JP2016035021A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in fluidity, flame retardancy, and mechanical characteristics and further excellent in bending resistance.SOLUTION: The polycarbonate resin composition contains, based on 100 pts.mass of a polycarbonate resin (A), 1.0-2.5 pts.mass of a core-shell type graft copolymer (B) having an Si content of 7-12 mass% and having a silicone/acrylic composite rubber as a core, 0.001-0.3 pt.mass of an organic sulfonic acid metal salt (C), and 0.05-1 pt.mass of a fluorine-containing resin (D).SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded article, and more particularly, to a polycarbonate resin composition excellent in fluidity, flame retardancy and mechanical properties, and further excellent in bending resistance, and a molded article thereof.

  Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics, and is widely used as, for example, electrical and electronic equipment materials, automotive materials, housing materials, and other parts manufacturing materials in industrial fields. .

  Recently, portable devices typified by tablet-type terminals and touch panel terminals are required to be large and thin. In addition to heat resistance and impact characteristics, housing parts and protective case parts maintain the shape of the product. Therefore, a polycarbonate resin that satisfies these conditions has been used.

  In particular, as a recent trend, in order to simplify the assembly of parts, for example, a shape called a snap fit for fitting parts to each other is manufactured by injection molding. In this case, if the toughness of the material is not sufficient, there will be a problem that the part for fitting will be damaged before mating, or there will be a problem that other thin parts will be easily damaged due to insufficient toughness. . Further, many parts having hinge portions are also used, and therefore, such parts are required to have a high degree of bending resistance.

  For such a purpose, for example, a method of increasing toughness by using a high molecular weight polycarbonate resin composition is generally known. However, when trying to improve by these methods, there is a problem that fluidity is lowered and thin-wall molding becomes difficult. Therefore, it has been difficult to obtain a polycarbonate resin composition that satisfies fluidity, material strength, and the like that can be formed into a thin wall and is excellent in bending resistance.

The present inventor previously proposed a polycarbonate resin thin molded article obtained by blending a core-shell type elastomer having an acrylic core / acrylic shell with a polycarbonate resin having a viscosity average molecular weight of 7000 to 12000 according to Patent Document 1. However, the number of breaks in the bending resistance test is not always sufficient, and it is difficult to say that the flame retardancy is sufficient, and higher bending resistance and flame retardancy are required.
Furthermore, in recent years, electrical and electronic equipment parts have been rapidly reduced in weight and thickness, and need high fluidity, excellent flame retardancy, and high bending resistance.

Japanese Patent Application No. 2013-180959

  The present invention has been made in view of such a problem, and an object of the present invention is to provide a polycarbonate resin material which is excellent in fluidity and flame retardancy at a thin wall and excellent in bending resistance.

As a result of intensive studies to develop the above-described excellent polycarbonate resin composition, the present inventor, as a core-shell type graft copolymer, cored a silicone / acrylic composite rubber having a Si content within a specific range. A polycarbonate resin composition containing an organic sulfonic acid metal salt and a fluorine-containing resin in combination with a specific content as a flame retardant is used for the flowability and flame retardancy at a thin wall. The inventors have found that it is excellent and has excellent bending resistance, and have reached the present invention.
The present invention is as follows.

[1] Core-shell type graft copolymer (B) having a core of a silicone / acrylic composite rubber having a Si content of 7 to 12% by mass relative to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition comprising 5 parts by mass, 0.001 to 0.3 parts by mass of an organic sulfonic acid metal salt (C) and 0.05 to 1 part by mass of a fluororesin (D).
[2] A core-shell type graft copolymer (B) further containing 0.2 to 1.0 part by mass of a core-shell type graft copolymer (E) having butadiene rubber as a core and having a silicone / acrylic composite rubber as a core And the ratio of the core-shell type graft copolymer (E) having butadiene rubber as the core is (B) 50 to 99% by mass: (E) 1 to 50% by mass of the polycarbonate resin composition according to the above [1] .
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight of 12000 to 16000.
[4] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [3].
[5] The molded article according to the above [4], which is a part for electrical and electronic equipment.
[6] The molded product according to [4], which is a battery pack housing part.
[7] The thin-walled resin molded product according to [4], which is a box-shaped molded product having a hinge structure.

  The polycarbonate resin composition of the present invention comprises a core-shell type graft copolymer (B) having a silicone / acrylic composite rubber having a Si content of 7 to 12% by weight as a core, an organic sulfonic acid metal salt (C) and the above-mentioned By containing in combination, the flame retardancy can be improved even with a thin thickness of 1.5 mm, the bending resistance can be improved, and the thin-wall moldability is excellent. The molded product can be particularly suitably used for various electrical and electronic parts, particularly battery pack molded products, housings, and the like, as molded products having a hinge structure and molded products having a fitting structure.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value.

[Overview]
The polycarbonate resin composition of the present invention comprises a core-shell type graft copolymer (B) having a silicone / acrylic composite rubber having a Si content of 7 to 12% by mass based on 100 parts by mass of the polycarbonate resin (A). It contains 1.0 to 2.5 parts by mass, 0.001 to 0.3 parts by mass of an organic sulfonic acid metal salt (C) and 0.05 to 1 parts by mass of a fluororesin (D).

[Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin (A) used for the polycarbonate resin composition of this invention.
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond, represented by a general formula: — [— O—X—O—C (═O) —] —. In the formula, X is generally a hydrocarbon group, but for imparting various properties, X introduced with a hetero atom or a hetero bond may be used.
The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the 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. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. 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, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

Among 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, , 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 (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,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
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) -3-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,
Cardio structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

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

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). 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.

In addition, when an example of a monomer that is a raw material of the aliphatic polycarbonate resin is given,
Ethane-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, spiro glycol and the like;

  1,2-benzenedimethanol, 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- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  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 polycarbonate resin The manufacturing method of 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 where a polycarbonate resin is produced 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. 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 a 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 which sodium hydroxide and water Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and it 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. Among these, it is preferable that the ratio is 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 monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. 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-hydroxybenzoic 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 a 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 a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. 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 a 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. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, carbonic acid diester may use 1 type and 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 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. Is more preferable. 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 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, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually 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 a 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, considering the stability of the polycarbonate resin and the 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, any compound that neutralizes the transesterification catalyst can be used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, 1 type may be used for a catalyst deactivator and it 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 viscosity average molecular weight [Mv] of the polycarbonate resin (A) is preferably in the range of 12,000 to 16,000. By using a polycarbonate resin having such a viscosity average molecular weight, a highly fluid polycarbonate resin composition effective for thin-wall molding can be obtained while maintaining heat resistance.

The viscosity average molecular weight [Mv] is determined by using the methylene chloride as a solvent and obtaining the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, and the Schnell viscosity formula, 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 [η _sp ] at each solution concentration [C] (g / dl).

  Moreover, 1 type may be used for polycarbonate resin (A), and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

[Core-shell type graft copolymer (B)]
The polycarbonate resin composition of the present invention is a graft copolymer comprising a rubbery polymer component containing an organosiloxane unit and a graft copolymer component, having a silicone / acrylic composite rubber as a core and a Si content of 7 The core shell type graft copolymer (B) which is -12 mass% is contained.
In the present invention, such a core-shell type graft copolymer (B) is added in an amount of 1.0 to 2.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It becomes possible to set it as the polycarbonate resin composition excellent in a flame retardance and bending resistance by containing in combination with 0.001-0.3 mass part.

  The core-shell type graft copolymer (B) is a core-shell type copolymer elastomer in which a silicone / acrylic composite rubber is used as a core layer, and a copolymer component obtained by graft copolymerization with a vinyl monomer is used as a shell layer around the silicone / acrylic composite rubber. is there.

Silicone rubber as a constituent component of the core layer includes polyorganosiloxane, for example, a polymer containing a dimethylsiloxane unit as a constituent unit, and a siloxane containing a vinyl polymerizable functional group as a constituent component. preferable.
A siloxane containing a vinyl polymerizable functional group is one that contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond. Among the siloxanes containing vinyl polymerizable functional groups, various alkoxysilane compounds containing vinyl polymerizable functional groups are preferable in consideration of reactivity with dimethylsiloxane. These siloxanes containing vinyl polymerizable functional groups can be used alone or as a mixture of two or more.
The polyorganosiloxane may be crosslinked with a siloxane-based crosslinking agent. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

  Examples of the acrylic polymer for constituting the composite rubber containing the acrylic polymer of the core layer include polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl acrylate / 2-ethylhexyl acrylate copolymer. it can. These may be used alone or in admixture of two or more. The composite rubber here preferably has a structure in which a silicone rubber and an acrylic polymer are intertwined so that they cannot be separated from each other.

  Aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; polyvalent compounds such as ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate Unsaturated carboxylic acid esters of alcohol; unsaturated carboxylic acid allyl esters such as allyl acrylate and allyl methacrylate; cross-linking monomers such as di- and triallyl compounds such as diallyl phthalate, diallyl sebacate, and triallyl triazine You can also

Examples of the copolymer component constituting the shell of the core-shell type graft copolymer (B) include acrylic, preferably polyalkyl (meth) acrylates, and include alkyl (meth) acrylate units and polyfunctional alkyls. A polymer containing a (meth) acrylate unit as a constituent component is preferred.
Examples of the alkyl (meth) acrylate include alkyl acrylates such as n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and alkyl methacrylates such as 2-ethylhexyl methacrylate and n-lauryl methacrylate. Or two or more can be used together.

Examples of the polyfunctional alkyl (meth) acrylate include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, and the like. These can be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in content of a polyfunctional alkyl (meth) acrylate unit, It is preferable that it is 0.1-2 mass% in 100 mass% of polyalkyl (meth) acrylate, 0.3-1 mass % Is more preferable.

  Moreover, as a copolymerization component which comprises the shell of a core-shell type graft copolymer (B), you may contain another vinyl monomer other than the said (meth) acrylic acid ester compound. Other vinyl 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, N -Maleimide compounds such as methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid, and anhydrides thereof (for example, maleic anhydride); and the like.

  Furthermore, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; polyvalent compounds such as ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate Unsaturated carboxylic acid esters of alcohol; unsaturated carboxylic acid allyl esters such as allyl acrylate and allyl methacrylate; cross-linking monomers such as di- and triallyl compounds such as diallyl phthalate, diallyl sebacate, and triallyl triazine You can also

  There are no particular restrictions on the production of the composite rubber, but usually an alkyl (meth) acrylate component and a polyfunctional alkyl (meth) acrylate component are added in the presence of a latex of a polyorganosiloxane rubber, a peroxide, A method of producing by emulsion graft polymerization or the like using a radical polymerization initiator such as an azo initiator or a redox polymerization initiator combined with an oxidizing agent / reducing agent is preferred.

The production of the core-shell type graft copolymer (B) is not particularly limited, but a vinyl monomer is preferably copolymerized in the presence of a latex of a composite rubber, preferably in the presence of a polymerization initiator similar to the above. Can be manufactured.
The composite rubber as the core is preferably composed of 1 to 99% by mass of silicone rubber and 1 to 99% by mass of acrylic rubber.

Moreover, Si content (total mass of Si atom) in a core-shell type graft copolymer (B) needs to be 7-12 mass%, and the upper limit should be 11 mass% or less. More preferably, it is 10.5 mass% or less. Moreover, it is preferable that it is 8 mass% or more, Furthermore, it is preferable that it is 9 mass% or more. By making Si content into such a range, a flame retardance and bending resistance can be improved.
Adjustment of Si content can be easily performed by adjusting the quantity of the silicone type rubber | gum at the time of manufacturing a core-shell type graft copolymer (B). It is also possible to select from commercially available products.
The Si content of the shell / graft copolymer (B) of the silicone / acrylic composite rubber core is a value detected by inductively coupled plasma emission spectrometry (ICP / AES method).

  The number average particle size of the core-shell type graft copolymer (B) used in the present invention is preferably 1000 nm or less, more preferably 800 nm or less, and further preferably 650 nm or less. The lower limit is preferably 50 nm or more, more preferably 80 nm or more, and further preferably 100 nm or more. By setting the number average particle size of the core-shell type graft copolymer (B) within such a range, flame retardancy, bending resistance and appearance of the molded product can be improved.

In addition, the number average particle diameter of the core-shell type graft copolymer (B) in the present invention refers to a core-shell type graft copolymer dispersed in a matrix polycarbonate resin (A) by observation with a transmission electron microscope (TEM) ( This is a value obtained by measuring the primary particle size of B).
Specifically, for example, it can be obtained in the following manner.
An ultra-thin section having a thickness of 100 nm cut out from the resin composition pellet of the present invention was further stained with osmium tetroxide vapor for 60 minutes and further with ruthenium tetroxide vapor for 60 minutes, and then observed with TEM and obtained by TEM observation. Using the obtained image, the primary particle diameter (average diameter) of 50 core-shell type graft copolymers (B) dispersed in the matrix is measured, and the number average is defined as the number average particle diameter.

Content of a core-shell type graft copolymer (B) is 1.0-2.5 mass parts with respect to 100 mass parts of polycarbonate resin (A). When the content of the core-shell type graft copolymer (B) is smaller than 1.0 part by mass, the effect of improving the bending resistance is insufficient, and when the content exceeds 2.5 parts by mass, flame retardancy is exhibited. The content of the core-shell type graft copolymer (B) that deteriorates and deteriorates the elastic modulus is preferably 1.0 to 2.4 parts by mass.

[Core-shell type graft copolymer with butadiene rubber as the core (E)]
The polycarbonate resin composition of the present invention includes a core-shell type graft copolymer (E) having a butadiene-based rubber component as a core in addition to the above core-shell type graft copolymer (B) having a silicone / acrylic composite rubber as a core. ) Is also preferable.

In the core-shell type graft copolymer (E), the rubber component forming the core is a butadiene rubber component. Specific examples of the diene rubber component forming the core include polybutadiene rubber, acrylonitrile-butadiene rubber, and styrene-butadiene. Preferred are butadiene rubbers such as rubber, ethylene-butadiene rubber, ethylene-propylene-butadiene terpolymer (EPDM), and more preferred are polybutadiene rubber and styrene-butadiene rubber.
These may be used alone or in admixture of two or more.

  Moreover, as a vinyl monomer graft-polymerized to butadiene rubber in the core-shell type graft copolymer (E), methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, etc. (Meth) acrylate monomers such as alkyl (meth) acrylates; aryl (meth) acrylates such as phenyl methacrylate, phenyl acrylate, naphthyl acrylate and naphthyl methacrylate; glycidyl group-containing (meth) acrylates such as glycidyl acrylate and glycidyl methacrylate; Is preferred, but methyl methacrylate is particularly preferred.

  In addition to the above (meth) acrylate monomer, other vinyl monomers can be copolymerized, for example, aromatic vinyl such as styrene and α-methylstyrene, acrylonitrile, methacrylonitrile. And unsaturated nitriles such as methyl vinyl ether and butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, and vinylidene halides such as vinylidene chloride and vinylidene bromide.

The content of the butadiene-based rubber component in the core-shell type graft copolymer (E) is preferably 50% by mass or more, more preferably 55%, when the total mass of the core-shell type graft copolymer (E) is 100% by mass. It is at least 70% by mass, more preferably at least 70% by mass, and preferably at most 95% by mass, more preferably at most 90% by mass, and even more preferably at most 85% by mass. By setting the butadiene content in such a range, flame retardancy and impact resistance can be improved.
When the butadiene content is less than the above lower limit, the effect of improving flame retardancy and impact resistance tends to be insufficient, and when the butadiene content exceeds the upper limit of the above range, the polycarbonate of the graft copolymer (E) The dispersibility in the resin (A) is extremely lowered, and there is a possibility that the impact resistance of the polycarbonate resin composition of the present invention is lowered and the appearance is poor.

The content of the vinyl monomer graft-polymerized to the butadiene rubber in the core-shell type graft copolymer (E) is preferably 2 when the total mass of the core-shell type graft copolymer (E) is 100% by mass. It is at least 5% by mass, more preferably at least 5% by mass, even more preferably at least 10% by mass, preferably at most 50% by mass, more preferably at most 45% by mass, even more preferably at most 30% by mass. By setting the content of the vinyl monomer to be grafted within the above range, flame retardancy and impact resistance can be dramatically improved.
When the proportion of the vinyl monomer to be grafted is less than 2% by mass, the dispersibility of the graft copolymer (E) in the polycarbonate resin is extremely lowered, and the impact resistance of the polycarbonate resin composition of the present invention is reduced. There is a possibility of causing a reduction or a poor appearance, and when it exceeds 50% by mass, there is a possibility of causing deterioration of flame retardancy.

  The core-shell type graft copolymer (E) preferably has an average particle size of 80 to 800 nm. If the average particle size is smaller than 80 nm, the flame retardancy may be deteriorated, and if it is larger than 800 nm, the appearance may be poor. Furthermore, the range of a preferable average particle diameter is 120-400 nm, and expression of the most stable impact resistance can be expected in this range.

  A method for producing the core-shell type graft copolymer (E) is known, and a known method can also be adopted in the present invention. The polymerization method for producing the graft copolymer (E) may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, and the copolymerization method may be one-stage graft or multi-stage graft. It may be. Of these, the emulsion polymerization is the easiest and preferred method.

  The content of the core-shell type graft copolymer (E) is preferably in the range of 0.2 to 1.0 part by mass, more preferably 0.3 part by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). Yes, more preferably 0.8 parts by mass or less, still more preferably 0.7 parts by mass or less. If it is less than 0.2 parts by mass, it is difficult to obtain the effect of improving flame retardancy and bending resistance, and if it exceeds 1.0 parts by mass, the elastic modulus is lowered and the flame retardancy of the polycarbonate resin composition is deteriorated. Easy to cause.

  The ratio of the core-shell type graft copolymer (B) having a silicone / acrylic composite rubber core and the core-shell type graft copolymer (E) having a butadiene rubber core is (B) 50 to 99% by mass: ( E) It is preferable that it is 1-50 mass%. When the core-shell type graft copolymer (E) exceeds 50% by mass, the bending resistance deteriorates, which is not preferable.

[Organic sulfonic acid metal salt (C)]
The polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt (C), and the content thereof is 0.001 to 0.3 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). By containing the organic sulfonic acid metal salt (C) in such an amount together with the core-shell type graft copolymer (B), the flame retardancy can be improved, and the polycarbonate resin has impact resistance and other machines. Bending resistance can be improved while maintaining good properties such as physical properties, heat resistance and electrical characteristics.

The metal of the organic sulfonic acid metal salt (C) is not particularly limited, but is preferably an alkali metal such as sodium, lithium, potassium, rubidium or cesium, or an alkaline earth such as beryllium, magnesium, calcium, strontium or barium. A metal is mentioned.
Among these, alkali metals are preferable, sodium, potassium, cesium or lithium is more preferable, sodium, potassium and cesium are more preferable, and sodium and potassium are particularly preferable. Of these, potassium is preferred from the viewpoints of flame retardancy and hydrolysis resistance.

  Among the organic sulfonic acid metal salts (C), preferred are fluorine-containing aliphatic sulfonic acid metal salts, fluorine-containing aliphatic sulfonic acid imide metal salts, aromatic sulfonic acid metal salts, and aromatic sulfonamide. Metal salts are mentioned.

  Among them, specific examples of preferable ones include potassium nonafluorobutanesulfonate, lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, cesium nonafluorobutanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, Containing at least one C—F bond in the molecule, such as potassium trifluoromethanesulfonate, potassium pentafluoroethanesulfonate, potassium heptafluoropropanesulfonate, potassium decafluoro-4- (pentafluoroethyl) cyclohexanesulfonate; Alkali metal salts of fluoroaliphatic sulfonic acids;

  At least one C—F in the molecule, such as magnesium nonafluorobutanesulfonate, calcium nonafluorobutanesulfonate, barium nonafluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, barium trifluoromethanesulfonate, etc. An alkaline earth metal salt of a fluorine-containing aliphatic sulfonic acid having a bond;

  Disodium difluoromethane disulfonate, dipotassium difluoromethane disulfonate, disodium tetrafluoroethane disulfonate, dipotassium tetrafluoroethane disulfonate, dipotassium hexafluoropropane disulfonate, dipotassium hexafluoroisopropane disulfonate, disodium octafluorobutane disulfonate An alkali metal salt of a fluorinated aliphatic disulfonic acid having at least one C—F bond in the molecule, such as dipotassium octafluorobutanedisulfonate; a metal salt of a fluorinated aliphatic sulfonic acid, such as

  Bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide sodium, In the molecule, such as potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane, etc. An alkali metal salt of a fluorine-containing aliphatic disulfonic imide having at least one C—F bond;

  Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorinated aliphatic sulfonimide having at least one C—F bond in the molecule; a metal salt of a fluorinated aliphatic sulfonic imide, such as

  Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate Etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule;

  Magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) calcium dodecylbenzenesulfonate in the molecule An alkaline earth metal salt of an aromatic sulfonic acid having an aromatic group of: an aromatic sulfonic acid metal salt, etc.

  Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonamides such as alkali metal salts of aromatic sulfonamides having at least one aromatic group in the molecule, such as salts.

Among the examples described above, fluorine-containing aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts are more preferable, and fluorine-containing aliphatic sulfonic acid metal salts are particularly preferable.
Further, as the fluorine-containing aliphatic sulfonic acid metal salt, an alkali metal salt of fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule is more preferable, and an alkali metal salt of perfluoroalkanesulfonic acid is particularly preferable. Specifically, potassium nonafluorobutanesulfonate is particularly preferable.
As the aromatic sulfonic acid metal salt, an alkali metal salt of an aromatic sulfonic acid is more preferable, and an alkali of diphenyl sulfone-sulfonic acid such as dipotassium 3,3′-disulfonic acid dipotassium and diphenylsulfone-3-sulfonic acid potassium. Metal salts; sodium paratoluenesulfonate, and alkali metal salts of paratoluenesulfonic acid such as potassium paratoluenesulfonate and cesium paratoluenesulfonate are particularly preferable, and alkali metal salts of paratoluenesulfonic acid are more preferable.

  In addition, 1 type may be used for organic sulfonic acid metal salt (C), and it may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the organic sulfonic acid metal salt (C) is 0.001 to 0.3 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), preferably 0.01 parts by mass or more, more preferably 0. 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, particularly preferably 0.07 parts by mass or more, and preferably 0.2 parts by mass or less. When the content is less than 0.001 part by mass, it is difficult to obtain sufficient flame retardancy, and when it exceeds 0.3 part by mass, thermal stability and hydrolysis resistance are likely to be lowered.

[Fluorine-containing resin (D)]
The polycarbonate resin composition of the present invention contains 0.05 to 1 part by mass of the fluororesin (D) with respect to 100 parts by mass of the polycarbonate resin (A). As the fluororesin (D), one type may be used, or two or more types may be used in any combination and in any ratio. By containing the fluorine-containing resin together with the above-mentioned components in such an amount, the melting characteristics of the resin composition can be improved, the dripping prevention property at the time of combustion is improved, and the flame retardancy is further improved. Can do.

  If the content of the fluorine-containing resin (D) is less than 0.05 parts by mass, the effect of improving flame retardancy tends to be insufficient, and if it exceeds 1 part by mass, the appearance of molded articles molded from the resin composition and machinery The mechanical strength is likely to decrease. The preferable content is 0.1 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), preferably 0.9 parts by mass or less, more preferably 0.8 parts by mass or less, and still more preferably. 0.6 parts by mass or less.

As the fluorine-containing resin (D), a fluoroolefin resin is preferable. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
Moreover, as this fluorine-containing resin, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. By having the ability to form fibrils, the dripping prevention property during combustion tends to be remarkably improved.

In addition, an organic polymer-coated fluoroolefin resin can also be suitably used as the fluorine-containing resin (D). By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed.
The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. And the like, and the like.

  From the viewpoint of dispersibility when blended with a polycarbonate resin, a monomer having a high affinity with the polycarbonate resin is preferable as the monomer for producing the organic polymer that coats the fluoroolefin resin. Monomers, (meth) acrylic acid ester monomers, and vinyl cyanide monomers are more preferred.

[Stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer and / or a phenolic antioxidant.
By containing a phosphorus stabilizer, the heat stability, heat discoloration resistance, weather resistance, etc. of the polycarbonate resin composition can be improved. Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include 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) octyl phosphite and the like. Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, and the like.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phosphorus stabilizer is 0.005 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). 0.5 parts by mass or less, preferably 0.4 parts by mass or less. If the content of the phosphorus stabilizer is below the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect is There is a possibility that it will hit a peak and become uneconomical.

  Examples of phenolic antioxidants include hindered phenolic antioxidants. 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 ′, ''-(Mesitylene-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, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4 6- di -tert- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such a phenolic antioxidant include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Is mentioned.
In addition, 1 type may contain phenolic antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  Content of a phenolic antioxidant is 0.005 mass part or more with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 0.01 mass part or more, and is 0.5 mass part or less. The amount is preferably 0.3 parts by mass or less and 0.2 parts by mass or less. When the content of the phenolic antioxidant is less than the lower limit of the above range, the effect as the phenolic antioxidant may be insufficient, and the content of the phenolic antioxidant is the upper limit of the above range. If the value is exceeded, the effect may reach its peak and not economical.

[Release agent]
Moreover, it is preferable that the polycarbonate resin composition of this invention contains a mold release agent (lubricant). 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, polysiloxane silicone oils, and the like.

  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, monovalent or polyvalent 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 alicyclic compounds.

  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.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine and comprise one ester may each be used 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerol monopalmitate, glycerol monostea 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. 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 even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). It is below mass parts. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins 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 resins), polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, and the like. It is done.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and a ratio.

-Resin additive Examples of the resin additive include an ultraviolet absorber, a dye / pigment, an antistatic agent, an antifogging agent, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[Production of polycarbonate resin composition]
There is no restriction | limiting in the method of manufacturing the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin (A), core-shell type graft copolymer (B), organic sulfonic acid metal salt (C) and fluorine-containing resin (D), and other components blended as necessary. Are mixed in advance using various mixers such as tumblers and Henschel mixers, and then melt kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. Can be mentioned.

Further, for example, it is possible to produce a polycarbonate resin composition without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. .
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. A polycarbonate resin composition can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

[Outflow]
The polycarbonate resin composition of the present invention has a flow rate per unit time of the resin composition (according to the method described in JIS K7210 Appendix C, using a high load type flow tester, 280 ° C., load 160 kgf / cm ^2. Is preferably 40 × 10 ⁻² cm ³ / sec or more, more preferably 50 × 10 ⁻² cm ³ / sec or more. Since the polycarbonate resin composition of the present invention has such an outflow amount, it is possible to achieve both excellent moldability and bending resistance.

[Number of bending breaks]
In addition, the polycarbonate resin composition of the present invention has a number of bending breaks of a molded product having a width of 13 mm and a thickness of 0.8 mm (according to JIS P8115, using an MIT folding resistance tester, with a clamp R of 0.38 mm, Measured at an angle of 135 °, a test speed of 175 cpm, and a tension of 1.5 kg.) Preferably shows a value of 7 times or more. The polycarbonate resin composition of the present invention is a resin material effective for a member having a hinge part and a fitting part by having such a number of bending breaks.

[Molding]
Since the polycarbonate resin composition of the present invention is excellent in fluidity, particularly thin wall fluidity, it is possible to reduce the thickness to 2 mm or less. The thickness of the thinnest portion is preferably 1.5 mm or less, more preferably 1.0 mm or less, and the upper limit is usually 0.1 mm or more, preferably 0.2 mm or more.
The molded product having a thin portion may be at least partially provided with a thin portion having a thickness equal to or smaller than the above-described thickness, and there is no limitation on the shape, size, and the like.

As a method for producing a thin molded article, a molding method generally adopted for a polycarbonate resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, 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, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method, and a molding method using a hot runner method can also be used.
Among these, injection molding methods such as an injection molding method, an ultra-high speed injection molding method, and an injection compression molding method are preferable.

  In particular, in order to mold a thin molded product, it is preferable to perform injection molding at a resin temperature of 305 to 360 ° C. The polycarbonate resin composition of the present invention is less susceptible to problems such as gas generation due to thermal decomposition of the resin during molding, and has excellent fluidity even under high molding conditions of a resin temperature of 305 to 360 ° C. It becomes possible to mold a desired thin molded product having a thickness of 2 mm or less, and particularly a thin molded product having a thin hinge portion.

  Examples of molded products include parts such as electrical / electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment, and particularly suitable for use in parts such as electrical and electronic equipment.

Examples of the electric / electronic devices include display devices such as personal computers, game machines, televisions, and electronic paper, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, and videos. Examples include a camera, a mobile phone, a tablet terminal, a touch panel terminal, a battery pack for these, a drive and reading device for a recording medium, a mouse, a numeric keypad, a CD player, an MD player, and a portable radio / audio player.
Among them, a casing of a portable device represented by a tablet terminal or a touch panel terminal, a protective case, a frame or casing of a battery pack, a reflection frame of various liquid crystal display devices, in particular, a molded product having a fitting portion, It can be suitably used as a box-shaped molded product having a hinge portion.

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.
In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.
Each component used in Examples and Comparative Examples is as shown in Table 1 below.

(Examples 1-5, Comparative Examples 1-5)
[Production of resin pellets]
Each component described in Table 1 was blended in the ratio (mass ratio) described in Table 2 below, mixed for 20 minutes with a tumbler, and then a twin screw extruder (TEX30HSST) manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. , Kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded into a strand is quenched in a water tank, pelletized using a pelletizer, and polycarbonate resin composition A product pellet was obtained.

[Outflow per unit time Q value (unit: × 10 ⁻² cm ³ / sec)]
After the pellets obtained by the above method are dried at 120 ° C. for 4 hours or more, the composition is compliant with JIS P8115 under the conditions of a temperature of 280 ° C. and a load of 1.60 kgf / cm ² using an elevated flow tester. The flow rate Q value (unit: x10 ⁻² cm ³ / sec) per unit time of the product 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 “Q value”.

[Flammability (flame retardant) evaluation UL94 test]
After drying the pellets obtained by the above-mentioned production method at 120 ° C. for 4 hours, injection was performed under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. using an SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. A UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm was molded.
The evaluation of the flammability (flame retardant) of each polycarbonate resin composition was performed by conditioning the obtained test specimen for UL test for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was conducted in accordance with UL94 test (combustion test of plastic materials for equipment parts) defined by Laboratories (UL).
In the table, “combustibility” is indicated.

[Bending elastic modulus (unit: MPa)]
The pellets obtained above were dried at 120 ° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an SG75MII type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. An ISO multipurpose specimen (4 mm thick) was molded.
Using this ISO multipurpose test piece, the flexural modulus was measured according to ISO178.
In the table, it is expressed as “flexural modulus”.

[Number of bending test fractures (unit: times)]
After the pellets obtained by the above method are dried at 120 ° C. for 4 hours, injection molding is performed under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. using an SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was formed.
Using this test piece, using an “MIT folding resistance tester” manufactured by Ueshima Seisakusho, in accordance with JIS P8115, the load is 1.5 kgf, the mounting clamp is R = 0.38 mm, the bending angle is 135 °, and the speed is 175 cpm. The bending resistance test was carried out under the conditions described above, and the number of reciprocating folds until ruptured (1 reciprocation = 1 time) was counted.
In the table, it is expressed as “number of bending test fractures”.
The results are shown in Table 2.

  Since the polycarbonate resin composition of the present invention is a resin material that is excellent in fluidity and elastic modulus and excellent in bending resistance, it is a component of electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, lighting equipment, etc. In particular, the present invention can be suitably used for a molded article having a hinge structure or a fitting portion, and the industrial utility is very high.

Claims (7)

  1.0-2.5 parts by mass of the core-shell type graft copolymer (B) having a silicone / acrylic composite rubber having a Si content of 7-12% by mass as a core with respect to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition comprising 0.001 to 0.3 part by mass of an organic sulfonic acid metal salt (C) and 0.05 to 1 part by mass of a fluororesin (D).   Further, the core-shell type graft copolymer (B) having a core-shell type graft copolymer (E) having a core of butadiene rubber and having a core of silicone / acrylic composite rubber, containing 0.2 to 1.0 parts by mass, and the butadiene rubber 2. The polycarbonate resin composition according to claim 1, wherein the ratio of the core-shell type graft copolymer (E) having a core of (B) is 50 to 99% by mass: (E) 1 to 50% by mass.   The polycarbonate resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight of 12,000 to 16,000.   The molded article formed by shape | molding the polycarbonate resin composition in any one of Claims 1-3. The molded article according to claim 4, which is a part for electric and electronic equipment. The molded article according to claim 4, which is a battery pack casing part. The thin-walled resin molded product according to claim 4, which is a box-shaped molded product having a hinge structure.