the amount of the phosphorus-based flame retardant used or which does not use a phosphorus-based flame retardant and which is highly flame-retardant is strongly desired.

In addition, the molded article obtained from these materials may cause damage such as breakage due to adhesion of chemicals such as hand cream and detergent, and in order not to cause such a problem, a thermoplastic having excellent chemical resistance is also desired. Resin composition.

Various materials have been proposed in order to improve flame retardancy, impact resistance and the like. example For example, Patent Document 1 proposes a flame-retardant thermoplastic resin composition comprising a graft copolymer containing 65 to 100% by weight of polyorganosiloxane, a polycarbonate resin, and phosphoric acid. Ester compound. Patent Document 2 proposes a graft copolymer comprising 10% by mass to 60% by mass of an aromatic or benzyl group in the presence of 40% by mass to 90% by mass of a polyorganosiloxane. The vinyl monomer of the (meth) acrylate monomer is obtained by polymerization. Further, Patent Document 3 proposes a thermoplastic resin composition comprising a composite rubber-based graft copolymer and a resin component, and the composite rubber-based graft copolymer is a polyorganosiloxane and a polyalkyl acrylate. Composite rubber-based graft copolymer, and the content of polyorganosiloxane is 30% by mass to 70% by mass, the volume average particle diameter is 300 nm to 2000 nm, and the particle size distribution Dw/Dn (mass average particle diameter/quantitative average particle size) The diameter is 1.0 to 2.0.

In addition, used in the automotive field, electrical. In a molded article such as an OA machine such as an electronic device or a printing machine, slidability, color rendering property (pigment coloring property), high impact resistance, and the like are required. In recent years, with the spread of hybrid automobiles or electric cars, there has been an increase in the number of slidability required to prevent clicks in embedded parts and the like in automobiles.

In order to improve the slidability of a thermoplastic resin, a method of adding a low molecular weight polytetrafluoroethylene or eucalyptus oil to a thermoplastic resin is known, but the impact strength of the thermoplastic resin is lowered. For this reason, for example, a polyorganosiloxane-containing graft copolymer obtained by graft-polymerizing a rubber component containing a polyorganosiloxane and a vinyl monomer is blended into a thermoplastic resin to prevent a decrease in strength. Give slidability.

For example, Patent Document 4 proposes an anthrone/acrylic composite rubber-based graft copolymer having a number average particle diameter of 300 nm to 2000 nm and a polyorganosiloxane having a content of 20% by mass to 70% by mass, and A thermoplastic resin composition comprising the composite rubber-based graft copolymer. Patent Document 5 describes a thermoplastic resin composition containing a polyorganosiloxane having a polyorganosiloxane having a polyorganosiloxane content of 60% by mass to 90% by mass and having excellent slidability. Patent Document 6 proposes a composite rubber-based graft copolymer having a high polyorganosiloxane content.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-17136

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-63706

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-179016

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-359889

[Patent Document 5] WO06/11384

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2011-26476

However, the molded body obtained in Patent Document 1 cannot satisfy the flame retardancy, impact resistance, and color developability. The molded article obtained in Patent Document 2 cannot satisfy the flame retardancy, impact resistance, and slidability. Further, the molded article obtained in Patent Document 3 cannot satisfy the flame retardancy and the slidability.

Patent Document 4 describes improvement in impact resistance and pigment colorability, but does not describe slidability. In the rubber-based graft copolymers of Patent Document 5 and Patent Document 6, since the volume average particle diameter is small, color rendering properties are insufficient.

An object of the present invention is to provide a thermoplastic resin composition which does not greatly impair the color developability and flame retardancy of a thermoplastic resin and has high impact resistance. Further, an object of the present invention is to provide a graft copolymer which can impart such a property to a thermoplastic resin (hereinafter, referred to as "the first problem").

In addition, an object of the present invention is to provide a thermoplastic resin composition excellent in balance of slidability, color developability, and impact strength, and a slidability improver which can impart such properties to a thermoplastic resin (hereinafter, these are called It is "the second subject").

The above "first problem" is solved by the following first invention group [1] to [25].

[1] A rubber-containing graft copolymer (G _F1 ) which is a rubber-containing graft obtained by graft-polymerizing a rubber containing a polyorganosiloxane (B1) with one or more vinyl monomers. The content of the component derived from the decane compound containing the vinyl polymerizable group in the polyorganosiloxane (B1) is 1% by mass to 10% by mass, and the volume average particle of the rubber-containing graft copolymer The content of the polyorganosiloxane (B1) in the rubber-containing graft copolymer is 70% by mass to 98% by mass, and is determined by the following formula (1). The graft ratio is 10% by mass or less.

Wa: mass of the acetone insoluble matter of the sample (g), wo: total amount of the sample (g), and R: fraction of the rubber containing the polyorganosiloxane (B1) in the additive raw material at the time of producing the graft copolymer (quality%).

[2] A rubber-containing graft copolymer (G _F2 ) which is a composite rubber containing polyorganosiloxane (B1) and polyalkyl (meth)acrylate (B2) and one or more kinds of ethylene The rubber-containing graft copolymer obtained by graft-polymerizing a base monomer, wherein the content of the component derived from the decane compound containing a vinyl polymerizable group in the polyorganosiloxane (B1) is 1% by mass to 10% by mass %, the volume average particle diameter of the rubber-containing graft copolymer is 300 nm to 2000 nm, and the content of the polyorganosiloxane (B1) in the rubber-containing graft copolymer is 70% by mass to 98 mass. %, and the acetone soluble matter is 5.0% by mass or more and 30.0% by mass or less.

[3] A rubber-containing graft copolymer (G _F3 ) which is a rubber-containing graft obtained by graft-polymerizing a rubber containing a polyorganosiloxane (B1) with one or more kinds of vinyl monomers. The content of the component derived from the decane compound containing the vinyl polymerizable group in the polyorganosiloxane (B1) is 1% by mass to 10% by mass, and the volume average particle of the rubber-containing graft copolymer The content of the polyorganosiloxane (B1) in the rubber-containing graft copolymer is 70% by mass to 98% by mass, and the composition derived from the polyfunctional vinyl monomer is 300 nm to 2000 nm. The content is more than 0% by mass and less than 5% by mass.

[4] The rubber-containing graft copolymer according to any one of [1] to [3] wherein the volume average particle diameter is from 400 nm to 1000 nm.

[5] The rubber-containing graft copolymer according to the above [2], wherein the ratio of the polyorganosiloxane (B1) and the polyalkyl (meth)acrylate (B2) is "B1/B2" It is "74/26~99/1" mass%.

[6] A thermoplastic resin composition containing the rubber-containing graft copolymer according to any one of the above [1] to [5] in an amount of 0.1 part by mass to 12 parts by weight based on 100 parts by mass of the thermoplastic resin (A). The parts by mass, the fluorine-based resin (C), 0.01 parts by mass to 5 parts by mass, and the flame retardant (D), 0.01 parts by mass to 10 parts by mass.

[7] The thermoplastic resin composition according to the above [6], wherein the thermoplastic resin (A) is a thermoplastic resin having at least one bond selected from the group consisting of a carbonate bond, an ester bond, and a guanamine bond.

[8] The thermoplastic resin composition according to the above [6], wherein the thermoplastic resin (A) is a polycarbonate resin.

[9] The thermoplastic resin composition according to any one of the above [6], wherein the flame retardant (D) is selected from the group consisting of a phosphorus-based flame retardant and an organic metal salt-based flame retardant. At least one flame retardant.

[10] A molded article obtained by molding the thermoplastic resin composition according to any one of the above [6] to [9].

[11] The rubber-containing graft copolymer according to any one of the above [1] to [5] wherein the content of the rubber containing polyorganosiloxane (B1) in 100% by mass of the above graft copolymer It is 85 mass% to 99 mass%.

[12] The rubber-containing graft copolymer according to the above [11], wherein the polysiloxane is crosslinked by 100% by mass of the monomer raw material for the polyorganosiloxane (B1). The amount of the phthalic acid compound containing the ethylene-based polymerizable group is from 0.7% by mass to 9.8 by mass, based on 100% by mass of the monomer raw material for the graft copolymer. %, and the amount of the polyfunctional vinyl monomer used exceeds 0% by mass and is less than 5% by mass.

[13] The rubber-containing graft copolymer according to the above [11], wherein the amount of the decane-based crosslinking agent is 100% by mass of the monomer raw material for the polyorganosiloxane (B1) The amount of the decane compound containing the ethylene-based polymerizable group is from 0.7% by mass to 9.8% by mass, and more than 0.1% by mass to 10% by mass, based on 100% by mass of the monomer raw material for the graft copolymer. The amount of the functional vinyl monomer used is 0.1% by mass or more and 3% by mass or less.

[14] The rubber-containing graft copolymer according to any one of the above [1] to [5] wherein the content of the rubber containing polyorganosiloxane (B1) in 100% by mass of the above graft copolymer It is 71% by mass or more and less than 85% by mass.

[15] The rubber-containing graft copolymer according to the above [14], wherein the grafting vinyl monomer contains a polyfunctional vinyl monomer, and the monomer raw material 100 mass for the graft copolymer In %, the amount of the polyfunctional vinyl monomer used is more than 0% by mass and not more than 4% by mass.

[16] The rubber-containing graft copolymer according to the above [14], wherein the grafting vinyl monomer contains a polyfunctional vinyl monomer, and the graft copolymer (G _F ) is used alone. The amount of the polyfunctional vinyl monomer used is from 0.1% by mass to 1% by mass based on 100% by mass of the bulk material.

[17] The rubber-containing graft copolymer according to [14] above, wherein the above-mentioned graft The vinyl monomer for branching does not contain a polyfunctional vinyl monomer, and the rubber containing polyorganosiloxane (B1) is a polyorganosiloxane (B1) and a polyalkyl (meth)acrylate (B2). a composite rubber having a polyfunctional vinyl monomer contained in a (meth) acrylate component for a composite rubber and a vinyl monomer for grafting, in 100% by mass of the monomer raw material for the graft copolymer; The total amount of the bodies used is more than 0% by mass and not more than 4% by mass.

[18] The rubber-containing graft copolymer according to the above [14], wherein the grafting vinyl monomer does not contain a polyfunctional vinyl monomer, and the rubber containing polyorganosiloxane (B1) is a composite rubber containing polyorganosiloxane (B1) and polyalkyl (meth) acrylate (B2), and 100% by weight of the monomer raw material for the above graft copolymer, (meth) for composite rubber The total amount of the polyfunctional vinyl monomer contained in the acrylate component and the vinyl monomer for grafting is 0.1% by mass to 1% by mass.

[19] The rubber-containing graft copolymer according to the above [14], wherein the graft vinyl monomer does not contain a polyfunctional vinyl monomer, and the above-mentioned rubber containing polyorganosiloxane (B1) The polyalkyl (meth) acrylate (B2) is not contained, and the amount of the decane-based crosslinking agent used is 0% by mass in 100% by mass of the monomer raw material for the polyorganosiloxane (B1). The amount of the decane compound containing a vinyl polymerizable group is from 0.7% by mass to 5% by mass based on 100% by mass of the monomer raw material for the graft copolymer.

[20] The rubber-containing graft copolymer according to the above [14], wherein the graft vinyl monomer does not contain a polyfunctional vinyl monomer, and the rubber containing polyorganosiloxane (B1) does not. Containing polyalkyl (meth) acrylate (B2), and polyorganisms as described above In 100% by mass of the monomer raw material for the decane (B1), the amount of the decane-based crosslinking agent used is 0.1% by mass to 1.6% by mass, and is 100% by mass of the monomer raw material for the graft copolymer. The amount of the decane compound containing a vinyl polymerizable group is from 0.7% by mass to 1.5% by mass.

[21] A thermoplastic resin composition containing the rubber-containing graft copolymer according to any one of the above [11] to [20] in an amount of 0.1 part by mass to 12 parts by weight based on 100 parts by mass of the thermoplastic resin (A). The mass fraction, the fluorine-based resin (C) is 0.01 parts by mass to 5 parts by mass, and the flame retardant (D) is 0.01 parts by mass to 10 parts by mass.

[22] The thermoplastic resin composition according to the above [21], wherein the thermoplastic resin (A) is a thermoplastic resin having at least one bond selected from the group consisting of a carbonate bond, an ester bond, and a guanamine bond.

[23] The thermoplastic resin composition according to the above [21], wherein the thermoplastic resin (A) is a polycarbonate resin.

[24] The thermoplastic resin composition according to any one of the above [21], wherein the flame retardant (D) is selected from the group consisting of a phosphorus-based flame retardant and an organic metal salt-based flame retardant. At least one flame retardant.

[25] A molded article obtained by molding the thermoplastic resin composition according to any one of the above [21] to [24].

The above "second problem" is solved by the following second invention group [26] to [36].

[26] A slidability improver comprising a rubber-containing graft copolymer (G _S ) powder obtained by graft-polymerizing a rubber containing a polyorganosiloxane and one or more vinyl monomers; The content of the polyorganosiloxane in the rubber-containing graft copolymer (G _S ) is 40% by mass to 95% by mass, and the mass average particle diameter of the latex of the rubber-containing graft copolymer (G _S ) Dw is 300 nm to 2000 nm.

[27] The slidability improver according to the above [26], wherein the rubber particle-containing graft copolymer (G _S ) has a particle size distribution (mass average particle diameter Dw / number average particle diameter Dn) of 1.0. ~2.0.

[28] The slidability improver according to the above [26], wherein the content of the polyorganosiloxane in the rubber-containing graft copolymer (G _S ) is 41% by mass to 74% by mass. .

The slidability improver according to any one of the above-mentioned [26], wherein the latex of the rubber-containing graft copolymer (G _S ) has a mass average particle diameter Dw of 400 nm to 1000 Nm.

[30] The slidability improver according to any one of the above [26], wherein the polyorganosiloxane containing rubber is a composite rubber containing a polyorganosiloxane and a polyalkyl acrylate. .

[31] A slidability improver and a thermoplastic resin according to any one of the above [26] to [30].

[32] The thermoplastic resin composition for a sliding member according to the above [31], wherein the content of the slidability improver is 4% by mass to 16% by mass, and the content of the thermoplastic resin is 96% by mass to 84% by mass.

[33] The thermoplastic resin composition for a sliding member according to the above [31], wherein the content of the slidability improver is from 5.1% by mass to 16% by mass, and the content of the thermoplastic resin is from 9.9% by mass to 84% by mass.

[23] The thermoplastic resin composition for a sliding member according to the above [31], wherein the content of the slidability improver is 7 mass% to 15 mass%, and the content of the thermoplastic resin is 93 mass% to 85 mass%.

[35] The thermoplastic resin composition for a sliding member according to any one of the above [31], wherein the thermoplastic resin is a polycarbonate resin.

[36] A sliding member formed by molding a thermoplastic resin composition according to any one of the above [31] to [35].

By blending the graft copolymer of the first invention group into a thermoplastic resin, a resin composition having high color resistance and flame retardancy without impairing the thermoplastic resin and having high impact resistance can be obtained.

By blending the slidability improver of the second invention group into a thermoplastic resin, it is possible to provide a resin composition which imparts slidability and is excellent in balance between color developability and impact strength.

1‧‧‧ gate

A, B‧‧‧ measuring points

FIG. 1 is a view showing measurement point A (near the gate) and measurement point B (center portion) of the arithmetic mean roughness Ra of the injection-molded test piece. Symbol 1 denotes a gate.

In the present invention, "(meth) acrylate" means at least one of "acrylate" and "methacrylate". In addition, "(co)polymer" means at least one of "polymer" and "copolymer".

Hereinafter, the present invention will be described in detail, but unless otherwise stated, all the descriptions of materials, manufacturing conditions, and the like are common to the first invention group and the second invention group.

<Graft copolymer containing rubber>

The rubber-containing graft copolymer of the present invention (hereinafter sometimes referred to simply as "graft copolymer") is obtained by graft-polymerizing a rubber containing a polyorganosiloxane (B1) with one or more kinds of vinyl monomers. a copolymer.

[Rubber containing polyorganosiloxane]

As the rubber containing a polyorganosiloxane, a polyorganosiloxane rubber or a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate is preferable.

[polyorganosiloxane]

The polyorganosiloxane is a polymer containing an organic siloxane unit as a constituent unit. The polyorganosiloxane rubber can be obtained by polymerizing a mixture of an organic siloxane having a "organo oxyalkylene" and a "decane compound containing a vinyl polymerizable group" or a component which is optionally used. Examples of the component to be used as a component include a decane-based crosslinking agent and a siloxane oligomer having a terminal blocking group.

As the organic siloxane, any of a chain organic siloxane and a cyclic organic siloxane can be used. The cyclic organic siloxane is preferred because of its high polymerization stability and fast polymerization rate. The cyclic organic siloxane having a cyclic ring of a 3-membered ring and a 7-membered ring is preferably the following. Hexamethylcyclotrioxane, octamethylcyclotetraoxane, decamethylcyclopentaoxane, dodecamethylcyclohexaoxane, trimethyltriphenylcyclotrioxane, four Methyltetraphenylcyclotetraoxane, octaphenylcyclotetraoxane, and the like. These may be used alone or in combination of two or more. Among these, it is easy to control the particle size distribution of the rubber containing polyorganosiloxane, and it is preferably 60% by mass or more of octamethylcyclotetraoxane.

[Chane compound containing a vinyl polymerizable group]

A decane compound containing a vinyl polymerizable group is used as a fluorene-based graft cross-linking agent. The decane compound containing a vinyl polymerizable group is a functional group having a decyloxy group and copolymerizable with a vinyl monomer. By using a decane compound containing a vinyl polymerizable group, a polyorganosiloxane having a functional group copolymerizable with a vinyl monomer can be obtained. By using such a graft cross-linking agent, the polyorganosiloxane can be grafted with a (meth)acrylic acid alkyl ester component or a vinyl monomer, which will be described later, by a radical polymerization.

Examples of the decane compound containing a vinyl polymerizable group include a decane represented by the formula (1).

[Chemical 1] RSiR ¹ _n (OR ² ) _3-n (1)

In the 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 alkoxy group, and examples thereof include a methyl group, an ethyl group, a propyl group, or a phenyl group. n represents 0, 1, or 2. R represents any one of the groups represented by the 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 represents hydrogen or methyl, p represents an integer of 1 to 6.

The functional group represented by the formula (2) includes a methacryloxyalkyl group. Examples of the decane having this group include the following. --methacryloxyethyl dimethoxymethyl decane, γ-methyl propylene methoxypropyl methoxy dimethyl decane, γ-methyl propylene methoxy propyl dimethoxy Methyl decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy ethoxy ethoxy diethyl decane, γ-methyl propylene methoxy propyl di ethoxy Methyl decane, δ-methacryloxybutyl butyl diethoxymethyl decane, and the like.

The functional group represented by the formula (3) is, for example, a vinyl phenyl group or the like. Examples of the decane having such a group include vinyl phenyl ethyl dimethoxy decane.

Examples of the fluorene oxide having a functional group represented by the formula (4) include vinyl trimethoxy decane and vinyl triethoxy decane.

The functional group represented by the formula (5) includes a mercaptoalkyl group. Examples of the decane having this group include the following. Γ-mercaptopropyl dimethoxymethyl decane, γ-mercaptopropyl methoxy dimethyl decane, γ-mercaptopropyl diethoxymethyl decane, γ-mercaptopropyl ethoxy dimethyl Decane, γ-mercaptopropyltrimethoxydecane, and the like.

Among these, from the viewpoint of economy, a decane compound containing a vinyl polymerizable group having a functional group represented by the formula (2), the formula (4), and the formula (5) can be preferably used. Among them, a decane compound containing a vinyl polymerizable group having a functional group represented by the formula (2) is more preferable.

These decane compounds containing a vinyl polymerizable group may be used alone or in combination of two or more. The content of the decane compound containing a vinyl polymerizable group in the 100% by mass of the organic siloxane mixture is from 1% by mass to 10% by mass, preferably from 1% by mass to 5% by mass. When the amount of the decane compound containing a vinyl polymerizable group is less than 1% by mass, the appearance of the obtained molded article is deteriorated, and impact resistance and flame retardancy are lowered. When the amount of the decane compound containing a vinyl polymerizable group exceeds 10% by mass, the impact resistance and flame retardancy of the obtained molded article become low.

As the decane-based crosslinking agent, those having a decyloxy group are preferred. By using a decane-based crosslinking agent, a polyorganosiloxane having a crosslinked structure can be obtained. Examples of the oxoxane-based crosslinking agent include trimethoxymethyl decane, triethoxy phenyl decane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, and tetrabutyl. A trifunctional or tetrafunctional crosslinking agent such as oxydecane. Among them, a tetrafunctional crosslinking agent is preferred, and tetraethoxy decane is more preferred. The content of the siloxane-based crosslinking agent is preferably from 0% by mass to 30% by mass, more preferably from 0.1% by mass to 30% by mass, even more preferably 0.1% by mass to 100% by mass of the organic oxane mixture. 10% by mass, particularly preferably 0.1% by mass to 1.8% by mass, most preferably 0.1% by mass to 1.6% by mass.

The alkoxysilane oligomer having a terminal blocking group means an alkyl group having an alkyl group or the like at the terminal of the organooxyalkylene oligomer and stopping the polymerization of the polyorganosiloxane. Oxygen oligo oligomers. Examples of the siloxane oxide oligomer having a terminal blocking group include hexamethyldioxane and 1,3-bis(3-glycidoxypropyl)tetramethyldioxane, and 1 , 3-bis(3-aminopropyl)tetramethyldioxane, methoxytrimethylnonane.

[Manufacturing method of polyorganosiloxane rubber]

The method for producing the polyorganosiloxane rubber is not particularly limited, and for example, the following production method can be employed.

First, an emulsion is prepared by emulsifying an organic sulfoxane mixture containing an organic siloxane and a silane compound containing a vinyl polymerizable group or a component which is optionally used, by using an emulsifier and water, and then using an acid catalyst. The polymerization is carried out at a high temperature. Then, the latex of the polyorganosiloxane rubber is obtained by neutralizing the acid with an alkaline substance.

In the production method, as a method of preparing the emulsion, a method of using a homomixer that performs micronization by shearing force generated by high-speed rotation; a discharge force generated by a high-pressure generator is used. A homogenizer or the like which performs micronization, and a method of mixing by high-speed stirring. Among these, the method using a homogenizer is a preferred method because the particle size distribution of the latex of the polyorganosiloxane rubber is narrowed.

Examples of the method for mixing the acid catalyst during the polymerization include (1) a method in which an organic oxoxane mixture, an emulsifier, and water and an acid catalyst are added at once, and the mixture is mixed; and (2) the acid catalyst aqueous solution is continuously connected. Or a method of adding one-time to an emulsion of an organic oxane mixture; (3) a method of adding an emulsion of an organic siloxane mixture to a high-temperature aqueous acid catalyst solution at a fixed rate and mixing them. In terms of easily controlling the particle size of the polyorganosiloxane, it is preferred to maintain the organic hydrazine at 70 ° C to 85 ° C. An emulsion of an oxane mixture, followed by a continuous or one-time addition of an aqueous acid catalyst solution.

In the case of the first invention group, the polymerization temperature is preferably 50 ° C or higher, more preferably 70 ° C or higher. Further, when the acid catalyst aqueous solution is added to the above emulsion to carry out polymerization, the polymerization time is usually 2 hours or longer, preferably 5 hours or longer.

In the case of the second invention group, the polymerization temperature is preferably from 50 ° C to 95 ° C, and more preferably from 70 ° C to 95 ° C. Further, when the acid catalyst is mixed with an organic oxane mixture, an emulsifier, and water to carry out polymerization after granulation, the polymerization time is preferably from 2 hours to 15 hours, more preferably from 5 hours to 10 hours.

Further, since the crosslinking reaction between stanols proceeds at a temperature of 30 ° C or lower, in order to increase the crosslinking density of the polyorganosiloxane, the polymerization may be carried out at a high temperature of 50 ° C or higher, and then at 30 ° C. The following temperatures are maintained for about 5 hours to 100 hours.

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

The emulsifier used in the above production method is not particularly limited as long as it can emulsify the organic siloxane mixture, but is preferably an anionic emulsifier or a nonionic emulsifier. Examples of the anionic emulsifier include the following. Sodium alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like.

Examples of the nonionic emulsifier include the following. Polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyryl phenyl ether, polyoxygen Ethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene diol, and the like.

These emulsifiers may be used alone or in combination of two or more.

The amount of the emulsifier used is preferably from 0.05 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass, per 100 parts by mass of the organooxane mixture. It can be adjusted to a desired particle diameter by the amount of the 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 organic siloxane mixture is sufficient, and by using the emulsifier in an amount of 10 parts by mass or less, the emulsifier can be suppressed. The coloration of the graft copolymer or the decrease in the thermal decomposition resistance of the resin composition is caused.

Examples of the acid catalyst used in the polymerization of the organooxane mixture include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid; and inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts may be used alone or in combination of two or more. Among these, when a mineral acid such as sulfuric acid, hydrochloric acid or nitric acid is used, the particle size distribution of the latex of the polyorganosiloxane rubber can be narrowed, and further, the emulsification in the latex of the polyorganosiloxane rubber can be reduced. The appearance of the molded body due to the agent component is poor. From the viewpoint of adjusting the desired particle diameter, for example, the amount of the acid catalyst used is preferably 0.1 parts by mass to 0.5 parts by mass per 100% of sulfuric acid based on 100 parts by mass of the organic siloxane mixture.

The mass average particle diameter Dw of the latex of the polyorganosiloxane rubber is preferably from 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 graft copolymer or the mass average particle diameter of the latex of the graft copolymer can be adjusted to 300 nm~2000 nm.

The particle size distribution (mass average particle diameter Dw / number average particle diameter Dn) of the latex of the polyorganosiloxane containing rubber is preferably from 1.0 to 1.7. By setting Dw/Dn to 1.0 to 1.7, a graft copolymer having high color rendering property can be obtained.

Further, the mass average particle diameter Dw and the number average particle diameter Dn of the latex of the rubber containing polyorganosiloxane, and the mass average particle diameter Dw, the number average particle diameter Dn, and the graft copolymer of the latex of the graft copolymer The method of measuring the volume average particle diameter will be described later.

In order to improve mechanical stability, an emulsifier may be added to the latex of the polyorganosiloxane containing rubber obtained by the above method as needed. The emulsifier is preferably an anionic emulsifier or a nonionic emulsifier similar to the emulsifier exemplified above.

[composite rubber]

In the present invention, as the rubber containing polyorganosiloxane, a composite rubber containing polyorganosiloxane (B1) and polyalkyl (meth)acrylate (B2) (hereinafter sometimes referred to simply as " Composite rubber"). The composite rubber is a rubber containing the above polyorganosiloxane and a polyalkyl (meth) acrylate having a glass transition temperature (Tg) of 0 ° C or less represented by the following FOX formula.

1/(273+Tg)=Σ(wi/(273+Tgi)).

In the above formula, Tg is the glass transition temperature (°C) of the copolymer, wi is the mass fraction of the monomer i, and Tgi is the glass transition of the homopolymer obtained by polymerizing the monomer i. Temperature (°C). The Tg value of the homopolymer is the value described in the first volume of the POLYMER HANDBOOK (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 (B2) constituting the composite rubber can be polymerized by an alkyl (meth) acrylate component (hereinafter sometimes simply referred to as "(meth) acrylate component for composite rubber)" obtain. The (meth) acrylate component for the composite rubber preferably contains "a (meth)acrylic acid alkyl ester having a Tg of 0 ° C or less and a "crosslinkable monomer".

Examples of the (meth)acrylic acid alkyl ester having a Tg of 0 ° C or less as a homopolymer include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate. Wait. These may be used alone or in combination of two or more. Among these, in view of the impact resistance of the thermoplastic resin composition and the gloss of the molded body, n-butyl acrylate is particularly preferred.

The "crosslinkable monomer" is exemplified by the following "polyfunctional vinyl monomer". Allyl (meth) acrylate, triallyl cyanurate, triallyl cyanurate, divinyl benzene, diallyl phthalate, ethylene glycol di(methyl) Acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol II (Meth) acrylate, triallyl trimellitate, and the like. These may be used alone or in combination of two or more.

[Manufacturing method of composite rubber]

The method for producing the composite rubber is not particularly limited. For example, it can be produced by an emulsion polymerization method, a suspension polymerization method or a fine suspension polymerization method, but an emulsion polymerization method is preferably used. Among them, a method of adding a (meth) acrylate component for a composite rubber to a latex of a polyorganosiloxane rubber and impregnating the rubber particles with a (meth) acrylate component is particularly preferable. The composite rubber is subjected to emulsion polymerization using a (meth) acrylate component to obtain a latex of a composite rubber.

As a method of preparing a mixture of a latex of a polyorganosiloxane rubber and a (meth) acrylate component for a composite rubber, the above-mentioned (meth)acrylic acid alkyl ester and the like are added to the latex of the polyorganosiloxane rubber. A method of functional vinyl monomer. After the (meth) acrylate component for the composite rubber is impregnated into the particles of the polyorganosiloxane rubber, the temperature is raised to cause a known radical polymerization initiator to function and polymerize. In the method of adding a (meth) acrylate component for a composite rubber to a latex of a polyorganosiloxane rubber, a method of adding all (meth) acrylate components for a composite rubber at once can be mentioned. A method of adding all (meth) acrylate components for a composite rubber at a fixed rate.

When a latex of a composite rubber is produced, an emulsifier may be added in order to stabilize the latex and control the mass average particle diameter of the latex of the composite rubber. The emulsifier is not particularly limited, and is preferably an anionic emulsifier or a nonionic emulsifier.

Examples of the anionic emulsifier include the following. Sodium alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene nonylphenyl ether, sodium sarcosinate, potassium fatty acid, sodium fatty acid , 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 alone or in combination of two or more.

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

Examples of the azo-based initiator include the following. Oil-soluble azo initiator such as 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobis(2-methylpropionate); 4,4'-azo double (4-cyanovaleric acid), 2,2'-azobis[N-(2-carboxymethyl)-2-methylpropionamidine hydrate, 2,2'-azobis-(N, Water-soluble azo system such as N'-dimethylene isobutyl hydrazine) dihydrochloride or 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride Starting agent. These may be used alone or in combination of two or more.

Examples of the peroxide include the following. Inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, diisopropylbenzene hydrogen peroxide, hydrogen peroxide to menthane, cumene hydroperoxide, tert-butyl hydroperoxide, and butyl peroxide Diacid, tert-butyl peroxy neodecanoate, tert-butyl peroxy neoheptanoate, tert-butyl peroxypivalate, peroxy-2-ethylhexanoic acid 1,1,3,3- Organic peroxides such as tetramethylbutyl ester and tert-butyl peroxy-2-ethylhexanoate. These peroxides may be used alone or in combination of two or more.

When a peroxide and a reducing agent are combined to form a redox initiator, it is preferred to reduce the above peroxide with sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, glucose, sorbose, inositol, and the like. Agent, and ferrous sulfate. Ethylenediaminetetraacetic acid disodium salt is used in combination.

These reducing agents may be used alone or in combination of two or more. Further, when sodium formaldehyde sulfoxylate is used as the reducing agent, it is preferred to suppress the amount of use as much as possible from the viewpoint of suppressing outgassing of the resin composition.

When an azo initiator is used, the amount thereof is preferably from 0.01 part by mass to 1 part by mass based on 100 parts by mass of the composite rubber.

When a redox-based initiator is used, the amount of the peroxide used is preferably from 0.01 part by mass to 10 parts by mass per 100 parts by mass of the (meth) acrylate component for the composite rubber. The amount of the reducing agent used is preferably 0.01 parts by mass to 1 part by mass based on 100 parts by mass of the composite rubber.

The ratio "B1/B2" of the polyorganosiloxane (B1) and the polyalkyl (meth)acrylate (B2) in the composite rubber is preferably "74/26 to 99/1" by mass, more preferably Good is "80/20~95/5" quality%. By setting the ratio of "B1/B2" to "74/26 to 99/1" by mass, the molded article obtained by molding is preferably excellent in impact strength.

[Graft Copolymer]

The rubber-containing graft copolymer of the present invention can be obtained by graft-polymerizing one or more kinds of vinyl monomers in the presence of a rubber containing a polyorganosiloxane. Therefore, in the graft copolymer of the present invention, the graft portion is composed of one or more vinyl sheets. The polymer of the body is formed. Hereinafter, the vinyl monomer will be described, but a "polyfunctional vinyl monomer" may be used as the vinyl monomer.

In the following description, the graft copolymer (G _F1 ), the graft copolymer (G _F2 ), and the graft copolymer (G _F2 ) of the "first form", the "second form", and the "third form" of the first invention group may be used. The graft copolymer (G _F3 ) is collectively referred to as a graft copolymer (G _F ). Further, the graft copolymer of the second invention group is referred to as a graft copolymer (G _S ).

In the first invention group, the volume average particle diameter of the graft copolymer (G _F ) is from 300 nm to 2000 nm. The volume average particle diameter is preferably from 400 nm to 1000 nm, more preferably from 400 nm to 800 nm, and particularly preferably from 410 nm to 550 nm. When the volume average particle diameter of the graft copolymer (G _F ) is 300 nm or more, the impact resistance (especially low-temperature impact resistance) of the molded body obtained by blending the graft copolymer (G _F ) into the thermoplastic resin ) became good. In addition, when the volume average particle diameter of the graft copolymer (G _F ) is 2000 nm or less, the coloring property and impact resistance of the molded body obtained by blending the graft copolymer (G _F ) into a thermoplastic resin ( In particular, the low-temperature impact resistance) became good, and the surface appearance became good.

In the first invention group, the content of the "polyorganosiloxane" in 100% by mass of the graft copolymer (G _F ) is 70% by mass to 98% by mass. The content is preferably from 70% by mass to 90% by mass, more preferably from 75% by mass to 85% by mass. When the content of the polyorganosiloxane is 70% by mass or more, the flame retardancy and the slidability of the molded article and the impact strength at a low temperature are good, and when the content of the polyorganosiloxane is 98% by mass or less The surface appearance of the molded body becomes good and preferable.

In the first invention group, the content of the "polyorganosiloxane containing rubber" in 100% by mass of the graft copolymer (G _F ) is preferably 71% by mass to 99% by mass, more preferably 85% by mass. 99% by mass. When the content of the rubber containing the polyorganosiloxane is 71% by mass or more, the impact strength of the molded article at a low temperature is sufficient, and when the content of the rubber containing the polyorganosiloxane is 99% by mass or less, The surface of the molded body is good in appearance and is preferable.

[Grafting rate]

The graft copolymer (G _F1 ) of the "first aspect" of the first invention group has a graft ratio of 10% by mass or less. When the graft ratio is 10% by mass or less, the slidability and flame retardancy of the molded body can be improved. The graft ratio is preferably -20% by mass or more. The graft ratio is more preferably from -20% by mass to 8% by mass, further preferably from -20% by mass to 5% by mass, particularly preferably from 5% by mass to 5% by mass. When the graft ratio is within this range, the obtained molded body exhibits high impact resistance, slidability, and flame retardancy.

Wa: mass of the acetone insoluble matter of the sample (g), wo: total amount of the sample (g), and R: fraction of the rubber containing the polyorganosiloxane (B1) in the additive raw material at the time of producing the graft copolymer (quality%).

Further, as described above, the graft ratio in the present invention is calculated based on the mass wa of the acetone-insoluble matter obtained experimentally and the fraction R of the rubber in the additive raw material. value. Theoretically, the mass wa of the acetone insolubles corresponds to the mass wr of the rubber containing the polyorganosiloxane and the mass wv of the component derived from the vinyl monomer graft-polymerized with the rubber containing the polyorganosiloxane. In total, "wo × R / 100" corresponds to the mass of the extracted polyorganosiloxane containing rubber.

However, in fact, in the total amount of the sample wo, in addition to the graft copolymer, a by-product of the polymerization reaction or an unreacted raw material is contained, and therefore it is also conceivable that the value of "wo × R / 100" exceeds the value of the sample. In the case of the mass wa" of the acetone insoluble matter, there may be a case where the graft ratio obtained experimentally becomes a negative value.

In order to make the value of the graft ratio into the above range, the following methods (1) to (4) are exemplified.

(1) When the target value of the rubber containing polyorganosiloxane (B1) in 100% by mass of the graft copolymer (G _F ) is from 85 to 99% by mass, the polyorganosiloxane (B1) In 100% by mass of the monomer raw material used, the amount of the phthalic oxide-based crosslinking agent used is 0% by mass to 30% by mass, preferably 0.1% by mass to 10% by mass based on the graft copolymer. In 100% by mass of the monomer raw material for (G _F ), the amount of the decane compound containing the vinyl polymerizable group is 0.7% by mass to 9.8% by mass, and the amount of the polyfunctional vinyl monomer used is set to The method is more than 0% by mass and less than 5% by mass, and is preferably 0.1% by mass or more and 3% by mass or less.

(2) When the content of the rubber containing the polyorganosiloxane (B1) in 100% by mass of the graft copolymer (G _F ) is less than 85% by mass, the vinyl monomer for grafting contains polyfunctional ethylene when group-containing monomer in the graft copolymer (G _F) with 100% by mass of the monomer raw material, the amount of the polyfunctional vinyl monomer is set at more than 0 mass% and 4 mass% or less, more It is preferably 0.1% by mass to 3% by mass, more preferably 0.1% by mass to 2% by mass, and still more preferably 0.1% by mass to 1% by mass.

(3) When the content of the rubber containing the polyorganosiloxane (B1) in 100% by mass of the graft copolymer (G _F ) is less than 85% by mass, the vinyl monomer for grafting does not contain polyfunctionality. a vinyl monomer, a rubber containing a polyorganosiloxane (B1), which is a composite rubber comprising a polyorganosiloxane (B1) and a polyalkyl (meth)acrylate (B2), in a graft copolymer ( In the case of 100% by mass of the monomer raw material for G _F ), the total amount of the polyfunctional vinyl monomer contained in the (meth) acrylate component for the composite rubber and the vinyl monomer for grafting is exceeded. 0% by mass and 4% by mass or less, preferably 0.1% by mass to 3% by mass, more preferably 0.1% by mass to 2% by mass, still more preferably 0.1% by mass to 1% by mass. Methods.

(4) When the content of the rubber containing the polyorganosiloxane (B1) in 100% by mass of the graft copolymer (G _F ) is less than 85% by mass, the vinyl monomer for grafting does not contain polyfunctionality. The vinyl monomer, the rubber containing polyorganosiloxane (B1) is a monomer raw material 100 for polyorganosiloxane (B1) when it is a rubber containing no polyalkyl (meth) acrylate (B2). In the mass %, the amount of the rhodium-based crosslinking agent used is from 0% by mass to 1.8% by mass, preferably from 0.1% by mass to 1.6% by mass, based on the single amount of the graft copolymer (G _F ). The amount of the decane compound containing the ethylene-based polymerizable group is from 0.7% by mass to 5% by mass, and preferably from 0.7% by mass to 1.5% by mass, based on 100% by mass of the bulk material.

[Acetone solubles]

The acetone soluble matter of the graft copolymer (G _F2 ) of the "second form" of the first invention group is 5.0% by mass or more and 30.0% by mass or less. The acetone soluble matter is more preferably 5.0% by mass or more and 20.0% by mass or less. The slidability, impact strength, and flame retardancy of the molded body obtained by blending the graft copolymer (G _F2 ) into a thermoplastic resin by the acetone soluble matter of 5.0% by mass or more and 30.0% by mass or less good. When such a graft copolymer (G _F2 ) is to be obtained, the amount and type of the decane compound and the polyfunctional vinyl monomer containing the vinyl polymerizable group must be appropriately selected. Specifically, the amount of the decane compound containing the ethylene-based polymerizable group is from 0.7% by mass to 9.8% by mass based on 100% by mass of the monomer raw material for the graft copolymer (G _F ). In 100% by mass of the monomer raw material for the oxane (B1), the amount of the phthalic oxide-based crosslinking agent used is 0% by mass to 30% by mass, preferably 0.1% by mass to 10% by mass, and In the 100% by mass of the monomer raw material for the graft copolymer (G _F ), the amount of the polyfunctional vinyl monomer used is more than 0% by mass, less than 5% by mass, and preferably 0.1% by mass. When the amount is more than 3% by mass and not more than 3% by mass, the graft copolymer having an acetone soluble matter of 5.0% by mass or more and 30.0% by mass or less can be obtained. The method for measuring the acetone soluble matter of the graft copolymer will be described later.

In the first invention group, the content of the component derived from the polyfunctional vinyl monomer in 100% by mass of the graft copolymer (G _F ) is not particularly limited, but is preferably 0% by mass or more and 10% by mass or less. More preferably, it is more than 0% by mass, less than 5% by mass, more preferably more than 0% by mass, and more preferably 3% by mass or less, particularly preferably 0.1% by mass or more and 1.5% by mass or less, and most preferably 0.1% by mass. The above is 1.0% by mass or less. The content of the component derived from the polyfunctional vinyl monomer is 0% by mass or more and 10% by mass or less, and the obtained molded article exhibits high impact resistance and slidability.

In the 100% by mass of the graft copolymer (G _F3 ) of the "third form" of the first invention group, the content of the component derived from the polyfunctional vinyl monomer is more than 0% by mass and less than 5% by mass, preferably 0.01% by mass or more and 3% by mass or less. When the content of the component derived from the polyfunctional vinyl monomer is within this range, the obtained molded article exhibits high impact resistance, slidability, and flame retardancy.

In the first invention group, the content of the component derived from the decane compound containing a vinyl polymerizable group in 100% by mass of the graft copolymer (G _F ) is not particularly limited, but is preferably 0.7% by mass to 9.8% by mass. More preferably, it is 0.7% by mass to 5% by mass, and more preferably 0.7% by mass to 1.5% by mass.

In the second invention group, the latex of the graft copolymer (G _S ) has a mass average particle diameter of 300 nm to 2000 nm. When the mass average particle diameter of the latex is 300 nm or more, the coloring property of the molded article obtained from the thermoplastic resin composition is good, and if the mass average particle diameter of the latex is 2000 nm or less, the impact resistance of the molded body at a low temperature is obtained. Good sex. The mass average particle diameter of the latex is preferably from 400 nm to 2000 nm, more preferably from 400 nm to 1000 nm, more preferably from 410 nm to 650 nm, and particularly preferably from 420 nm to 550 nm.

In the second invention group, the particle size distribution (mass average particle diameter Dw / number average particle diameter Dn) of the latex of the graft copolymer (G _S ) is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.5. When the particle size distribution (Dw/Dn) of the latex is 2.0 or less, the color developability (pigment coloring property) of the molded article 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 second invention group, the content of the "polyorganosiloxane" in the graft copolymer (G _S ) is 40% by mass to 95% by mass. When the content is 40% by mass or more, the slidability of the molded body is sufficiently exhibited, and the impact resistance at low temperatures is also good. In addition, when the content is 95% by mass or less, the color developability (pigment coloring property) of the molded body is good. The content is preferably from 41% by mass to 74% by mass, more preferably from 50% by mass to 70% by mass.

In the second invention group, the content of the "polyorganosiloxane containing rubber" in 100% by mass of the graft copolymer (G _S ) is preferably 65 to 99% by mass, more preferably 80% by mass. 95% by mass. When the content of the rubber containing the polyorganosiloxane is 65% by mass or more, the impact strength of the molded article at a low temperature is sufficient, and when the content is 99% by mass or less, the surface appearance of the molded article is improved. good.

In the present invention, the rubber containing polyorganosiloxane (B1) is preferably a composite rubber containing polyorganosiloxane (B1) and polyalkyl (meth)acrylate (B2). Further, it is more preferably a composite rubber containing a polyorganosiloxane and a polyalkyl acrylate, and more preferably a composite rubber containing a polyorganosiloxane and a polybutyl acrylate. When the rubber containing the polyorganosiloxane (B1) is a composite rubber, the impact resistance of the molded body becomes good. Further, when the rubber containing the polyorganosiloxane (B1) is a composite rubber, the flame retardancy of the molded body becomes good.

In the graft copolymer of the present invention, the graft portion is formed of a polymer of one or more kinds of vinyl monomers, and the glass transition temperature of the polymer represented by the above FOX formula exceeds 0 ° C, preferably 50 ° C. the above. The vinyl monomer used in the graft polymerization is not particularly limited, and examples thereof include the following. Styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-methoxystyrene, An aromatic vinyl monomer such as o-methoxy styrene, 2,4-dimethyl styrene, chlorostyrene, bromostyrene, vinyl toluene, vinyl naphthalene or vinyl anthracene; (meth)acrylic acid Ester, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (methyl) 4-tert-butylphenyl acrylate, monobromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, (methyl) (meth) acrylate such as monochlorophenyl acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, naphthyl (meth) acrylate; (meth) acrylate, (methyl) a carboxyl group-containing monomer such as carboxyethyl acrylate; a cyanide vinyl monomer such as (meth)acrylonitrile; a vinyl ether monomer such as vinyl methyl ether or vinyl ethyl ether; vinyl benzoate or acetic acid; a vinyl carboxylate monomer such as vinyl ester or vinyl butyrate; a vinyl monomer having a glycidyl group such as glycidyl (meth)acrylate or allyl glycidyl ether; ethylene, propylene, butylene And other olefins. These vinyl monomers may be used alone or in combination of two or more.

When two or more types are used, the 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 cyanurate, divinyl benzene, diallyl phthalate, ethylene glycol di(methyl) Acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol II (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) acrylate such as methyl (meth) acrylate, the obtained graft copolymer is a polycarbonate resin. The thermoplastic resin (A) is excellent in compatibility and dispersibility. In addition, when one or more vinyl monomers contain an aromatic vinyl monomer such as styrene, the molded article obtained by molding the thermoplastic resin composition is excellent in flame retardancy. Therefore, it is preferred to use the vinyl monomers alone or in combination of the vinyl monomers.

Various chain transfer agents and graft crosslinking agents for adjusting the molecular weight and graft ratio of the graft polymer may be added to the raw materials used for the graft polymerization.

[Method for Producing Graft Copolymer]

For the polymerization method of the graft portion, for example, one or more kinds of vinyl monomers for graft polymerization are added to the latex of the rubber containing polyorganosiloxane, and the polymerization is carried out in one step or in multiple stages. method. When the polymerization is carried out in a plurality of stages, it is preferred to divide one or more kinds of vinyl monomers for graft polymerization, and then gradually or continuously add them to the latex of the polyorganosiloxane rubber for polymerization. . The polymerization method of this polymerization method is excellent in stability, and a latex of a graft copolymer having a desired particle diameter and particle size distribution can be stably obtained.

At the time of polymerization of the graft portion, an emulsifier may be added to the raw material as needed. The emulsifier may be the same emulsifier as the emulsifier used in the production of the composite rubber, and is preferably an anionic emulsifier or a nonionic emulsifier. The amount of the emulsifier used is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 0.2 part by mass to 5 parts by mass, per 100 parts by mass of the vinyl monomer for graft polymerization.

The polymerization initiator used for the polymerization of the graft portion may, for example, be the same polymerization initiator as the polymerization initiator used in the production of the composite rubber, preferably an azo initiator or a redox initiator. Agent.

When the powder of the graft copolymer is recovered from the latex of the graft copolymer, any of a spray drying method and a solidification method can be used.

The spray drying method is a method in which a latex of a graft copolymer is sprayed into a dryer in the form of minute droplets, and a heating gas for drying is blown and dried. Examples of the method of generating the fine droplets include a rotary disk type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type. The capacity of the dryer can be any small capacity as used in the laboratory, to any of a large-scale capacity as used in the industry. The temperature of the heating gas for drying is preferably 200 ° C or lower, more preferably 120 ° C to 180 ° C.

It is also possible to spray-dry together the latex of two or more kinds of graft copolymers separately produced. Further, in order to prevent powder characteristics such as clogging during spray drying and bulk specific gravity, an optional component such as cerium oxide may be added to the latex of the graft copolymer, followed by spray drying.

The solidification method is a method in which the latex of the graft copolymer is coagulated, and the graft copolymer is separated, and then recovered and dried. First, the latex of the graft copolymer is placed in hot water in which a coagulant is dissolved, and salting out and solidification are carried out to separate the graft copolymer. Then, the separated wet graft copolymer is subjected to dehydration or the like, and then the graft copolymer having a reduced water content is recovered. 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 particularly preferably calcium acetate. These coagulants may be used alone or in combination of two or more. When used together In the case of a solid solution, it is necessary to select a combination which does not form a water-insoluble salt. For example, when calcium acetate is used in combination with sulfuric acid or a sodium salt thereof, a calcium salt which is insoluble in water is formed, which is not preferable.

The above coagulant is usually used as an aqueous solution. The concentration of the coagulant aqueous solution is preferably 0.1% by mass or more, particularly preferably 1% by mass or more, from the viewpoint of stably solidifying the graft copolymer and recovering it. In addition, when the amount of the coagulant remaining in the graft copolymer recovered is large, the thermal decomposition resistance of the molded article is deteriorated. Therefore, the concentration of the coagulant aqueous solution is preferably 20% by mass or less, and particularly preferably 15% by mass or less. . The amount of the coagulant aqueous solution with respect to the latex is not particularly limited, and is preferably 10 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the latex.

The method of bringing the latex into contact with the aqueous solution of the coagulant is not particularly limited, and the following methods are usually mentioned. (1) a method of stirring an aqueous solution of a coagulant, a method of continuously adding a latex thereto and maintaining a fixed time; (2) continuously injecting a coagulant aqueous solution and a latex into a container with a mixer at a fixed ratio while causing two The person contacts and then continuously withdraws a mixture containing the condensed polymer and water from the container. The temperature at which the latex is brought into contact with the aqueous solution of the coagulant 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 is washed with water of about 1 to 100 mass times, and the wet graft copolymer is filtered using a flow dryer or a press dehydrator. The drying temperature and the drying time may be appropriately determined depending on the Tg of the obtained graft copolymer. Further, the graft copolymer discharged from the press dehydrator or the extruder may be recovered without being directly sent to an extruder or a molding machine for producing a resin composition, and mixed with a thermoplastic resin to obtain A shaped body is obtained.

In the present invention, from the viewpoint of heat decomposition resistance of the resin composition obtained by mixing with a thermoplastic resin, the graft copolymer is preferably recovered by a solidification method.

In the powder of the graft copolymer recovered as described above, when the vinyl monomer is graft-polymerized, it may be polymerized without grafting and bonding with a rubber containing polyorganosiloxane. (co)polymer.

<Thermoplastic resin composition>

The graft copolymer of the first invention group can be used as a thermoplastic resin composition by mixing with a thermoplastic resin (A). The thermoplastic resin composition is preferably a thermoplastic resin composition containing a thermoplastic resin (A), a graft copolymer (G _F ), a fluorine resin (C), and a flame retardant (D).

[Thermoplastic resin (A)]

The thermoplastic resin (A) is exemplified by the following. Polypropylene (PP), polyethylene (Polyethylene, PE) and other olefin-based resins; polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate. Styrene copolymer (Methacrylate-Styrene, MS), styrene. Acrylonitrile copolymer (Styrene-Acrylonitrile, SAN), styrene. Styrene-Maleic Anhydride (SMA), acrylonitrile. Butadiene. Acrylonitrile-Butadiene-Styrene (ABS), acrylate. Styrene. Acrylic ester-Styrene-Acrylonitrile (ASA), acrylonitrile. Ethylene. Acrylic rubber. Styrene (St) resin such as styrene copolymer (Acrylonitrile-Ethylene propylene rubber-Styrene, AES); acrylic acid (Ac) resin such as polymethylmethacrylate (PMMA); polycarbonate resin (PC) Resin); Polyamide (PA) resin; Polyethylene Terephthalate (PET), Polybutylene Terephthalate (PBT), Poly Lactic Acid , PLA), etc. Polyethersulfone (PEs) resin; (modified) polyphenylene ether ((m-) Polyphenylene Ether, (m-) PPE) resin, polyoxymethylene (POM) resin, polysulfone (Polysulfone) , PSO) resin, polyarylate (PAr) resin, polyphenylene sulfide (PPS) resin, thermoplastic polyurethane (PU) resin and other engineering plastics; styrene elastomer, Olefin-based elastomer, vinyl chloride-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamine-based elastomer, fluorine-based elastomer, 1,2-polybutadiene, trans 1 Thermoplastic elastomer such as 4-polyisoprene (Thermoplastic Ela Stomer, TPE); alloys of PC resin and St-based resin such as PC/ABS, alloys of PVC resin and St-based resin such as polyvinyl chloride (PVC)/ABS, PA resin such as PA/ABS, and St-based resin Alloy, alloy of PA resin and TPE, alloy of PA resin and polyolefin resin such as PA/PP, alloy of PC resin and PEs resin such as PC/PBT, olefin resin such as polyolefin resin/TPE and PP/PE Alloys such as alloys, PPE/HIPS, PPE/PBT and PPE/PA, PPE resin, alloys such as PVC/PMMA, and alloys such as alloys of Ac resin; hard vinyl chloride resin, semi-rigid Vinyl chloride tree A PVC-based resin such as a fat or soft vinyl chloride resin.

The thermoplastic resin (A) is preferably selected from the group consisting of a carbonate bond, an ester bond, and a guanamine bond from the viewpoint of improving the impact resistance and flame retardancy of the obtained molded article. At least one type of thermoplastic resin. Examples of the thermoplastic resin having at least one bond selected from the group consisting of a carbonate bond, an ester bond, and a guanamine bond include a PC resin, PBT, PET, PA resin, and PLA. Further, a resin called an alloy blend containing these resins may also be used. Further, a PC-based resin containing 50% by mass or more of an aromatic polycarbonate unit is particularly preferable.

The PC-based resin is a thermoplastic aromatic polycarbonate polymer or copolymer which may have a branch, by reacting an aromatic hydroxy compound with a diester of carbonyl dichloride or carbonic acid, or by making an aromatic hydroxy compound and a small amount. The polyhydroxy compound is obtained by reacting a diester of carbonyl dichloride or carbonic acid. The method for producing the aromatic polycarbonate resin is not particularly limited, and a known method, that is, a phosgene method (interfacial polymerization method), a melting method (transesterification method), or the like can be employed. The PC-based resin tends to have an influence on the thermal stability and hydrolytic stability of the terminal OH group. Therefore, in the present invention, the following aromatic polycarbonate resin may be used: it is produced by a melting method and The aromatic polycarbonate resin in which the amount of OH groups at the terminal is adjusted by adjusting the degree of pressure reduction during the reaction or the like is adjusted.

Examples of the PC-based resin include the following. Products manufactured by Mitsubishi Engineering-Plastics (shares) under the trade names Iupilon S-1000, Iupilon S-2000, Iupilon S-3000, Iupilon H-3000 or Iupilon H-4000; or products manufactured by Teijin Chemicals Co., Ltd. Name Panlite L1250, Panlite L1225 or Panlite K1300, etc.

The amount of the graft copolymer (G _F ) to be used with respect to the thermoplastic resin (A) is preferably 0.1 parts by mass to 12 parts by mass based on 100 parts by mass of the thermoplastic resin (A), and the graft copolymer (G _F ) is added. It is more preferably 0.5 parts by mass to 10 parts by mass, and still more preferably 1 part by mass to 8 parts by mass. When the amount of the graft copolymer (G _F ) used is from 0.1 part by mass to 12 parts by mass, a resin composition capable of providing a molded article excellent in impact resistance and surface appearance can be obtained.

[Fluororesin (C)]

The fluorine-based resin (C) can be used for the purpose of preventing dripping during combustion. As the fluorine-based resin (C), a known fluorine-based resin can be used, and a suitable compound can be used, and a commercially available product can also be used. As a commercial item, the following are mentioned, for example. "Polyflon FA-500" (trade name, Daikin Industries (manufactured by Daikin Industries) (manufactured)), etc., such as "BLENDEX B449" (trade name, manufactured by Galata Chemicals) Polytetrafluoroethylene; "Metablen A-3000", "Metablen A-3750", "Metablen A-3800" (trade name, manufactured by Mitsubishi Rayon (share)), etc. . These fluorine-based resins (C) may be used alone or in combination of two or more.

Among the fluorine-based resins (C), the dispersibility in the obtained molded body is excellent, and the mechanical properties, heat resistance and flame retardancy of the molded article are excellent, and SAN modified polytetrafluoroethylene is preferred. Acrylic modified polytetrafluoroethylene, more preferably acrylic modified polytetrafluoroethylene.

As a SAN modified polytetrafluoroethylene, or acrylic modified polytetrafluoroethylene The content of the polytetrafluoroethylene in the olefin is preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 70% by mass based on 100% by mass of the fluororesin (C). When the content is 10% by mass or more, the obtained molded article is excellent in flame retardancy. In addition, when the content is 80% by mass or less, the obtained molded article is excellent in appearance.

The blending amount of the fluorine-based resin (C) is preferably 0.01 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, even more preferably 0.3 parts by mass, based on 100 parts by mass of the thermoplastic resin (A). 2 parts by mass. When the compounding amount is 0.01 parts by mass or more, the obtained molded body is excellent in flame retardancy. In addition, when the blending amount is 5 parts by mass or less, the original properties of the thermoplastic resin (A) are not impaired.

[Flame retardant (D)]

As the flame retardant (D), a known flame retardant can be used, and examples thereof include the following. A halogen-based flame retardant comprising a combination of a halogenated compound such as a halogenated bisphenol A, a halogenated polycarbonate oligomer, or a brominated epoxy compound, and a flame retardant auxiliary agent such as cerium oxide; an organic salt-based flame retardant; a phosphate ester system Phosphorus-based flame retardants such as flame retardants and halogenated phosphate-based flame retardants; sulfonic acid-based flame retardants such as metal salts of aromatic sulfonic acids and metal salts of perfluoroalkanesulfonic acids; branched phenyl fluorenone compounds An anthrone-based flame retardant such as an organic polyoxyalkylene such as a phenylfluorenone resin.

Among these flame retardants (D), a non-halogen type or a molded body obtained is excellent in flame retardancy, and is preferably a phosphorus-based flame retardant such as a phosphate-based flame retardant; An organic metal salt-based flame retardant such as an acid metal salt or a perfluoroalkanesulfonic acid metal salt is more preferably an organic metal salt-based flame retardant.

The tone of the flame retardant (D) relative to 100 parts by mass of the thermoplastic resin (A) The amount is preferably from 0.01 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass. When the compounding amount is 0.01 parts by mass or more, the obtained molded body is excellent in flame retardancy. In addition, when the compounding amount is 10 parts by mass or less, the original properties of the thermoplastic resin (A) are not impaired. If the blending amount is too small, the flame retarding effect of the obtained molded body is lowered. Further, when the amount is too large, the mechanical strength of the resin molded body is lowered.

Examples of the phosphorus-based flame retardant include red phosphorus, coated red phosphorus, a polyphosphate compound, a phosphate compound, a phosphonate compound, a phosphite compound, and a phosphinate compound. A phosphazene compound or the like. Among these, a phosphate compound is preferred. Examples of the phosphate ester compound include the following. Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl phosphate, tolyl diphenyl phosphate, octyl phosphate Diphenyl ester, isopropyl phenyl diphosphate, tris(butoxyethyl) phosphate, triisobutyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, tri-(isopropyl) phosphate Phenyl) ester, 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(xy-2,6-xylylene), bisphenol A double Diphenyl phosphate), resorcinol diphenyl diphosphate, octyl diphenyl phosphate, divinyl ethyl ester phosphate, dihydroxy butyl acrylate phosphate, ethylene disodium phosphate, tributyl phosphate Phenyldiphenyl ester, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl) phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate Ester, 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.

The blending amount of the phosphorus-based flame retardant is preferably from 1 part by mass to 10 parts by mass, more preferably from 2 parts by mass to 8 parts by mass, even more preferably from 3 parts by mass to 6 parts by mass per 100 parts by mass of the thermoplastic resin (A). Within the range of parts by mass.

Since the organic metal salt-based flame retardant exhibits a flame retarding effect by being added in a very small amount, it is difficult to reduce the heat resistance of the molded article, and it is advantageous in that the molded article is sufficiently provided with antistatic properties. The organometallic salt-based flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound refers to a metal salt compound containing an anion component and a cationic component, and the anion component includes an organic acid having a fluorine-substituted hydrocarbon group, and the cationic component contains a metal ion. Among them, a metal salt of a fluorine-substituted organic sulfonic acid, a metal salt of a fluorine-substituted organic sulfate, and a metal salt of a fluorine-substituted organic phosphate are preferable. The fluorine-containing organometallic salt compound may be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferred, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferred.

In addition, as the organic metal salt-based flame retardant other than the fluorine-containing organometallic salt compound, a metal salt of an organic sulfonic acid having no fluorine atom is preferable. Examples of the metal salt include a metal salt of an aliphatic sulfonic acid and a metal salt of an aromatic sulfonic acid. Among them, a metal salt of an aromatic sulfonic acid is preferred.

Examples of the metal species of the metal ion constituting the organic metal salt-based flame retardant include an alkali metal such as sodium or potassium, and an alkaline earth metal such as calcium. Specific examples of the organic metal salt-based flame retardant include the following. Potassium salt of 4-methyl-N-(4-methylphenyl)sulfonyl-benzenesulfonamide, potassium diphenylsulfonium-3-sulfonate, diphenylphosphonium-3,3'-disulfonate Potassium acid, sodium p-toluenesulfonate, sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, perfluoromethylbutanesulfonic acid Sodium, potassium perfluoromethylbutanesulfonate, sodium perfluorooctanesulfonate, potassium perfluorooctanesulfonate, tetraethylammonium salt of perfluorobutanesulfonic acid, and the like. Among these, potassium perfluorobutanesulfonate is preferred. These may be used alone or in combination of two or more.

The compounding amount of the organometallic salt-based flame retardant is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.03 parts by mass to 1 part by mass, and still more preferably 0.05 parts by mass, based on 100 parts by mass of the thermoplastic resin (A). ~0.5 parts by mass.

[Antioxidant (E)]

The thermoplastic resin composition of the first invention group may contain an antioxidant (E) as needed. The antioxidant (E) is a component for the purpose of suppressing oxidative decomposition of the resin when the molded article is produced, and also for improving the flame retardancy of the molded article. The antioxidant (E) is not particularly limited as long as it is an antioxidant used in usual molding. As a specific example, the following are mentioned, for example. Tris[N-(3,5-di-t-butyl-4-hydroxybenzyl)]isocyanurate (made by ADEKA (shares), Adekastab AO-20, etc.), four [ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxymethyl]methane (manufactured by BASF, Irganox 1010, etc.), bis(3-tert-butyl- 4-hydroxy-5-methylphenylpropionic acid) ethylene bis(oxyethylene) (manufactured by BASF Corporation, Irganox 245, etc.), octadecyl 3,5-di-t-butyl-4-hydroxyphenylpropionate (BASF Manufactured by the company, Irganox 1076, etc., butylene-1,1-bis-(2-methyl-4-hydroxy-5-t-butyl-phenyl) (Manufactured by Aidico (Stock), Adekastab AO-40 Et,1,1,3-1,3-(2-methyl-4-hydroxy-5-t-butylphenyl)butane (manufactured by Yoshitomi Fine Chemicals Co., Ltd., Yoshinox 930, etc.) Phenolic antioxidant; bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol pyrite Ester (manufactured by Eddy Co., Ltd., Adekastab PEP-36, etc.), tris(2,4-di-t-butylphenyl) phosphite (manufactured by Eddy Co., Ltd., Adekastab 2112, etc.), 2 , a phosphorus-based antioxidant such as 2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite (manufactured by Eddy Co., Adekastab HP-10, etc.); 3,3'-thio-dipropionate (manufactured by Jifu Fine Chemicals Co., Ltd., Yoshinox DLTP), Dimyristoyl 3,3'-thio-dipropionate (Jifu Fine Chemicals (Shares) A sulfur-based antioxidant such as manufactured by Yoshinox DMTP).

The amount of the antioxidant (E) is preferably from 0 part by mass to 2 parts by mass, more preferably from 0.01 part by mass to 1 part by mass, even more preferably from 0.05 part by mass to 0.8 parts by mass per 100 parts by mass of the thermoplastic resin (A). Parts by mass. By setting the blending amount to 2 parts by mass or less, it is possible to suppress a decrease in impact resistance of the molded article.

[Other additives]

In the thermoplastic resin composition of the first invention group, the following components may be further adjusted as needed. Plasticizers, lubricants; mold release agents (such as pentaerythritol tetrastearate, etc.); nucleating agents, antistatic agents, stabilizers, fillers; reinforcing materials (such as glass fiber, carbon fiber, mica, kaolin, talc, CaCO ₃ and glass flakes (glass flake)); pigments and pigments. These may be used alone or in combination of two or more.

[Preparation method of resin composition]

The method for producing the thermoplastic resin composition of the first invention group is not particularly limited. For example, it can be prepared by using a V-type agitator or a Henschel mixer or the like to form a thermoplastic resin (A), a graft copolymer (G _F ), and an optional fluorine-based resin (C). The flame retardant (D), the antioxidant (E), and various additives are mixed and dispersed, and then the mixture is subjected to an extruder or a Banbury mixer, a pressure kneader, a roll, or the like. Melt and knead. The mixing of the above components may be carried out batchwise or continuously, and the order of mixing the components is not particularly limited. The melt-kneaded product can be used as a pellet and used for various forms.

<Formed body>

The molding method of the thermoplastic resin composition of the first invention group includes a usual molding method for molding a thermoplastic resin composition, such as an injection molding method, an extrusion molding method, a blow molding method, and a calender molding method.

The molded body of the first invention group has excellent impact resistance, flame retardancy, and color rendering properties, and thus is used in the automotive field, the OA machine field, home appliances, and electrics. Various materials such as the electronic field are widely used industrially. More specifically, it can be used as an electronic machine part, an automobile structural member, an automobile interior part, and a light reflection board. More specifically, it can be used as a personal computer frame, a mobile phone frame, a personal digital assistant frame, a portable game machine frame, a printing machine, a photocopying machine, and the like. External components.

<Slidability improver>

The "slidability improver (H)" of the second invention group contains the powder of the above graft copolymer (G _S ). The graft copolymer (G _S ) is limited to a specific range due to the content of the polyorganosiloxane, and the mass average particle diameter of the latex of the graft copolymer (G _S ) is limited to a specific range, so it is most suitable for use. It is a slidability improver. Therefore, the effect of improving the slidability is large, and the color rendering property (pigment coloring property) and the balance between the molded appearance and the impact strength are excellent. The polyorganosiloxane containing rubber used for the production of the graft copolymer (G _S ) is preferably a composite rubber containing a polyorganosiloxane and a polyalkyl acrylate.

<The thermoplastic resin composition for sliding members>

The slidability improver (H) of the second invention group can be used as a thermoplastic resin composition for a sliding member by mixing with a thermoplastic resin (K).

[Thermoplastic resin (K)]

The thermoplastic resin (K) is the same as the thermoplastic resin (A). Among these, the following resins or alloys are preferred. St-based resin, PC-based resin, PA resin, PET resin, PBT resin, (m-) PPE resin, POM resin, PU resin; alloy of PC-based resin such as PC/ABS and St-based resin, PA resin such as PA/ABS Alloy with St resin, alloy of PA resin and TPE, alloy of PA resin such as PA/PP and polyolefin resin, alloy of PC resin and PE resin such as PC/PBT, PPE system such as PPE/PBT and PPE/PA An alloy or the like of the resins. Among them, the thermoplastic resin (K) is more preferably a PC-based resin because the effect of the present invention is exhibited. These resins may be used alone or in combination of two or more.

Examples of the PC-based resin include reacting an aromatic dihydroxy compound with a dicarbonyl chloride or a carbonic acid diester, or reacting an aromatic dihydroxy compound and a small amount of a polyhydroxy compound with a carbonyl dichloride or a carbonic acid diester. And the polymer obtained. The PC-based resin may be either linear or branched. Further, the polycarbonate resin may be either a homopolymer or a copolymer.

Examples of the aromatic dihydroxy compound include 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), tetramethylbisphenol A, and bis(4-hydroxyphenyl)-p-pair. Isopropylbenzene, hydroquinone, resorcinol and 4,4-dihydroxydiphenyl. These may be used alone or in combination of two or more. In addition, as an aromatic dihydroxy compound, A compound having one or more tetraalkyl phosphonium sulfonate bonded thereto is used.

When the PC-based resin to be branched is used as a PC-based resin, a part of the aromatic dihydroxy compound may be replaced with a branching agent. As a branching agent, the following are mentioned, for example. Phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,4,6-dimethyl-2,4,6-tris(4- Hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-3,1,3,5-tris(4-hydroxyphenyl)benzene, Polyhydroxyl compound such as 1,1,1-tris(4-hydroxyphenyl)ethane; 3,3-bis(4-hydroxyaryl)fluorenone (ie, isatin bisphenol), 5-chloroindole , 5,7-dichloropurine and 5-bromo ruthenium. The amount of the branching agent used is usually from 0.01 mol% to 10 mol%, preferably from 0.1 mol% to 2 mol%, based on the aromatic dihydroxy compound.

The PC-based resin is preferably a PC-based resin obtained from an aromatic dihydroxy compound containing bisphenol A from the viewpoint of heat resistance and flexibility. In addition, as the PC-based resin, a copolymer having a PC-based resin as a main component such as a copolymer of a polycarbonate and a polymer having a decane structure or an oligomer can be used. The PC-based resin may be used singly or in combination of two or more.

The viscosity average molecular weight of the PC-based resin is preferably from 16,000 to 30,000, more preferably from 18,000 to 28,000. The viscosity average molecular weight of the PC-based resin is a value obtained by converting the viscosity of the solution measured at a temperature of 25 ° C using dichloromethane as a solvent. When the viscosity average molecular weight is 30,000 or less, the melt fluidity of the resin composition containing the slidability improver tends to be good, and the viscosity average molecular weight is 16,000 or more, and the impact resistance of the molded article of the present invention is present. The tendency to become good.

When the molecular weight of the PC-based resin is to be adjusted, for example, one of m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, or a long-chain alkyl-substituted phenol is used. The valent aromatic hydroxy compound may be substituted for a part of the above aromatic dihydroxy compound.

The method for producing the PC-based resin is not particularly limited, and it can be produced by a known dicarbonyl carbonyl method (interfacial polymerization method) or a melting method (transesterification method). In addition, an aromatic polycarbonate resin which is produced by a melt method and whose amount of OH group at the end is adjusted by adjusting the degree of pressure reduction during the reaction or the like can be used.

[Thermoplastic resin composition]

The thermoplastic resin composition containing the slidability improver of the second invention group is one containing the slidability improver (H) and the thermoplastic resin (K). The thermoplastic resin composition preferably has a content of the slidability improver (H) of 4% by mass to 16% by mass and a content of the thermoplastic resin (K) of 96% by mass to 84% by mass. When the content of the slidability improving agent (H) is 4% by mass or more, the slidability improving effect of the sliding member is sufficient, and when it is 16% by mass or less, the coloring property (pigment coloring property) and the molded appearance of the sliding member are good.

The thermoplastic resin composition is more preferably a content of the slidability improver (H) of 5.1% by mass to 16% by mass, and a content of the thermoplastic resin (K) of 94.9% by mass to 84% by mass. The thermoplastic resin composition is particularly preferably a content of the slidability improver (H) of 7 mass% to 15 mass%, and a content of the thermoplastic resin (K) of 93 mass% to 85 mass%.

The above resin composition may contain, for example, the following components within the range which does not impair the original purpose. Reinforcing materials or fillers such as glass fiber, metal fiber, metal flake, carbon fiber; 2,6-di-butyl-4-methylphenol, 4,4 ' -butylene-bis(3-methyl-6- Phenolic antioxidants such as tributyl phenol); three (mixed phenyl, monophenyl and dinile phenyl) phosphites, diphenyl. Phosphite-based antioxidants such as isodecyl phosphite; dilauryl thiodipropionate, dimyristyl thiodipropionate, a sulfur-based antioxidant such as thiodipropionate; a benzotriazole system such as 2-hydroxy-4-octyloxydiphenyl ketone or 2-(2-hydroxy-5-methylphenyl)benzotriazole Ultraviolet absorber; light stabilizer such as bis((2,2,6,6)-tetramethyl-4-piperidinyl); antistatic agent such as hydroxyalkylamine or sulfonate; ethylenebisstearylamine , metal soap and other lubricants; and tetrabromophenol A, decabromophenol oxide, tetrabromobisphenol A (TBA) epoxy oligomer, TBA polycarbonate oligomer, antimony trioxide, phosphoric acid A flame retardant such as phenyl ester (TPP) or phosphate; a polytetrafluoroethylene (hereinafter sometimes abbreviated as "PTFE (Polytetrafluoroethylene)"), a hard polymer obtained by polymerizing a vinyl monomer, and An anti-drip agent such as a modified fluororesin (for example, PTFE modified with a vinyl polymer or the like) in which a fluororesin is mixed.

[Preparation method of resin composition]

The method for producing the thermoplastic resin composition of the second invention group is not particularly limited, but a melt mixing method is preferably used. In addition, a small amount of solvent may be used as needed.

Specifically, it can be prepared by blending a predetermined amount of the slidability improver (H) and the thermoplastic resin (K) as essential components, and optionally The composition is first mixed, for example, using a Henschel mixer, a drum, or the like. Then, the obtained mixture is kneaded by a usual kneader such as a roll, a Banbury mixer, a uniaxial extruder, or a twin-screw extruder. These may be operated in batches or continuously, and the order of mixing the components is not particularly limited.

The thermoplastic resin composition of the present invention preferably has a granular form.

<Formed body>

The molding method of the thermoplastic resin composition of the second invention group includes a usual molding method for molding a thermoplastic resin composition, for example, an injection molding method, an extrusion molding method, a blow molding method, a calender molding method, and the like.

Since the thermoplastic resin composition of the second invention group contains the graft copolymer (G _S ), it is excellent in balance of slidability, color rendering property (pigment coloring property), impact resistance, and molding appearance. The use of the thermoplastic resin composition is not particularly limited, and can be used, for example, in the automotive field, OA machine field, home appliance, and electric. Various materials such as electronics, construction materials, toys, stationery, etc. In particular, since it has excellent balance of slidability, color rendering property, and impact strength, it can be used as a sliding member of the following products, for example. Car, OA machine, electrical. Parts such as electronic machine products, especially business machines. Dynamic machine bearings, gears, switch parts, camera module parts, sliding screws, gears, cams, pulleys, reels, bushes, spacers, rollers, Bearing, bearing retainer, audio tape recorder, tape guide mechanical end face material, valve seat, V-ring, sucker rod Rod packing, piston ring, the rotating shaft of the compressor. Sleeve, piston, impeller, vane, rotor, guide rail, and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. Examples 1 to 14 and Comparative Examples 1 to 17 are related to the first invention group. Examples 21 to 29 and Comparative Examples 21 to 27 were related to the second invention group.

Prior to the examples, various evaluation methods, as well as Production Example 1 to Production Example 3, Production Example 5, and Production Example 6 of the latex of the polyorganosiloxane rubber, and Production Example 4 of the powder containing polytetrafluoroethylene were carried out. Description. In the following description, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated.

The test piece for each evaluation relating to the first invention group was a resin composition obtained by using a 100 t injection molding machine (SE-100DU manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 310 ° C and a mold temperature of 90 ° C. (or its granules) formed.

The test piece for each evaluation relating to the second invention group was a resin composition obtained by using a 100 t injection molding machine (SE-100DU manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C. (or its granules) formed.

<1. Evaluation method>

(1) Graft ratio

The graft ratio [%] was calculated from the above formula (1) based on the mass ratio wa of the acetone-insoluble matter obtained experimentally and the fraction R of the rubber in the additive raw material.

(2) Solid content

The latex of the polyorganosiloxane rubber of mass w _{1 was} dried by a hot air dryer at 180 ° C for 30 minutes, and the mass w ₂ of the residue after drying was measured, and the solid content [%] was calculated by the following formula.

Solid content [%] = w ₂ / w ₁ × 100 (2).

(3) Mass average particle size and particle size distribution (Dw/Dn)

Diluted "Latex of Polyorganosiloxane" or "Latex of Graft Copolymer" into a concentration of about 3% using deionized water as a sample, and manufactured by MATEC. The mass average particle diameter Dw and the particle size distribution (Dw/Dn) of the latex were measured by a CHDF2000 type particle size distribution meter.

The measurement was carried out under the following standard conditions recommended by Martek.

Cartridge: Capillary filter cartridge for particle separation (trade name: C-202)

Carrier solution: special carrier solution (trade name: 2XGR500)

Liquidity of carrier solution: roughly neutral

Flow rate of carrier solution: 1.4 ml/min

Carrier solution pressure: approximately 4,000 psi (2,600 kPa)

Measuring temperature: 35 ° C

Sample usage: 0.1 ml.

Further, as the standard particle diameter material, 12 kinds of particles having a particle diameter ranging from 40 nm to 800 nm are used, and the particles are monodisperse polystyrene having a known particle diameter manufactured by DUKE Corporation. .

(4) Acetone solubles

The following dispersion was centrifuged at 14,000 rpm for 30 minutes at 4 ° C using a centrifugal separator (CRG SERIES (trade name) manufactured by Hitachi, Ltd.), and the dispersion was a powder 1 of a graft copolymer. g Dispersion liquid obtained by dissolving in 50 g of acetone and refluxing and extracting operation at 70 ° C for 6 hours. The separated acetone soluble matter is removed by decantation to obtain an acetone insoluble matter.

A vacuum dryer of the obtained insoluble in acetone for 24 hours to determine the mass of ₃ w insoluble in acetone and dried at 50 ℃, and is calculated by the following formula in the graft copolymer powder acetone soluble [ %].

Acetone solubles [%] = (1-w ₃ ) × 100 (3).

(5) Volume average particle size

The volume average particle diameter of the graft copolymer was determined by the following method.

The latex of the graft copolymer was diluted with deionized water, and then the median diameter in the volume average was determined using a laser diffraction scattering type particle size distribution analyzer (SALD-7100 manufactured by Shimadzu Corporation). The sample concentration of the latex is appropriately adjusted in such a manner as to become an appropriate range in the scattered light intensity monitor attached to the device. As the standard particle diameter material, 12 kinds of particles having a particle diameter of 20 nm to 800 nm which are monodisperse polystyrene having a known particle diameter are used.

(6) Charpy impact strength

Test pieces (length 80.0 mm, width 10.0 mm, thickness 4 mm, with V-notch (notch)) at 23 ° C and -30 ° C according to JIS K 7111 The impact strength of the satay.

(7) Total light transmittance

According to JIS K 7375, the total light transmittance in the D65 light source was measured on a test piece (length 100 mm, width 50 mm, thickness 2 mm) using a HAZE Meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.

(8) Color rendering (pigmentation)

The L* of the test piece (length 100 mm, width 50 mm, thickness 2 mm) was measured in accordance with JIS Z 8729 (representation of the color of the object using the L*a*b* color system). The tristimulus values (XYZ) were measured under the following measurement conditions in accordance with JIS Z8722 using a spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. Then, the L* value was calculated using the Commission Internationale de I'Éclairage (CIE) color difference formula.

Device: Spectrophotometer SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd., 0°-45° split mode)

Measuring range: 380 nm to 780 nm, Determination of light source: C light (2° field of view).

(9) Flame retardancy

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

(10) Appearance (visual evaluation)

Forming a test piece (length 100.0 mm, width 50.0 mm, thickness 2 mm) into a flow mark near the gate (before the gate of the formed body) The appearance of the pattern seen in a stripe shape or the surface roughness was visually observed and evaluated by the following criteria.

++: No flow marks or rough surfaces are visible.

+: Slightly visible flow marks or rough surfaces, but not significant.

-: Flow marks or surface roughness are slightly noticeable.

--: Flow marks or surface roughness are significant.

(11) Appearance (arithmetic mean roughness Ra of the surface of the formed body)

The flat sheet of the test piece (length 100.0 mm, width 50.0 mm, thickness 2 mm) is formed, as shown in Fig. 1, at the point A (near the gate) and the point B (center portion), by the contact surface A roughness meter (Surfcom 1400D manufactured by Tokyo Precision Industries Co., Ltd.) was used, and a surface roughness of the flat plate was measured at a driving speed of 0.3 mm/sec using a 1 μmR, 55° conical diamond needle (010-2528). The measurement length was set to 4 mm, the cutoff wavelength was set to 0.8 mm, and the cutoff category was set to Gaussian. After the inclination correction of the average line of the extraction curve by the least square line is performed, the arithmetic mean roughness (Ra) is measured by the method according to JIS B0601-2001, and is formed as a shape An indicator of the smoothness of the surface of the body.

(12) Slidability

A flat sheet of a test piece (length 100 mm, width 50 mm, thickness 2 mm) was formed, and a pin-plate type friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to mount the load W. [N]: 30 N, moving distance: 20 mm, moving speed: 2 mm/s, measuring temperature: measuring friction force F[N] at 23 ° C, The "dynamic friction coefficient" is measured by the following formula.

Dynamic friction coefficient [-]=F[N]/W[N]...(4).

(13) Chemical resistance

The test piece (length 127 mm, width 12.7 mm, thickness 1.5 mm) was formed, and the evaluation chemicals were applied to the test piece by a 1/4 ellipse method at 23 ° C, and after standing for 48 hours, the test piece was allowed to stand on the test piece. The position of the damage or crack is determined by the following formula to determine the "critical strain (%)". As the evaluation chemical, Mypet manufactured by Kao (share) as a weak alkaline detergent was used.

The "critical strain (%)" refers to the lowest strain that is affected by the chemical when the molded article comes into contact with the chemical under a fixed strain. It can be said that the higher the number of "critical strain (%)", the better the chemical resistance.

A: the long axis of the clamp (12 cm), B: the short axis of the clamp (4 cm), t: the thickness of the test piece (0.15 cm), and the distance from the end of the X: crack to the long axis of the ellipse center [ Cm].

(14) black feeling

The test piece (length 100 mm, width 50 mm, thickness 2 mm) was visually observed and judged by the following criteria.

○: black, ×: Gray.

<Manufacturing example>

[Manufacturing Example 1] Production of latex (S-1) of polyorganosiloxane rubber:

2 parts of tetraethoxy decane (TEOS), 2 parts of γ-methyl propylene methoxy propyl dimethoxymethyl decane (DSMA), and octamethylcyclotetraoxane (Mituto, Japan) (Momentive Performance Materials Japan) (manufactured by Monetive Performance Materials Japan, product name: TSF404) 96 parts were mixed to obtain 100 parts of an organic oxane mixture. An aqueous solution obtained by dissolving 1 part of sodium dodecylbenzenesulfonate (DBSNa) in 150 parts of deionized water was added to the above mixture, and the mixture was stirred at 10,000 rpm for 5 minutes by a homomixer, and then subjected to a pressure of 20 MPa. A stable premixed emulsion was obtained by passing twice in the homogenizer.

Then, after adding the above emulsion to a separable flask having a capacity of 5 liters equipped with a cooling condenser, the emulsion was heated to a temperature of 80 ° C, and then 0.20 parts of sulfuric acid and deionized water 49.8 were continuously supplied over 3 minutes. a mixture of parts. The polymerization was carried out after heating to a temperature of 80 ° C for 6 hours, followed by cooling to room temperature (25 ° C), and the obtained reaction liquid was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction liquid to pH 7.0 to obtain a latex (S-1) of a polyorganosiloxane rubber. The evaluation results of this latex are shown in Table 1.

[Production Example 2] Production of latex (S-2) of polyorganosiloxane rubber:

2 parts of TEOS, 0.5 parts of DSMA, and a mixture of cyclic organoaluminoxanes (manufactured by Shintosu Silicon Co., Ltd., product name: DMC, ring-shaped organic oxirane of 3-membered ring to 6-membered ring) 97.5 parts of the mixture was mixed to obtain 100 parts of an organic oxane mixture. An aqueous solution obtained by dissolving 0.68 parts of sodium dodecylbenzenesulfonate (DBSNa) and 0.68 parts of dodecylbenzenesulfonic acid (DBSH) in 200 parts of deionized water was added to the above mixture, using a homomixer at 10,000. After stirring for 2 minutes at rpm, the mixture was passed twice in a homogenizer at a pressure of 20 MPa to obtain a stable premixed emulsion.

Then, after the emulsion was placed in a separable flask having a capacity of 5 liters equipped with a cooling condenser, the emulsion was heated to a temperature of 85 ° C, and the temperature was maintained for 6 hours, and then polymerization was carried out, followed by cooling to room temperature. (25 ° C) and the obtained reaction was kept at room temperature for 12 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction liquid to pH 7.0 to obtain a latex (S-2) of a polyorganosiloxane rubber. 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 TSF404 were mixed to obtain 100 parts of an organic oxane mixture. An aqueous solution obtained by dissolving 1 part of DBSNa in 170 parts of deionized water was added to the above mixture, and the mixture was stirred at 10,000 rpm for 5 minutes by a homomixer, and then passed through a homogenizer twice at a pressure of 20 MPa. Stable premixed emulsion.

Then, after adding the above emulsion to a separable flask having a capacity of 5 liters with a cooling condenser, the emulsion was heated to a temperature of 80 ° C, and then, for 3 minutes. The mixture was continuously charged with a mixture of 0.20 parts of sulfuric acid and 14.7 parts of deionized water. The polymerization was carried out after heating to a temperature of 80 ° C for 6 hours, followed by cooling to room temperature (25 ° C), and the obtained reaction liquid was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction liquid to pH 7.0 to obtain a latex (S-3) of a polyorganosiloxane rubber. The evaluation results of this latex are shown in Table 1.

[Production Example 4] Production of powder (J-1) containing polytetrafluoroethylene:

6.0 parts of ethylenic acid dipotassium sulphate as an emulsifier and 230 parts of deionized water were added to a separable flask having a capacity of 2 liters equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen gas introduction port, and nitrogen gas was used. It was stirred under air flow for 30 minutes at room temperature. Further, the above-described dipotassium alkenyl succinate is used in a state of being dissolved in a part of the above deionized water in advance.

Then, the temperature of the liquid in the flask was raised to 70 ° C, and then an aqueous solution obtained by dissolving 0.2 part of potassium persulfate in 3 parts of deionized water was added to the flask. Further, a mixture containing 50 parts of methyl methacrylate (MMA), 30 parts of styrene (St), 20 parts of n-butyl acrylate (n-BA), and 0.1 part of n-octyl mercaptan was added dropwise over 4 hours. In the flask, radical polymerization was carried out. After the completion of the dropwise addition, the temperature of the liquid in the flask was maintained at 70 ° C for 1 hour, and a latex (p2-1) containing a vinyl polymer (p2) was obtained. The content of the vinyl polymer (p2) in the latex was 30%.

In the reactor having a capacity of 5 liters equipped with a stirring device, 166.7 parts of the above-mentioned latex (p2-1) and "Fluon AD939E" (made of Asahi Glass Co., Ltd.), PTFE, which is a latex containing a PTFE-based polymer (p1), were added. 60% concentration, PTFE The mass average molecular weight was about 15 million, and the concentration of polyoxyalkylene alkyl ether was 3%) 83.3 parts, and the mixture was stirred for 5 minutes to obtain a latex (j-1). The latex contained 50 parts of PTFE, 2.5 parts of polyoxyalkylene alkyl ether, and 50 parts of the above vinyl polymer (p2).

Then, 325 parts of an aqueous calcium acetate solution containing 5.0 parts of calcium acetate as a coagulating agent was added to a flask having a capacity of 10 liters. After the aqueous solution was heated to a temperature of 80 ° C, the latex (j-1) was slowly added dropwise to the aqueous solution while stirring, and the polymer was coagulated to obtain a slurry. Thereafter, the temperature of the slurry was raised to 90 ° C, and stirring was continued for 5 minutes. Then, the obtained precipitate was separated from the slurry, filtered, washed with water, and dried to obtain 100 parts of a powder (J-1) containing polytetrafluoroethylene.

[Production Example 5] Production of polyorganosiloxane (Latex) (S-4):

2 parts of tetraethoxy decane (TEOS), 0.5 parts of γ-methyl propylene methoxy propyl dimethoxymethyl decane (DSMA), and octamethylcyclotetraoxane (Mituto, Japan) 97.5 parts of the product manufactured by the company, product name: TSF-404) was mixed, and 100 parts of a mixture of a naphthenic mixture was obtained. 150 parts of deionized water in which 1.0 part of sodium dodecylbenzenesulfonate (DBSNa) was dissolved was added thereto, and stirred at 10,000 rpm for 5 minutes by a homomixer, and then passed through a homogenizer twice at a pressure of 20 MPa. A stable premixed organic alkane emulsion is obtained.

The emulsion was placed in a separable flask having a capacity of 5 liters equipped with a cooling condenser, and a mixture of 0.20 parts of sulfuric acid and 49.8 parts of deionized water was introduced over 3 minutes. The aqueous solution was maintained at 80 ° C for 7 hours and then cooled to room temperature (25 ° C). Then, after the reaction was kept at room temperature for 6 hours, 10% hydrogen was used. An aqueous solution of sodium oxide was added to neutralize to pH 7.0 to obtain a latex (S-4) of polyorganosiloxane. The evaluation results of this latex are shown in Table 1.

[Manufacturing Example 6] Production of polyorganosiloxane (S-5):

In a mixture of 2 parts of TEOS, 0.5 parts of DSMA, and 97.5 parts of a cyclic organooxane mixture (manufactured by Shin-Etsu Chemical Co., Ltd., product name: DMC), 100 parts of an organic siloxane mixture was obtained. To this was added 300 parts of deionized water in which 0.68 parts of DBSNa was dissolved, and the mixture was stirred at 10,000 rpm for 2 minutes using a homomixer, and then passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion.

On the other hand, 10 parts of dodecylbenzenesulfonic acid (DBSH) and 90 parts of deionized water were poured into a separable flask having a capacity of 5 liters equipped with a cooling condenser to prepare an aqueous solution.

The premixed emulsion was added dropwise to the aqueous solution heated to 90 ° C over 4 hours, and after the completion of the dropwise addition, the temperature was maintained for 2 hours, and then cooled to room temperature (25 ° C). Then, the reactant was maintained at room temperature for 12 hours, and then neutralized to pH 7.0 with a 10% aqueous sodium hydroxide solution to obtain a latex (S-5) of polyorganosiloxane. The evaluation results of this latex are shown in Table 1.

[Example 1]

79.7 parts of the latex (S-1) of the polyorganosiloxane rubber obtained in Production Example 1 was extracted into a separable flask having a capacity of 5 liters in terms of a polymer, and 46 parts of deionized water was added thereto. mixing. Then, 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 to the separable flask.

Nitrogen gas exchange in the atmosphere of the flask was carried out by circulating a nitrogen gas stream in the separable flask, and then the temperature of the liquid was raised to 50 °C. When the liquid temperature became 50 ° C, 0.001 parts of ferrous sulfate (Fe), 0.003 parts of ethylenediaminetetraacetic acid disodium salt (EDTA), and 0.18 parts of sodium formaldehyde sulfoxylate (SFS) were dissolved in deionized water. The aqueous solution was formed in 4.2 parts, and radical polymerization was started. In order to complete the polymerization of the acrylate component, the liquid temperature was maintained at 70 ° C for 1 hour to obtain a latex of a composite rubber of polyorganosiloxane and polybutyl acrylate.

In the state where the temperature of the latex of the above composite rubber was maintained at 70 ° C, a mixed droplet of 9.5 parts of MMA, 0.5 part of n-BA, and 0.03 part of t-butyl hydroperoxide (t-BH) was added over 1.0 hour. Polymerization was carried out in the latex. After completion of the dropwise addition, the liquid temperature was maintained at 70 ° C for 1 hour, and then cooled to 25 ° C to obtain a latex of a polyorganosiloxane-containing graft copolymer (G-1). The volume average particle diameter of the graft copolymer (G-1) is shown in Table 2.

Then, 500 parts of an aqueous solution having a calcium acetate concentration of 1% by mass was maintained at a temperature of 40 ° C while stirring, and 300 parts of the latex in which the graft copolymer (G-1) was gradually added dropwise thereto was solidified. The obtained graft copolymer was subjected to filtration and dehydration. Further, 10 times of water was added to 100 parts of the graft copolymer, and then washed in a flask equipped with a stirrer for 10 minutes, followed by filtration and dehydration. This operation was repeated twice, and then dried to obtain a powder of the graft copolymer (G-1). The graft ratio and volume average particle diameter of the graft copolymer (G-1) are shown in Table 2.

[Example 2 and Example 3, Comparative Example 1 to Comparative Example 3, and Comparative Example 5]

The type and amount of each raw material used in Example 1 were changed as shown in Table 2. In addition to the conditions of Example 1, a polyorganosiloxane-containing graft copolymer (G-2, G-3, G'-1, G'-2, G'-3, and G) was produced in the same manner as in Example 1. '-5), and further obtained its powder. The graft ratio and volume average particle diameter of each of the obtained graft copolymers are shown in Table 2.

[Example 4]

90 parts of the latex (S-1) of the polyorganosiloxane rubber obtained in Production Example 1 was extracted into a separable flask having a capacity of 5 liters in terms of a polymer, and 46 parts of deionized water was added thereto. mixing. Then, a mixture of 0.5 part of AMA and 0.07 part of CHP was added to the separable flask. Nitrogen gas exchange in the atmosphere of the flask was carried out by circulating a nitrogen gas stream in the separable flask, and then the temperature of the liquid was raised to 50 °C. At the time when the liquid temperature became 50 ° C, an aqueous solution obtained by dissolving 0.001 parts of ferrous sulfate (Fe), 0.003 parts of EDTA, and 0.18 parts of SFS in 4.2 parts of deionized water was added to start radical polymerization. In order to complete the polymerization of the allyl methacrylate component, the liquid temperature was maintained at 70 ° C for 1 hour. In this manner, the graft polymerization in the first stage was carried out. Thereafter, a mixed liquid of 9 parts of MMA, 0.5 part of n-BA, and 0.1 part of CHP was added dropwise over 1.0 hour to carry out polymerization. In this manner, the second stage graft polymerization was carried out. Then, the state in which the liquid temperature was 70 ° C was maintained for 1 hour, and then cooled to 25 ° C to obtain a latex of a polyorganosiloxane-containing graft copolymer (G-4). The graft ratio and volume average particle diameter of the graft copolymer (G-4) are shown in Table 2. Thereafter, a powder of the graft copolymer (G-4) was obtained in the same manner as in Example 1.

[Example 5]

The type and amount of each raw material used in Example 4 were changed as shown in Table 2. A polyorganosiloxane-containing graft copolymer (G-5) was produced in the same manner as in Example 4 except that the conditions were the same, and a powder thereof was obtained. The graft ratio and volume average particle diameter of the obtained graft copolymer are shown in Table 2.

[Comparative Example 4]

A latex of a composite rubber of polyorganosiloxane and n-butyl acrylate was obtained in the same manner as in Example 1 except that the kind and amount of each raw material used in Example 1 were changed to those shown in Table 2.

In a state where the temperature of the latex of the above composite rubber was maintained at 65 ° C, a mixed liquid of 5.0 parts of AMA and 0.3 parts of CHP was charged to carry out polymerization. In this manner, the graft polymerization in the first stage was carried out. After the introduction, the liquid temperature was maintained at 65 ° C for 1 hour, and then a mixed liquid of 15.0 parts of phenyl methacrylate (PhMA) and 0.2 part of CHP was added dropwise thereto over 10 minutes to carry out polymerization. In this manner, the second stage graft polymerization was carried out. Then, the liquid temperature was maintained at 65 ° C for 1 hour, and then cooled to 25 ° C to obtain a latex of a polyorganosiloxane-containing graft copolymer (G'-4). The graft ratio and volume average particle diameter of the graft copolymer (G'-4) are shown in Table 2.

Thereafter, a powder of the graft copolymer (G'-4) was obtained in the same manner as in Example 1. The graft ratio and volume average particle diameter of the obtained graft copolymer are shown in Table 2.

[Example 6 to Example 12, Comparative Example 6 to Comparative Example 15]

The graft copolymers (G-1, G- obtained in Example 1, Example 3, Example 4, Example 5 or Comparative Examples 1 to 5) were blended in the amounts described in Table 3 or Table 4. 3, G-4, G-5, G'-1~G'-5) powder, organic sulfonic acid metal salt (made by Di Aisheng (DIC) (share), trade name: Megafac F-114), as Anti-drip agent Polytetrafluoroethylene-containing powder J-1 obtained in Production Example 3, and polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name; Iupilon S-2000F, viscosity average molecular weight: 22,000), and A phenolic antioxidant (manufactured by Ciba Japan Co., Ltd., trade name: Irganox 245), and a phosphorus-based antioxidant (manufactured by Eddy Co., Ltd., trade name: Adekastab PEP36). The compound was melt-mixed using a twin-screw extruder (L/D=30) having a cylinder inner diameter of 30 mm at a cylinder temperature of 280 ° C and a screw speed of 150 rpm to obtain a polycarbonate resin composition. Things. Then, the polycarbonate resin composition is formed into pellets.

The obtained pellets were dried at 80 ° C for 12 hours, and then supplied to a 100 t injection molding machine (manufactured by Sumitomo Heavy Industries Co., Ltd., trade name; SE-100DU) at a cylinder temperature of 280 ° C and a mold of 90 ° C. The temperature was subjected to injection molding to obtain each test piece. Then, using each test piece, the measurement of the sand impact strength, the measurement of the total light transmittance, and the UL-94V test were performed, and the evaluation results shown in Table 3 or Table 4 were obtained.

[Example 13, Example 14, Comparative Example 16, Comparative Example 17]

Powders and aromatic phosphates of the graft copolymers (G-1, G-2, G'-1) obtained in Example 1, Example 2 or Comparative Example 1 were blended in the amounts shown in Table 5. Flame retardant (manufactured by Daiha Chemical Industry Co., Ltd., trade name: PX-200), powdered polytetrafluoroethylene-containing powder J-2 (anti-drip agent), manufactured by Mitsubishi Rayon Co., Ltd., trade name : Metablen A-3800), and polycarbonate resin (Iupilon S-2000F). A polycarbonate resin composition and each test piece were obtained in the same manner as in Example 6 except for the above. The evaluation results are shown in Table 5.

[Comparison of performance of resin composition of the first invention group]

The resin composition of Example 6 in which 1.0 part of the graft copolymer (G-1) was blended was more excellent in flame retardancy, impact resistance, and total light transmittance than the resin composition of Comparative Example 6. In addition, it was found that the resin composition of Example 7 in which 3.1 parts of the graft copolymer (G-1) was blended was more excellent in flame retardancy, impact resistance, and total light transmittance than the resin composition of Comparative Example 7. It is understood that Example 8 of the graft copolymer (G-1), the graft copolymer (G-3), the graft copolymer (G-4), or the graft copolymer (G-5) is blended with 5.3 parts. The resin composition of Example 11 was more excellent in flame retardancy, impact resistance, total light transmittance, and appearance balance than the resin compositions of Comparative Examples 8 to 11. The resin composition of Comparative Example 8 has a volume average particle diameter of the graft copolymer (G'-1) of less than 300 nm, and the polyorganosiloxane (B1) is derived from a component of a decane compound containing a vinyl polymerizable group. Since the content is less than 1% by mass, the flame retardancy, the total light transmittance, and the appearance in the vicinity of the gate are low. In the resin composition of Comparative Example 9, since the content of the polyorganosiloxane of the graft copolymer (G'-2) was less than 70% by mass, the flame retardancy was low. The resin composition of Comparative Example 10 had a graft ratio of the graft copolymer (G'-3) of more than 10% by mass, and the amount of the polyfunctional vinyl monomer used was 0% by mass, and did not contain the polyalkyl acrylate. Since the ester (B2) is low in flame retardancy, low-temperature impact strength, and appearance near the gate. In the resin composition of the comparative example 11, the content of the component derived from the decane compound containing the vinyl polymerizable group in the polyorganosiloxane (B1) of the graft copolymer (G'-5) is less than 1% by mass. Flame retardancy, low-temperature impact strength, total light transmittance, and appearance near the gate are low. Since the resin composition of Comparative Example 12 did not contain a graft copolymer, the impact strength was low.

It is understood that the resin composition of Example 12 in which 10.0 parts of the graft copolymer (G-1) was blended had flame retardancy, impact strength, total light transmittance, and the resin composition of Comparative Example 13 to Comparative Example 15, The balance between slidability and chemical resistance is superior. In the resin composition of Comparative Example 13, since the content of the polyorganosiloxane in the graft copolymer (G'-2) was less than 70% by mass, the flame retardancy and the slidability were low. The resin composition of Comparative Example 14 has less than 5% by mass of acetone-soluble matter of the graft copolymer (G'-4) and a graft ratio of more than 10% by mass, so flame retardancy, slidability, and chemical resistance. Sex is low grade. Since the resin composition of Comparative Example 15 does not contain a graft copolymer, low-temperature impact strength, slidability, and chemical resistance are low.

When the phosphorus-based flame retardant was used, the resin compositions of Examples 13 and 14 were more excellent in flame retardancy and low-temperature impact resistance than the resin composition of Comparative Example 16. The resin composition of the comparative example 16 has a volume average particle diameter of the graft copolymer (G'-1) of less than 300 nm, and the polyorganosiloxane (B1) is derived from a component of a decane compound containing a vinyl polymerizable group. The content is less than 1% by mass, so the flame retardancy and low-temperature impact strength are low. Further, since the resin composition of Comparative Example 17 did not contain a graft copolymer, the flame retardancy and the low-temperature impact strength were low.

The following is an example of the second invention group.

[Example 21]

272.1 parts of a polyorganosiloxane (S-4) obtained in Production Example 5 was placed in a separable flask having a capacity of 5 liters equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirring device (polyorganoindene). The oxane is 80 parts). Further, adding deionized After mixing 50 parts of water, a mixture of 10.0 parts of butyl acrylate (n-BA), 0.18 parts of allyl methacrylate (AMA), and 0.04 parts of cumene hydroperoxide (CHP) was added.

Nitrogen gas exchange in the atmosphere of the flask was carried out by circulating a nitrogen gas stream in a separable flask, and then the temperature was raised to 60 °C. The liquid temperature was changed to 60 ° C, and an aqueous solution containing 0.001 parts of ferrous sulfate (Fe), 0.003 parts of ethylenediaminetetraacetic acid disodium salt (EDTA), 0.3 parts of sodium formaldehyde sulfoxylate (SFS), and 2.5 parts of deionized water was added. Thereafter, the liquid temperature was maintained at 70 ° C for 1 hour to obtain a latex of a composite rubber.

While maintaining the temperature of the latex of the above composite rubber at 70 ° C, 9.5 parts of methyl methacrylate (MMA), 0.5 part of butyl acrylate (n-BA), and a third butyl peroxide were added dropwise over 60 minutes. A mixture of hydrogen (t-BH) of 0.05 parts was used for the polymerization.

After completion of the dropwise addition, the liquid temperature was maintained at 70 ° C for 1 hour, and then cooled to 25 ° C to obtain a latex of the graft copolymer (G-21). Table 6 shows the measurement results of the mass average particle diameter Dw and the particle diameter distribution Dw/Dn of the graft copolymer in the latex.

Then, 500 parts of an aqueous solution having a calcium chloride concentration of 5.0% by mass was heated to a temperature of 60 ° C and stirred. 340 parts of the above latex was slowly added dropwise thereto and allowed to solidify. The obtained graft copolymer was subjected to filtration and dehydration. Further, 10 times of water was added to 100 parts of the graft copolymer, and then washed in a flask equipped with a stirrer for 10 minutes, followed by filtration and dehydration. This operation was repeated twice, and then dried to obtain a powder of the graft copolymer (G-21). The powder of the graft copolymer (G-21) can be used as a slidability improver.

[Example 22]

3 parts of the graft copolymer (G-21) obtained in Example 21, 97 parts of PC resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Iupilon S-2000F), carbon black (manufactured by Mitsubishi Chemical Corporation) 960B) Manual mixing. The obtained resin composition was melt-mixed using a 30 mmφ twin-screw extruder (L/D = 30) at a cylinder temperature of 280 ° C and a screw rotation speed of 150 rpm to form pellets.

The obtained pellets were dried at 80 ° C for 12 hours, and then supplied to a 100 t injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name; SE-100DU) at a cylinder temperature of 280 ° C and 80 ° C. The mold temperature is injection molded. Use of a family mold according to JIS K7152 to obtain sand impact strength (length 80.0 mm, width 10.0 mm, thickness 4 mm, with V-notch), slidability, color rendering (length 100 mm) Each test piece for evaluation of 50 mm in width and 2 mm in thickness). The various evaluation results of the particles used and the respective test pieces are shown in Table 7.

[Example 23 and Example 24]

A thermoplastic resin composition, pellets, and test pieces were obtained in the same manner as in Example 22 except that the amounts of the graft copolymer (G-21) and the PC resin were changed. The various evaluation results are shown in Table 7.

[Example 25]

Polymerization was carried out in the same manner as in Example 21 except that the composition shown in Table 6 was changed to obtain a graft copolymer (G-25). The evaluation results of the graft copolymer are shown in Table 6.

[Examples 26 to 29]

The amount of the graft copolymer (G-25) and PC resin used is set as shown in Table 7. The thermoplastic resin composition, the pellet, and the test piece were obtained in the same manner as in Example 21 except for the value. The various evaluation results are shown in Table 7.

[Comparative Example 21]

The graft copolymer (G'-21) was obtained in the same manner as in Example 21 except that the raw materials in the graft polymerization were set to the compositions shown in Table 6. The evaluation results of the graft copolymer are shown in Table 6.

[Comparative Example 22 and Comparative Example 23]

A thermoplastic resin composition, pellets, and test pieces were obtained in the same manner as in Example 21 except that the amounts of the graft copolymer (G'-21) and the PC resin were used as the values shown in Table 7. The various evaluation results are shown in Table 7.

[Comparative Example 24]

A graft copolymer (G'-24) was obtained in the same manner as in Example 21 except that the raw materials in the graft polymerization were set to the compositions shown in Table 6. The evaluation results of the graft copolymer are shown in Table 6.

[Comparative Example 25 to Comparative Example 27]

A thermoplastic resin composition, pellets, and test pieces were obtained in the same manner as in Example 21 except that the amounts of the graft copolymer (G'-24) and the PC resin were used as the values shown in Table 7. The various evaluation results are shown in Table 7.

[Comparison of performance of resin composition of the second invention group]

As is clear from the examples 22 to 24 and the examples 26 to 29, the thermoplastic resin composition using the slidability improver of the present invention is excellent in slidability, and further, color developability and sand impact strength. And the formed appearance has also been well received. result.

On the other hand, in the thermoplastic resin composition of Comparative Example 22 and Comparative Example 23, since the content of the polyorganosiloxane in the slidability improver used was small, the slidability and the sand impact strength at low temperatures were low. In the thermoplastic resin compositions of Comparative Example 25 and Comparative Example 26, since the mass average particle diameter of the slidability improver used is small, color rendering properties are low, and flow marks are likely to occur in the vicinity of the gate during molding, resulting in poor molding appearance. . In the thermoplastic resin of Comparative Example 27, since the slidability improver was not used, the slidability was low, and the sand impact strength at a low temperature was also remarkably inferior.

[Industrial availability]

Flame retardancy, impact resistance, color rendering property, slidability, and resistance of the resin composition obtained by blending the graft copolymer (G _F ) of the first invention group into a thermoplastic resin (particularly, a polycarbonate resin) Excellent chemical properties. The resin composition is used in the field of OA equipment such as the automotive field, printing machine, and mobile phones. Materials such as electronics are useful.

The slidability, color developability (pigment coloring property), and impact strength of the resin composition obtained by blending the slidability improver of the powder containing the graft copolymer (G _S ) in the thermoplastic resin to the second invention group Excellent balance and good appearance. The molded article obtained from the resin composition can be widely used for automobiles, building materials, toys, stationery, and the like, and can be widely used in various fields including OA machines and home electric appliances, and can be used as a sliding member.

1‧‧‧ gate

A, B‧‧‧ measuring points

Claims (22)

A rubber-containing graft copolymer (G _F1 ) which is a rubber-containing graft copolymer obtained by graft-polymerizing a rubber containing polyorganosiloxane (B1) with one or more kinds of vinyl monomers The content of the component derived from the decane compound containing a vinyl polymerizable group in the polyorganosiloxane (B1) is 1% by mass to 10% by mass, and the volume average particle diameter of the rubber-containing graft copolymer is 300%. The content of the polyorganosiloxane (B1) in the rubber-containing graft copolymer is 70% by mass to 98% by mass, and the graft ratio determined by the following formula (1) is from nm to 2000 nm. 10% by mass or less, Wa: mass of the acetone insoluble matter of the sample (g), wo: total amount of the sample (g), and R: fraction of the rubber containing the polyorganosiloxane (B1) in the additive raw material at the time of producing the graft copolymer (quality%). A rubber-containing graft copolymer (G _F2 ) which is a composite rubber containing polyorganosiloxane (B1) and polyalkyl (meth)acrylate (B2) and one or more vinyl monomers a rubber-containing graft copolymer obtained by graft polymerization, wherein the content of the component derived from the decane compound containing a vinyl polymerizable group in the polyorganosiloxane (B1) is 1% by mass to 10% by mass, The rubber-containing graft copolymer has a volume average particle diameter of 300 nm to 2000 nm, and the content of the polyorganosiloxane (B1) in the rubber-containing graft copolymer is 70% by mass to 98% by mass, and The acetone soluble matter is 5.0% by mass or more and 30.0% by mass or less. A rubber-containing graft copolymer (G _F3 ) which is a rubber-containing graft copolymer obtained by graft-polymerizing a rubber containing polyorganosiloxane (B1) with one or more kinds of vinyl monomers The content of the component derived from the decane compound containing a vinyl polymerizable group in the polyorganosiloxane (B1) is 1% by mass to 10% by mass, and the volume average particle diameter of the rubber-containing graft copolymer is 300%. The content of the polyorganosiloxane (B1) in the rubber-containing graft copolymer is 70% by mass to 98% by mass, and the content of the component derived from the polyfunctional vinyl monomer exceeds nm to 2000 nm. 0% by mass, less than 5% by mass. The rubber-containing graft copolymer according to any one of claims 1 to 3, wherein the volume average particle diameter is from 400 nm to 1000 nm. The rubber-containing graft copolymer according to claim 2, wherein the ratio of the polyorganosiloxane (B1) to the polyalkyl (meth)acrylate (B2) is "B1/B2" "74/26~99/1" mass%. A thermoplastic resin composition containing the rubber-containing graft copolymer according to any one of claims 1 to 3, in an amount of 0.1 part by mass to 12 parts by mass, based on 100 parts by mass of the thermoplastic resin (A). The fluorine-based resin (C) is 0.01 parts by mass to 5 parts by mass, and the flame retardant (D) is 0.01 parts by mass to 10 parts by mass. The thermoplastic resin composition according to claim 6, wherein the thermoplastic resin (A) is a thermoplastic resin having at least one bond selected from the group consisting of a carbonate bond, an ester bond, and a guanamine bond. The thermoplastic resin composition according to claim 6, wherein the thermoplastic resin (A) is a polycarbonate resin. The thermoplastic resin composition according to claim 6, wherein the flame retardant (D) contains at least one flame retardant selected from the group consisting of a phosphorus-based flame retardant and an organic metal salt-based flame retardant. A molded body obtained by molding a thermoplastic resin composition as described in claim 6 of the patent application. A slidability improver comprising a rubber-containing graft copolymer (G _S ) powder obtained by graft-polymerizing a rubber containing a polyorganosiloxane and one or more kinds of vinyl monomers, and the above-mentioned content The content of the polyorganosiloxane in the graft copolymer (G _S ) of the rubber is 40% by mass to 95% by mass, and the mass average particle diameter Dw of the latex of the rubber-containing graft copolymer (G _S ) is 300. Nm~2000 nm. The slidability improver according to claim 11, wherein the latex particle size distribution (mass average particle diameter Dw/number average particle diameter Dn) of the rubber-containing graft copolymer (G _S ) is 1.0~ 2.0. The slidability improver according to claim 11, wherein the content of the polyorganosiloxane in the rubber-containing graft copolymer (G _S ) is from 41% by mass to 74% by mass. The slidability improver according to claim 11, wherein the rubber-containing graft copolymer (G _S ) has a mass average particle diameter Dw of 400 nm to 1000 nm. Slidability as described in any one of claims 11 to 14 The modifier, wherein the polyorganosiloxane containing rubber is a composite rubber comprising a polyorganosiloxane and a polyalkyl acrylate. A thermoplastic resin composition for a sliding member, which comprises the slidability improver and the thermoplastic resin according to any one of claims 11 to 14. A thermoplastic resin composition for a sliding member, which comprises the slidability improver according to item 15 of the patent application and a thermoplastic resin. The thermoplastic resin composition for a sliding member according to claim 16, wherein the content of the slidability improver is 4% by mass to 16% by mass, and the content of the thermoplastic resin is 96% by mass to 84% by mass. The thermoplastic resin composition for a sliding member according to claim 16, wherein the content of the slidability improver is from 5.1% by mass to 16% by mass, and the content of the thermoplastic resin is from 9.9% by mass to 84% by mass. The thermoplastic resin composition for a sliding member according to claim 16, wherein the content of the slidability improver is 7 mass% to 15 mass%, and the content of the thermoplastic resin is 93 mass% to 85% mass%. The thermoplastic resin composition for a sliding member according to claim 16, wherein the thermoplastic resin is a polycarbonate resin. A sliding member formed by molding a sliding member for a sliding member according to claim 16 of the patent application.