JP2017088737A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which gives a molded article excellent in impact resistance and optical characteristics.SOLUTION: The polycarbonate resin composition contains a polycarbonate resin (A), a polycarbonate-organosiloxane copolymer (B) having specific constituent units, and a rubber-containing graft copolymer (C) obtained by graft-polymerizing a vinyl monomer (c2) onto a polyorganosiloxane-based rubber (C1). The proportion of the polyorganosiloxane-based rubber (C1) is 80-99 mass% in 100 mass% of the total of the polyorganosiloxane-based rubber (C1) and the vinyl monomer (c2). The rubber-containing graft copolymer (C) is contained in an amount of 0.1-2.8 pts.mass based on 100 pts.mass of the total of the polycarbonate resin (A) and the polycarbonate-organosiloxane copolymer (B).SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded body.

Polycarbonate resins are general-purpose engineering plastics that are excellent in transparency, impact resistance, heat resistance, and the like, and are therefore used as materials for automobile members, OA equipment members, electrical and electronic members, and the like.
In recent years, these materials tend to be used with a reduced thickness for the purpose of reducing the size and weight. In order to develop sufficient impact resistance even when the material is thinned, an example using a resin composition in which a polyorganosiloxane rubber is blended with a polycarbonate resin is disclosed in the following Patent Document 1. It is disclosed. However, although the molded body made of the polycarbonate resin composition described in Patent Document 1 is improved in impact resistance, it is inferior in optical properties, and thus its use is limited.

JP 2004-331726 A

  The present invention provides a polycarbonate resin composition that provides a molded article excellent in impact resistance and optical properties.

The present invention has the following aspects.
[1] Polycarbonate resin (A),
A polycarbonate-organosiloxane copolymer (B) having a structural unit represented by the chemical formula (I) and a structural unit represented by the chemical formula (II), and a vinyl monomer (c2) to the polyorganosiloxane rubber (C1) A polycarbonate resin composition comprising a rubber-containing graft copolymer (C) obtained by graft polymerization,
The proportion of the polyorganosiloxane rubber (C1) is 80 to 99% by mass in a total of 100% by mass of the polyorganosiloxane rubber (C1) and the vinyl monomer (c2),
A polycarbonate resin composition comprising 0.1 to 2.8 parts by mass of a rubber-containing graft copolymer (C) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polycarbonate-organosiloxane copolymer (B).

式中、Ｘは炭素数１〜８のアルキレン基、炭素数２〜８のアルケニレン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルケニレン基、炭素数６〜１２のアリーレン基、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−Ｏ−、または−ＣＯ−を示し、Ｒ_１およびＲ_２はそれぞれ独立に水素原子または炭素数１〜８のアルキル基を示し、ｍは平均繰り返し数を示す。

式中、Ｒ_３およびＲ_４はそれぞれ独立に、水素原子、ハロゲン原子、または炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数６〜１２のアリール基を示し、ｎは平均繰り返し数を示す整数である。

In the formula, X is an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkenylene group having 5 to 15 carbon atoms, or an arylene having 6 to 12 carbon atoms. Group, —S—, —SO—, —SO ₂ —, —O—, or —CO—, each of R ₁ and R ₂ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m Indicates the average number of repetitions.

In the formula, R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n Is an integer indicating the average number of repetitions.

[2] The polycarbonate resin composition according to [1], wherein the structural unit represented by the chemical formula (I) is a structural unit represented by the chemical formula (III).

式中、ｍは平均繰り返し数を示す。

In the formula, m represents the average number of repetitions.

[3] The polycarbonate resin composition according to [1] or [2], wherein the average repeating number n of the structural unit represented by the chemical formula (II) is 1 to 40.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the structural unit represented by the chemical formula (II) is a structural unit represented by the chemical formula (IV).

[5] The proportion of the polycarbonate-organosiloxane copolymer (B) is 1 to 50% by mass in a total of 100% by mass of the polycarbonate resin (A) and the polycarbonate-organosiloxane copolymer (B). The polycarbonate resin composition according to any one of [1] to [4].
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the polyorganosiloxane rubber (C1) is an organosiloxane-acrylic composite rubber.
[7] The polycarbonate resin composition according to any one of [1] to [6], wherein the vinyl monomer (c2) includes a (meth) acrylic acid ester monomer.
[8] A molded article comprising the polycarbonate resin composition according to any one of [1] to [7].

  The polycarbonate resin composition of the present invention can give a molded article excellent in impact resistance and optical properties.

The following definitions of terms apply throughout this specification and the claims.
“Structural unit” means that in a polymer formed by polymerizing monomers, a structural unit derived from the monomer and a part of the structural unit is converted into another structure by treating the polymer. Is a structured unit.
The “mass average molecular weight” is a polystyrene equivalent mass average molecular weight measured by gel permeation chromatography (GPC).
“(Meth) acrylate” is a general term for acrylate and methacrylate.

(Polycarbonate resin (A))
The polycarbonate resin (A) is not particularly limited as long as it is a polymer compound having a carbonate ester bond (—O—C (O) —O—) in the main chain.
As the polycarbonate resin (A), an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor is usually mentioned. Specifically, what was manufactured by making bivalent phenol and a carbonate precursor react by a solution method or a melting method is mentioned. More specifically, those produced by reacting dihydric phenol with phosgene and those produced by reacting dihydric phenol with diphenyl carbonate and the like by a transesterification method can be mentioned.
In the present specification, the dihydric phenol refers to a compound having two phenolic hydroxy groups in the molecule.

Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and 2,2-bis ( 3,3-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethyl) Phenyl) propane, bis (hydroxyaryl) alkanes such as 4,4′-dihydroxydiphenyl, bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis ( 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, Examples thereof include bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, and halogen-substituted products thereof. In addition to these, examples of the dihydric phenol include hydroquinone, resorcin, and catechol.
As the dihydric phenol, bis (hydroxyphenyl) alkane is preferable, and bisphenol A is particularly preferable from the viewpoint of cost.
A dihydric phenol may be used individually by 1 type and may use 2 or more types together.

Examples of the carbonate precursor include carbonyl dihalide, carbonyl diester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.
A carbonate precursor may be used individually by 1 type, and may use 2 or more types together.

  The polycarbonate resin (A) may have a branched structure. As a branching agent for introducing a branched structure into the polycarbonate resin (A), 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1 , 3,5-triisopropylbenzene, phloroglycine, trimellitic acid, isatin bis (o-cresol) and the like.

The polycarbonate resin (A) is obtained by reacting a dihydric phenol and a carbonate precursor in the presence of an ester precursor (a compound having two carboxyl groups in the molecule such as terephthalic acid or an ester-forming derivative thereof). It may be a polyester-polycarbonate resin.
The polycarbonate resin (A) may be a mixture of various polycarbonate resins.

In the production of the polycarbonate resin (A), phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, or the like may be used to adjust the molecular weight.
The viscosity average molecular weight of the polycarbonate resin (A) can be calculated by a viscosity method, preferably 15,000 to 30,000, and more preferably 17,000 to 25,000. If the viscosity average molecular weight is within the above range, the moldability of the polycarbonate resin composition tends to be excellent.
Examples of the viscosity method include a measurement method using an Ubbelohde viscometer at 20 ° C. in methylene chloride.
The polycarbonate resin (A) is preferably an aromatic polycarbonate resin because a molded article having excellent transparency can be obtained.

(Polycarbonate-organosiloxane copolymer (B))
The polycarbonate-organosiloxane copolymer (B) used in the present invention is a copolymer containing a structural unit represented by the chemical formula (I) and a structural unit represented by (II).

式中、Ｘは炭素数１〜８のアルキレン基、炭素数２〜８のアルケニレン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルケニレン基、炭素数６〜１２のアリーレン基、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−Ｏ−、または−ＣＯ−を示し、Ｒ_１およびＲ_２はそれぞれ独立に水素原子または炭素数１〜８のアルキル基を示し、ｍは平均繰り返し数を示す。

In the formula, X is an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkenylene group having 5 to 15 carbon atoms, or an arylene having 6 to 12 carbon atoms. Group, —S—, —SO—, —SO ₂ —, —O—, or —CO—, each of R ₁ and R ₂ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m Indicates the average number of repetitions.

式中、Ｒ_３およびＲ_４はそれぞれ独立に、水素原子、ハロゲン原子、または炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数６〜１２のアリール基を示し、ｎは平均繰り返し数を示す。

In the formula, R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n Indicates the average number of repetitions.

  The structural unit represented by the chemical formula (I) is not particularly limited, but the structural unit represented by the chemical formula (III) is preferable because the heat resistance of the molded body tends to be excellent.

Examples of the structural unit represented by the chemical formula (I) other than the structural unit represented by the chemical formula (III) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) Phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-t -Butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4- Droxy-3,5-tetramethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2- Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3,5-dibromophenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 1,1-bis (4-hydroxyphenyl) cyclododecane, etc. Bis (hydroxyaryl) cycloalkanes; 4,4′-dihydroxyphenyl ether, 4,4 ′ Dihydroxy aryl ethers such as dihydroxy-3,3′-dimethylphenyl ether, dihydroxy diaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4 , 4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, and the like; 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3 ′ Dihydroxy diaryl sulfones such as dimethyldiphenyl sulfone; Dihydroxy diphenyls such as 4,4′-dihydroxydiphenyl; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Methylpheny ) Dihydroxydiarylfluorenes such as fluorene; bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis ( Dihydroxydiaryladamantanes such as 4-hydroxyphenyl) -5,7-dimethyladamantane; 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) ) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene and the like.
These structural units may be used alone or in admixture of two or more.

  The structural unit represented by the chemical formula (II) is not particularly limited, but the structural unit represented by the chemical formula (IV) is preferable because the impact resistance of the molded body is excellent.

  The content of the structural unit represented by the chemical formula (I) is preferably 70 to 98% by mass, more preferably 85 to 98% by mass, and still more preferably 90 to 90% in the polycarbonate-organosiloxane copolymer (B). 97% by mass. The content of the structural unit represented by the chemical formula (II) is preferably 2 to 30% by mass, more preferably 2 to 15% by mass, and still more preferably in the polycarbonate-organosiloxane copolymer (B). 3 to 10% by mass. If the content of the structural unit represented by the chemical formula (II) is 2% by mass or more, the impact resistance tends to be excellent. If the content of the structural unit represented by the chemical formula (II) is 30% by mass or less, the heat resistance tends to be excellent.

In the polycarbonate-organosiloxane copolymer (B), the average repeating number m of the structural units in the chemical formula (I) and the chemical formula (III) is preferably 1 to 500, more preferably 10 to 300, and 40 to 200. Further preferred. If the average repetition number m is 1 or more, the impact resistance of the molded product tends to be excellent. If the average repetition number m is 500 or less, the moldability tends to be excellent.
In the polycarbonate-organosiloxane copolymer (B), the average repeating number n of the structural units in the chemical formula (II) and the chemical formula (IV) is preferably 1 to 40, more preferably 5 to 30, and 10 to 30. Further preferred. If the average repeat number n is 1 or more, the impact resistance tends to be excellent. When the average number of repetitions n is 30 or less, the heat resistance tends to be excellent.

  The mass average molecular weight of the polycarbonate-organosiloxane copolymer (B) is preferably 10,000 to 100,000, more preferably 20,000 to 70,000, and further preferably 30,000 to 60,000. If the weight average molecular weight of the polycarbonate-organosiloxane copolymer (B) is 10,000 or more, a molded article excellent in impact resistance tends to be obtained. If the mass average molecular weight of the polycarbonate-organosiloxane copolymer (B) is 100,000 or less, a resin composition having excellent moldability tends to be obtained.

(Rubber-containing graft copolymer (C))
The rubber-containing graft copolymer (C) of the present invention is a rubber-containing graft copolymer obtained by graft-polymerizing a vinyl monomer (c2) to a polyorganosiloxane rubber (C1).
The rubber-containing graft copolymer (C) of the present invention has a polyorganosiloxane rubber (C1) content of 100% by mass in total of the polyorganosiloxane rubber (C1) and the vinyl monomer (c2). It is 80-99 mass%, Preferably it is 85-95 mass%, More preferably, it is 85-90 mass%. If the content of the polyorganosiloxane rubber (C1) is 80% by mass or more, the resulting molded article tends to have excellent impact resistance, and if it is 99% by mass or less, the rubber-containing graft copolymer (C ) Tends to improve dispersibility when blended with resin.
The rubber-containing graft copolymer (C) of the present invention is obtained by polymerizing the vinyl monomer (c2) in a total of 100% by mass of the polyorganosiloxane rubber (C1) and the vinyl monomer (c2). The graft part to be obtained is 1 to 20% by mass, preferably 5 to 15% by mass, and more preferably 10 to 15% by mass.

(Polyorganosiloxane rubber (C1))
The polyorganosiloxane rubber (C1) is one or two selected from polyorganosiloxane (C1-1) and polyorganosiloxane-acrylic composite rubber (C1-2).
The rubber-containing graft copolymer (C) of the present invention is preferably a polyorganosiloxane-acrylic composite rubber (C1-2) because the molded article has excellent color developability.

(Polyorganosiloxane (C1-1))
The polyorganosiloxane (C1-1) is an organosiloxane, if necessary, a graft cross-linking agent for polyorganosiloxane (hereinafter referred to as “siloxane cross-linking agent”), a cross-linking agent for polyorganosiloxane (hereinafter referred to as “siloxane cross-linking agent”). And an organosiloxane mixture composed of a siloxane oligomer having a terminal blocking group and the like.

  As the organosiloxane, either a chain organosiloxane or a cyclic organosiloxane can be used. Cyclic organosiloxane is preferable because of high polymerization stability and a high polymerization rate. As the cyclic organosiloxane, a cyclic organosiloxane having 3 or more members is preferable, and a 3 to 6 membered cyclic organosiloxane is more preferable. Examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclohexane. Tetrasiloxane is mentioned. These may be used alone or in combination of two or more.

  As the siloxane crosslinking agent, those having 3 or 4 functional groups capable of bonding to the organosiloxane are preferable. Examples of the siloxane crosslinking agent include trialkoxyalkylsilanes such as trimethoxymethylsilane; trialkoxyarylsilanes such as triethoxyphenylsilane; tetramethoxysilanes, tetraethoxysilanes, tetran-propoxysilanes, tetrabutoxysilanes, and the like. An alkoxysilane is mentioned. These may be used alone or in combination of two or more. Among these, tetraalkoxysilane is preferable, and tetraethoxysilane is more preferable.

  As the siloxane crossing agent, those that can be bonded to the organosiloxane via a siloxane bond and form a bond with a vinyl monomer such as a monomer or a vinyl monomer constituting a poly (meth) acrylate. preferable. Considering the reactivity with organosiloxane, an alkoxysilane compound having a vinyl group is preferred. By using a siloxane crossing agent, a polyorganosiloxane having a functional group polymerizable with an arbitrary vinyl copolymer can be obtained. When the polyorganosiloxane has a functional group polymerizable with an arbitrary vinyl monomer, the polyorganosiloxane can be chemically bonded to the poly (meth) acrylic acid alkyl ester or the vinyl monomer.

Examples of the siloxane-based graft crossing agent include siloxane represented by the chemical formula (V).
RSi (R ₅ ) _l (OR ₆ ) _(3-1) (V)
In chemical formula (V), R ₅ represents a methyl group, an ethyl group, a propyl group, or a phenyl group. R ₆ represents an organic group in the alkoxy group, and examples thereof include a methyl group, an ethyl group, a propyl group, and a phenyl group. l represents 0, 1 or 2; R represents any group represented by chemical formulas (V-1) to (V-4).
[Chemical Formulas (V1) to (V4)]
_{CH 2 = C (R 7)} -COO- (CH 2) p - (V-1)
_{CH 2 = C (R 8)} -C 6 H 4 - (V-2)
_{CH 2 = CH- (V-3} )
_{HS- (CH 2) q - (} V-4)
In these formulas, R ₇ and R ₈ each represent hydrogen or a methyl group, p represents an integer of 1 to 6, and q represents an integer of 1 to 6.

Examples of the functional group represented by the chemical formula (V-1) include a methacryloyloxyalkyl group. Examples of the siloxane having this group include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxy. Mention may be made of propylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane.
Examples of the functional group represented by the chemical formula (V-2) include a vinylphenyl group. Examples of the siloxane having this group include vinylphenylethyldimethoxysilane.
Examples of the siloxane having a functional group represented by the chemical formula (V-3) include vinyltrimethoxysilane and vinyltriethoxysilane.
Examples of the functional group represented by the chemical formula (V-4) include a mercaptoalkyl group. Examples of the siloxane having this group include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, γ-mercaptopropylethoxydimethylsilane, and γ-mercaptopropyltrimethoxysilane. be able to.
These siloxane grafting agents may be used alone or in combination of two or more.

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

  The content of organosiloxane in 100% by mass of the organosiloxane mixture is preferably in the range of 60 to 100% by mass, and more preferably in the range of 70 to 100% by mass. The content of the siloxane crossing agent in 100% by mass of the organosiloxane mixture is preferably in the range of 0 to 10% by mass. The content of the siloxane crosslinking agent in 100% by mass of the organosiloxane mixture is preferably in the range of 0 to 30% by mass. The content of the siloxane oligomer having a terminal blocking group in 100% by mass of the organosiloxane mixture is preferably 0 to 20% by mass.

(Production method of polyorganosiloxane (C1-1))
There is no restriction | limiting in particular as a manufacturing method of polyorganosiloxane (C1-1), For example, the following manufacturing methods are employable.
First, an emulsion is prepared by emulsifying an organosiloxane mixture containing an organosiloxane, a siloxane-based crosslinking agent as required, a siloxane-based graft crossing agent as required, and a siloxane oligomer having a terminal blocking group as necessary with an emulsifier and water. To prepare. After the preparation of the emulsion, polymerization is performed at a high temperature under the presence of an acid catalyst, and then an alkaline substance is added to neutralize the acid to obtain a polyorganosiloxane latex.
In this specification, latex refers to a system in which polymer particles are stably dispersed in a solution.
In this production method, emulsion preparation methods include a method using a homomixer that makes fine particles by shearing force by high-speed rotation, a method that mixes by high-speed agitation using a homogenizer that makes fine particles by jet output from a high-pressure generator, etc. Is mentioned. Among these, the method using a homogenizer is a preferable method because the particle size distribution of the polyorganosiloxane latex becomes narrow.
As a method of mixing the acid catalyst during polymerization, a method of adding and mixing together with an organosiloxane mixture, an emulsifier and water, a method of adding an acid catalyst aqueous solution all together in an emulsion of an organosiloxane mixture, an organosiloxane Examples include a method in which the emulsion of the mixture is dropped into a high-temperature acid aqueous solution at a constant speed and mixed, but since the particle diameter of the polyorganosiloxane is easy to control, the emulsion of the organosiloxane mixture is kept at a high temperature, and then A method in which the acid catalyst aqueous solution is added all at once is preferred.

The polymerization temperature is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower. The polymerization time is usually 2 hours or longer, preferably 5 hours or longer when the acid catalyst aqueous solution is added all at once to the emulsion of the organosiloxane mixture for polymerization. Usually, the polymerization time is 10 hours or less.
Furthermore, since a crosslinking reaction between silanols proceeds at a temperature of −150 ° C. or higher and 30 ° C. or lower, in order to increase the crosslinking density of the polyorganosiloxane, a temperature of −150 ° C. or higher and 30 ° C. or lower is used for 5 hours to 100 hours. It can also be held for about an hour.
The polymerization reaction of polyorganosiloxane can be terminated by neutralizing the polyorganosiloxane latex produced by the above polymerization reaction to pH 6-8 with an alkaline substance such as sodium hydroxide, potassium hydroxide, aqueous ammonia solution or the like.

The emulsifier used in the above production method is not particularly limited as long as an organosiloxane can be emulsified, but an anionic emulsifier or a nonionic emulsifier is preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, and sodium polyoxyethylene nonyl phenyl ether sulfate.
Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, and polyoxyethylene polyoxypropylene glycol. .
These emulsifiers may be used individually by 1 type, and may use 2 or more types together.
The use amount of the emulsifier is preferably 0.05 to 12 parts by mass with respect to 100 parts by mass of the organosiloxane mixture, and the polyorganosiloxane (C1-1) is adjusted to a desired particle size by the use amount of the emulsifier. Is possible.
By using 0.001 to 10 parts by mass of an emulsifier with respect to 100 parts by mass of the organosiloxane mixture, the particle diameter of the polyorganosiloxane (C1-1) can be adjusted to 10 to | 2000 nm.

  Examples of the acid catalyst used for polymerization of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts are used alone or in combination of two or more. Among these, when mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid are used, the particle size distribution of the polyorganosiloxane latex can be narrowed. Is preferable in that it can be reduced.

The mass average particle diameter of the polyorganosiloxane latex is preferably 10 nm to 1000 nm. Furthermore, it is more preferable that it is 10 nm-500 nm.
As the mass average particle diameter of the polyorganosiloxane latex, a value measured by the following method can be adopted.
A polyorganosiloxane latex diluted with deionized water to a concentration of about 3% is used as a sample and measured using a CHDF 2000 particle size distribution meter manufactured by MATEC.
The measurement can be performed under the following conditions.
Cartridge: Dedicated capillary cartridge for particle separation (trade name: C-202)
Carrier liquid: Dedicated carrier liquid (trade name: 2XGR500)
Flow rate: 1.4 ml / min Pressure: about 4000 psi
Measurement temperature: 35 ° C
Amount used: 0.1 ml

(Polyorganosiloxane-acrylic composite rubber (C1-2))
In the present invention, the polyorganosiloxane rubber (C1) includes a polymer composed of the polyorganosiloxane (C1-1) and the acrylic vinyl monomer (c3), and if necessary, a crosslinkable monomer. It is also possible to use an acrylic composite rubber (C1-2) containing a structural unit composed of (c4) or a structural unit composed of an acrylic crossover agent (c5).

When the acrylic composite rubber (C1-2) is used, the glass transition temperature (both Tg) of the polymer comprising the acrylic vinyl monomer (c3) is improved in order to improve the coagulation property and impact resistance of the molded product. Is preferably −150 ° C. to 0 ° C., more preferably −130 ° C. to −20 ° C., and further preferably −120 ° C. to −40 ° C.
As the numerical value of Tg of the polymer, the value calculated by the Fox formula (Formula 1) is used. The numerical value described in POLYMER HANDBOOK Volume 1 (WILEY-INTERSCIENCE) is used for the numerical value of Tg of the homopolymer.
1 / (273 + Tg) = Σ (wi / (273 + Tgi)) (Equation 1)
However, each symbol represents the following.
Tg: Glass transition temperature (° C)
wi: weight fraction of monomer i Tgi: glass transition temperature (° C.) of homopolymer obtained by polymerizing monomer i

Examples of the acrylic vinyl monomer (c3) include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate and n-butyl acrylate; methyl methacrylate, ethyl methacrylate, methacrylic acid Examples thereof include alkyl methacrylates such as dodecyl, n-butyl methacrylate and i-butyl methacrylate.
The polymer composed of the acrylic vinyl monomer (c3) preferably has a mass average molecular weight of 1,000 or more and 1,000,000 or less, and more preferably 5,000 or more and 300,000 or less.

The crosslinkable monomer (c4) is a polyfunctional monomer having two or more polymerizable unsaturated bonds. For example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, diacryl Examples include acid 1,6-hexanediol and triallylic acid triallyl, and these can be used alone or in combination of two or more.
The acrylic crossover agent (c5) is a polyfunctional monomer having two or more polymerizable unsaturated bonds having different reactivities. By having groups with different reactivities, unsaturated groups are incorporated into the composite rubber while being polymerized together with other components, and a graft copolymer can be formed. Examples thereof include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and the like can be used alone or in combination of two or more. Since the acrylic cross-linking agent (c5) has two or more polymerizable unsaturated bonds like the cross-linkable monomer, it also has a function as a cross-linking agent.

The content of the polyorganosiloxane (C1-1) in 100% by mass of the polyorganosiloxane-acrylic composite rubber (C1-2) is preferably 0.1% by mass or more and 99.9% by mass or less, 5 mass% or more and 99.9 mass% or less are more preferable, and 7 mass% or more and 99.9 mass% or less are especially preferable. If the content of the polyorganosiloxane is 0.1% by mass or more, the impact resistance tends to be excellent. If the polyorganosiloxane content is 99.9% by mass or less, the heat resistance tends to be excellent.
The content of the polymer composed of the acrylic vinyl monomer (c3) in 100% by mass of the polyorganosiloxane-acrylic composite rubber (C1-2) is 0.1% by mass or more and 99.9% by mass or less. It is preferably 0.1% by mass or more and 95% by mass or less, and more preferably 0.1% by mass or more and 93% by mass or less.
The polymer content of the crosslinkable monomer (c4) or the acrylic crossover agent (c5) in 100% by mass of the polyorganosiloxane-acrylic composite rubber (C1-2) is 0% by mass to 20% by mass. It is preferable that it is 0.1 mass% or more and 15 mass% or less, and 0.1 mass% or more and 10 mass% or less are especially preferable.

(Production method of polyorganosiloxane-acrylic composite rubber (C1-2))
The production method of the polyorganosiloxane-acrylic composite rubber (C1-2) is not particularly limited and can be produced by, for example, an emulsion polymerization method, a suspension polymerization method, or a fine suspension polymerization method. It is preferable to use a legal method.
Examples of the method for producing the polyorganosiloxane-acrylic composite rubber (C1-2) include a method of synthesizing a polymer of the acrylic vinyl monomer (c3) in the presence of the polyorganosiloxane latex. As a method for synthesizing a polymer of acrylic vinyl monomer (c3) in the presence of polyorganosiloxane latex, first, acrylic vinyl monomer (c3) is added to polyorganosiloxane latex, After impregnating the organosiloxane with the acrylic vinyl monomer (c3), a known radical polymerization initiator is allowed to act to polymerize the acrylic vinyl monomer (c3).
When the crosslinkable monomer (c4) or the acrylic crossing agent (c5) is used, these may be added simultaneously with the acrylic vinyl monomer (c3).
In this production method, as a method of adding a radical polymerization initiator to the polyorganosiloxane latex impregnated with the acrylic vinyl monomer (c3), a method of adding the whole amount to the polyorganosiloxane latex at once, A method of adding dropwise to the siloxane latex at a constant rate can be mentioned.
The polymerization temperature is preferably 30 ° C. or higher and 100 ° C. or lower, and more preferably 40 ° C. or higher and 90 ° C. or lower. The polymerization time is 1 hour or longer, preferably 2 hours or longer. Usually, the polymerization time is 100 hours or less.

When producing a latex of polyorganosiloxane-acrylic composite rubber (C1-2), in order to stabilize the latex and control the particle size of polyorganosiloxane-acrylic composite rubber (C1-2), An emulsifier can be added. The emulsifier is not particularly limited, and an anionic emulsifier and a nonionic emulsifier are preferable.
Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate, sodium alkyl sulfate, polyoxyethylene alkyl sodium sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate, sodium sarcosine, fatty acid potassium, fatty acid sodium, alkenyl. Examples include dipotassium succinate, rosin acid soap, polyoxyethylene alkyl sodium phosphate, and polyoxyethylene alkyl calcium phosphate.
Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene tribenzyl phenyl ether. These emulsifiers can be used alone or in combination of two or more.

Examples of the radical polymerization initiator used for the production of the acrylic vinyl monomer (c3) polymer include azo initiators, peroxides, and redox initiators in which peroxides are combined with oxidizing agents and reducing agents. Used. These can be used alone or in combination of two or more.
Examples of the azo initiator include oil-soluble azo initiators such as 2,2′-azobisisobutyronitrile and dimethyl 2,2′-azobis (2-methylpropionate), 4,4′- Azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxymethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis- (N, N′-di) And water-soluble azo initiators such as methyleneisobutylamidine) dihydrochloride and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride. These can be used alone or in combination of two or more.
Examples of the peroxide include inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, Succinic acid peroxide, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2- Organic peroxides such as ethyl hexanoate and t-butyl peroxy-2-ethyl hexanoate can be mentioned. These peroxides can be used alone or in combination of two or more.
As the redox initiator in combination with a reducing agent, a peroxide, a reducing agent such as sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, dextrose, sorbose, inositol, and sulfuric acid first An initiator combining iron / ethylenediaminetetraacetic acid disodium salt is preferred.
These oxidizing agents and reducing agents can be used alone or in combination of two or more.

When an azo initiator is used as the radical polymerization initiator, the azo initiator is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the graft copolymer.
When a peroxide is used as the radical polymerization initiator, the peroxide is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the graft copolymer.
When a redox initiator is used as the radical polymerization initiator, the amount of peroxide used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the graft copolymer, and the amount of reducing agent used is It is preferable that it is 0.01-1 mass part with respect to 100 mass parts of graft copolymers.
Chain transfer agents such as t-dodecyl mercaptan, n-octyl mercaptan, and α-methylstyrene can also be used in the production of the acrylic vinyl monomer (c3) polymer.

The mass average particle diameter of the polyorganosiloxane-acrylic composite rubber (C1-2) is preferably 10 nm to 1000 nm, and more preferably 200 nm to 1000 nm.
As the mass average particle diameter of the polyorganosiloxane-acrylic composite rubber (C1-2), a value measured by the following method can be adopted.
A polyorganosiloxane latex diluted with deionized water to a concentration of about 3% is used as a sample and measured using a CHDF 2000 particle size distribution meter manufactured by MATEC.
The measurement can be performed under the following conditions.
Cartridge: Dedicated capillary cartridge for particle separation (trade name: C-202)
Carrier liquid: Dedicated carrier liquid (trade name: 2XGR500)
Flow rate: 1.4 ml / min Pressure: about 4000 psi
Measurement temperature: 35 ° C
Amount used: 0.1 ml

(Vinyl monomer (c2))
The rubber-containing graft copolymer (C) of the present invention is a rubber-containing graft copolymer obtained by graft-polymerizing a vinyl monomer (c2) to a polyorganosiloxane rubber (C1).
Although a vinyl monomer (c2) is not specifically limited, It is preferable that a (meth) acrylic acid ester monomer (c2-1) and another monomer (c2-2) as needed are included.
The content of the (meth) acrylic acid ester monomer (c2-1) in 100% by mass of the vinyl monomer (c2) is 20 to 100% by mass because dispersibility in the polycarbonate resin is improved. It is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass, and most preferably 95 to 100% by mass. preferable.

Examples of the (meth) acrylic acid ester monomer (c2-1) include methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate. Acid ester; Acrylic acid ester such as methyl acrylate, ethyl acrylate, n-butyl acrylate, glycidyl acrylate, and the like. These may be used alone or in combination of two or more.
The (meth) acrylic acid ester monomer (c2-1) is methyl methacrylate and acrylic acid from the viewpoints of polymerizability, solidification, powder characteristics such as bulk specific gravity, and good compatibility with polycarbonate resin. More preferably, it is at least one of n-butyl.
The content of methyl methacrylate in 100% by mass of the (meth) acrylic acid ester monomer (c2-1) is preferably 0.1 to 100% by mass, and more preferably 20 to 100% by mass. Preferably, it is 50-100 mass%, More preferably, it is 80-100 mass%.

Examples of the other monomer (c2-2) include aromatic compounds having a vinyl group such as styrene and α-methylstyrene; compounds having a cyano group and a vinyl group such as acrylonitrile and methacrylonitrile; ethylene dimethacrylate Examples include crosslinkable monomers such as glycol, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, polyfunctional methacrylic group-modified silicone, and allyl methacrylate. It is done. N-butyl acrylate and methyl acrylate are preferred because of excellent polymerizability, coagulability, powder characteristics, and the like.
The content of the other monomer (c2-2) in 100% by mass of the vinyl monomer (c2) is preferably 0 to 80% by mass because the dispersibility in the polycarbonate resin is improved. More preferably, it is -50 mass%, It is more preferable that it is 0-20 mass%, It is especially preferable that it is 0-10 mass%, It is most preferable that it is 0-5 mass%.

The polymer obtained by polymerizing the vinyl monomer (c2) improves the powder properties such as coagulation property and bulk specific gravity. Therefore, the glass transition temperature preferably exceeds 0 ° C., and is 50 to 200 ° C. It is more preferable that it is 80-150 degreeC.
The value of Tg of the copolymer is a value calculated by the Fox formula (Formula 1). In addition, said Tg is the value calculated | required about the polymer obtained by superposing | polymerizing the monomer remove | excluding the crosslinkable monomer from the vinyl monomer (c2), and the glass transition of a vinyl monomer (c2). It will be used as temperature. The numerical value described in POLYMER HANDBOOK Volume 1 (WILEY-INTERSCIENCE) is used for the numerical value of Tg of the homopolymer.
1 / (273 + Tg) = Σ (wi / (273 + Tgi)) (Equation 1)
However, each symbol represents the following.
Tg: Glass transition temperature (° C)
wi: weight fraction of monomer i Tgi: glass transition temperature (° C.) of homopolymer obtained by polymerizing monomer i

[Method for producing rubber-containing graft copolymer (C)]
The rubber-containing graft copolymer (C) of the present invention is obtained by polymerizing the vinyl monomer (c2) in the presence of the polyorganosiloxane rubber (C1). That is, the rubber-containing graft copolymer (C) of the present invention is obtained by graft polymerization of the vinyl monomer (c2) to the polyorganosiloxane rubber (C1).
As the polymerization initiator used for the graft polymerization, the same polymerization initiator as used for the production of the acrylic vinyl monomer (c3) can be used.
As the emulsifier used for the graft polymerization, the same emulsifier as used for the production of the acrylic vinyl monomer (c3) can be used.
Moreover, the same chain transfer agent as the chain transfer agent used for manufacture of an acrylic vinyl monomer (c3) can be used for graft polymerization.
The volume average particle diameter of the rubber-containing graft copolymer (C) in the latex is preferably 10 to 3000 nm, more preferably 10 to 1000 nm, and still more preferably 10 to 450 nm. More preferably, it is 10-250 nm, Most preferably, it is 50-250 nm. If the average particle diameter of the rubber-containing graft copolymer (C) in the latex is 10 to 3000 nm, the dispersibility of the rubber-containing graft copolymer (C) in the resin will be good.

The latex of the rubber-containing graft copolymer (C) obtained by emulsion polymerization can be recovered as a powder of the rubber-containing graft copolymer (C) by a treatment such as spray drying, freeze drying, or coagulation. it can. Among these, since the dispersibility of the rubber-containing graft copolymer (C) in the resin is good, the spray drying method is preferable, and impurities such as an emulsifier can be removed and the purity is good. Therefore, the coagulation method is preferable.
In addition, an antioxidant and an additive can be mix | blended with the latex of a rubber containing graft copolymer (C) as needed.

In the coagulation method, a graft copolymer latex is poured into hot water in which calcium chloride, calcium acetate, aluminum sulfate, etc. are dissolved, and the graft copolymer is salted out, washed, coagulated after washing. To obtain a rubber-containing graft copolymer (C) having a reduced water content by dehydrating the obtained wet graft copolymer. It is a method of drying using a pressure dehydrator or a hot air dryer.
Examples of the coagulant used for coagulating the graft copolymer from latex include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate, and acids such as sulfuric acid. Calcium is particularly preferred. These coagulants may be used alone or in combination of two or more, but when used in combination, it is necessary to select a combination that does not form an insoluble salt in water. For example, the combined use of calcium acetate and sulfuric acid or a sodium salt thereof is not preferable because a calcium salt insoluble in water is formed.
The coagulant is usually dissolved in an aqueous solution and used as an aqueous coagulant solution. The concentration of the coagulant in the coagulant aqueous solution is preferably 0.1% by mass or more from the viewpoint of stably coagulating and recovering the graft copolymer. Further, from the viewpoint of reducing the amount of the coagulant remaining in the recovered graft copolymer and suppressing the deterioration of the electrical properties of the molded product, the concentration of the coagulant aqueous solution is 20% by mass or less, particularly 15% by mass. The following is preferable. The amount of the coagulant aqueous solution is not particularly limited, but is preferably 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the latex.
The method of bringing the latex into contact with the coagulant aqueous solution is not particularly limited. Usually, while stirring the coagulant aqueous solution, the method of continuously adding the latex therein and holding it for a certain period of time, the coagulant aqueous solution and the latex, Examples include a method in which a mixture containing a coagulated polymer and water is continuously withdrawn from the container by continuously injecting into a container equipped with a stirrer at a constant ratio. The temperature at which the latex is brought into contact with the coagulant aqueous solution is not particularly limited, but is preferably 30 ° C. or higher and 100 ° C. or lower. Although contact time is not specifically limited, For example, they are 0.1 hours or more and 10 hours or less.
The agglomerated rubber-containing graft copolymer (C) is washed with about 1 to 100 times by weight of water, and the wet rubber-containing graft copolymer (C) body filtered is a fluid dryer or a press dehydrator. Etc. and dried. The drying temperature and drying time may be appropriately determined depending on the rubber-containing graft copolymer (C) to be obtained, and are, for example, from 1 hour to 96 hours at 30 ° C. to 90 ° C. In addition, without collecting the rubber-containing graft copolymer (C) discharged from the press dehydrator or the extruder, it is sent directly to the extruder or molding machine for producing the resin composition, and mixed with other thermoplastic resins. Thus, a molded body can be obtained.
In the present invention, the rubber-containing graft copolymer (C) is preferably recovered using a coagulation method from the viewpoint of heat decomposability when a resin composition is obtained.
In order to suppress blocking during drying and improve powder characteristics such as bulk specific gravity, a plurality of polymer latexes may be added during coagulation. Moreover, you may dry by adding inorganic fillers, such as a silica, a talc, and calcium carbonate; polyacrylic acid ester, polyvinyl alcohol, polyacrylamide, etc. Moreover, suitable antioxidant, an additive, etc. can also be added.
In the spray drying method, the latex of the rubber-containing graft copolymer (C) is sprayed in the form of fine droplets and dried by applying hot air to the latex. As a device for generating droplets, any of a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, a pressurized two-fluid nozzle type, etc. can be used. Moreover, the dryer can be used from a small-sized one used in a laboratory to a large-scale one used industrially.
The temperature of hot air introduced into the apparatus (hot air inlet temperature), that is, the maximum temperature of hot air that can come into contact with the rubber-containing graft copolymer (C) is preferably 200 ° C. or less, particularly preferably 120 to 180 ° C. . Further, when spray-drying, the latex of the rubber-containing graft copolymer (C) may be a single latex or a mixture of a plurality of latexes. Furthermore, in order to improve powder characteristics such as blocking and bulk specific gravity during spray drying, an optional component such as silica can be added to perform spray drying.

(Polycarbonate resin composition)
The polycarbonate resin composition of the present invention comprises a polycarbonate resin (A), a polycarbonate-organosiloxane copolymer (B), and a rubber-containing graft copolymer (C). The polycarbonate resin composition of the present invention may contain components other than the polycarbonate resin (A), the polycarbonate-organosiloxane copolymer (B), and the rubber-containing graft copolymer (C) as necessary. .

(Other ingredients)
The polycarbonate resin composition of the present invention includes various additives such as antioxidants, ultraviolet absorbers, light stabilizers, nucleophiles, flame retardants, and various fillers such as glass, mica, and rubber particles as necessary. May be included.
The polycarbonate resin composition of the present invention may contain a resin other than the polycarbonate resin as long as the effects of the present invention are not impaired.

(Composition of polycarbonate resin composition)
In this invention, it is preferable that a polycarbonate-organosiloxane copolymer (B) is 1-50 mass% among the total 100 mass% of polycarbonate resin (A) and a polycarbonate-organosiloxane copolymer (B). It is more preferable that it is 1-35 mass%, and it is further more preferable that it is 1-25 mass%. If the polycarbonate-organosiloxane copolymer (B) is 1% by mass or more, the impact resistance of the molded product tends to be excellent, and if it is 50% by mass or less, the heat aging resistance of the molded product tends to be excellent.
In the present invention, the content of the rubber-containing graft copolymer (C) is 0.1 to 2.8 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polycarbonate-organosiloxane copolymer (B). It is a mass part, Preferably it is 0.5-2.5 mass part, More preferably, it is 0.5-2 mass part. If the content of the rubber-containing graft copolymer (C) is 0.1 parts by mass or more, the impact resistance of the molded product tends to be excellent, and if it is 2.8 parts by mass or less, the rubber-containing graft in the molded product The dispersibility of the copolymer (C) tends to be excellent.

(Manufacturing method of polycarbonate resin composition)
The polycarbonate resin composition of the present invention is obtained by melt-kneading a polycarbonate resin (A), a polycarbonate-organosiloxane copolymer (B), a rubber-containing graft copolymer (C), and other components as necessary. Can be manufactured by.
Examples of the melt kneading apparatus include a Banbury mixer, a kneader, a roll, a kneader ruder, a single screw extruder, a twin screw extruder, a multi-screw extruder, and the like.
<Method for producing molded body>
The polycarbonate resin composition of the present invention can be produced by a known method such as an injection molding method, an extrusion molding method, or a compression molding method. As the molding method, an injection molding method and an extrusion molding method are preferable because they can be molded into a desired shape.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
In the examples, “part” means “part by mass”. The ratio of each structural unit of the polymer and the method for obtaining the weight average molecular weight and the evaluation method of the molded product are as follows.
(Percentage of structural units)
The ratio of each structural unit of the polymer was calculated from the charged amount of monomer.
(Mass average molecular weight)
About the polymer melt | dissolved in tetrahydrofuran (THF), the elution curve was measured by the gel permeation chromatography (GPC), and the mass mean molecular weight of the polymer was computed based on the analytical curve by a standard polystyrene.
(Izod impact strength)
The sheet-like molded body was measured at a measurement temperature of 23 ° C. according to ASTM D256 (thickness: 1/4 inch, unit: kJ / m ² ).
(optical properties)
Using a haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd., trade name), the total light transmittance (unit:%) of a molded product having a thickness of 2 mm was measured with a D65 light source.

[Production of rubber-containing graft copolymer (C)]
(Manufacture of polyorganosiloxane rubber (C1))
Production of polyorganosiloxane (C1-1-1) 97.5 parts of cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC), 2 parts of tetraethoxysilane (TEOS) as siloxane crosslinker and siloxane 0.5 parts of γ-methacryloyloxypropyldimethoxymethylsilane (DSMA) was mixed as a crossing agent to obtain 100 parts of an organosiloxane mixture. An aqueous solution prepared by dissolving 0.68 parts of sodium dodecylbenzenesulfonate (DBSNa), 0.68 parts of dodecylbenzenesulfonic acid (DBSH) and 200 parts of deionized water is added to the mixture, and the mixture is mixed with a homomixer. After stirring at 10,000 rpm for 2 minutes, the mixture was passed twice through a homogenizer at a pressure of 20 MPa to obtain a stable premixed emulsion.
The emulsion was then charged into a 5 liter separable flask equipped with a cooling condenser. The emulsion was heated to 85 ° C. and maintained for 6 hours for a polymerization reaction, then cooled to 25 ° C. and held at room temperature for 12 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane rubber (C1-1-1) latex.
The solid content of this latex was 28.3%. The latex had a number average particle size (Dn) of 86 nm, a mass average particle size (Dw) of 254 nm, and a Dw / Dn of 2.95.

(Production of polyorganosiloxane (C1-1-2))
2 parts of TEOS, 2 parts of DSMA and 96 parts of octamethylcyclotetrasiloxane (product name: TSF404, manufactured by Momentive Performance Materials Japan) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution in which 1 part of DBSNa is dissolved in 150 parts of deionized water is added to the above mixture, stirred at 10,000 rpm for 5 minutes with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa to obtain a stable premixed emulsion. It was.
Next, the emulsion was placed in a separable flask having a capacity of 5 liters equipped with a cooling condenser. The emulsion was heated to 80 ° C., and a mixture of 0.2 part of sulfuric acid and 49.8 parts of distilled water was continuously added for 3 minutes. The polymerization reaction was maintained for 7 hours while heated to 80 ° C., then cooled to 25 ° C. and held for 6 hours. A 5% aqueous sodium hydroxide solution was added to neutralize the pH of the reaction solution to 7.0 to obtain a latex of polyorganosiloxane rubber (C1-1-2).
The latex had a solid content of 29.8%, Dn measured by a capillary particle size distribution meter of 384 nm, Dw of 403 nm, and Dw / Dn = 1.05.

(Production of polyorganosiloxane-acrylic composite rubber (C1-2))
The polyorganosiloxane rubber (C1-1-1) latex obtained in Production Example 1 was collected in a separable flask having a capacity of 5 liters and 9.9 parts in terms of polymer, and 100 parts of deionized water was added and mixed. Then, in this separable flask, 77.5 parts of n-butyl acrylate (n-BA) and 1.6 parts of allyl methacrylate (AMA), tert-butyl hydroperoxide (t-BH) 0 as an initiator .25 parts of the mixture was added.
The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the liquid temperature was raised to 50 ° C. When the temperature reaches 50 ° C., 0.001 part of ferrous sulfate (Fe), 0.003 part of ethylenediaminetetraacetic acid disodium salt (EDTA), 0.3 part of sodium formaldehyde sulfoxylate (SFS) are added to 2 parts of deionized water. An aqueous solution dissolved in 5 parts was added to initiate radical polymerization. In order to complete the polymerization of the acrylate component, the liquid temperature of 65 ° C. was maintained for 1 hour to obtain a latex of a composite rubber (C1-2) of polyorganosiloxane and n-BA.

[Production of rubber-containing graft copolymer (C)]
(Production Example 1)
Mixing 11 parts of methyl methacrylate (MMA) and 0.03 parts of t-BH as vinyl monomer (c2) while maintaining the latex temperature of the composite rubber (C1-2) at 65 ° C The liquid was dropped into the latex for 1.5 hours for polymerization. After completion of dropping, the liquid temperature was maintained at 65 ° C. for 1 hour, and then cooled to 25 ° C. to obtain a latex of a rubber-containing graft copolymer (C-1). Table 1 shows the volume average particle diameter of the rubber-containing graft copolymer (C-1).

Next, while stirring 500 parts of an aqueous solution having a calcium acetate concentration of 1% by mass at 30 ° C., 300 parts of the latex of the rubber-containing graft copolymer (C-1) was gradually dropped into the solution and solidified. did. The obtained rubber-containing graft copolymer (C-1) was filtered and dehydrated. Furthermore, after adding 10 times the amount of water to 100 parts of the rubber-containing graft copolymer (C-1), the mixture was washed for 10 minutes in a flask equipped with a stirrer, filtered and dehydrated. This operation was repeated twice, followed by drying to obtain a rubber-containing graft copolymer (C-1) powder.
(Production Examples 2 and 3)
Rubber-containing graft copolymers (C-2) and (C-3) were obtained in the same manner as in Production Example 1 except that the types and amounts of the respective raw materials used in Production Example 1 were changed to the conditions shown in Table 1. .

[Production of polycarbonate resin composition]
Example 1
95 parts of Iupilon S-2000F (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) as the polycarbonate resin (A) and chemical formula (III) m = 117 and chemical formula (IV) n = as the polycarbonate-organosiloxane copolymer (B) A rubber-containing graft copolymer (C-1) produced in Production Example 1 with respect to 100 parts in total of 5 parts of a 19-mer polycarbonate-organosiloxane copolymer (B) having a mass average molecular weight of 52,000. 1 part is put into a polyethylene bag, the polyethylene bag is shaken well by hand, and the mixture added to the polyethylene bag is hand blended, and then a twin screw extruder (manufactured by Ikekai Co., Ltd., trade name: PCM30). ) Was melt kneaded at 280 ° C. and the extruded strand was cut into pellets to obtain pellets.

  The pellets were molded using an injection molding machine (SE100DU, manufactured by Sumitomo Heavy Industries, Ltd.) at a molding temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain a sheet-like molded body having a thickness corresponding to each evaluation. The evaluation results are shown in Table 2.

(Examples 2 to 4)
A sheet-like molded body having a thickness corresponding to each evaluation was obtained in the same manner as in Example 1 except that the type and amount of each raw material used in Example 1 were changed to the conditions shown in Table 2. The evaluation results are shown in Table 2.
(Comparative Example 1)
A sheet having a thickness corresponding to each evaluation in the same manner as in Example 1 except that the polycarbonate resin (A) and the polycarbonate-organosiloxane copolymer (B) were used and the rubber-containing graft copolymer (C) was not used. A shaped molded body was obtained. The evaluation results are shown in Table 2. Since the rubber-containing graft copolymer (C) was not used, the impact strength was low.
(Comparative Example 2)
The rubber-containing graft copolymer (C-3) produced in Production Example 3 was used instead of the rubber-containing graft copolymer (C-1), and the number of added parts of the rubber-containing graft copolymer was changed to 3 parts. In the same manner as in Example 1, a sheet-like molded body having a thickness corresponding to each evaluation was obtained. The evaluation results are shown in Table 2. Due to the large amount of the rubber-containing graft copolymer, the optical properties were poor.
(Comparative Example 3)
A sheet-like molded body having a thickness corresponding to each evaluation was obtained in the same manner as in Example 1 except that the number of added parts of the rubber-containing graft copolymer was changed to 3 parts. The evaluation results are shown in Table 2. Due to the large amount of the rubber-containing graft copolymer, the optical properties were poor.

  The molded body made of the polycarbonate resin composition of the present invention includes members (housing, etc.) of various devices (electrical devices, electronic devices, OA devices, mobile phones, tablet terminals, printers, etc.), optical recording media, automobile parts (automobiles) It is useful as exterior materials, automotive interior materials, etc.), building materials, and various sheets.

Claims (8)

Polycarbonate resin (A),
A polycarbonate-organosiloxane copolymer (B) having a structural unit represented by the chemical formula (I) and a structural unit represented by the chemical formula (II), and a vinyl monomer (c2) to the polyorganosiloxane rubber (C1) A polycarbonate resin composition comprising a rubber-containing graft copolymer (C) obtained by graft polymerization,
The proportion of the polyorganosiloxane rubber (C1) is 80 to 99% by mass in a total of 100% by mass of the polyorganosiloxane rubber (C1) and the vinyl monomer (c2),
A polycarbonate resin composition comprising 0.1 to 2.8 parts by mass of a rubber-containing graft copolymer (C) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polycarbonate-organosiloxane copolymer (B).

In the formula, X is an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkenylene group having 5 to 15 carbon atoms, or an arylene having 6 to 12 carbon atoms. Group, —S—, —SO—, —SO ₂ —, —O—, or —CO—, each of R ₁ and R ₂ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m Indicates the average number of repetitions.

In the formula, R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n Is an integer indicating the average number of repetitions. The polycarbonate resin composition according to claim 1, wherein the structural unit represented by the chemical formula (I) is a structural unit represented by the chemical formula (III).

In the formula, m represents the average number of repetitions.   The polycarbonate resin composition according to claim 1 or 2, wherein an average repeating number n of the structural unit represented by the chemical formula (II) is 1 to 40. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the structural unit represented by the chemical formula (II) is a structural unit represented by the chemical formula (IV).

  The proportion of the polycarbonate-organosiloxane copolymer (B) is 1 to 50% by mass in a total of 100% by mass of the polycarbonate resin (A) and the polycarbonate-organosiloxane copolymer (B). 5. The polycarbonate resin composition according to any one of 4 above.   The polycarbonate resin composition according to any one of claims 1 to 5, wherein the polyorganosiloxane rubber (C1) is an organosiloxane-acrylic composite rubber.   The polycarbonate resin composition according to any one of claims 1 to 6, wherein the vinyl monomer (c2) contains a (meth) acrylic acid ester monomer.   The molded object which consists of a polycarbonate resin composition of any one of Claims 1-7.