JP6467909B2 - Polycarbonate resin composition and molded body - Google Patents

Description

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

Polycarbonate resin (hereinafter sometimes referred to as “PC resin”) is used for various applications because of its excellent heat resistance, impact resistance, etc., but has a high molding processing temperature and poor fluidity. Has drawbacks.
Therefore, polymer alloys in which ABS resin (acrylonitrile-butadiene-styrene copolymer) is blended with PC resin are used as materials in OA equipment such as copying machines, printers and facsimiles, and in electrical and electronic fields such as personal computers and mobile phones. Widely used.

  These parts are thinned year by year for the purpose of miniaturization, weight reduction, high functionality, and the like. Therefore, it is required to have high fluidity suitable for thin-wall molding, good mechanical properties such as impact resistance, and excellent flame resistance and heat resistance even in thin and light-weight molded products. ing.

  In order to meet this demand, attempts have been made to improve the ABS resin by increasing the blending ratio. However, although high fluidity is obtained, inconveniences such as surface impact resistance, impact resistance, flame retardancy, and heat resistance decrease occur.

  Therefore, an attempt has been made to improve impact resistance by adding a polyorganosiloxane-based impact strength improver to the aforementioned polymer alloy (Patent Document 1). However, although the impact resistance is improved, there is a problem that the pigment colorability is lowered due to the low refractive index of polyorganosiloxane.

Japanese Patent Laid-Open No. 6-1897

  An object of the present invention is to provide a polycarbonate resin composition and a molded body having both excellent impact resistance and pigment colorability. Furthermore, by using a flame retardant in combination, a polycarbonate resin composition and a molded article excellent in flame retardancy are provided.

The above-described problem is solved by any of the following inventions [1] to [4].
[1] A polycarbonate resin composition comprising a polycarbonate resin, a (co) polymer containing an aromatic vinyl monomer unit and / or a vinyl cyanide monomer unit, and a rubber-containing graft copolymer, The rubber-containing graft copolymer is obtained by polymerizing the grafting vinyl monomer (b) in the presence of the rubber (A) containing the polyorganosiloxane (A1) and the vinyl polymer (A2). A polycarbonate resin composition having a refractive index of (A) in the range of 1.47 to 1.56.
[2] The polycarbonate resin composition according to [1], wherein the rubber (A) has a volume average particle diameter in the range of 300 to 2000 nm.
[3] The polycarbonate resin composition according to [1] or [2], further including a flame retardant.
[4] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [3].

  The polycarbonate resin composition and molded article of the present invention have both excellent impact resistance and pigment colorability. Furthermore, by using a flame retardant together, the polycarbonate resin composition and molded article of the present invention are excellent in flame retardancy.

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

"Polycarbonate resin composition"
The polycarbonate resin composition of the present invention contains a polycarbonate resin, a (co) polymer containing an aromatic vinyl monomer unit and / or a vinyl cyanide monomer unit, and a rubber-containing graft copolymer.
The polycarbonate resin composition of the present invention preferably further contains a flame retardant.

<Polycarbonate resin>
As the polycarbonate resin, any conventionally known one can be used, and specifically, an aromatic polycarbonate resin, an aliphatic polycarbonate resin, an aromatic-aliphatic polycarbonate resin, or the like can be used.

  The polycarbonate resin is obtained, for example, by a phosgene method in which various dihydroxy diaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxy diaryl compound is reacted with a carbonate such as diphenyl carbonate. A typical polycarbonate resin includes a polycarbonate produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, and bis (4- Hydroxyphenyl) phenylmethane and the like. These may be used alone or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin is preferably 10,000 to 40,000, and more preferably 15,000 to 30,000. When the viscosity average molecular weight of the polycarbonate resin is 10,000 or more, the molecular weight is hardly lowered when the polycarbonate resin composition is molded at a high temperature, and the impact strength retention rate and heat resistance colorability of the obtained molded product are further improved. . On the other hand, when the viscosity average molecular weight of the polycarbonate resin is 40,000 or less, a polycarbonate resin composition having excellent melt fluidity can be obtained.
The “viscosity average molecular weight” is a molecular weight obtained by conversion from solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.

  Examples of the polycarbonate resin include the following. Product names Iupilon S-1000, Iupilon S-2000, Iupilon S-3000, Iupilon H-3000 or Iupilon H-4000 manufactured by Mitsubishi Engineering Plastics Co., Ltd .; Light L1225 or Panlite K1300. These shapes are usually pellets, but flaky PC resin may be used. For example, trade names “Iupilon S-1000F”, “Iupilon S-2000F”, “Iupilon H-3000F” manufactured by Mitsubishi Engineering Plastics Co., Ltd. can be used.

<(Co) polymer containing aromatic vinyl monomer unit and / or vinyl cyanide monomer unit>
A (co) polymer containing an aromatic vinyl monomer unit and / or a vinyl cyanide monomer unit (hereinafter sometimes referred to as “(co) polymer”) is an aromatic vinyl monomer. Aromatic vinyl monomer and / or vinyl cyanide monomer as raw material for vinyl cyanide monomer unit, and other vinyl monomers copolymerizable with it if necessary Can be obtained by polymerizing by a known method.
The (co) polymer includes an aromatic vinyl monomer that is a raw material for the aromatic vinyl monomer unit and / or a vinyl cyanide monomer that is a raw material for the vinyl cyanide monomer unit, and, if necessary, Even if it is obtained by graft polymerization of this with another vinyl monomer copolymerizable to a rubbery polymer (excluding rubber containing polyorganosiloxane) by a known method. Good.
The (co) polymer contributes to improvement of moldability (fluidity) of the polycarbonate resin composition.

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

  Examples of the vinyl cyanide monomer include the following. Acrylonitrile, methacrylonitrile. These may be used alone or in combination of two or more. Of these, acrylonitrile is preferably used because heat resistance, mechanical strength, and chemical resistance can be imparted while maintaining transparency.

  Examples of other vinyl monomers include the following. (Meth) acrylic acids such as acrylic acid and methacrylic acid; alkyl (meta) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate ) Acrylates; α, β-unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, etc. Maleimide compounds. These may be used alone or in combination of two or more.

  Examples of rubber polymers include polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, etc. Diene rubber, random copolymer and block copolymer of ethylene-propylene, copolymer of ethylene and alpha olefin, copolymer of ethylene-unsaturated carboxylic acid ester such as ethylene-methacrylate, ethylene-butyl acrylate, etc. Polymers, acrylic ester-butadiene copolymers, for example, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene-hexadiene copolymer Ethylene such as coalescence Propylene non-conjugated diene terpolymers, butylene - isoprene copolymer, chlorinated polyethylene and the like, used in these one or two or more.

  The content of aromatic vinyl monomer units in the (co) polymer (100% by mass) is 0 to 100% by mass, the content of vinyl cyanide monomer units is 0 to 100% by mass, and other vinyl units. The content of the monomer unit is preferably 0 to 30% by mass, the aromatic vinyl monomer unit 30 to 85% by mass, the vinyl cyanide monomer unit 15 to 70% by mass, and the other monomer units 0 to 20%. More preferably, the aromatic vinyl monomer unit is 50 to 80% by mass, the vinyl cyanide monomer unit is 20 to 50% by mass, and the other monomer unit is 0 to 10% by mass. From the viewpoint of excellent mechanical properties of the obtained molded body, the other monomer units are preferably 30% by mass or less.

Specific examples of the (co) polymer include styrene resin, acrylonitrile resin, styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-N-phenylmaleimide copolymer, methyl methacrylate-styrene copolymer, methacryl Acid methyl-styrene-acrylonitrile copolymer, styrene-butadiene copolymer (SBR resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-ethylenepropylene-styrene copolymer (AES resin), acrylonitrile- A chlorinated polyethylene-styrene copolymer (ACS resin), an acrylonitrile-acrylic elastic body-styrene copolymer (AAS resin), and a methyl methacrylate-butadiene-styrene copolymer (MBS resin).
Styrene resin, AS resin, and ABS resin are preferable. These are preferable because they can be easily molded.

When a styrene resin or AS resin is used as the (co) polymer, the upper limit of the weight average molecular weight (Mw) is preferably 200,000, more preferably 110,000, and the lower limit is preferably 30,000. . If the weight average molecular weight is within the above range, the fluidity will be good.
When an ABS resin is used as the (co) polymer, the rubber polymer content in 100% by mass of the ABS resin is preferably 10 to 90% by mass, and more preferably 10 to 70% by mass. If the content of the rubbery polymer is within the above range, the fluidity will be good.

  The method for producing the (co) polymer is not particularly limited, and a commonly known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, emulsion polymerization or the like is used. It is also possible to blend separately (co) polymerized resins.

As a compounding ratio of the PC resin and the (co) polymer, “PC resin / (co) polymer” is preferably “50/50 to 99/1” mass%, and “50/50 to 90/10”. “% By mass” is more preferable, and “60/40 to 90/10” mass% is more preferable.
When the blending ratio of the PC resin and the copolymer is within the above range, the resulting resin composition is excellent in the balance between fluidity, heat resistance and flame retardancy.

<Rubber-containing graft copolymer>
The rubber-containing graft copolymer mainly exhibits the effect of improving the impact strength of the molded product.
The rubber-containing graft copolymer is obtained by polymerizing the grafting vinyl monomer (b) in the presence of the rubber (A) containing the polyorganosiloxane (A1) and the vinyl polymer (A2). It is a polymer in which the refractive index of the rubber (A) is in the range of 1.47 to 1.56 (hereinafter sometimes referred to as “graft copolymer”). The volume average particle diameter of the rubber (A) is preferably in the range of 300 to 2000 nm.

[Polyorganosiloxane (A1)]
The polyorganosiloxane (A1) is a polymer containing an organosiloxane unit as a constituent unit. The polyorganosiloxane can be obtained by polymerizing an organosiloxane or an “organosiloxane mixture” containing at least one kind of an organosiloxane and components used as necessary. Examples of components used as necessary include a siloxane-based crosslinking agent, a siloxane-based graft crossing agent, and a siloxane oligomer having a terminal blocking group.

  As the organosiloxane, any of chain organosiloxane, alkoxysilane compound, and cyclic organosiloxane can be used. Among these, an alkoxysilane compound and a cyclic organosiloxane are preferable, and a cyclic organosiloxane is more preferable because of high polymerization stability and a high polymerization rate.

  The alkoxysilane compound is preferably a bifunctional alkoxysilane compound, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, Examples thereof include methylphenyldiethoxysilane.

  The cyclic organosiloxane is preferably a 3- to 7-membered ring. For example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetra Mention may be made of methyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These can be used individually by 1 type or in combination of 2 or more types. Among these, the main component is preferably octamethylcyclotetrasiloxane because the particle size distribution can be easily controlled.

  As the organosiloxane, it is preferable to use an organosiloxane which is a cyclic dimethylsiloxane and / or a bifunctional dialkylsilane compound because a graft copolymer having higher impact resistance can be obtained.

  The cyclic dimethylsiloxane is a cyclic siloxane having two methyl groups on a silicon atom, and examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used individually by 1 type or in combination of 2 or more types.

  A bifunctional dialkylsilane compound is a silane compound having two alkoxy groups and two alkyl groups on a silicon atom, and examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane. These can be used individually by 1 type or in combination of 2 or more types.

  As the siloxane-based crosslinking agent, those having a siloxy group are preferable. By using a siloxane-based crosslinking agent, a polyorganosiloxane having a crosslinked structure can be obtained. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. An agent can be mentioned. Among these, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is more preferable. The content of the siloxane-based crosslinking agent is preferably 0 to 30% by mass and more preferably 0.1 to 30% by mass in 100% by mass of the organosiloxane mixture. By setting the content of the siloxane-based crosslinking agent to 0.1 to 30% by mass, a graft copolymer having good impact resistance can be obtained.

  The siloxane-based graft crossing agent has a siloxy group and a functional group polymerizable with a vinyl monomer. By using a siloxane-based graft crossing agent, a polyorganosiloxane having a functional group polymerizable with a vinyl monomer can be obtained. Since the polyorganosiloxane has a functional group capable of polymerizing with a vinyl monomer, the polyorganosiloxane, a vinyl monomer for rubber (a2) and a vinyl monomer for graft (b) described later are grafted by radical polymerization. Can be made.

  Examples of the siloxane graft crossing agent include siloxanes represented by the formula (I).

RSiR ¹ _n (OR ² ) _(3-n) (I)

In formula (I), R ¹ represents a methyl group, an ethyl group, a propyl group, or a phenyl group. R ² represents an organic group in the alkoxyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, and a phenyl group. n represents 0, 1 or 2. R represents any group represented by formulas (I-1) to (I-4).

^{_{CH 2 = C (R 3)}} -COO- (CH 2) p - (I-1)
_{^{CH 2 = C (R 4)}} -C 6 H 4 - (I-2)
_{CH 2 = CH- (I-3} )
_{HS- (CH 2) p- (I} -4)

In these formulas, R ³ and R ⁴ each represent hydrogen or a methyl group, and p represents an integer of 1 to 6.

  Examples of the functional group represented by the formula (I-1) include a methacryloyloxyalkyl group. Examples of the siloxane having this group include the following. β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyl Diethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and the like.

  Examples of the functional group represented by the formula (I-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 formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.

  Examples of the functional group represented by the formula (I-4) include a mercaptoalkyl group. Examples of the siloxane having this group include the following. γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, γ-mercaptopropylethoxydimethylsilane, γ-mercaptopropyltrimethoxysilane and the like.

  These siloxane-based graft crossing agents can be used alone or in combination of two or more. The content of the siloxane-based graft crossing agent is preferably 0 to 20% by mass and more preferably 0.05 to 20% by mass with respect to 100% by mass of the organosiloxane mixture. By setting the content of the siloxane-based graft crossing agent to 0.05 to 20% by mass, a graft copolymer having good impact resistance can be obtained.

  The siloxane oligomer having a terminal blocking group means a siloxane oligomer having an alkyl group or the like at the terminal of the organosiloxane oligomer and stopping the polymerization of the polyorganosiloxane.

  Examples of the siloxane oligomer having a terminal blocking group include hexamethyldisiloxane, 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. And methoxytrimethylsilane.

[Production method of polyorganosiloxane (A1)]
There is no restriction | limiting in particular as a manufacturing method of polyorganosiloxane (A1), For example, the following manufacturing methods are employable. First, 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 required is emulsified with an emulsifier and water. Prepare an emulsion. Thereafter, the mixture is polymerized at a high temperature using an acid catalyst, and then the acid is neutralized with an alkaline substance to obtain a polyorganosiloxane latex. In the following description of the production method, the case where an “organosiloxane mixture” is used as a raw material for polymerization will be described, but the same production process can be applied to the case where “organosiloxane” is used.

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

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

  The polymerization temperature is preferably 50 ° C. or higher, and more preferably 70 ° C. or higher. 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.

  Furthermore, since the crosslinking reaction between silanols proceeds at a temperature of 30 ° C. or lower, in order to increase the cross-linking density of the polyorganosiloxane, the resulting latex is polymerized at a high temperature of 50 ° C. It can also be held at the following temperature for about 5 to 100 hours.

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

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

  Examples of nonionic emulsifiers include the following. Polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol and the like. These emulsifiers can be used individually by 1 type or in combination of 2 or more types.

  The amount of the emulsifier used is preferably 0.05 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the organosiloxane mixture. Depending on the amount of emulsifier used, the particle diameter of the polyorganosiloxane latex can be adjusted to a desired value. If the usage-amount of an emulsifier is 0.05 mass part or more, the emulsification stability of the emulsion of an organosiloxane mixture will be enough. If the amount of the emulsifier is 10 parts by mass or less, the amount of the emulsifier remaining in the powder of the graft copolymer can be sufficiently reduced, so that the heat decomposability and surface of the resin composition containing the graft copolymer and the resin can be reduced. Deterioration of appearance can be suppressed.

  Examples of the acid catalyst used for polymerization of the organosiloxane mixture include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more. Among these, the use of mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid can narrow the particle size distribution of the polyorganosiloxane latex, and further, the thermal decomposition of the molded product due to the emulsifier component in the polyorganosiloxane latex. It is possible to achieve a reduction in property and a reduction in appearance defects.

  It is preferable that the usage-amount of an acid catalyst is 0.005-5 mass parts with respect to 100 mass parts of organosiloxane. When the amount of the acid catalyst used is 0.005 parts by mass or more, the polyorganosiloxane can be polymerized in a short time. Moreover, if the usage-amount of an acid catalyst is 5 mass parts or less, a molded object with favorable thermal decomposition resistance and an external appearance can be obtained.

  Further, since the amount of the acid catalyst used is a factor that determines the particle diameter of the polyorganosiloxane, the amount of the acid catalyst used is 0.005 to 1.5 mass in order to obtain a polyorganosiloxane having a particle diameter described later. More preferably, it is a part.

  The mass average particle diameter of the polyorganosiloxane latex is preferably in the range of 250 to 1000 nm. By setting the mass average particle diameter of the polyorganosiloxane latex in the range of 250 to 1000 nm, the volume average particle diameter of the rubber (A) can be adjusted in the range of 300 to 2000 nm.

  The “mass average particle size / number average particle size (Dw / Dn)” of the polyorganosiloxane latex is preferably in the range of 1.0 to 1.7. By setting Dw / Dn within the range of 1.0 to 1.7, a graft copolymer having high pigment colorability can be obtained.

  As the values of Dw and Dn, values measured by the following method can be adopted. Using a polyorganosiloxane latex diluted to a concentration of about 3% with deionized water, the particle size is measured using a CHDF2000 particle size distribution meter manufactured by MATEC, USA. The median diameter is used as the average particle diameter.

The measurement can be performed under the following standard conditions recommended by MATEC.
Cartridge: dedicated capillary cartridge for particle separation (trade name; C-202),
Carrier liquid: dedicated carrier liquid (trade name: 2XGR500),
Carrier liquid: almost neutral,
Carrier liquid flow rate: 1.4 ml / min,
Carrier liquid pressure: about 4,000 psi (2,600 kPa),
Measurement temperature: 35 ° C
Sample usage: 0.1 ml.
Further, as the standard particle size substance, 12 types of particles having a particle size of 40 to 800 nm, which are monodispersed polystyrenes having a known particle size manufactured by DUKE, USA, are used.

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

[Vinyl polymer (A2)]
Examples of the vinyl polymer (A2) of the present invention include a polymer obtained by polymerizing a vinyl monomer for rubber (a2).

[Vinyl monomer for rubber (a2)]
Examples of the vinyl monomer for rubber (a2) include the following monomers. Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate; ethyl acrylate, n-propyl acrylate, n-butyl acrylate Alkyl acrylates such as i-butyl acrylate and 2-ethylhexyl acrylate; phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4, Estes such as 6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, and trichlorophenyl (meth) acrylate Group is a phenyl group or substituted phenyl group aryl (meth) acrylate; acrylonitrile, methacrylonitrile vinyl cyanide monomers such as nitriles. These can be used alone or in combination of two or more.

  Among these, from the viewpoint of adjusting the refractive index of the rubber (A) within the range of 1.47 to 1.56, the vinyl monomer for rubber (a2) is an aromatic vinyl monomer and / or ester. It is preferable to use an aryl (meth) acrylate whose group is a phenyl group or a substituted phenyl group. That is, the vinyl polymer (A2) is preferably a polymer containing an aromatic vinyl monomer unit and / or an aryl (meth) acrylate unit in which the ester group is a phenyl group or a substituted phenyl group. The content of the vinyl polymer (A2) in 100% by mass of the rubber (A) is preferably 15 to 90% by mass, more preferably 20 to 60% by mass, and 45 to 60%. More preferably, it is mass%.

  The rubber vinyl monomer (a2) preferably contains a crosslinkable monomer. Examples of the crosslinkable monomer include the following polyfunctional monomers. Allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol diester dimethacrylate, propylene glycol diester dimethacrylate, 1,3-butylene glycol diester dimethacrylate, 1,4-butylene glycol diester dimethacrylate 1,6-hexanediol diacrylate, triallyl trimellitic acid and the like. These can be used alone or in combination of two or more.

  The content of the crosslinkable monomer in 100% by mass of the vinyl monomer for rubber (a2) is preferably 0.1 to 10% by mass, and more preferably 0.1 to 5% by mass. It is more preferable that it is 0.3-5 mass%, and it is especially preferable that it is 0.3-3 mass%. If the content of the crosslinkable monomer is 0.1% by mass or more and 10% by mass or less, it is more preferable because the impact resistance of the graft copolymer is improved.

  There is no restriction | limiting in particular as a manufacturing method of a vinyl polymer (A2), For example, although it can manufacture by an emulsion polymerization method, a suspension polymerization method, and a fine suspension polymerization method, it is preferable to use an emulsion polymerization method.

  As the radical polymerization initiator used for polymerization of the vinyl monomer for rubber (a2), an azo initiator, a peroxide, and a redox initiator in which a peroxide and a reducing agent are combined are used. These can be used alone or in combination of two or more. Of these, azo initiators and redox initiators are preferred.

  Examples of the azo initiator include the following. 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis Oil-soluble azo initiators such as (2-butyronitrile), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxymethyl) -2-methylpropiona [Midine] hydrate, 2,2′-azobis- (N, N′-dimethyleneisobutylamidine) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride Water-soluble azo initiators such as These can be used individually by 1 type or in combination of 2 or more types.

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

  When a peroxide is used as a redox initiator in combination with a reducing agent, the above peroxide, a reducing agent such as sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, dextrose, sorbose, inositol, and sulfuric acid It is preferable to use a combination of monoiron and ethylenediaminetetraacetic acid disodium salt. These reducing agents can be used individually by 1 type or in combination of 2 or more types.

  The radical polymerization initiator used for the polymerization of the vinyl monomer for rubber (a2) preferably has a solubility in water at 20 ° C. of 5% by mass or less, more preferably 2% by mass or less. preferable. By polymerizing using this radical polymerization initiator, a graft copolymer having excellent impact resistance can be obtained.

  Examples of the radical polymerization initiator having a solubility in water at 20 ° C. of 5% by mass or less include the following. Cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis ( 2-methylpropionate), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile) and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The solubility of the radical polymerization initiator in water at 20 ° C. can be known from catalogs of various radical polymerization initiators.

  When the azo initiator is used, the amount of the radical polymerization initiator used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the monomers. In the case of a redox initiator, the amount of peroxide used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers. It is preferable that the usage-amount of a reducing agent is 0.01-1 mass part with respect to a total of 100 mass parts of a monomer.

[Rubber (A)]
The rubber (A) of the present invention contains a polyorganosiloxane (A1) and a vinyl polymer (A2). Examples of the rubber (A) include rubbers having the following structures (1) to (3).
(1) A rubber having a multilayer structure in which a core of polyorganosiloxane (A1) is covered with a shell of a vinyl polymer (A2),
(2) A rubber having a multilayer structure in which the core of the vinyl polymer (A2) is covered with a shell of the polyorganosiloxane (A1),
(3) Composite rubber containing polyorganosiloxane (A1) and vinyl polymer (A2).

  The rubber (A) is preferably a “composite rubber” containing a polyorganosiloxane (A1) and a vinyl polymer (A2). The graft copolymer obtained from such a composite rubber has good impact resistance. The rubber (A) is more preferably a “composite rubber” composed of a polyorganosiloxane (A1) and a vinyl polymer (A2).

  In the present invention, the refractive index of the rubber (A) is in the range of 1.47 to 1.56, preferably in the range of 1.47 to 1.54, and preferably 1.47 to 1.53. More preferably, it is in the range, and further preferably in the range of 1.49 to 1.52. By setting the refractive index of the rubber (A) in the range of 1.47 to 1.56, a resin composition having excellent pigment colorability and impact resistance can be obtained. If the refractive index of rubber | gum (A) is 1.47 or more, the pigment colorability of a resin composition becomes favorable and is preferable. Moreover, if the refractive index of rubber | gum (A) is 1.56 or less, the impact resistance of a resin composition will become favorable and is preferable. The refractive index of the rubber (A) can be adjusted by adjusting the content of the polyorganosiloxane in the rubber (A), the type of vinyl monomer for rubber (a2) and the amount used.

The refractive index of the rubber (A) is calculated using the following formula (Formula 1) described in POLYMER HANDBOOK 4th Edition (Wiley Interscience).
<Formula 1>
n = v1n1 + v2n2 + v3n3 + (Formula 1)
In the formula, “n1, n2, n3,...” Represents the refractive index of each monomer homopolymer at 20 ° C., and values described in POLYMER HANDBOOK 4th Edition can be used. In the formula, “v1, v2, v3,...” Represents the volume fraction of each monomer.

  The rubber (A) of the present invention preferably has a polyorganosiloxane (A1) content of 10 to 85% by mass and a vinyl polymer (A2) content of 90 to 15% by mass. More preferably, the content is 40 to 80% by mass, the content of the vinyl polymer (A2) is 60 to 20% by mass, the content of the polyorganosiloxane (A1) is 40 to 55% by mass, and the vinyl polymer. More preferably, the content of (A2) is 60 to 45% by mass. By setting the content of the polyorganosiloxane (A1) to 10 to 85% by mass and the content of the vinyl polymer (A2) to 90 to 15% by mass, the impact resistance of the resin composition containing the graft copolymer, The balance between pigment colorability and flame retardancy is improved.

  The content of the alkyl (meth) acrylate unit in the rubber (A) is preferably 0 to 35% by mass and 0 to 30% by mass based on the total 100% by mass of the rubber (A). Is more preferable, 0 to 20% by mass is further preferable, and 0 to 15% by mass is particularly preferable. By setting the content of the alkyl (meth) acrylate unit to 0 to 35% by mass, the resin composition containing the graft copolymer has a good balance of impact resistance, pigment colorability, and flame retardancy.

There is no restriction | limiting in particular as a manufacturing method of rubber | gum (A). Examples of the method for producing the rubber having the structures (1) to (3) described above include the following methods.
Rubber having the structure of (1): A method of polymerizing the rubber vinyl monomer (a2) in the presence of a polyorganosiloxane latex to obtain a rubber (A) latex,
(2) Rubber having a structure: vinyl polymer (A2) A method of polymerizing an organosiloxane mixture in the presence of latex to obtain a latex of rubber (A),
Rubber having the structure of (3):
[3-1] The vinyl monomer for rubber (a2) is added to the polyorganosiloxane latex, and the vinyl monomer for rubber (a2) is impregnated into the polyorganosiloxane particles. ) To obtain a latex of rubber (A), and
[3-2] An organosiloxane mixture is added to the vinyl polymer (A2) latex, the vinyl polymer (A2) particles are impregnated with the organosiloxane mixture, and then the organosiloxane is polymerized to obtain a latex of rubber (A). Method.
As a method for obtaining the rubber having the structure (3), the method [3-1] is preferable from the viewpoint of easy adjustment of the particle diameter.

  As the method of [3-1], first, after adding the vinyl monomer for rubber (a2) to the polyorganosiloxane latex and impregnating the polyorganosiloxane, a known radical polymerization initiator is used. Is used for polymerization. In this method, examples of the method for adding the vinyl monomer for rubber (a2) include a method in which the entire amount thereof is added to the polyorganosiloxane latex at once, or a method in which the vinyl monomer is added dropwise at a constant rate.

  In producing the latex of the rubber (A), an emulsifier can be added to stabilize the latex and control the particle size of the rubber (A). Examples of the emulsifier include the same emulsifiers as those used in the production of the polyorganosiloxane latex, and anionic emulsifiers and nonionic emulsifiers are preferable.

  The volume average particle size (Dv) of the rubber (A) is preferably in the range of 80 to 2000 nm. If the volume average particle diameter of the rubber (A) is 80 nm or more, the impact resistance and pigment colorability of the resin composition containing the graft copolymer will be good. Moreover, if the volume average particle diameter is 2000 nm or less, the surface appearance and impact resistance of the molded article are improved, which is preferable. The volume average particle diameter of the rubber (A) is more preferably in the range of 300 to 1000 nm, more preferably in the range of 400 to 1000 nm, from the viewpoint of achieving a good balance between the impact resistance and pigment colorability of the resin composition. More preferably.

  The volume average particle diameter / number average particle diameter (Dv / Dn) of the rubber (A) is preferably in the range of 1.0 to 2.0, and preferably in the range of 1.0 to 1.5. More preferred. Dv / Dn represents the particle size distribution, and the closer to 1.0, the higher the monodispersity. If Dv / Dn is 2.0 or less, the pigment colorability of the resin composition is good, which is preferable. The method for measuring Dv / Dn will be described later in the Examples section.

[Vinyl monomer for grafting (b)]
The grafting vinyl monomer (b) is polymerized in the presence of the rubber (A) to form a graft portion made of a vinyl polymer on the rubber (A), thereby obtaining a polyorganosiloxane-containing graft copolymer. be able to.

  Examples of the vinyl monomer (b) for grafting include the following. Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate; ethyl acrylate, n-butyl acrylate, methyl acrylate, etc. Alkyl acrylates; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2, Estes such as 4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate Aryl (meth) acrylate group is a phenyl group or substituted phenyl group. These can be used individually by 1 type or in combination of 2 or more types.

  The grafting vinyl monomer (b) may contain a crosslinkable monomer. In this case, the amount of the crosslinkable monomer used in 100% by mass of the grafting vinyl monomer (b) is: It is preferable that it is 0.005 mass% or less.

  From the viewpoint of further improving the pigment colorability of the resin composition, the refractive index of the “polymer” obtained when the vinyl monomer for grafting (b) is polymerized alone is in the range of 1.45 to 1.60. It is preferable that it is in the range, and it is more preferable that it exists in the range of 1.50-1.60. By setting the refractive index of the polymer within the range of 1.50 to 1.60, the impact resistance and pigment colorability of the resin composition can be further improved. The refractive index of the polymer is more preferably in the range of 1.52 to 1.59.

  The refractive index of the polymer is calculated using the same formula as the refractive index of the rubber (A). The type and amount of the grafting vinyl monomer (b) are adjusted so that the refractive index of the polymer falls within the range of 1.45 to 1.60.

  From the viewpoint of adjusting the refractive index of the polymer within the range of 1.45 to 1.60, the grafting vinyl monomer (b) is an aromatic vinyl monomer, alkyl (meth) acrylate, vinyl cyanide. It is preferable to contain at least one selected from the group consisting of an aryl (meth) acrylate in which the monomer and the ester group are a phenyl group or a substituted phenyl group. Moreover, it is more preferable to contain the aryl (meth) acrylate whose ester group is a phenyl group or a substituted phenyl group from a compatible viewpoint with a graft copolymer and polycarbonate resin.

  Selected from aromatic vinyl monomer, alkyl (meth) acrylate, vinyl cyanide monomer, and aryl (meth) acrylate in which the ester group is a phenyl group or a substituted phenyl group in the grafting vinyl monomer (b). The content of the one or more monomers is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and more preferably 50 to 100% by mass with respect to 100% by mass of the vinyl monomer for grafting. More preferably, it is 100 mass%.

  The content of the rubber (A) in the graft copolymer is preferably 10 to 99% by mass with respect to 100% by mass of the graft copolymer. If the rubber (A) content is 10% by mass or more, the impact strength of the resin composition will be sufficient, and if it is 99% by mass or less, the surface appearance of the molded article will be good. From the viewpoint of making the impact strength of the resin composition better, the content of the rubber (A) is more preferably 50 to 95% by mass with respect to 100% by mass of the graft copolymer, and 65 to 90% by mass. More preferably.

  Examples of the graft copolymerization method include a method in which the grafting vinyl monomer (b) is added to the rubber (A) latex and the polymerization is performed in one or more stages. When polymerizing in multiple stages, it is preferable to divide the total amount of the vinyl monomer for grafting (b) in the presence of the latex of the rubber (A), and add or sequentially add to polymerize. . Such a polymerization method has good polymerization stability and can stably obtain a latex having a desired particle size and particle size distribution.

  For the latex of rubber (A) obtained by the method of [3-1] described above, the total amount of the vinyl monomer for grafting (b) is divided and added sequentially or continuously, Polymerization is preferred.

  In the polymerization of the graft portion, an emulsifier can be added as necessary. Examples of the emulsifier used for the polymerization of the graft portion include the same emulsifiers as those described above when the rubber (A) is produced, and anionic emulsifiers and nonionic emulsifiers are preferable.

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

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

  The spray drying method is a method in which a latex of a graft copolymer is sprayed in the form of fine droplets in a drier and dried by applying a heating gas for drying to the latex. Examples of the method for generating fine droplets include a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type. The capacity of the dryer may be a small capacity as used in a laboratory or a large capacity as used industrially. The temperature of the heating gas for drying is preferably 200 ° C. or less, and more preferably 120 to 180 ° C. Two or more types of graft copolymer latices produced separately may be spray dried together. 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 the latex of the graft copolymer and spray dried.

  The coagulation method is a method of coagulating the latex of the graft copolymer, separating, recovering, and drying the graft copolymer. First, a graft copolymer latex is introduced into hot water in which a coagulant is dissolved, salted out, and solidified to separate the graft copolymer. Next, the graft copolymer in which the moisture content is reduced by dehydration or the like is recovered from the separated wet graft copolymer. 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, sodium nitrate, and calcium acetate, and acids such as sulfuric acid, and calcium acetate is particularly preferable. These coagulants can be used singly or in combination of two or more, but when two or more are used, it is necessary to select a combination that does not form a water-insoluble salt. For example, the combined use of calcium acetate and sulfuric acid or a sodium salt thereof is not preferable because a calcium salt insoluble in water is formed.

  The above-mentioned coagulant is usually used as an aqueous solution. The concentration of the aqueous solution of the coagulant is preferably 0.1% by mass or more, particularly 1% by mass or more from the viewpoint of stably coagulating and recovering the graft copolymer. Further, from the viewpoint of reducing the amount of the coagulant remaining in the recovered graft copolymer and preventing the deterioration of the molding appearance 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, but the following methods are usually mentioned. (1) A method in which a latex is continuously added to the coagulant aqueous solution while stirring the coagulant aqueous solution and maintained for a certain period of time. (2) The coagulant aqueous solution and the latex are continuously mixed in a container equipped with a stirrer at a constant ratio. A method of continuously extracting a mixture containing a coagulated polymer and water from a container by bringing them into contact with each other. The temperature at which the latex is brought into contact with the coagulant aqueous solution is not particularly limited, but is preferably 30 ° C. or higher and 100 ° C. or lower. The contact time is not particularly limited.

  The coagulated graft copolymer is washed with about 1 to 100 times by weight of water, and the wet graft copolymer separated by filtration is dried using a fluid dryer, a press dehydrator or the like. The drying temperature and drying time may be appropriately determined depending on the obtained graft copolymer. In addition, it is possible to directly send to the extruder or molding machine that produces the resin composition without collecting the graft copolymer discharged from the press dehydrator or extruder, and to obtain a molded body by mixing with the polycarbonate resin. It is.

  In the present invention, the graft copolymer is preferably recovered using a coagulation method from the viewpoint of thermal decomposition resistance of a resin composition obtained by mixing with a polycarbonate resin.

  The content of the graft copolymer is preferably in a range of 0.5 to 30% by mass, more preferably in a total of 100% by mass of the polycarbonate resin, (co) polymer, and graft copolymer. Is in the range of 1 to 20% by mass, more preferably in the range of 2 to 15% by mass. When the content is 0.5% by mass or more, the obtained molded article is excellent in impact resistance. Moreover, it is excellent in fluidity | liquidity and the heat resistance of the molded object obtained as this content is 30 mass% or less.

<Flame Retardant>
The polycarbonate resin composition of the present invention preferably contains a flame retardant. By using a flame retardant, it is possible to obtain a resin composition with more excellent flame retardancy. As the flame retardant, a known flame retardant can be used, and examples thereof include the following. Halogen flame retardants comprising a combination of halogenated compounds such as halogenated bisphenol A, halogenated polycarbonate oligomers, brominated epoxy compounds, and flame retardant aids such as antimony oxide; organic salt flame retardants; phosphate ester flame retardants, Phosphorus flame retardants such as halogenated phosphoric acid ester flame retardants; sulfonic acid flame retardants such as metal salts of aromatic sulfonic acids and metal salts of perfluoroalkane sulfonic acids; branched phenyl silicone compounds and phenyl silicone resins Silicone flame retardants such as organopolysiloxanes. Among these flame retardants, phosphorus-based flame retardants are preferred because they are non-halogen-based and the resulting molded articles are excellent in flame retardancy.

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

  As a compounding quantity of the said flame retardant, it is preferable that it is 1-30 mass parts with respect to a total of 100 mass parts of polycarbonate resin, a (co) polymer, and a graft copolymer, More preferably, it is 5-20 masses. Within the range of the part.

<Other ingredients>
The polycarbonate resin composition of the present invention may contain additives such as other thermoplastic resins, antioxidants, mold release agents and the like within a range not impairing the effects of the present invention.
As the other thermoplastic resins, almost all known thermoplastic resins can be used. Specific examples of other thermoplastic resins include olefin resins such as polypropylene (PP) and polyethylene (PE), high impact polystyrene (HIPS), (meth) acrylic acid ester / styrene copolymer (MS), styrene Acrylic resin (Ac resin) such as maleic anhydride copolymer (SMA), polymethyl methacrylate (PMMA), polyamide resin (PA resin), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc. Polyester resins (PEs resins), (modified) polyphenylene ether resins (PPE resins), polyoxymethylene resins (POM resins), polysulfone resins (PSO resins), polyarylate resins (PAr) Resin), polyphenylene resin (PPS resin), heatable Engineering plastics such as flexible polyurethane resin (PU resin), olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, fluorine elastomer, 1,2-polybutadiene, transformer 1,4 -Thermoplastic elastomer (TPE) such as polyisoprene, PVC resin such as polyvinyl chloride (PVC) / ABS / St resin alloy, PA resin such as PA / ABS / St resin alloy, PA resin / TPE Alloys, PA resins such as PA / PP / polyolefin resins, PBT resins / TPE, PC resins such as PC / PBT / PEs resins alloys, polyolefin resins / TPE, olefin resins such as PP / PE Mutual alloy, PPE / HIP , PPE / PBT, PPE-based resin alloys such as PPE / PA, and a polymer alloy such as PVC resin / Ac resin alloy such as PVC / PMMA, rigid, semi-rigid, such as soft vinyl chloride resin. These may be used alone or in combination of two or more. Furthermore, a compatibilizing agent such as a graft copolymer can be used in combination.

  Examples of the additive include a dripping inhibitor, an antioxidant, a release agent, an ultraviolet absorber / light stabilizer, and a bluing agent.

(Anti-drip agent)
It is effective and preferable to use a dripping inhibitor in combination with a flame retardant. Examples of the anti-dripping agent include fluorine resins such as polytetrafluoroethylene, silicone rubber, polycarbonate / diorganosiloxane copolymer, siloxane polyetherimide, and liquid crystal polymer. A fluororesin is preferable.

  A well-known thing can be used as a fluororesin, what was synthesize | combined suitably may be used and a commercial item may be used. As a commercial item, the following are mentioned, for example. Polytetrafluoroethylene such as “Polyflon FA-500” (trade name, manufactured by Daikin Industries, Ltd.); SAN-modified polytetrafluoroethylene such as “BLENDEX B449” (trade name, manufactured by Galata Chemicals); Acrylic-modified polytetrafluoroethylene such as “3000”, “methabrene A-3750”, “methabrene A-3800” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). These fluororesins may be used alone or in combination of two or more.

  Among these fluororesins, SAN-modified polytetrafluoroethylene and acrylic-modified polytetrafluoroethylene are excellent in dispersibility in the obtained molded product, and the molded product is excellent in mechanical properties, heat resistance, and flame retardancy. Acrylic modified polytetrafluoroethylene is preferable.

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

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

〔Antioxidant〕
Antioxidants may be blended by adding to the graft copolymer latex, or blended when the polycarbonate resin, (co) polymer, and graft copolymer are mixed to produce a polycarbonate resin composition. May be.

  The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants, and phenolic antioxidants and / or phosphorus-based antioxidants. Antioxidants are more preferred. By using a phenol-based antioxidant and / or a phosphorus-based antioxidant, the coloring suppression effect at the time of molding becomes better.

  Examples of the phenol-based antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane and the like.

  Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable, and specific octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) is preferable. Propionate, pentaerythritol-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like. Among these, pentaerythritol-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferable.

  Examples of phosphorus antioxidants include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, and trioctadecyl phosphite. Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl- 4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol phosphite. Among these, trisnonylphenyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionic acid ester, ditridecyl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodipropionic acid ester, and distearyl. −3,3′-thiodipropionic acid ester, lauryl stearyl-3,3′-thiodipropionic acid ester, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3- Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. Among these, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

  The addition amount of the antioxidant is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin, (co) polymer, and graft copolymer. 0.01 parts by weight or more is more preferable. Moreover, 1 mass part or less is preferable with respect to 100 mass parts of polycarbonate resin compositions, as for the addition amount of antioxidant, 0.5 mass part or less is more preferable, and 0.3 mass part or less is further more preferable. If the addition amount of the antioxidant is within the above range, the coloration suppressing effect at the time of molding tends to be good.

〔Release agent〕
The mold release agent is blended for the purpose of further improving the mold release from the cooling roll during sheet molding or the mold during injection molding.
Examples of the release agent include higher fatty acid esters of mono- or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin wax, olefin wax containing carboxy group and / or carboxylic anhydride group, silicone oil, And organopolysiloxane. These may be used alone or in combination of two or more.

  The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, behenic acid monoglyceride, and behenyl behenate. , Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene And sorbitan monostearate, 2-ethylhexyl stearate and the like. Among these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferable. A stearic acid ester is more preferable as a mold release agent from the viewpoints of mold release and transparency.

  As the stearic acid ester, a partial or total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and stearic acid is preferable. Examples of the partial ester or total ester of monohydric or polyhydric alcohol and stearic acid include ethylene glycol distearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, penta Examples include erythritol monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, butyl stearate, sorbitan monostearate, 2-ethylhexyl stearate and the like. Among these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate and stearyl stearate are more preferable, and ethylene glycol distearate and stearic acid monoglyceride are more preferable.

  As the higher fatty acid, a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable, and an unsubstituted saturated fatty acid having 10 to 30 carbon atoms is more preferable. Examples of such higher fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid. Among these, saturated fatty acids having 16 to 18 carbon atoms are preferable. Examples of such saturated fatty acids include palmitic acid and stearic acid, and stearic acid is particularly preferable.

  The addition amount of the release agent is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin, (co) polymer, and graft copolymer. More preferably 1 part by mass or more. The amount of the release agent added is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin composition. When the content of the release agent in the polycarbonate resin composition is within the above range, there is an advantage that the molded body is easily released from the mold at the time of molding, and the molded body is easily obtained.

[Ultraviolet absorber / light stabilizer]
The discoloration of the polycarbonate resin composition of the present invention by ultraviolet rays is remarkably small as compared with the conventional polycarbonate resin composition, but contains one or more of ultraviolet absorbers and light stabilizers for the purpose of further improvement. May be.
The ultraviolet absorber / light stabilizer is not particularly limited as long as it is a compound having ultraviolet absorbing ability. Examples of the compound having ultraviolet absorbing ability include organic compounds and inorganic compounds. Among these, an organic compound is preferable because it is easy to ensure affinity with the polycarbonate resin and is easily dispersed uniformly.

  The molecular weight of the organic compound having ultraviolet absorbing ability is not particularly limited, but is preferably 200 or more, more preferably 250 or more, preferably 600 or less, more preferably 450 or less, and further preferably 400 or less.

  Examples of the compound having ultraviolet absorbing ability include benzotriazole compounds, benzophenone compounds, malonic acid ester compounds, triazine compounds, benzoate compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, oxalic acid anilide compounds, and the like. Is mentioned. Among these, benzotriazole compounds, hydroxybenzophenone compounds, and malonic ester compounds are preferable. These may be used alone or in combination of two or more.

  More specific examples of the benzotriazole compounds include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl- 5'-hexylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t -Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-dodecylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, methyl-3- (3- (2H-benzotriazol-2-yl ) -5-t-butyl-4-hydroxyphenyl) propionate and the like.

  Examples of the benzophenone compounds include hydroxybenzophenone compounds such as 2,2'-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-octoxybenzophenone.

  Examples of the malonic ester compounds include 2- (1-arylalkylidene) malonic esters, tetraethyl-2,2 '-(1,4-phenylene-dimethylidene) -bismalonate, and the like.

  Examples of the triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3. , 5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine, 2- (4,6-diphenyl-1,3 , 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by Ciba Geigy Japan, "Tinuvin 1577FF").

  Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.

  Examples of the oxalic acid anilide compound include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant, Sanduvor VSU).

  The total amount of UV absorber and light stabilizer added can be appropriately selected according to the type of UV absorber or light stabilizer, but polycarbonate resin, (co) polymer, and graft copolymer. 0.001-5 mass parts is preferable with respect to a total of 100 mass parts.

[Bluing agent]
The bluing agent is blended for the purpose of canceling the yellowness of the molded body.
As the bluing agent, any bluing agent that can be used in conventional polycarbonate resins can be used without any problem. In general, anthraquinone dyes are easily available and preferred.

  Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No. (Color Index No.) 60725], generic name Solvent Violet 31 [CA. No. 68210], generic name Solvent Violet 33 [CA. No. 60725], generic name Solvent Blue 94 [CA. No. 61500], generic name Solvent Violet 36 [CA. No. 68210], generic name Solvent Blue97 [manufactured by Bayer "Macrolex Violet RR"], generic name Solvent Blue45 [CA. No. 61110].

The amount of the blueing agent added is preferably 0.1 × 10 ⁻⁴ to 2 × 10 ⁻⁴ parts by mass with respect to 100 parts by mass in total of the polycarbonate resin, (co) polymer, and graft copolymer.

[Other additives]
In addition to the above-mentioned additives, the polycarbonate resin composition can be used in various known additives such as a flame retardant aid, a hydrolysis inhibitor, an antistatic agent, a foaming agent, a dye, and the like as long as the effects of the present invention are not impaired. Reinforcing agents and fillers such as pigments, glass fibers, metal fibers, metal flakes, and carbon fibers can be contained.

<Production method of polycarbonate resin composition>
The polycarbonate resin composition of the present invention is produced by mixing a polycarbonate resin, a copolymer containing an aromatic vinyl monomer unit and / or a vinyl cyanide monomer unit, and a rubber-containing graft copolymer. can do. Specifically, for example, a pellet-like polycarbonate resin, a copolymer containing an aromatic vinyl monomer unit and / or a vinyl cyanide monomer unit, and a rubber-containing graft copolymer are used using an extruder. A polycarbonate resin composition can be obtained by mixing, extruding into a strand, and cutting into a pellet with a rotary cutter or the like.

  Moreover, when a polycarbonate resin composition contains another component, as a blending method of the other component, any method may be used as long as it is a commonly used blending method. For example, a method of mixing and kneading with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc., or a solution mixed in a common good solvent such as methylene chloride Although the blending method etc. are mentioned, this is not specifically limited.

  The polycarbonate resin composition of the present invention thus obtained is further added with various additives as required, and once formed into pellets directly or by a melt extruder, an extrusion molding method, an injection molding method, a compression molding method. It can be formed into a desired shape by a generally known forming method such as a method.

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

  The molded body of the present invention can be widely used industrially as various materials in the automotive field, OA equipment field, home appliance, electrical / electronic field and the like. More specifically, it can be used as a casing such as an electronic device, various parts, automobile structural members, automobile interior parts, and a light reflecting plate. More specifically, it can be used as an interior / exterior member of a personal computer casing, a mobile phone casing, a portable information terminal casing, a portable game machine casing, a printer, a copying machine, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Prior to Examples, various evaluation methods and Production Examples 1 to 3 of polyorganosiloxane latex will be described. Production Examples 4 to 7 are examples relating to the production and evaluation of a graft copolymer, and Examples 1 to 5 and Comparative Examples 1 to 5 are examples relating to the production and evaluation of a polycarbonate resin composition. In the production examples and examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
<Evaluation method>

(1) Solid content The polyorganosiloxane latex of mass w1 was dried with a hot air dryer at 180 ° C. for 30 minutes, the mass w2 of the residue after drying was measured, and the solid content [%] was calculated by the following formula.
Solid content [%] = w2 / w1 × 100

(2) Volume average particle diameter, number average particle diameter, Dv / Dn
"Rubber latex" or "graft copolymer latex" is diluted with deionized water, and rubber particles and graft copolymer are used using a laser diffraction / scattering particle size distribution analyzer (SALD-7100, manufactured by Shimadzu Corporation). The volume average particle diameter Dv and the number average particle diameter Dn of the combined particles were measured, and Dv / Dn was calculated.

  In the above measurement, the refractive index calculated from the monomer composition of the rubber (A) or graft copolymer was used. The median diameter was used as the particle diameter. Further, the sample concentration of the rubber latex was appropriately adjusted so as to be within an appropriate range in the scattering intensity monitor attached to the apparatus.

(3) Charpy impact strength According to JIS K 7111, the Charpy impact strength of a test piece (length 80.0 mm × width 10.0 mm × thickness 4 mm, with V notch) was measured at temperatures of 23 ° C. and −30 ° C. did.

(4) Pigment colorability In accordance with ISO 14782, using Nippon Denshoku Industries Co., Ltd. HAZE Meter NDH4000, the total light transmittance in a D65 light source about a test piece (length 100mm, width 50mm, thickness 2mm). Was measured. A higher total light transmittance indicates a better pigment colorability.

(5) Flame retardancy A UL-94V test (vertical test method) was performed on 1/16 inch test pieces (length 127 mm, width 12.7 mm, thickness 1.6 mm).

[Production Example 1] (Production of polyorganosiloxane latex ( _AS- 1))
2 parts of tetraethoxysilane (TEOS), 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane (DSMA) and octamethylcyclotetrasiloxane (product name: TSF404) 96 manufactured by Momentive Performance Materials Japan Co., Ltd. Parts were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution in which 1 part of sodium dodecylbenzenesulfonate (DBSNa) is dissolved in 150 parts of deionized water is added to the mixture, stirred at 10,000 rpm for 5 minutes with a homomixer, and then applied to a homogenizer at a pressure of 20 MPa. Passed twice to obtain a stable premixed emulsion.

The emulsion is then placed in a separable flask having a capacity of 5 liters equipped with a cooling condenser, the emulsion is heated to a temperature of 80 ° C., and then a mixture of 0.20 parts of sulfuric acid and 49.8 parts of distilled water. Was continuously charged over 3 minutes. The polymerization reaction was carried out while maintaining the state heated to 80 ° C. for 7 hours, and then cooled to room temperature (25 ° C.), and the resulting reaction product was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane latex (A _S -1).

The solid content of the polyorganosiloxane latex (A _S -1) was 29.8%. The latex had a number average particle size (Dn) of 384 nm, a mass average particle size (Dw) of 403 nm, and Dw / Dn of 1.05 as measured by a capillary particle size distribution meter.

Production Example 2 (Production of polyorganosiloxane latex _(A S -2))
Cyclic organosiloxane mixture (trimer: 5%, tetramer: 85%, pentamer: 3%, hexamer: 6%, heptamer: 1% mixture. Manufactured by Shin-Etsu Chemical Co., Ltd. Product name: DMC) 97.5 parts, TEOS 2 parts and DSMA 0.5 part were mixed to obtain 100 parts of an organosiloxane mixture. A solution prepared by dissolving 0.68 parts of DBSNa and 0.68 parts of DBSH in 200 parts of deionized water was added to this, and the mixture was stirred for 2 minutes at 10,000 rpm with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa. A premixed emulsion was obtained.

Next, after the emulsion was put in 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 the state heated to 85 ° C. was maintained for 6 hours to cause a polymerization reaction. After that, it was cooled to room temperature (25 ° C.), and the obtained reaction product was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane latex (A _S -2).

The solid content of the polyorganosiloxane latex (A _S -2) was 28.3%. Moreover, the weight average particle diameter (Dw) by the capillary particle size distribution meter of this latex was 224 nm, the number average particle diameter (Dn) was 86 nm, and Dw / Dn was 2.60.

[Production Example 3] (Production of polyorganosiloxane latex _(A S -3))
97.5 parts of DMC, 2 parts of TEOS and 0.5 part of DSMA were mixed to obtain 100 parts of an organosiloxane mixture. 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 with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa to obtain a stable premixed emulsion. .

On the other hand, 10 parts of DBSH and 90 parts of deionized water were injected into a separable flask equipped with a cooling condenser to prepare an aqueous medium.
With the aqueous solution heated to 90 ° C., the above premixed emulsion was added dropwise over 4 hours, and after completion of the dropwise addition, the state heated to 85 ° C. was maintained for 2 hours for polymerization reaction, and then brought to room temperature (25 ° C.). Upon cooling, the resulting reaction was kept at room temperature for 6 hours. Then, 5% sodium hydroxide aqueous solution was added and the reaction liquid was neutralized to pH 7.0, and polyorganosiloxane latex ( _AS- 3) was obtained.

Solids content of the polyorganosiloxane latex _(A S -3) was 19.2%. Moreover, the weight average particle diameter (Dw) of this latex by capillary particle size distribution meter was 62 nm, the number average particle diameter (Dn) was 58 nm, and Dw / Dn was 1.07.

[Production Example 4] (Production of graft copolymer (G-1))
Taken polyorganosiloxane latex _(A S -1) 100.67 parts obtained in Production Example 1 (30.0 parts of a polymer basis) to the separable flask 5-liter, was added to 160 parts of deionized water Mixed. Next, a mixture of 39 parts of styrene (St), 1.0 part of allyl methacrylate (AMA) and 0.16 part of cumene hydroperoxide (CHP) was added to the separable flask, and the mixture was stirred at room temperature for 1 hour. Impregnated with organosiloxane. In addition, this mixture is a mixture of the vinyl monomer (a2) for rubber | gum used as the raw material of a vinyl polymer (A2).

  The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the liquid temperature was raised to 50 ° C. When the liquid temperature reached 50 ° C., 0.001 part of ferrous sulfate (Fe), 0.003 part of disodium ethylenediaminetetraacetate (EDTA) and 0.24 part of sodium formaldehyde sulfoxylate (SFS) were removed. An aqueous solution dissolved in 10 parts of ionic water was added to initiate radical polymerization. In order to complete the polymerization of the vinyl monomer component, the state of 65 ° C. was maintained for 1 hour from the time when the liquid temperature dropped to 65 ° C. to obtain a latex of rubber (A-1) containing polyorganosiloxane and styrene. . When this latex was evaluated, the refractive index of the rubber (A-1) was 1.515, the volume average particle diameter (Dv) was 433 nm, and Dv / Dn was 1.16.

  A liquid mixture of 28.5 parts of methyl methacrylate (MMA), 1.5 parts of methyl acrylate (MA) and 0.16 parts of t-butyl hydroperoxide (t-BH) in a state where the liquid temperature of the latex is 65 ° C. Was dropped into the latex over 1 hour to initiate and continue the graft polymerization reaction. After completion of the dropwise addition, the temperature was kept at 60 ° C. or higher for 1 hour and then cooled to room temperature to obtain a latex of the polyorganosiloxane-containing graft copolymer (G-1). The refractive index of the graft part was 1.489. The volume average particle diameter (Dv) of the graft copolymer particles was 525 nm.

  Next, 500 parts of an aqueous solution having a calcium acetate concentration of 1% by mass is heated to 60 ° C., and while stirring, 340 parts of the latex of the graft copolymer (G-1) is gradually dropped into the aqueous solution to be solidified. It was. The obtained graft copolymer (G-1) was filtered, washed, dehydrated and then dried to obtain a powder of the graft copolymer (G-1).

[Production Examples 5 to 6] (Production of graft copolymer (G-2, 3))
The graft copolymer (G-2 to 3) was prepared in the same manner as in Production Example 4 except that the polyorganosiloxane latex (A _S -1) was changed to A _S -2 or A _S -3 in Production Example 4. A powder was obtained. Table 1 shows the volume average particle diameter of the graft copolymer particles.

[Production Example 7] (Production of graft copolymer (G′-1))
The graft copolymer (G′-1) was prepared in the same manner as in Production Example 4 except that St used for the vinyl monomer for rubber (a2) in Production Example 4 was changed to n-butyl acrylate (nBA). A powder was obtained. Table 1 shows the volume average particle diameter of the graft copolymer particles.

Abbreviations in Table 1 are as follows.
St: styrene nBA: n-butyl acrylate AMA: allyl methacrylate MMA: methyl methacrylate MA: methyl acrylate tBH: t-butyl hydroperoxide CHP: cumene hydroperoxide
The numerical values in parentheses in the column of polyorganosiloxane and vinyl monomer (a2) in Table 1 indicate the composition ratio (% by mass) in 100% by mass of rubber (A).

[Examples 1-5, Comparative Examples 1-5]
Polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon S-2000F, viscosity average molecular weight 22,000), AS resin (UMG-ABS Co., Ltd., trade name: AP-H), ABS resin ( UMG-ABS Co., Ltd., trade name: RB) and the graft copolymer (G-1 to 3 and G′-1) powders obtained in Production Examples 4 to 7 in the amounts shown in Table 2. Blended. The blend was melt-mixed at a cylinder temperature of 280 ° C. and a screw rotation speed of 150 rpm using a twin-screw extruder (L / D = 30) having a cylinder inner diameter of 30 mm to obtain a polycarbonate resin composition. Next, this polycarbonate resin composition was shaped into pellets.

  The obtained pellets were dried at 80 ° C. for 12 hours and then supplied to a 100-ton injection molding machine (trade name: SE-100DU, manufactured by Sumitomo Heavy Industries, Ltd.), and injection molding was performed at a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. Each test piece was obtained. Subsequently, Charpy impact strength, pigment colorability, and flame retardance were evaluated using each test piece, and the evaluation results shown in Table 2 were obtained.

Abbreviations in Table 2 are as follows.
PC resin: Polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon S-2000F)
AP-H: AS resin (manufactured by UMG-ABS, trade name: AP-H)
RB: ABS resin (UMG-ABS Co., Ltd., trade name: RB)
PX-200: Flame retardant, 1,3-phenylenebis (di-2,6-xylenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200)
A-3800: Anti-drip agent, polytetrafluoroethylene (PTFE) -containing powder (trade name A-3800, manufactured by Mitsubishi Rayon Co., Ltd.)
Irg1076: phenolic antioxidant (manufactured by BASF, trade name: Irganox1076)
ADK2112: Phosphorous antioxidant (manufactured by ADEKA, trade name: ADK STAB 2112)

  As shown in Table 2, the polycarbonate resin compositions (H-1 to 3, 6, 9) of Examples 1 to 5 constitute the respective graft copolymers (G-1 to G-3). Since the refractive index of the rubbers (A-1 to A-3) in the range of 1.47 to 1.56, both the impact resistance and the pigment colorability were good. Since the polycarbonate resin composition (H-6) of Example 4 further contains a flame retardant, both the impact resistance and the flame retardancy were good.

  The polycarbonate resin composition (H-4) of Comparative Example 1 had poor pigment colorability because the refractive index of the rubber (A′-1) constituting the graft copolymer (G′-1) was low.

  Since the polycarbonate resin composition (H-5) of Comparative Example 2 did not contain a graft copolymer, the impact resistance was poor.

  The polycarbonate resin composition (H-7) of Comparative Example 3 had poor flame retardancy because the refractive index of the rubber (A′-1) constituting the graft copolymer (G′-1) was low.

  Since the polycarbonate resin composition (H-8) of Comparative Example 4 did not contain a graft copolymer, the impact resistance and flame retardancy were poor.

  The polycarbonate resin composition (H-10) of Comparative Example 5 had poor pigment colorability due to the low refractive index of the rubber (A′-1) constituting the graft copolymer (G′-1).

  The polycarbonate resin composition of the present invention is excellent in impact resistance, pigment colorability and flame retardancy. This resin composition is useful as a material in the fields of automobiles, OA equipment such as printers, and electric / electronic fields such as mobile phones.

Claims (4)

A polycarbonate resin composition comprising a polycarbonate resin, a (co) polymer containing aromatic vinyl monomer units and / or vinyl cyanide monomer units, and a rubber-containing graft copolymer,
The blending ratio of the polycarbonate resin and the (co) polymer containing the aromatic vinyl monomer unit and / or vinyl cyanide monomer unit is 50 to 99/50 to 1,
The rubber-containing graft copolymer is an aryl (meth) acrylate in which an aromatic vinyl monomer and / or an ester group is a phenyl group or a substituted phenyl group as a polyorganosiloxane (A1) and a vinyl monomer for rubber (a2). Obtained by polymerizing the vinyl monomer for grafting (b) in the presence of the rubber (A) containing the vinyl polymer (A2) using
A polycarbonate resin composition in which the refractive index of the rubber (A) is in the range of 1.47 to 1.56. The polycarbonate resin composition according to claim 1, wherein the rubber (A) has a volume average particle diameter in the range of 300 to 2000 nm. The polycarbonate resin composition according to claim 1 or 2, further comprising a flame retardant. The molded object obtained by shape | molding the polycarbonate resin composition of any one of Claims 1-3.