JP7025936B2 - Polycarbonate resin composition and molded products - Google Patents

Description

The present invention relates to a polycarbonate resin composition and a molded product, and more particularly to a polycarbonate resin composition and a molded product having excellent flame retardancy, impact resistance and thermal stability, as well as excellent hue and moisture heat resistance.

Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, dimensional stability, etc. as a general-purpose engineering plastic, and because of its excellent properties, it is industrially used as a raw material in the fields of automobiles, OA equipment, electrical and electronic fields, etc. Widely used.

There is a strong demand for flame-retardant resin materials, mainly for applications such as OA equipment and home appliances, and in order to meet these demands, polycarbonate resins, halogen compounds, phosphorus compounds, siloxane compounds, and polyfluoroethylene are used in polycarbonate resins. Many techniques have been proposed to make flame-retardant by blending such materials.
For example, Patent Document 1 describes impact resistance by blending a polycarbonate resin with a specific phosphoric acid ester compound, a composite rubber-based graft copolymer having a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component. It is stated that a resin composition having excellent flame retardancy can be obtained. Further, in Patent Document 2, a resin composition obtained by blending a phosphorus-based flame retardant, a polyfluoroethylene resin and a specific multilayer structure polymer with an aromatic polycarbonate resin has flame retardancy, thermal stability, and impact resistance. It is described that it is useful as a large-sized molded product or a thin-walled molded product because it has excellent properties and has an effect of improving the appearance. Further, Patent Document 3 describes a flame-retardant resin composition comprising a polycarbonate resin, a composite rubber-based graft copolymer, a phosphoric acid ester compound, and polytetrafluoroethylene as a material having excellent impact resistance, moldability, and fluidity. The thing is listed.

In OA equipment, home appliances, etc., the molded products are becoming thinner year by year for the purpose of miniaturization, weight reduction, high functionality, etc., and their required performance is becoming more sophisticated, flame retardant, impact resistance, and further. There is a demand for a polycarbonate resin composition having thermal stability that can withstand high-temperature molding and further excellent in hue and moisture heat resistance.

Further, the flame-retardant polycarbonate / styrene resin alloy composition is suitable as a member for electrical / electronic equipment such as computers, notebook personal computers, various mobile terminals, printers, copiers, and office automation / information equipment. It is used.
Among them, the polycarbonate / styrene resin alloy composition flame-retarded by a phosphorus-based flame retardant is extremely excellent in moldability due to the plasticizing effect of the phosphorus-based flame retardant, and is therefore the most common for obtaining thin-walled and large-sized molded products. Composition (see, for example, Patent Documents 4 to 6).
However, especially in OA equipment, home appliances, etc., the molded products are becoming thinner year by year for the purpose of miniaturization, weight reduction, high functionality, etc., and in order to obtain higher moldability, the processing temperature should not be raised. In addition, since the residence time tends to be extended, the polycarbonate / styrene resin alloy as described above cannot maintain high impact strength or yellowing occurs to obtain a molded product having a desired hue. It has the problem of not being able to do it.
As described above, the polycarbonate / styrene resin alloy is required to have flame retardancy, impact resistance, thermal stability capable of withstanding high temperature molding, and further excellent in hue and moisture heat resistance.

Japanese Unexamined Patent Publication No. 08-259791 Japanese Unexamined Patent Publication No. 2001-123056 Japanese Unexamined Patent Publication No. 11-21441 Japanese Patent No. 3638806 Japanese Patent No. 4080851 Japanese Patent No. 4157271

An object (problem) of the present invention is to provide a polycarbonate resin composition and a molded product having excellent flame retardancy, impact resistance, hue and moisture heat resistance, and thermal stability capable of withstanding high temperature molding.

As a result of diligent studies to achieve the above problems, the present inventor has added a polycarbonate resin or a polycarbonate resin / ABS resin alloy, a phosphoric acid ester compound, a phosphite-based antioxidant, and 2,6-di-tert. We have found that the above problems can be solved by containing -butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol in a specific amount, and have completed the present invention. ..
The present invention relates to the following polycarbonate resin compositions and molded articles.

[1] A graft containing an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2), and a diene-based rubbery polymer component (b3) with respect to 100 parts by mass of the polycarbonate resin (A). Polymer (B) 0 to 40 parts by mass, phosphate ester compound (C) 10 to 30 parts by mass, phosphite-based antioxidant (D) 0.001 to 1.0 part by mass, and 2,6-di-. A polycarbonate resin composition comprising 0.00001 to 0.1 parts by mass of tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E).
[2] The phosphite-based antioxidant (D) is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol and / or bis (2,4-dicumylphenyl) pentaerythritol. The polycarbonate resin composition according to the above [1], which is diphosphite.
[3] The polycarbonate resin composition according to the above [1] or [2], further containing 1 to 20 parts by mass of the core / shell type elastomer (F) with respect to 100 parts by mass of the polycarbonate resin (A).
[4] The polycarbonate resin composition according to any one of the above [1] to [3], further containing 1 to 10 parts by mass of talc (G) with respect to 100 parts by mass of the polycarbonate resin (A).
[5] The polycarbonate resin composition according to any one of the above [1] to [4], further containing 0.01 to 7 parts by mass of the white pigment (H) with respect to 100 parts by mass of the polycarbonate resin (A). ..
[6] The polycarbonate resin composition according to the above [5], wherein the white pigment (H) is titanium oxide.
[7] Containing a phosphite-based antioxidant (D) and 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E). The polycarbonate resin composition according to any one of the above [1] to [6], wherein the total amount is 0.002 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A).
[8] Mass ratio of 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) to phosphite-based antioxidant (D) The polycarbonate resin composition according to any one of the above [1] to [7], wherein (E) / (D) is 0.001 to 1.
[9] A molded product obtained by molding the polycarbonate resin composition according to any one of the above [1] to [8].

The polycarbonate resin composition of the present invention has excellent flame retardancy and impact resistance, has a high degree of thermal stability that can withstand high-temperature molding, and is also excellent in hue and moisture heat resistance.

Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below.
In addition, in this specification, "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value, unless otherwise specified. Further, "part" means a mass part based on a mass standard unless otherwise specified.

The polycarbonate resin composition of the present invention has an aromatic vinyl monomer component (b1), a cyanide vinyl monomer component (b2), and a diene-based rubbery polymer component (b1) with respect to 100 parts by mass of the polycarbonate resin (A). 0 to 40 parts by mass of the graft copolymer (B) containing b3), 10 to 30 parts by mass of the phosphate ester compound (C), 0.001 to 1.0 part by mass of the phosphite-based antioxidant (D), and It is characterized by containing 0.00001 to 0.1 parts by mass of 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E). do.

[Polycarbonate resin (A)]
There is no limitation on the type of the polycarbonate resin (A) used in the polycarbonate resin composition of the present invention. Further, one type of the polycarbonate resin (A) may be used, or two or more types may be used in any combination and in any ratio.
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula:-[-O-X-OC (= O)-]-. In the formula, X is generally a hydrocarbon, but a heteroatom or an X having a heterobond introduced may be used to impart various properties.

Further, the polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, and any of them can be used. Of these, aromatic polycarbonate resins are preferable from the viewpoints of heat resistance, mechanical properties, electrical properties, and the like.

The specific type of the polycarbonate resin is not limited, and examples thereof include a polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting with cyclic ether using carbon dioxide as a carbonate precursor may also be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, as the copolymer, various copolymer forms such as a random copolymer and a block copolymer can be selected. Usually, such a polycarbonate polymer becomes a thermoplastic resin.

Among the monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

2,2'-Dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1 , 7-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other dihydroxynaphthalene;

2,2'-Dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxydiaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-Bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-Bis (3-methyl-4-hydroxyphenyl) propane,
2,2-Bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-Bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-Bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-Bis [2- (4-Hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-Bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-Bis (4-hydroxyphenyl) butane,
2,2-Bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-Bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-Bis (4-hydroxyphenyl) octane,
4,4-Bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardo-structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4'-Dihydroxydiphenylsulfide,
Dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4,4'-Dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;
And so on.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (particularly from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferable.
As the aromatic dihydroxy compound, one type may be used, or two or more types may be used in any combination and ratio.

To give an example of a monomer that is a raw material for an aliphatic polycarbonate resin,
Etan-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;

Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4 Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

Glycols such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiroglycol;

1,2-Benzene dimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-Hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4'-biphenyldimethanol, 4,4'-biphenyldiethanol, 1,4- Aralkyldiols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

1,2-Epoxide ethane (ie, ethylene oxide), 1,2-epoxypropane (ie, propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl Cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane; and the like.

Among the monomers used as raw materials for the polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of carbonate precursors. As the carbonate precursor, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of the carbonyl halide include phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds.

Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditril carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate form of dihydroxy compound, monocarbonate form of dihydroxy compound, and cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.

The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

Other matters concerning the polycarbonate resin (A) The molecular weight of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 10,000 or more. It is 14,000 or more, more preferably 15,000 or more, and usually 40,000 or less, preferably 33,000 or less, more preferably 30,000 or less. By setting the viscosity average molecular weight to the lower limit of the above range or more, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used in applications with high mechanical strength requirements. On the other hand, by setting the viscosity average molecular weight to the upper limit of the above range or less, it is possible to suppress and improve the decrease in fluidity of the polycarbonate resin composition of the present invention, improve the molding processability, and facilitate the molding process.
Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned suitable range may be mixed.

The viscosity average molecular weight [Mv] is defined as the ultimate viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using a Ubbelohde viscometer using methylene chloride as a solvent. , Η = 1.23 × 10 ^-4 Mv ^0.83 means a value calculated from. The ultimate viscosity [η] is a value calculated by the following formula by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

The terminal hydroxyl group concentration of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but is usually 1,000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. Thereby, the retention heat stability and the color tone of the polycarbonate resin composition of the present invention can be further improved. Further, the lower limit thereof is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly for the polycarbonate resin produced by the melt transesterification method. This makes it possible to suppress a decrease in molecular weight and further improve the mechanical properties of the polycarbonate resin composition of the present invention.

The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the polycarbonate resin. The measuring method is colorimetric quantification by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88 215 (1965)).

The polycarbonate resin (A) is not limited to an embodiment containing only one type of polycarbonate resin, and includes, for example, an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in a sense.), Or it may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, a polycarbonate resin is used as a copolymer with an oligomer or a polymer having a siloxane structure for the purpose of further improving flame retardancy and impact resistance; a phosphorus atom for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; Even if it is configured as a copolymer mainly composed of a polycarbonate resin, such as a copolymer with an oligomer or a polymer having an olefin structure; a copolymer with a polyester resin oligomer or a polymer for the purpose of improving chemical resistance; good.

Further, in order to improve the appearance and fluidity of the molded product, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Further, the contained polycarbonate ligomer is preferably 30 parts by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin (A) may be not only a virgin raw material but also a polycarbonate resin recycled from a used product (so-called material recycled polycarbonate resin). Examples of the used products include optical recording media such as optical disks; light guide plates; automobile windowpanes, automobile headlamp lenses, vehicle transparent members such as windshields; containers such as water bottles; glasses lenses; soundproof walls, etc. Examples include building materials such as glass windows and corrugated sheets. In addition, non-conforming products, crushed products obtained from sprue, runners, etc., pellets obtained by melting them, and the like can also be used.

[Graft copolymer (B) containing aromatic vinyl monomer component (b1), vinyl cyanide monomer component (b2) and diene-based rubbery polymer component (b3)]
The graft copolymer (B) that may be contained in the polycarbonate resin composition of the present invention includes an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2), and a diene-based rubbery polymer. It is a graft copolymer containing the component (b3). The graft copolymer (B) is preferably an aromatic vinyl monomer component (b1) of 40 to 80% by mass, a cyanide vinyl monomer component (b2) of 10 to 30% by mass, and a diene-based rubbery polymer. It is preferably composed of 10 to 50% by mass of the component (b3) and 0 to 30% by mass of the other monomer component (b4).

Examples of the aromatic vinyl monomer component (b1) in the graft copolymer (B) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene and p-tert. -Butylstyrene, vinylnaphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, tribromstyrene and the like can be mentioned, with styrene being particularly preferable.
The ratio of the aromatic vinyl monomer component (b1) in the graft copolymer (B) is preferably in the range of 40 to 80% by mass, more preferably 40% by mass, based on 100% by mass of the graft copolymer (B). It is 45% by mass or more, more preferably 50% by mass or more, particularly preferably 55% by mass or more, more preferably 75% by mass or less, still more preferably 70% by mass or less, and particularly preferably 65% by mass or less.

Examples of the vinyl cyanide monomer component (b2) in the graft copolymer (B) include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
The ratio of the vinyl cyanide monomer component (b2) in the graft copolymer (B) is preferably in the range of 10 to 30% by mass, more preferably 10 to 30% by mass, based on 100% by mass of the graft copolymer (B). It is 12% by mass or more, more preferably 14% by mass or more, particularly preferably 15% by mass or more, more preferably 28% by mass or less, still more preferably 26% by mass or less, and particularly preferably 25% by mass or less.

As the diene-based rubbery polymer component (b3) of the graft copolymer (B), for example, a rubber component such as polybutadiene, polyisoprene, or a styrene-butadiene copolymer is used, and the diene-based rubbery polymer component (diene-based rubbery polymer component (b3). The proportion of b3) in the graft copolymer (B) is preferably in the range of 10 to 50% by mass, more preferably 13% by mass or more, still more preferably 13% by mass, based on 100% by mass of the graft copolymer (B). It is 14% by mass or more, particularly preferably 15% by mass or more, and more preferably 45% by mass or less.

Further, another monomer component (b4) copolymerizable with these may be copolymerized. In this case, examples of the other copolymerizable vinyl monomer include maleimide, N-methylmaleimide, and N-. Maleimide-based monomers such as cyclohexylmaleimide and N-phenylmaleimide, acrylamide-based monomers such as acrylamide and N-methylacrylamide, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, and unsaturated acids such as acrylic acid and methacrylic acid. , Glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate and the like.
The ratio of the other monomer component (b4) in the graft copolymer (B) is preferably in the range of 0 to 30% by mass, more preferably 20 in 100% by mass of the graft copolymer (B). It is mass% or less, more preferably 10 mass% or less.

Specific examples of the graft copolymer (B) include acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer and the like. Is preferably exemplified, and among them, an acrylonitrile-butadiene-styrene copolymer, particularly an ABS resin is preferable.

The graft copolymer (B) is usually produced by a method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and any method can be used.

The content of the graft copolymer (B) is 0 to 40 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A).
In the first aspect, the preferred content of the graft copolymer (B) is 10 to 40 parts by mass, more preferably 12 parts by mass or more, still more preferably 15 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). By mass or more, particularly preferably 18 parts by mass or more, preferably 35 parts by mass or less, further preferably 30 parts by mass or less, particularly preferably 27 parts by mass or less, more preferably 12 to 35 parts by mass, still more preferable. Is 15 to 30 parts by mass, particularly preferably 18 to 27 parts by mass.
Further, the content of the graft copolymer (B) in the second aspect, which does not contain the graft copolymer (B) or contains a small amount, is 0 parts by mass or 0 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is preferably more than 0 parts by mass and less than 10 parts by mass, preferably 0 parts by mass or more and less than 8 parts by mass, further preferably 0 parts by mass or more and less than 6.5 parts by mass, and 0 parts by mass or more and less than 5 parts by mass. Is particularly preferable.

[Phosphate ester compound (C)]
The polycarbonate resin composition of the present invention contains a phosphoric acid ester compound (C) as a flame retardant. The phosphoric acid ester compound (C) may be a small molecule, an oligomer, or a polymer, but from the viewpoint of thermal stability, the phosphoric acid ester represented by the general formula (1). Compounds are particularly preferred.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ、炭素数１～６のアルキル基又はアルキル基で置換されていてもよい炭素数６～２０のアリール基を示し、ｐ、ｑ、ｒ及びｓは、それぞれ０又は１であり、ｋは０から５の整数であり、Ｘ^１はアリーレン基を示す。）

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, respectively. , P, q, r and s are 0 or 1, respectively, k is an integer from 0 to 5, and X ¹ represents an arylene group.)

The phosphoric acid ester compound represented by the above formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of condensed phosphoric acid esters having different k, k is a mixture thereof. It becomes an average value. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

Further, X ¹ represents a divalent arylene group, for example, resorcinol, hydroquinone, bisphenol A, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. It is the basis. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3'-dihydroxybiphenyl are particularly preferred.

Further, p, q, r and s in the formula (1) represent 0 or 1, respectively, and are preferably 1 among them.

Further, R ¹ , R ² , R ³ and R ⁴ each indicate an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such an aryl group include a phenyl group, a cresyl group, a xylyl group, an isopropylphenyl group, a butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a p-cumylphenyl group and the like. A group, a cresyl group and a xylyl group are more preferable.

Specific examples of the phosphoric acid ester compound represented by the formula (1) include
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyldiphenyl phosphate (CDP), 2-ethylhexyldiphenyl phosphate (EHDP), tert-butylphenyldiphenyl phosphate, bis- ( Aromatic phosphate esters such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
And so on.

The acid value of the phosphoric acid ester compound represented by the formula (1) is preferably 0.2 mgKOH / g or less, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH / g or less. Particularly preferably, it is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by mass or less, further preferably 0.9 parts by mass or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the thermal stability and hydrolysis resistance of the polycarbonate resin composition of the present invention are likely to deteriorate.

The content of the phosphoric acid ester compound (C) is 10 to 30 parts by mass, preferably 11 parts by mass or more, more preferably 12 parts by mass or more, and more preferably 12 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Is 28 parts by mass or less, more preferably 25 parts by mass or less, preferably 11 to 30 parts by mass, further preferably 12 to 30 parts by mass, particularly preferably 15 to 30 parts by mass, and most preferably 15 to 28 parts by mass. Is. When the blending amount of the phosphoric acid ester compound (C) is less than 10 parts by mass, the flame retardancy is insufficient, and when it exceeds 30 parts by mass, a remarkable decrease in heat resistance and a decrease in mechanical properties are likely to occur.

[Phosphite-based antioxidant (D)]
The polycarbonate resin composition of the present invention contains a phosphite-based antioxidant (D). The phosphite compound is a trivalent phosphorus compound represented by the general formula: P (OR) ₃ , and R represents a monovalent or divalent organic group.

Among the phosphite-based antioxidants, a phosphite-based antioxidant having a spiro-ring skeleton is preferable, and in particular, a phosphite compound having a pentaerythritol diphosphite structure represented by the following general formula (2) is the present invention. It is preferable because the heat-resistant discoloration property of the polycarbonate resin composition can be effectively enhanced.

（式中、Ｒ^５及びＲ^６は、それぞれ同一であっても異なっていてもよく、炭素数６以上３０以下のアリール基を表す。）

(In the formula, R ⁵ and R ⁶ may be the same or different, respectively, and represent an aryl group having 6 or more and 30 or less carbon atoms.)

Examples of the phosphite compound represented by the above formula (2) include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-dikumilphenyl) penta. Ellisritol diphosphite and the like are particularly preferred. Specific examples of such an organic phosphite compound include "ADEKA STAB PEP-36" manufactured by ADEKA and "Doverphos S-9228" manufactured by Doverchemical.

The phosphite-based antioxidant (D) may contain one kind or two or more kinds in any combination and ratio.

The content of the phosphite-based antioxidant (D) is 0.001 to 1.0 part by mass, preferably 0.002 part by mass or more, and more preferably 0.002 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is 0.003 parts by mass or more, preferably 0.8 parts by mass or less, more preferably 0.65 parts by mass or less, and further preferably 0.5 parts by mass or less. If the content of the phosphite-based antioxidant (D) is less than 0.001 part by mass, the hue and moisture heat resistance will be insufficient, and if it exceeds 1.0 part by mass, the impact resistance and moisture heat resistance will be poor. On the contrary, it tends to get worse.

[2,6-di-tert-butyl-p-cresol, 2,4-bis- (α, α-dimethylbenzyl) phenol (E)]
The polycarbonate resin composition of the present invention contains 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E).
The content of 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) is based on 100 parts by mass of the polycarbonate resin (A). It is 0.00001 to 0.1 parts by mass, preferably 0.00005 parts by mass or more, more preferably 0.0001 parts by mass or more, still more preferably 0.0002 parts by mass or more, and particularly preferably 0.0003 parts by mass or more. It is more preferably 0.0004 parts by mass or more, preferably 0.09 parts by mass or less, more preferably 0.08 parts by mass or less, and further preferably 0.07 parts by mass or less. It is preferably 0.0002 to 0.09 parts by mass, more preferably 0.0003 to 0.08 parts by mass, and further preferably 0.0003 to 0.07 parts by mass. If the content of 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) is less than 0.00001 parts by mass, the hue, Moisture and heat resistance becomes insufficient, and if it exceeds 0.1 parts by mass, impact resistance and moisture and heat resistance tend to deteriorate.

Then, the content of the phosphite-based antioxidant (D) and the content of 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) The total is preferably 0.002 to 1 part by mass, more preferably 0.003 part by mass or more, still more preferably 0.005 part by mass or more, and more preferably 0.005 part by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). , More preferably 0.9 mass or less, still more preferably 0.8 mass or less, preferably 0.003 to 0.9 parts by mass, and even more preferably 0.005 to 0.8 parts by mass.
Further, the content of 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) and the phosphite-based antioxidant (D). The mass ratio (E) / (D) is preferably 0.001 to 1, more preferably 0.005 to 0.8, still more preferably 0.01 to 0.5, and 0.02 to 0.5. Is particularly preferable.

[Core / Shell Elastomer (F)]
The polycarbonate resin composition of the present invention contains a core / shell type elastomer (F).
The core / shell type elastomer is preferably a core / shell type graft copolymer type, and is preferably a diene rubber such as polybutadiene, a polybutyl acrylate rubber, a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkylacrylate rubber. A core / shell-type graft co-weight consisting of a shell layer formed by copolymerizing at least one rubber component selected from an IPN-type composite rubber or the like and a (meth) acrylic acid ester around the core layer. Coalescence is mentioned.

Among them, a graft copolymer type elastomer having a diene-based rubbery polymer as a core layer and a shell layer obtained by graft-copolymerizing a (meth) acrylic acid ester compound with the core layer is preferably used. The method for producing the graft copolymer may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like.

The diene rubber of the core layer includes polybutadiene, (partially) hydrogenated polybutadiene, and a butadiene-styrene copolymer, (partially) hydrogenated polybutadiene-styrene copolymer, butadiene-styrene block copolymer, and (partially) water. One or more vinyl-based monomers that can copolymerize with butadiene and butadiene, such as polybutadiene-styrene block copolymers, butadiene-acrylonitrile copolymers, and acrylic rubber copolymers containing butadiene-isobutyl acrylate as a main component. Examples thereof include butadiene-based rubbers such as a copolymer with the above, and isobutylene-based rubbers such as polyisobutylene, polyisobutylene-styrene copolymer, and polyisobutylene-styrene block copolymer, and butadiene-based rubber is particularly preferable.

The butadiene rubber is obtained by copolymerizing 95 to 100% by mass of 1,3-butadiene and 0 to 5% by mass of one or more vinyl-based monomers copolymerizable with 1,3-butadiene. Polybutadiene, butadiene-styrene copolymer, and butadiene-styrene block copolymer obtained by copolymerizing with the above are more preferable, and polybutadiene in which 1,3-butadiene is substantially 100% by mass is particularly preferable. Polybutadiene Substantially 100% by mass means a rubber composed only of butadiene, but contains a trace amount of other components for the purpose of improving the thermal stability of the rubbery polymer and for facilitating the particle size control. You may. However, at this time, the other component is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less in the butadiene rubber.

Further, as the (meth) acrylic acid ester compound to be graft-polymerized on the diene rubber, a methacrylic acid alkyl ester such as methyl methacrylate, ethyl methacrylate, or n-butyl acrylate;
Aryl methacrylates such as phenyl methacrylate and naphthyl methacrylate;
Examples thereof include glycidyl group-containing methacrylates such as glycidyl acrylate and glycidyl methacrylate; among them, methacrylic acid alkyl ester is preferable and methyl methacrylate is more preferable from the viewpoint of balance between heat resistance and polycarbonate resin.
In addition, one kind or two or more kinds of the said (meth) acrylic acid ester compounds can be used.

Further, in addition to the above (meth) acrylic acid ester compound, other vinyl-based monomers may be contained, if desired. Other vinyl-based monomers include, for example,
Aromatic vinyls such as styrene and α-methylstyrene;
Unsaturated nitriles such as acrylonitrile and methacrylonitrile;
Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;
Maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide;
Α, β-Unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (eg, maleic anhydride);
And so on.

Furthermore, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene;
Unsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate;
Unsaturated carboxylic acid allyl esters such as allyl acrylate and allyl methacrylate;
Crosslinkable monomers such as di and triallyl compounds such as diallyl phthalate, diallyl sebacate, and triallyl triazine can also be used in combination.

The content of the diene rubber in such a preferable core / shell type elastomer is 50 in 100% by mass of the total of the diene rubber, the (meth) acrylic acid ester compound, other monomers and the crosslinkable monomer. It is preferably ~ 95% by mass, more preferably 70 to 90% by mass, and even more preferably 75 to 85% by mass.

The (meth) acrylic acid ester compound to be graft-copolymerized with the diene rubber is preferably 50 to 100% by mass in the total of 100% by mass of the (meth) acrylic acid ester compound, other monomers and the crosslinkable monomer. It is by mass, more preferably 75 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably substantially 100% by mass.

The method for producing the graft copolymer of the core / shell type elastomer is not particularly limited, and any production method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization may be used, and the copolymerization method may be used. Although it may be a one-step graft or a multi-step graft, the emulsion polymerization method is preferable and the multi-step emulsion polymerization method is more preferable from the viewpoint of easy control of productivity and particle size. Examples of this multi-stage emulsification polymerization method include the polymerization methods described in JP-A-2003-261629.

Further, the average particle size of the core / shell type elastomer (F) is preferably 160 to 240 nm. If the average particle size is smaller than the above lower limit, the impact resistance of the polycarbonate resin composition of the present invention is likely to be insufficient, and if the average particle size exceeds the above upper limit, the polycarbonate resin composition of the present invention is likely to be insufficient. The flame retardancy and fire resistance of polycarbonate are likely to decrease, the impact resistance during high-temperature molding is also reduced, and the initial hue is also likely to deteriorate. The average particle size is more preferably 170 to 220 nm, and even more preferably 180 to 210 nm.
The average particle size is determined by the volume average particle size D50 when the graft copolymer solution after the completion of polymerization is measured by a dynamic light scattering method. For the measurement, for example, "Microtrack Particle Size Analyzer 9230UPA" manufactured by Nikkiso Co., Ltd. can be used.

Examples of such a core / shell type elastomer include "Paraloid (registered trademark, the same shall apply hereinafter) EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", and "Paraloid EXL2311" manufactured by Rohm and Haas Japan. "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", "Paraloid KCZ201", "Metabrene (registered trademark, the same shall apply hereinafter) C-223A", "Metabren E-901" manufactured by Mitsubishi Chemical Corporation. , "Metabren E-875A", "Metabren S-2001", "Metabren SRK-200", "Kaneka (registered trademark, same below) M511", "Kaneace M711", "Kaneace M600", "Kaneace" "M400", "Kaneka M580", "Kaneace MR-01" and the like can be mentioned.

The content of the core / shell type elastomer (F) is preferably 1 to 20 parts by mass, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). In particular, it is 4 parts by mass or more, more preferably 15 parts by mass or less, further preferably 12 parts by mass or less, particularly 10 parts by mass or less, more preferably 2 to 15 parts by mass, still more preferably 3 to 3 parts by mass. It is 12 parts by mass, most preferably 4 to 10 parts by mass. When the content of the core / shell type elastomer (F) is smaller than the lower limit of the above range, the impact resistance of the polycarbonate resin composition of the present invention is insufficient and the content exceeds the upper limit of the above range. Is likely to cause deterioration of flame retardancy, impact resistance, hue, and moisture heat resistance.

[White pigment (G)]
The polycarbonate resin composition of the present invention also preferably contains a white pigment (G). By containing the white pigment, it becomes possible to whiten the resin molded product. Examples of the white pigment include titanium oxide, ZnS, ZnO and the like, and titanium oxide is more preferable.

As the titanium oxide, it is preferable to use a commercially available titanium oxide containing 80% by mass or more of titanium oxide in terms of whiteness. Examples of the titanium oxide include titanium monoxide (TIO), dititanium trioxide (Ti ₂ O ₃ ), titanium dioxide (TIO ₂ ) and the like, and any of these may be used, but titanium dioxide is preferable. .. Further, as the titanium oxide, one having a rutile-type crystal structure is preferably used.

The average primary particle size of the white pigment is preferably 1 μm or less, more preferably 0.001 to 0.5 μm, and further preferably 0.002 to 0.1 μm. .. By setting the average particle size of the white pigment in such a range and the blending amount within the range described later, a molded product having a high degree of whiteness can be obtained.

The content of the white pigment (G) is preferably 0.01 to 7 parts by mass, more preferably 0.1 part by mass or more, and further preferably 0.2 by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is 5 parts by mass or more, more preferably 6 parts by mass or less, and further preferably 5 parts by mass or less.
Only one kind of white pigment may be contained, or two or more kinds may be contained. When two or more types are included, the total amount is preferably in the above range.

[Fluoropolymer]
The polycarbonate resin composition of the present invention preferably contains a fluoropolymer.
Examples of the fluoropolymer include fluoroolefin resins. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perflualkyl vinyl ether copolymer resin and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril-forming ability.

Examples of the fluoroethylene resin having a fibril-forming ability include "Teflon (registered trademark) 6J" and "Teflon (registered trademark) 640J" manufactured by Mitsui Dupont Fluorochemical Co., Ltd., "Polyflon F201L" and "Polyflon F103" manufactured by Daikin Industries, Ltd. , "Polyflon FA500B", "Polyflon FA500H" and the like. Further, as commercially available products of the aqueous dispersion of the fluoroethylene resin, for example, "Teflon (registered trademark) 31-JR" manufactured by Mitsui-DuPont Fluorochemical Co., Ltd., "Fluon D-210C" manufactured by Daikin Industries, Ltd. and the like can be mentioned. Further, a fluoroethylene polymer having a multilayer structure obtained by polymerizing a vinyl-based monomer can also be used, and as such a fluoroethylene polymer, a polystyrene-fluoroethylene composite or a polystyrene-acrylonitrile-fluoroethylene can be used. Examples thereof include a composite, a polymethylmethacrylate-fluoroethylene complex, a polybutylbutylmethacrylate-fluoroethylene complex, and specific examples thereof include "Metabrene A-3800" manufactured by Mitsubishi Chemical Co., Ltd. and "Blendex" manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. It should be noted that one type of anti-dripping agent may be contained, and two or more types may be contained in any combination and ratio.

As the fluoropolymer in the present invention, it is preferable to use a fluoropolymer having a standard specific gravity value of 2.15 to 2.22. If the standard specific density is less than 2.15, the appearance of the molded product tends to deteriorate, which is not preferable. Further, when the standard specific gravity exceeds 2.22, the drip resistance tends to decrease, which is not preferable. The value of the standard specific density is preferably 2.155 to 2.215, more preferably 2.16 to 2.1, particularly preferably 2.16 to 2.20, and 2.165. It is most preferably ~ 2.19. The standard specific gravity (also referred to as SSG) is a value measured by a water substitution method using a sample molded in accordance with ASTM D4895.

The average particle size of the fluoropolymer is not particularly limited, but is preferably 300 to 1,000 μm. If the average particle size is less than 300 μm, the drip resistance of the polycarbonate resin composition may decrease, and if it exceeds 1,000 μm, the fluoropolymer tends to aggregate, and the molded product is white. It is not preferable because it may cause poor appearance such as point foreign matter. From such a viewpoint, the average particle size of the fluoropolymer is more preferably 350 to 800 μm, further preferably 380 to 750 μm, and particularly preferably 400 to 700 μm.

The content of the fluoropolymer is preferably 0.01 to 1 part by mass, more preferably 0.03 part by mass or more, still more preferably 0.05 part by mass or more, and particularly preferably 0.05 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). Is 0.1 parts by mass or more, more preferably 0.8 parts by mass or less, still more preferably 0.7 parts by mass or less. If the content of the fluoropolymer is less than 0.01 parts by mass, the flame-retardant effect of the anti-dripping agent is insufficient, and if the content exceeds 1 part by mass, a molded product obtained by molding a polycarbonate resin composition. The appearance is poor and the mechanical strength is likely to decrease.

[Release agent]
Further, the polycarbonate resin composition of the present invention preferably contains a mold release agent.
Preferred examples of the release agent include an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, bechenic acid, lignoseric acid, cellotic acid, melicinic acid, tetrariacontanic acid, montanic acid and adipine. Acids, azelaic acid and the like can be mentioned.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same one as the above-mentioned aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term aliphatic is used as a term including an alicyclic compound.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Can be mentioned.

The above ester may contain an aliphatic carboxylic acid and / or an alcohol as impurities. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, as the aliphatic carboxylic acid and the alcohol which are combined to form one ester, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, fisher-tropus wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but a mixture of constituents and various molecular weights can be used as long as the main component is within the above range.

Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

The above-mentioned mold release agent may contain one kind or two or more kinds in any combination and ratio.

The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is less than the mass part. If the content of the release agent is less than the lower limit of the above range, the effect of the release property may not be sufficient, and if the content of the release agent exceeds the upper limit of the above range, the hydrolysis resistance There is a possibility that the mold will be reduced and the mold will be contaminated during injection molding.

[Phenolic compounds other than 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E)]
Further, the polycarbonate resin composition of the present invention is a phenolic compound other than 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E). May include.
Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-) tert-Butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) ] Methyl] Phosphoate, 3,3', 3'', 5,5', 5''-Hexa-tert-butyl-a, a', a''-(mesitylen-2,4,6-triyl) tri -P-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine- 2-Ilamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 2,4-di-tert- Examples include butylphenol.

When a phenolic compound other than 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) is contained, the content is a polycarbonate resin. (A) With respect to 100 parts by mass, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, and particularly preferably 0.3 part by mass or less.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other resins, additives and the like in addition to those described above, if necessary, as long as the desired physical properties are not significantly impaired.
Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and the like. Styre resin such as acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resin such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin ; Polyetherimide resin; Polyurethane resin; Polyphenylene ether resin; Polyphenylene sulfide resin; Polysulfone resin and the like.
In addition, 1 type may be contained in other resin, and 2 or more types may be contained in arbitrary combinations and ratios.
However, when the other resin is contained, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further 5 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (A). In particular, it is preferably 3 parts by mass or less.

Examples of the resin additive include an ultraviolet absorber, a dye pigment, an antistatic agent, an anti-fog agent, an anti-blocking agent, a fluidity improver, a plasticizer, a dispersant, an antibacterial agent and the like. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained in arbitrary combinations and ratios.

[Molded product]
The polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a molded body. There are no restrictions on the shape, pattern, color, dimensions, etc. of this molded product, and it may be arbitrarily set according to the intended use of the molded product.

Examples of molded bodies include parts such as electrical / electronic equipment, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building materials, various containers, and lighting equipment. Among these, it is particularly suitable for use in the housing of electrical / electronic equipment and OA equipment, and is particularly suitable for housing of printers, copiers, projectors, modems, routers, and the like.

As a method for producing the molded product, any molding method generally adopted for the polycarbonate resin composition can be adopted. For example, an injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, a molding method using a heat insulating mold, and a rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermal molding method, rotary molding method, laminated molding method, press molding method, Blow molding method and the like can be mentioned. Further, a molding method using a hot runner method can also be used.

Among the above, injection molding methods such as an injection molding method, an ultra-high speed injection molding method, and an injection compression molding method are preferable.
The polycarbonate resin composition of the present invention has excellent thermal stability even under high-temperature molding conditions. When the polycarbonate resin composition of the present invention contains the graft copolymer (B) in an amount of 10 to 40 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), the resin temperature is as high as 260 ° C. or higher. Since the thermal stability is excellent even under molding conditions, it is possible to perform injection molding at a resin temperature of 265 ° C. or higher, particularly 270 ° C. or higher. The upper limit of the resin temperature at this time is preferably about 280 ° C. When the content of the graft copolymer (B) in the polycarbonate resin composition of the present invention is 0 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), the resin temperature is 290 ° C. or higher. Since the thermal stability is excellent even under high temperature molding conditions, it is possible to perform injection molding at a resin temperature of 290 ° C. or higher, particularly 300 ° C. or higher. The upper limit of the resin temperature at this time is preferably about 320 ° C.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and carried out without departing from the gist of the present invention.

Each component used in the following Examples and Comparative Examples is shown in Table 1 below.

(Examples 1 to 23, Comparative Examples 1 to 20)
[Manufacturing of resin pellets]
Each component other than the C component shown in Table 1 above was mixed in the proportions shown in Tables 2 to 6 below (all listed in parts by mass), mixed in a tumbler for 20 minutes, and then Japan Steel Works equipped with 1 vent. It is supplied to the Japan Steel Works twin-screw extruder (TEX30α) from the upstream feeder, and the C component is supplied from the middle of the barrel at the ratio (parts by mass) shown in Tables 2 to 6 while discharging at a rotation speed of 250 rpm. The mixture was kneaded under the conditions of a mass of 40 kg / hour and a barrel temperature of 260 ° C., and the molten resin extruded into a strand shape was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of a resin composition.

[Preparation of test piece]
The pellets obtained by the above-mentioned manufacturing method are dried at 80 ° C. for 5 hours, and then used under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 40 ° C. using an injection molding machine (SE100DU type) manufactured by Sumitomo Heavy Industries, Ltd. A UL94-5V test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm was formed by injection molding.
Similarly, after the pellets obtained by the above-mentioned manufacturing method are dried at 80 ° C. for 5 hours, a mold is used at a cylinder temperature of 270 ° C. using an injection molding machine (NEX80III, mold clamping force 80T) manufactured by Nissei Resin Industry Co., Ltd. Injection molding was performed under the condition of a temperature of 40 ° C. to form an ISO multipurpose test piece (3 mm).

[Flame retardance evaluation]
To evaluate the flame retardancy of each resin composition, the UL test test piece (1.5 mm thick) obtained above was subjected to humidity control for 48 hours in a constant temperature room at a temperature of 23 ° C. and a humidity of 50%, and UL94. It was performed in accordance with the -5V standard.

[Impact resistance (Charpy impact value)]
Using the 270 ° C. molded ISO multipurpose test piece (3 mm) obtained by the above method, the notched Charpy impact strength (unit: kJ / m ² ) was measured and evaluated according to ISO179.

[Initial hue (initial b value)]
The pellets obtained by the above manufacturing method are dried at 80 ° C. for 5 hours, and then injection molded at a cylinder temperature of 270 ° C. and a mold temperature of 40 ° C. using an injection molding machine (SE100DU type) manufactured by Sumitomo Heavy Industries, Ltd. Then, a three-stage plate having portions having thicknesses of 1.0 mm, 2.0 mm, and 3.0 mm was obtained.
For the 3.0 mm thick part of the 3-stage plate, use a spectrocolorimeter (CM3600d) manufactured by Konica Minolta, set the light source to D65, set the field of view to 10 degrees, and set the initial hue (SCI normal measurement mode). Initial b value) was measured.

[Hue after moist heat test (b value after moist heat test)]
Next, the three-stage plate was held at 65 ° C. and 85% humidity for 1000 hours, and then the hue after the moist heat test (b value after the moist heat test) was measured.
The above evaluation results are shown in Tables 2 to 6 below.

(Examples 24 to 28, Comparative Examples 21 to 27)
[Manufacturing of resin pellets]
Each component other than the C component shown in Table 1 above was blended in the proportion shown in Table 7 below (all listed in parts by mass), mixed in a tumbler for 20 minutes, and then manufactured by Japan Steel Works, Ltd. with 1 vent. It is supplied to the steel twin-screw extruder (TEX30α) from the upstream feeder, and the C component is supplied from the middle of the barrel at the ratio (parts by mass) shown in Table 7, while the rotation speed is 250 rpm and the discharge rate is 40 kg / hour. The molten resin extruded into strands was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of the resin composition.

[Preparation of test piece]
After the pellets obtained by the above-mentioned manufacturing method are dried at 80 ° C. for 5 hours, they are used under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 40 ° C. using an injection molding machine (SE100DU type) manufactured by Sumitomo Heavy Industries, Ltd. Injection molding was performed to mold a UL test test piece having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm.
Similarly, the pellets obtained by the above-mentioned manufacturing method are dried at 80 ° C. for 5 hours, and then used by an injection molding machine (NEX80III, mold clamping force 80T) manufactured by Sumitomo Heavy Industries, Ltd. at a cylinder temperature of 300 ° C. and gold. Injection molding was performed under the condition of a mold temperature of 40 ° C. to form an ISO multipurpose test piece (3 mm).

[Flame retardance evaluation]
For the evaluation of flame retardancy of each resin composition, the UL test test piece obtained above was conditioned for 48 hours in a constant temperature room at a temperature of 23 ° C. and a humidity of 50%, and conformed to the UL94-V standard. I went there.

Further, in the same manner as described above, impact resistance (Charpy impact value), initial hue (initial b value),
The hue after the moist heat test (b value after the moist heat test) was evaluated.
The evaluation results are shown in Table 7 below.

The polycarbonate resin composition of the present invention has a high degree of thermal stability that can withstand high-temperature molding, and has excellent flame retardancy and impact resistance, as well as excellent hue and moisture heat resistance. It can be suitably used for parts such as information terminal equipment, mechanical parts, home appliances, vehicle parts, building materials, various containers, lighting equipment, and the like.

Claims (8)

For 100 parts by mass of polycarbonate resin (A)
0 to 40 parts by mass of a graft copolymer (B) containing an aromatic vinyl monomer component (b1), a cyanide vinyl monomer component (b2) and a diene-based rubbery polymer component (b3),
10 to 30 parts by mass of the phosphate ester compound (C), 0.001 to 1.0 part by mass of the phosphite-based antioxidant (D), and 2,6-di-tert-butyl-p-cresol and / or 2 , 4-Bis- (α, α-dimethylbenzyl) Phenol (E) contains 0.00001 to 0.1 parts by mass , and the phosphite-based antioxidant (D) contains bis (2,6-di-tert-). A polycarbonate resin composition comprising butyl-4-methylphenyl) pentaerythritol diphosphite and / or bis (2,4-dicumylphenyl) pentaerythritol diphosphite . The polycarbonate resin composition according to claim 1, further containing 1 to 20 parts by mass of the core / shell type elastomer (F) with respect to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition according to claim 1 or 2 , further containing 1 to 10 parts by mass of talc (G) with respect to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition according to any one of claims 1 to 3 , further containing 0.01 to 7 parts by mass of the white pigment (H) with respect to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition according to claim 4 , wherein the white pigment (H) is titanium oxide. Total content of phosphite-based antioxidant (D) and 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) The polycarbonate resin composition according to any one of claims 1 to 5 , wherein the amount is 0.002 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). Mass ratio (E) of 2,6-di-tert-butyl-p-cresol and / or 2,4-bis- (α, α-dimethylbenzyl) phenol (E) and phosphite-based antioxidant (D) The polycarbonate resin composition according to any one of claims 1 to 6 , wherein / (D) is 0.001 to 1. A molded product obtained by molding the polycarbonate resin composition according to any one of claims 1 to 7 .