JP5427767B2 - Aromatic polycarbonate resin composition, molded product comprising the same, and method for producing molded product - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition, a molded article comprising the same, and a method for producing the molded article. Specifically, the aromatic resin has high hardness, high gloss, and excellent balance of fluidity, impact resistance, and flame retardancy. The present invention relates to a polycarbonate resin composition, a molded product comprising the same, and a method for producing the molded product.

Conventionally, aromatic polycarbonate resins have excellent transparency, impact resistance, heat resistance, etc., and the resulting molded products are also excellent in dimensional stability, etc., so housings for electrical and electronic equipment, automotive parts, etc. It is widely used as a raw material resin for manufacturing precision molded products such as optical disc-related parts. In particular, in a case of a home appliance, an electronic device, an image display device, or the like, a product with high commercial value can be obtained by making use of its beautiful appearance.
However, molded products made of aromatic polycarbonate resin alone have a lower surface hardness compared to products made of metal or glass, so they are inferior in scratch resistance, and when they are wiped with cloth or handled roughly, It has the disadvantage of being easily scratched.

  On the other hand, a method for forming a coating film with high surface hardness on the surface of a product using an aromatic polycarbonate resin has been proposed, and as a film material, for example, a coating agent of silicon resin or acrylic resin is known. However, these have a problem in the adhesion of the coating film, and it is difficult to coat a product having a complicated shape, the price is expensive, and there is a limit to industrial use. In addition, a method of painting the product surface is also known, but this method, like coating, is difficult to obtain a uniform coating film depending on the product shape. If the coating film thickness is not thick, the effect of improving the surface hardness is low. Furthermore, there exists a fault which impairs an external appearance by peeling of a coating surface or a coating-film surface.

  Also known is a method of blending a polycarbonate resin with a high hardness inorganic compound, but this method has a slight effect of improving the surface hardness, and when an inorganic compound is added, the refractive index of the additive And the refractive index of the aromatic polycarbonate resin are different, there is a drawback that transparency, which is a major characteristic of the aromatic polycarbonate resin, is impaired.

  On the other hand, in order to obtain an aromatic polycarbonate resin having excellent transparency and rigidity, a method of adding a compound selected from the group of biphenyl compounds, terphenyl compounds and polycaprolactones to aromatic polycarbonate resins has been proposed (for example, patents). References 1-3). However, according to the results of the study by the present inventors, this method cannot satisfy the requirement for high scratch resistance and is still insufficient for use in the above-mentioned industrial products.

In addition, many scratch-resistant compositions in which an aromatic polycarbonate resin is mixed with an acrylate such as methyl methacrylate or an ABS resin have been proposed.
For example, Patent Document 4 describes that a vinyl cyanide compound-aromatic vinyl compound copolymer and methyl methacrylate are blended. Patent Document 5 describes a resin composition comprising a polyester resin and an ABS resin, a polycarbonate resin, and polymethyl methacrylate. Patent Document 6 describes blending a copolymer composed of a vinyl monomer that is reactive with (meth) alkyl acrylate-aromatic vinyl-polycarbonate resin. Further, Patent Document 7 proposes blending a rubber-modified graft copolymer such as ABS resin and a vinyl monomer copolymer such as polymethyl methacrylate.

  However, these methods do not have a sufficient balance between impact resistance and flame retardancy, and it is difficult to say that these methods are resin compositions having excellent hardness and gloss.

Japanese Patent Laid-Open No. 03-143950 Japanese Patent Laid-Open No. 05-257002 JP 2000-169695 A JP 2001-49072 A JP 2001-234040 A JP 2008-56798 A WO2009 / 128601

  In view of the above-mentioned problems of the prior art, the object of the present invention is an aromatic polycarbonate resin composition having high hardness and high gloss, and excellent balance of fluidity, impact resistance and flame retardancy, and a molded product comprising the same, Another object of the present invention is to provide a method for producing a molded article.

  As a result of intensive studies to achieve the above problems, the present inventor has (a) an aromatic vinyl monomer, (b) a vinyl cyanide monomer, (c) a methyl methacrylate monomer, and (D) Graft copolymer obtained by graft copolymerization of monomers selected from other copolymerizable monomers with (a), (b) and (c) as essential components, and acrylonitrile-ethylenepropylene- When a specific amount of styrene resin and acrylic resin with specific hardness are mixed in polycarbonate resin, aromatic polycarbonate resin with high hardness, high gloss and excellent balance of fluidity, impact resistance and flame retardancy The inventors have found that a composition can be obtained and have completed the present invention.

That is, according to 1st invention of this invention, (B) (a) aromatic vinyl-type monomer, (b) vinyl cyanide monomer with respect to 100 mass parts of (A) aromatic polycarbonate resin, A monomer selected from (c) methyl methacrylate monomer and (d) another copolymerizable monomer was graft copolymerized with (a), (b) and (c) as essential components. 1 to 30 parts by mass of graft copolymer, 3 to 10 parts by mass of (C) acrylonitrile-ethylenepropylene-styrene (co) polymer, and (D) acrylic (co) heavy having a pencil hardness higher than F There is provided a molded article obtained by molding an aromatic polycarbonate resin composition containing 25 to 50 parts by mass of a coalescence, and having a pencil hardness in the range of F to 2H .

Further, according to the second aspect of the present invention, in the first invention, (D) acrylic (co) polymer, Po Li, which is a polymethyl methacrylate-based (co) polymer A carbonate resin molded article is provided.

According to the third invention of the present invention, in the first or second invention, (E) the elastomer is contained in an amount of 1 to 10 parts by mass with respect to 100 parts by mass of the (A) aromatic polycarbonate resin. Po polycarbonate resin molded article is provided to.

Further, according to the fourth aspect of the present invention, in the third invention, the (E) elastomer, Po polycarbonate resin molded article is provided, which is a core / shell type graft copolymer .

According to the fifth invention of the present invention, in any one of the first to fourth inventions, (F) the ultraviolet absorber is used in an amount of 0.1 to 1 with respect to 100 parts by mass of (A) the aromatic polycarbonate resin. Po polycarbonate resin molded article is provided which is characterized by containing parts by mass.

According to a sixth invention of the present invention, in any one of the first to fifth inventions, (G) the condensed phosphate ester flame retardant is added to 5 parts by weight of 100 parts by weight of the (A) aromatic polycarbonate resin. Po polycarbonate resin molded article characterized by containing 40 parts by weight is provided.

According to the seventh invention of the present invention, in the sixth invention, 0.5 to 2 parts by mass of (H) polytetrafluoroethylene is contained with respect to 100 parts by mass of (A) aromatic polycarbonate resin. Po polycarbonate resin molded article is provided, characterized in that.

According to the eighth invention of the present invention, in the sixth or seventh invention, (I) glass beads having an average particle diameter of 10 to 30 μm are added to 10 parts by mass of (A) 100 parts by mass of the aromatic polycarbonate resin. Po polycarbonate resin molded article is provided which is characterized by containing 40 parts by weight.

According to a ninth aspect of the present invention, there is provided a polycarbonate resin molded product according to any one of the first to eighth aspects, wherein the molded product is a casing.

According to a tenth aspect of the present invention , any one of the first to ninth aspects is characterized in that the mold surface immediately before filling the molten resin is heated to a temperature equal to or higher than the glass transition temperature of the resin composition and injection molding is performed . A method for producing a polycarbonate resin molded article of the invention is provided.

Furthermore, according to the eleventh aspect of the present invention, there is provided the method for producing a polycarbonate resin molded product according to the tenth aspect , wherein the mold surface is heated by high frequency electromagnetic induction heating.

  According to the aromatic polycarbonate resin composition of the present invention, a molded product comprising the same, and a method for producing the same, the aromatic polycarbonate resin composition having high hardness and high gloss and excellent balance of fluidity, impact resistance and flame retardancy And a molded product made of the same can be obtained.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

[1. Overview]
The aromatic polycarbonate resin composition of the present invention comprises (B) (a) an aromatic vinyl monomer, (b) a vinyl cyanide monomer, (c) with respect to (A) 100 parts by mass of the aromatic polycarbonate resin. A graft copolymer obtained by graft-copolymerizing a monomer selected from methyl methacrylate monomer and (d) other copolymerizable monomer with (a), (b), and (c) as essential components 5-30 parts by mass of a polymer, (C) 1-20 parts by mass of an acrylonitrile-ethylenepropylene-styrene (co) polymer, and (D) an acrylic (co) polymer having a pencil hardness higher than F. It contains 10 to 50 parts by mass.

[2. Aromatic polycarbonate resin (A)]
The type of the aromatic polycarbonate resin used in the aromatic polycarbonate resin composition of the present invention is not limited, and only one type may be used, and two or more types are used in any combination and in any ratio. May be.
The aromatic polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by a general formula — (— O—X ¹ —O—C (═O) —) —. In the formula, X ¹ is generally a hydrocarbon, but for imparting various properties, X ¹ into which a hetero atom or a hetero bond is introduced may be used.
The aromatic polycarbonate resin refers to a polycarbonate resin in which carbons directly bonded to carbonic acid bonds are aromatic carbons. Aromatic polycarbonate is excellent from the viewpoints of heat resistance, mechanical properties, electrical characteristics, etc., among various polycarbonates.

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the aromatic polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The aromatic polycarbonate polymer may be linear or branched. Furthermore, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit, or may be a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. Normally, such an aromatic polycarbonate polymer is a thermoplastic resin.

  Examples of the aromatic dihydroxy compound among the monomers used as the raw material for the aromatic polycarbonate resin are as follows.

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, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-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) Dihydroxy diaryl 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 (4-hydroxy-3,5-dimethylphenyl) 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,
1,2-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,
1,10-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,
1,4-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) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;
Dihydroxy diaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;
Dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide;
And dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;

Of these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable in terms of impact resistance and heat resistance. (Ie bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

Among the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.
Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.
Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-Manufacturing method of aromatic polycarbonate resin The manufacturing method of aromatic polycarbonate resin is not specifically limited, Arbitrary methods are employable. 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. Hereinafter, a particularly preferable one of these methods will be specifically described.

.. Interfacial polymerization method First, the case of producing an aromatic polycarbonate resin by the interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. An aromatic polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.
The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and the method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. In particular, it is preferably set to 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the molecular weight regulator include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of an aromatic polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where an aromatic polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired aromatic polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. It is more preferable to use the above. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the aromatic polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, an aromatic polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the degree of pressure reduction during the transesterification reaction, and the like. In addition, the molecular weight of the aromatic polycarbonate resin obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing an aromatic polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.
The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, in consideration of the stability of the aromatic polycarbonate resin and the aromatic polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

  The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is arbitrary and may be appropriately selected and determined. However, the viscosity average molecular weight [Mv] is preferably 10,000 to 40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength tends to be insufficient, and when the viscosity average molecular weight exceeds 40,000, the fluidity is poor and the moldability tends to be deteriorated. The viscosity average molecular weight is more preferably 16,000 to 40,000, still more preferably 18,000 to 30,000. The molecular weight can be adjusted to such a range by a known method such as controlling the amount of the molecular weight regulator as described later.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, Schnell's viscosity formula, That is, it means a value calculated from η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

-Other matters regarding aromatic polycarbonate resin The terminal hydroxyl group concentration of the aromatic polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the aromatic polycarbonate resin composition of the present invention can be further improved. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of an aromatic polycarbonate resin produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the aromatic polycarbonate resin composition of this invention can be improved more.
The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin. The measuring method is performed by colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by a titanium tetrachloride / acetic acid method.

  In addition, aromatic polycarbonate resin (A) is not limited to the aspect containing only 1 type of aromatic polycarbonate resin, 2 or more types of aromatic polycarbonate resin from which a monomer composition, molecular weight, terminal hydroxyl group concentration, etc. differ is mixed. May be used. Moreover, you may use combining as an alloy (mixture) which mixed another thermoplastic resin with aromatic polycarbonate resin.

  Further, for example, for the purpose of further improving flame retardancy and impact resistance, an aromatic polycarbonate resin is a copolymer with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with monomer, oligomer or polymer having phosphorus atom; copolymer with monomer, oligomer or polymer having dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene to improve optical properties A copolymer with an oligomer or polymer having an olefinic structure such as; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; May be.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated 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; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[3. Graft copolymer (B)]
The aromatic polycarbonate resin composition of the present invention comprises (a) an aromatic vinyl monomer, (b) a vinyl cyanide monomer, (c) a methyl methacrylate monomer, and (d) other copolymerizable monomers. A graft copolymer (B) obtained by graft-copolymerizing a monomer selected from the monomers (a), (b) and (c) as essential components (hereinafter referred to as polymer (B) or (B 1) to 30 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A).

Examples of the (a) aromatic vinyl monomer in the present invention include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, o, p-dichlorostyrene, and the like, from the viewpoint of rigidity and impact resistance. Styrene and α-methylstyrene are preferred. These monomers can be used not only alone but also in combination of two or more.
Examples of the (b) vinyl cyanide monomer include acrylonitrile and methacrylonitrile. These monomers can be used not only alone but also in combination of two or more.

  (D) As monomers selected from other copolymerizable monomers, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate Acrylic acid esters such as dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, Phenyl methacrylate and ben Α- or β-unsaturated dicarboxylic acids such as methacrylic acid esters such as methyl methacrylate, maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide And carboxylic acid amides such as acrylamide and methacrylamide. These monomers can be used not only alone but also in combination of two or more.

  In the present invention, the ratio of (a) aromatic vinyl monomer, (b) vinyl cyanide monomer, (c) methyl methacrylate monomer and (d) other copolymerizable monomer (A) 15-90% by weight of aromatic vinyl monomer, (b) 2-60% by weight of vinyl cyanide monomer, (c) 8-60% by weight of methyl methacrylate monomer, and (d) It is preferable that it is 0-70 mass% of the other monomer which can be copolymerized. Outside this range, the appearance is impaired due to the poor compatibility of the aromatic polycarbonate resin (A) and the acrylic (co) polymer (D) whose pencil hardness described below is higher than F, and fluidity and impact resistance. There is a tendency to lack the balance of pencil hardness.

[4. Acrylonitrile-ethylenepropylene-styrene (co) polymer (C)]
The aromatic polycarbonate resin composition of the present invention may be referred to as acrylonitrile-ethylenepropylene-styrene-based (co) polymer (C) (hereinafter referred to as polymer (C) or (C) component or component (C)). ) In an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
By blending such a polymer (C) with such a graft copolymer (B) and an acrylic (co) polymer (D) described later in such an amount, the aromatic polycarbonate of the present invention is blended. A balance of high impact resistance while maintaining the excellent hardness and gloss of the resin composition can be achieved.

The acrylonitrile-ethylenepropylene-styrene (co) polymer (C) used in the aromatic polycarbonate resin composition of the present invention is a thermoplastic (co) obtained by copolymerizing at least acrylonitrile, ethylene, propylene and styrene. It is a polymer.
The acrylonitrile-ethylenepropylene-styrene-based (co) polymer (C) may further use other vinyl monomers, and other vinyl monomers used include other methacrylonitriles and the like. Olefins such as vinyl cyanide and 1-butene, α-methylstyrene, p-methylstyrene, vinylxylene, dimethylstyrene, pt-butylstyrene, styrene derivatives such as bromostyrene and dibromostyrene, and conjugates such as butadiene and isoprene Examples include diene and (meth) acrylate compounds, and these may be used by further mixing two or more kinds.

Among these, preferable additional (co) polymerization vinyl monomers include CH ₂ ═CR ¹ —COOR ² (wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group.) The alkyl group represented by R ² is preferably an alkyl group having 1 to 8 carbon atoms, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid. Examples include propyl, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic acid-n-octyl. The alkyl group of the (meth) acrylic acid alkyl ester may be linear or branched. These may be used alone or in combination of two or more.
Of these, acrylonitrile-ethylenepropylene-styrene-methyl methacrylate (co) polymer using methyl methacrylate, that is, methyl methacrylate, is particularly preferable.

  The acrylonitrile-ethylenepropylene-styrene (co) polymer (C) is produced by a method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or bulk / suspension polymerization, and is used in a copolymerization reaction. Known initiators, chain transfer agents and the like can be used as necessary.

By using the above-mentioned acrylonitrile-ethylenepropylene-styrene-based (co) polymer (C), a composition having high hardness and high gloss can be obtained, and fluidity, impact resistance, flame retardancy can be obtained. Thus, it is possible to obtain an excellent aromatic polycarbonate resin composition with a good balance between them.
The content of the acrylonitrile-ethylenepropylene-styrene-based (co) polymer (C) is 1 to 20 parts by mass, preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). When the content is less than 1 part by mass, the effect of maintaining the impact resistance of the polycarbonate resin is not sufficiently obtained, and when the use ratio exceeds 20 parts by mass, the hardness of the polycarbonate resin tends to decrease. It is not preferable.

[5. Acrylic (co) polymer (D)]
The acrylic (co) polymer (D) (hereinafter sometimes referred to as polymer (D) or (D) component or component (D)) is a polymer or copolymer using an acrylic monomer. Any one can be used as long as it has a pencil hardness higher than F except for the same polymer (C) described above.
The (co) polymer component (D) has an acrylic monomer as a main constituent unit, and specifically, an alkyl methacrylate or an alkyl acrylate whose alkyl group usually has 1 to 18 carbon atoms. A copolymer obtained by homopolymerization of the above, copolymerization of the two, and a vinyl monomer copolymerizable with alkyl methacrylate or alkyl acrylate is preferable. When the alkyl group has 19 or more carbon atoms, the copolymerization reaction becomes difficult.

  Examples of such alkyl methacrylate or alkyl acrylate include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, Examples thereof include butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and the like.

  Examples of vinyl monomers copolymerizable with these include styrene, α-methylstyrene, acrylonitrile, vinyl acetate and the like. The preferred mixing ratio of alkyl methacrylate or alkyl acrylate and vinyl monomer copolymerizable therewith is 40 to 95% by weight of alkyl methacrylate, 5 to 60% by weight of alkyl acrylate, and copolymerizable. It is 0-30 mass% of another monomer.

  In particular, the acrylic (co) polymer (D) used in the present invention is preferably an alkyl methacrylate having 1 to 18, particularly 1 to 8 carbon atoms, and an alkyl acrylate. Is a methyl methacrylate-methyl acrylate copolymer obtained by copolymerizing the vinyl monomer.

  The acrylic (co) polymer (D) is a polyfunctional monomer having two or more non-conjugated double bonds per molecule that can be copolymerized with an acrylic acid alkyl ester or a methacrylic acid alkyl ester. However, it may be of a crosslinked type produced by copolymerization, preferably by adding about 0.1 to 20% by weight.

  The polyfunctional monomer having two or more non-conjugated double bonds is mainly used for crosslinking an elastic body component to obtain a crosslinked elastic body. Specific examples thereof include, for example, trimethylolpropane tri (meth) acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol dimethacrylate, propylene glycol diallyl ether, divinylbenzene, diethylene glycol dimethacrylate, 1,6-hexane. Examples include diol dimethacrylate. Of these, trimethylolpropane tri (meth) acrylate and the like are preferable.

  The acrylic (co) polymer (D) can be produced by suspension polymerization of the above monomers. For example, it can be obtained by suspending polyvinyl alcohol as a dispersant for polymerization, filtering, washing, sieving and drying.

In the present invention, an acrylic (co) polymer (D) having a surface hardness higher than "F" in pencil hardness is used. When the polymer (D) has a pencil hardness higher than F, when the resin composition of the present invention is used as a molded product, no scratch marks remain even if it is rubbed, and the molded product is excellent in scratch resistance. Here, the pencil hardness is as described above.
The pencil hardness of the polymer (D) is preferably F or more, more preferably H or more, further preferably 2H or more, and particularly preferably 3H or more.

  The polymer (D) having such hardness can be selected by appropriately adjusting the type of monomer to be used, its use ratio, molecular weight and the like, and can also be selected from commercially available products.

  Content of an acrylic type (co) polymer (D) is 10-50 mass parts with respect to 100 mass parts of aromatic polycarbonate resin (A), Preferably it is 13-50 mass parts. When the proportion of the acrylic (co) polymer (D) used is less than 10 parts by mass, the effect of improving the high hardness and high gloss of the polycarbonate resin cannot be obtained sufficiently, and the usage rate exceeds 50 parts by mass. Is not preferred because the impact resistance and the like of the polycarbonate resin tend to decrease, flame retardancy is difficult to obtain, and the polycarbonate resin and the acrylic (co) polymer are easily peeled off in layers. .

[6. Elastomer (E)]
The polycarbonate resin composition of the present invention preferably contains an elastomer (E) as another component. By containing the elastomer, the impact resistance of the polycarbonate resin composition can be improved.

  The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

  The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same shall apply hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kaneace (registered trademark, the same applies hereinafter) M-511 "," Kaneace M-600 "," Kaneace M-400 "manufactured by Kaneka Corporation "Kane Ace M-580 , "Kane Ace MR-01", and the like.

  The preferable content of the elastomer is 1 to 10 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). If the amount is less than 1 part by mass, the impact resistance improvement effect by the elastomer is insufficient, and if it exceeds 10 parts by mass, the appearance of the molded product obtained by molding the polycarbonate resin composition and the heat resistance are reduced. The lower limit of the content is preferably 2 parts by mass or more, more preferably 4 parts by mass or more, and the upper limit of the content is preferably 9 parts by mass or less, more preferably 8 parts by mass or less.

[7. UV absorber (F)]
It is preferable to mix | blend a ultraviolet absorber (F) with the composition of this invention. Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; Examples include ultraviolet absorbers. Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “UV5411”, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, manufactured by Adeka Corporation, “Tinuvin P”, “Cinuvin 234” manufactured by Ciba Specialty Chemicals , "Tinubin 326", "Tinubin 327", "Tinubin 328 Etc. The.

The content of the ultraviolet absorber (F) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more with respect to 100 parts by mass of the aromatic polycarbonate resin (A), and the upper limit thereof. Is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less.
If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[8. Condensed phosphate ester flame retardant (G)]
The composition of the present invention preferably contains a condensed phosphate ester (G). The condensed phosphate ester (G) is preferably represented by the following general formula.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して水素原子または有機基を表す。ただし、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４が全て水素原子の場合を除く。Ｘは２価の有機基を表し、ｐは０または１であり、ｑは１以上の整数、ｒは０または１以上の整数を表す。）

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or an organic group, except that R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms. X represents a divalent organic group, p is 0 or 1, q represents an integer of 1 or more, and r represents 0 or an integer of 1 or more.)

  In the above general formula, the organic group includes, for example, an alkyl group, a cycloalkyl group, and an aryl group with or without a substituent, and the substituent includes an alkyl group, an alkoxy group, an alkylthio group, and an aryl group. Group, aryloxy group, arylthio group, halogen atom, halogenated aryl group and the like. Further, a group in which these substituents are combined, or a group in which these substituents are combined by combining with an oxygen atom, a sulfur atom, a nitrogen atom, or the like may be used. The divalent organic group refers to a divalent or higher group formed by removing one carbon atom from the above organic group. Examples thereof include an alkylene group, a phenylene group, a substituted phenylene group, and a polynuclear phenylene group derived from bisphenols.

  Specific examples of the condensed phosphate ester represented by the above general formula include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl Phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) phosphate, Bis (2,3-dibromopropyl) -2,3-dichlorophosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl phosphate, Scan phenol A tetra cresyl diphosphate, bisphenol A tetra xylylene distearate phosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetra cresyl phosphate, various ones such as hydroquinone tetra xylylene distearate phosphate are exemplified.

  The content of the condensed phosphate ester compound is preferably 5 to 40 parts by mass, more preferably 7 to 35 parts by mass, and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). When the content is less than 5 parts by mass, the flame retardancy tends to be insufficient, and when it exceeds 40 parts by mass, heat resistance and mechanical properties are likely to deteriorate, which is not preferable.

[9. Polytetrafluoroethylene (H)]
The aromatic polycarbonate resin composition of the present invention preferably contains polyfluoroethylene (H). As polytetrafluoroethylene, polytetrafluoroethylene having fibril forming ability is preferable. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Examples of polytetrafluoroethylene having fibril-forming ability include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., and Polyflon F201L, FA500B, and FA500C manufactured by Daikin Chemical Industries, Ltd. Examples of the aqueous dispersion of polytetrafluoroethylene include Fluon D-1 manufactured by Daikin Chemical Industries, Ltd. and polytetrafluoroethylene compounds having a multilayer structure formed by polymerizing vinyl monomers. Any type can be used for the resin composition of the present invention.

  In order to further improve the appearance of a molded product obtained by injection molding a flame retardant resin composition containing polytetrafluoroethylene, a specific coated polytetrafluoroethylene (hereinafter referred to as coated polytetrafluoroethylene) coated with an organic polymer is used. May be abbreviated as fluoroethylene). The specific coated polytetrafluoroethylene is such that the content ratio of polytetrafluoroethylene in the coated polytetrafluoroethylene falls within the range of 40 to 95% by mass, of which 43 to 80% by mass, and further 45 It is preferable to be -70% by mass, particularly 47-60% by mass. As the specific coated polyfluoroethylene, for example, Metablene A-3800, A-3700, KA-5503 manufactured by Mitsubishi Rayon Co., Poly TS AD001 manufactured by PIC Co., etc. can be used.

  The preferable compounding amount of polytetrafluoroethylene (H) is 0.5 to 2 parts by mass, more preferably 0.6 to 1.5 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). .7 to 1.3 parts by mass are particularly preferred. In the case of coated polytetrafluoroethylene, the amount added corresponds to the amount of pure polytetrafluoroethylene. When the blending amount of polytetrafluoroethylene is less than 0.5 parts by mass, the flame retardant effect is insufficient. On the other hand, when it exceeds 2 parts by mass, the appearance of the molded product may be deteriorated.

[10. Glass beads (I)]
The aromatic polycarbonate resin composition of the present invention preferably contains glass beads (I). The glass beads (I) to be used are usually spherical ones having an average particle diameter of 3 to 100 μm. It is preferable that the compounding quantity of a glass bead is 10-40 mass parts per 100 mass parts of polycarbonate resin (A).
If the blending amount of the glass beads is less than 10 parts by mass, the effect of improving the surface gloss and scratch resistance, the improvement of rigidity and the reinforcing effect are insufficient, and if it exceeds 40 parts by mass, a polycarbonate resin having a low molecular weight and a low melt viscosity is used. Even if it is used, the fluidity is poor, the moldability is deteriorated, and the flame retardancy is difficult. A more preferable blending amount of the glass beads is 15 to 35 parts by mass.

A more preferable particle size of the glass beads is an average particle size of 10 to 30 μm. If the average particle size is less than 10 μm, the moldability of the polycarbonate resin composition tends to be impaired, and if it exceeds 30 μm, the surface appearance of the molded product tends to be impaired, and the scratch resistance tends to be insufficient.
As long as the characteristics of the polycarbonate resin composition of the present invention are not impaired, the glass beads may be surface-treated with, for example, a silane compound or an epoxy compound in order to improve the affinity with the polycarbonate resin.

[11. Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include stabilizers, antioxidants, mold release agents, dyes and pigments, fluorescent whitening agents, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, Plasticizers, dispersants, antibacterial agents and the like can be mentioned.

-Stabilizer As a stabilizer, a phosphorus compound is mentioned, for example. Any known phosphorous compound can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.

  The content of the stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and usually 1 part by mass with respect to 100 parts by mass of the polycarbonate resin. Part or less, preferably 0.7 part by weight or less, more preferably 0.5 part by weight or less. If the amount of the stabilizer is too small, the heat stabilizing effect may be insufficient. If the amount of the stabilizer is too large, the effect may reach a peak and may not be economical.

-Antioxidant As an antioxidant, a hindered phenolic antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 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 ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [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-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the polycarbonate resin. Or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

-Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. It is done.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. 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, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  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. Is mentioned.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol 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, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.
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 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 or less with respect to 100 parts by mass of the polycarbonate resin. It is. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

-Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; quinoline, anthraquinone, heterocyclic and methyl dyes.

Among these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based dyes and the like are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[12. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the aromatic polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, Aromatic polycarbonate resin (A), a graft copolymer (B), acrylonitrile-ethylene Propylene-styrene-based (co) polymer (C), acrylic-based (co) polymer (D), and other components that are blended as necessary, such as tumbler, Henschel mixer, super mixer, ribbon Examples thereof include a method in which mixing is performed in advance using various mixers such as a blender, followed by melt kneading using a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[13. Molding method]
The aromatic polycarbonate resin composition of the present invention can be produced by molding pelletized pellets by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets.
Examples of molding methods include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating molds. Molding method used, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. A molding method using a hot runner method can also be used. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

When the aromatic polycarbonate resin composition contains the glass beads described above, the mold surface immediately before filling the mold with the molten resin when the polycarbonate resin composition containing each component including the glass beads is injection-molded Is preferably heated to a temperature equal to or higher than the glass transition temperature (Tg) of the resin composition, and then the molten resin composition is injected and injected into the mold cavity.
The mold surface may be heated by heating only the cavity surface of the mold, and it is not necessary to heat the entire mold. As such a heating method, a method of heating by incorporating a heat transfer heater near the cavity surface inside the mold, a method of heating by infrared heating etc. by inserting a heater on the cavity side with the male and female molds opened Alternatively, a method of injecting high-temperature steam between both male and female molds and heating can be used.

As a preferable heating means, it is possible to use high frequency electromagnetic induction heating, in particular, insert a donut-shaped high frequency induction coil for high frequency electromagnetic induction heating, for example, between both dies when the male and female molds are opened, Preferably only the cavity surface is heated rapidly. Due to electromagnetic induction, an induced current is generated on the mold surface, Joule heat is generated, and only the mold surface generates heat in a short time. The heating may be performed by adjusting the heating output and the time while detecting the temperature with a temperature sensor. Usually, the heating time is about 1 second to 1 minute, preferably 1 second to 30 seconds.
The temperature of the mold surface immediately before resin filling is not the glass transition temperature of the aromatic polycarbonate resin alone, but the glass transition temperature (Tg) of the resin composition or higher. As is well known, the glass transition temperature of the polycarbonate resin composition is measured by a differential thermal analyzer (DSC). However, as far as the inventors have studied, the above-described composition of the present invention has a single endothermic peak. As shown, it is determined from the peak temperature.

The mold surface temperature immediately before filling is set to be higher than the Tg of the resin composition, but is 5 ° C. to 60 ° C., more preferably 10 ° C. to 50 ° C., particularly 20 ° C. to Tg of the resin composition. It is preferable to increase the temperature by 40 ° C.
The mold temperature other than the mold cavity surface is preferably set to an optimum mold temperature for injection molding the polycarbonate resin composition, usually about 40 ° C to 120 ° C.
By raising the mold surface temperature immediately before filling to Tg or more of the resin composition, the glass pearl is prevented from floating on the mold surface during injection injection, and a molded article having excellent surface gloss and scratch resistance can be obtained. . It is common sense in the field of injection molding that mold temperature is too high and the mold surface is likely to be in close contact with the mold surface, resulting in defective mold release and deformation after mold release. The temperature at the time is kept high only on the mold surface, but the others are normal temperatures. Therefore, after filling, the mold is cooled as usual, and the molded product is taken out.

[14. Molding]
A preferable molded article obtained by molding the composition of the present invention is a resin composition having a high hardness, high gloss, and excellent balance of impact resistance and flame retardancy. Therefore, a car navigation or car audio housing, an instrument panel Can be used suitably as electrical / electronic / OA equipment casings for automobile interior parts such as console boxes, center clusters, meter clusters, flat display panels, personal computers, PDAs, televisions, videos, cameras, printers, fax machines, etc. it can.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
The measurement / evaluation methods used in the examples and comparative examples are as follows.

[Measurement and evaluation method]
[1. Fluidity evaluation]
After drying the pellets obtained by the production method described later at 80 ° C. for 4 hours or more, using a high load type flow tester, the effluent Q value per unit time of the composition under the conditions of 240 ° C. and 160 kgf load ( (Unit: × 10 ⁻² cc / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. In the table, it is expressed as “fluidity”.

[2. Impact resistance evaluation]
Impact resistance (Izod impact strength) (unit: J / m):
In accordance with ASTM D256, an Izod impact strength (unit: J / m) was measured at a temperature of 23 ° C. for a notched specimen having a thickness of 3.2 mm formed by the method described later. The larger the value, the better the impact resistance. In the table, “Izod” is used.

[3. Heat resistance evaluation]
DTUL (load deflection temperature):
Using an ISO multi-purpose test piece molded by the method described later, the measurement was performed in accordance with ISO 75-1 & 2 under the condition of load 1.80 MPa (Method A). In the table, “DTUL” is used.

[4. Surface hardness evaluation]
Pencil hardness:
According to JIS K5400, a scratch test was performed 5 times on a 3 mm-thick flat plate test piece molded by the method described below to evaluate the hardness. In the table, it is expressed as “pencil hardness”.

[5. Appearance evaluation]
Surface appearance:
A 3 mm-thick flat plate test piece molded by the method described later was visually judged according to the following criteria, and the appearance was evaluated.
◯: Good △: Slight silver and delamination are observed.
X: Silver is generated and delamination occurs, resulting in poor gloss.

[6. Flame retardant evaluation]
The flame retardancy of each polycarbonate resin composition was evaluated by conditioning a test specimen for UL test obtained by the method described below for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. -Conducted in accordance with UL94 test (combustion test of plastic materials for equipment parts) defined by Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied. In the table, “flame retardant” is indicated.

(Examples 1 , 4 to 8, Reference Examples 2 to 3, Comparative Examples 1 to 5)
Each material to be described later is mixed in a tumbler for 20 minutes with the contents shown in the following tables (all parts unless otherwise specified), and then mixed in a twin screw extruder (TEX30XCT) manufactured by Nippon Steel Works with 1 vent. Supplied, kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 260 ° C., the molten resin composition extruded in a strand form is rapidly cooled in a water tank, pelletized using a pelletizer, and polycarbonate resin A pellet of the composition was obtained.

[Molding specimen]
The obtained pellets were dried at 80 ° C. for 5 hours and then injected with an injection molding machine (“M150AII-SJ” manufactured by Meiki Seisakusho) under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 75 ° C., and a molding cycle of 50 seconds. Molding was performed to produce a 3.2 mm thick Izod impact test piece and a 50 × 90 × 3 mm thick flat plate test piece.
Furthermore, after drying the obtained pellets at 80 ° C. for 5 hours, the cylinder temperature was 260 ° C., the mold temperature was 75 ° C., using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., Cycap M-2, clamping force 75T). Injection molding was performed under conditions of a molding cycle of 50 seconds to produce an ISO multipurpose test piece, which was used for DTUL (heat resistance) evaluation.
Also, in the flammability test, the obtained pellets were dried at 80 ° C. for 5 hours, and then molded with an injection molding machine (“J50-EP” manufactured by Nippon Steel) with a cylinder temperature of 260 ° C. and a mold temperature of 75 ° C. A test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 2 mm was formed by injection molding under a cycle of 30 seconds.
The measurement results for these test pieces are shown in Tables 2 to 4 below.

  The used materials are as follows. The pencil hardness of each material used as the aromatic polycarbonate resin (A), the acrylic copolymer (D) and the other copolymer (N) is [4. [Surface hardness evaluation]

[Materials used]
(A) Aromatic polycarbonate resin:
(A-1) Trade name “Iupilon (registered trademark) S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 22,000, pencil hardness 2B
(A-2) Trade name “Iupilon (registered trademark) E-2000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 28,000, pencil hardness 2B

(B) Acrylonitrile-styrene-methyl methacrylate copolymer:
Product name “S900N” manufactured by UMG ABS Co., Ltd.
(C) Acrylonitrile-ethylenepropylene-styrene copolymer:
Product name “E700N” manufactured by UMG ABS Co., Ltd.
(B + C) A mixture containing 33% by mass of an acrylonitrile-styrene-methyl methacrylate copolymer, 17% by mass of an acrylonitrile-ethylenepropylene-styrene copolymer, and 50% by mass of an acrylic copolymer. Pencil hardness 2H
(D) Methyl methacrylate-methyl acrylate copolymer:
Product name “Acrypet VH001” manufactured by Mitsubishi Rayon Co., Ltd., pencil hardness 2H

(E) Elastomer (E-1) Core / shell type copolymer comprising alkyl acrylate polymer (core) / alkyl methacrylate polymer (shell):
Product name "Paraloid EXL-2315" manufactured by Rohm and Haas Co., Ltd.
(E-2) Core / shell copolymer comprising butadiene polymer (core) / alkyl acrylate / alkyl methacrylate copolymer (shell):
Product name "Paraloid EXL-2633" manufactured by Rohm and Haas Co., Ltd.
(E-3) Core / shell copolymer comprising a composite rubber (core) / alkyl methacrylate polymer (shell) comprising a dimethylsiloxane polymer and an alkyl acrylate polymer:
Product name "METABBRENE S-2001" manufactured by Mitsubishi Rayon Co., Ltd.

(F) UV absorber:
2- (2′-Hydroxy-5′-tert-octylphenyl) -2H-benzotriazole Product name “Chisorb 709” manufactured by Cypro Kasei Co., Ltd.
(G) Flame retardant:
Condensed phosphate ester: resorcinol (dixylenyl phosphate)
Product name “PX200” manufactured by Daihachi Chemical Co., Ltd.

(H) Polytetrafluoroethylene (PTFE):
Product name "Polyflon F-201L" manufactured by Daikin Industries, Ltd.
(I) Glass beads:
Product name “EGB731B” manufactured by Potters Barotini Co., Ltd. Average particle size 20 μm

(J) Phosphorus heat stabilizer:
Tris (2,4-di-tert-butylphenyl) phosphite Product name “ADK STAB 2112” manufactured by Asahi Denka Kogyo Co., Ltd.
(K) Phenolic antioxidants:
Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals, Inc., “trade name: Irganox 1010”
(L) Release agent:
Pentaerythritol tetrastearate Cognis Japan Co., Ltd. trade name “Roxyol VPG861”
(M) Colorant: Carbon Black Trade name “# 900” manufactured by Mitsubishi Chemical Corporation

Moreover, the following (N-1) and (N-2) were used in a comparative example as a copolymer component which does not satisfy | fill the prescription | regulation of the copolymer component (B) of this invention, (C), (D). .
(N-1) Methyl methacrylate-butadiene-styrene copolymer:
Product name “Denka TP Polymer TH-23” manufactured by Denki Kagaku Kogyo Co., Ltd., pencil hardness 3B
(N-2) Acrylonitrile-butadiene-styrene copolymer:
Product name “Stylac (registered trademark) T9701” manufactured by Asahi Kasei Corporation, pencil hardness 2H

(Example 9 )
Each material containing glass beads shown in Table 3 below was blended in the proportions shown in Table 3, and pelletized in the same manner as in Examples 1 and 4 to 8 to obtain pellets of a polycarbonate resin composition.
The obtained pellets were measured for glass transition temperature (Tg) using a differential thermal analysis (DSC) apparatus manufactured by SEIKO Instrument. The measurement is carried out using nitrogen gas with a carrier gas of 60 ml / min, and the measurement temperature change is 30 ° C. (20 ° C./min)→250° C., hold for 3 minutes (20 ° C./min)→30° C., hold for 3 minutes (20 ° C./min) ) → It was carried out under the condition of 250 ° C. The Tg of each pellet was 105 ° C. (Example 9) and 120 ° C. (Example 10).

Using the above pellets, the mold cavity surface temperature immediately before injection filling was set to 130 ° C., and each of the various test pieces was injection molded by the above method.
The mold is heated by inserting a high frequency induction coil of a high frequency electromagnetic induction heating device between the male and female molds in an open state, and heating the cavity surface at a frequency of 20 KHz and an output of 15 KW on the cavity surface of the female mold. I went there. The mold surface temperature was adjusted by adjusting the irradiation time between 1 second and 20 seconds.
The induction coil was immediately extracted, the mold was closed to a predetermined clearance, the molten resin composition was immediately injected and filled into the mold cavity, and water cooling was performed until the mold cooled to 80 ° C.
After cooling, the mold was opened and the molded product was taken out.
The evaluation results are shown in Table 3.

From the results of the examples and comparative examples, the following can be understood.
In Examples 1 to 5 (Table 2), the blending ratios of the components (B), (C), and (D) were changed within the specified range of the present invention. It can be seen that the surface hardness is significantly higher than that of Comparative Examples 3 to 4 (Table 4) in which these are not prescribed, and the impact strength and the appearance are also excellent. In Examples 2 to 3, the type of elastomer was changed, but the hardness was slightly reduced, but the impact resistance was improved.
Examples 6 to 10 (Table 3) are formulated with a flame retardant, but UL has a very high flame resistance as V-0 and has a high hardness of F to 2H, and is excellent in strength and appearance. . In Examples 9 to 10, when glass beads were blended, the deterioration of the appearance was suppressed to Δ by heating the mold surface, and the hardness was remarkably improved.

Comparative Examples 1 and 2 using components (B), (C) and (D) outside the scope of the present invention, and copolymers N-1 and N- which are not components (B), (C) and (D) It can be seen that in Comparative Examples 3 and 4 using 2, the surface hardness is as low as B to 2B. It can be seen that the polycarbonate resin composition is inferior in the total light transmittance and the degree of dispersion, and the impact resistance is not good. Moreover, in Comparative Examples 2-5, it can be understood that UL is bad, such as V-2 and NR, and impact resistance and appearance are bad, regardless of the flame retardant formulation.
Therefore, from the above examples and comparative examples, a resin composition or molded article having high hardness and high gloss and excellent balance of fluidity, impact resistance and flame retardancy can be obtained for the first time by the constitution of the present invention. It was confirmed that.

  Since the aromatic polycarbonate resin composition of the present invention is a resin material having high hardness and high gloss and excellent balance of fluidity, impact resistance and flame retardancy, the molded product is used for car navigation and car audio. Chassis, instrument panel, console box, center cluster, meter cluster and other automobile interior parts, flat display panel, PC, PDA, TV, video, camera, printer, FAX, etc. It can be used in a wide range of fields such as industrial applicability.

Claims (11)

(B) (A) aromatic vinyl monomer, (b) vinyl cyanide monomer, (c) methyl methacrylate monomer and (d) with respect to 100 parts by mass of (A) aromatic polycarbonate resin 1 to 30 parts by mass of a graft copolymer obtained by graft-copolymerizing a monomer selected from other copolymerizable monomers with (a), (b) and (c) as essential components; C) Aromatic polycarbonate resin containing 3 to 10 parts by mass of acrylonitrile-ethylenepropylene-styrene (co) polymer and (D) 25 to 50 parts by mass of acrylic (co) polymer having a pencil hardness higher than F A polycarbonate resin molded article obtained from the composition , wherein the pencil hardness is in the range of F to 2H . Wherein (D) acrylic (co) polymer, polymethyl methacrylate (co) po polycarbonate resin molded article according to claim 1, which is a polymer. (E) elastomer, (A) an aromatic respect polycarbonate resin 100 parts by mass, Po polycarbonate resin molded article according to claim 1 or 2, characterized in that it contains 1 to 10 parts by weight. (E) elastomer, Po polycarbonate resin molded article according to claim 3, characterized in that the core / shell type graft copolymer. (F) a UV absorber, (A) an aromatic respect polycarbonate resin 100 parts by mass, Po Li according to any one of claims 1 to 4, characterized in that it contains 0.1 to 1 parts by weight Carbonate resin molded product . (G) 5-40 mass parts of condensed phosphate ester type flame retardants are contained with respect to 100 mass parts of (A) aromatic polycarbonate resin, It is any one of Claims 1-5 characterized by the above-mentioned. Po polycarbonate resin molded article. (H) poly tetrafluoroethylene, (A) an aromatic respect polycarbonate resin 100 parts by mass, Po polycarbonate resin molded article according to claim 6, characterized in that it contains 0.5 to 2 parts by weight. (I) glass beads having an average particle size of 10 to 30 [mu] m, (A) 100 parts by mass of the aromatic polycarbonate resin, port polycarbonate according to claim 6 or 7, characterized in that it contains 10 to 40 parts by weight Resin molded product . Polycarbonate resin molded article according to any one of claims 1 to 8, the molded article is characterized in that it is a housing. The method for producing a polycarbonate resin molded article according to any one of claims 1 to 9, wherein the mold surface immediately before filling the molten resin is heated to a glass transition temperature or higher of the resin composition and injection molding is performed. . The method for producing a polycarbonate resin molded article according to claim 10 , wherein the mold surface is heated by high-frequency electromagnetic induction heating.