JP2018002978A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having extremely high flame retardancy. SOLUTION: To 100 parts by mass of a polycarbonate resin (A), 0.05 to 0.15 parts by mass of an aromatic sulfonic acid metal salt flame retardant (B), a rubber polymer component containing an organosiloxane unit and a graft are grafted. 0.1 to 1.5 parts by mass of the graft copolymer (C) having a Si content of 4 to 20% by mass and 0.05 to 1 parts by mass of the fluoropolymer (D). A polycarbonate resin composition, wherein the mass ratio (C / B) of (C) and (B) is 4 to 15. [Selection diagram] None

Description

  The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having an extremely high flame retardancy.

  Polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical characteristics. For example, it is widely used as a material for manufacturing parts in electrical and electronic equipment parts, vehicle parts, housing members, and other industrial fields. ing.

  As a polycarbonate resin composition excellent in fluidity, elastic modulus, and bending resistance, the present applicant previously prepared a polycarbonate resin containing a siloxane unit-containing elastomer and a phosphorus stabilizer and / or a phenolic antioxidant as a polycarbonate resin. The composition is a polycarbonate resin composition that is suitable for parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment, and is particularly useful for a molded product having a hinge structure and a fitting portion. Proposed (see Patent Document 1).

  In recent years, parts such as electrical and electronic equipment and information terminal equipment have been required to have high flame retardancy. Particularly recently, V-0 in UL-94 is of course much higher flame retardancy. It is being requested to clear the level of 5VA. In addition, the flame retardance of UL-94 standard is V-2, V-1, V-0, 5VB, 5VA in order from low to high flame retardance.

Therefore, even in the polycarbonate resin composition as described above, a flame retardance of 5 VA is strongly desired.
As means for imparting flame retardancy to a polycarbonate resin, a halogen-based flame retardant has been conventionally used, and in recent years, a phosphorus-based flame retardant and an organic sulfonic acid metal salt-based flame retardant have been used. Patent Document 1 described above describes that it is preferable to contain various flame retardants, but there is no example of actually blending flame retardants in the examples.

Japanese Patent Laying-Open No. 2015-187243

  An object of the present invention is to provide a polycarbonate resin composition that achieves a high flame retardancy of 5 VA level in a system in which a siloxane-containing elastomer is blended with a polycarbonate resin as described above.

In order to solve the above-mentioned problems, the inventor has made extensive studies on the combination of a siloxane-containing elastomer and various flame retardants, and as a result, has specifically selected the amount of the siloxane-containing elastomer and the type and amount of the flame retardant. Then, it was found that a high flame retardancy of 5 VA level could be achieved for the first time by setting the ratio of both in a specific range, and the present invention was completed.
The present invention relates to the following polycarbonate resin composition.

[1] 0.05 to 0.15 parts by mass of an aromatic sulfonic acid metal salt flame retardant (B), 100 parts by mass of the polycarbonate resin (A), and a rubbery polymer component containing an organosiloxane unit and a graft copolymer 0.1 to 1.5 parts by mass of the graft copolymer (C) having a Si content of 4 to 20% by mass and 0.05 to 1 part by mass of the fluoropolymer (D) comprising a polymerization component, A polycarbonate resin composition having a mass ratio (C / B) of (C) and (B) of 4 to 15.
[2] The polycarbonate resin composition according to the above [1], wherein the aromatic sulfonic acid metal salt flame retardant (B) is a paratoluenesulfonic acid alkali metal salt.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the flame retardancy at 3 mm thickness is 5 VA.

  In the polycarbonate resin composition of the present invention, the content of the aromatic sulfonic acid metal salt flame retardant (B) is 0.05 to 0.15 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and Si The content of the graft copolymer (C) consisting of a rubbery polymer component containing an organosiloxane unit and a graft copolymer component having a content of 4 to 20% by mass is 0.1 to 1.5 parts by mass, Furthermore, after adjusting the mass ratio (C / B) of (C) and (B) to 4 to 15, and containing 0.05 to 1 part by mass of the fluoropolymer (D), flame retardancy at a thickness of 3 mm Can exhibit extremely high flame retardancy of 5VA.

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.

  The polycarbonate resin composition of the present invention is a rubbery material containing 0.05 to 0.15 parts by mass of an aromatic sulfonic acid metal salt flame retardant (B) and 100 parts by mass of the polycarbonate resin (A). 0.1 to 1.5 parts by mass of a graft copolymer (C) having a Si content of 4 to 20% by mass and a fluoropolymer (D) of 0.05 to 0.05 and comprising a polymer component and a graft copolymer component. 1 mass part is contained, The mass ratio (C / B) of said (C) and (B) is 4-15, It is characterized by the above-mentioned.

[Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin (A) used in this invention, A polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C (═O) —] —.
In the formula, X is generally a hydrocarbon, but for imparting various properties, X into which a hetero atom or a hetero bond is introduced 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) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
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;

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

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

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (especially from the viewpoint of impact resistance and heat resistance). That is, 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 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 described in detail.

-Interfacial polymerization method First, the case where a polycarbonate resin is manufactured 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; 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 isopropenyl 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 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 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 is 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, and above all, 1.01 mol or more. It 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 like, 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, 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 polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

The molecular weight of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, more preferably 17000 or more. In addition, it is usually 40000 or less, preferably 30000 or less, more preferably 25000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. . On the other hand, by setting the viscosity average molecular weight to be equal to or less than the upper limit of the above range, it is possible to suppress and improve the fluidity of the resin composition, and to improve the molding processability and easily perform the molding process.
Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

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. , 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).

  The terminal hydroxyl group concentration of the 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 polycarbonate resin can be improved more. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a resin composition can be improved more.

  In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  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 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 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).
However, the regenerated polycarbonate resin is preferably 80% by mass or less of the polycarbonate resin, and more preferably 50% by mass or less. 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.

[Aromatic sulfonic acid metal salt flame retardant (B)]
The polycarbonate resin composition of the present invention contains an aromatic sulfonic acid metal salt flame retardant (B).
The aromatic sulfonic acid metal salt is preferably a metal salt of benzene and alkyl or alkenyl benzene, and the metal of the metal salt is preferably an alkali metal or an alkaline earth metal.

  Specific examples of the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium. Of these, sodium and potassium are preferable as the alkali metal, and magnesium, calcium and cesium are preferable as the alkaline earth metal from the viewpoint of compatibility with the polycarbonate resin and imparting flame retardancy. Of these, sodium and potassium are particularly preferable.

Examples of aromatic sulfonic acid metal salts include sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, sodium toluenesulfonate, potassium toluenesulfonate, sodium dodecylbenzenesulfonate, sodium styrenesulfonate, and the like. In particular, sodium paratoluenesulfonate and potassium paratoluenesulfonate are preferred.
The aromatic sulfonic acid metal salt flame retardant (B) may be a mixture of two or more.

  Content of an aromatic sulfonic-acid metal salt type flame retardant (B) needs to exist in the range of 0.05-0.15 mass part with respect to 100 mass parts of polycarbonate resin (A). Such an amount of the aromatic sulfonic acid metal salt flame retardant (B) is 0.1 to 1.5 parts by mass of the graft copolymer (C) described in detail below, and (C) and (B). The flame retardant property of 5 VA can be achieved for the first time by containing them so that the mass ratio (C / B) is 4 to 15. When the content of the flame retardant (B) is less than the lower limit value of the range, the flame retardancy may be insufficient, and when the content of the flame retardant (B) exceeds the upper limit value of the range, There is a possibility that the flame retardancy becomes insufficient and the appearance of the molded product is poor. Content of a flame retardant (B) becomes like this. Preferably it is 0.06 mass part or more, Preferably it is 1.2 mass part or less, More preferably, it is 1.0 mass part or less, More preferably, it is 0.9 mass part or less.

[Graft Copolymer (C)]
The polycarbonate resin composition of the present invention is a graft copolymer rubber comprising a rubbery polymer component containing an organosiloxane unit and a graft copolymer component, and has a Si content of 4 to 20% by mass. Contains coalescence (C).

  The graft copolymer (C) is a core / shell type in which a rubbery polymer component containing an organosiloxane unit 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 rubber layer. It is an elastomer.

The silicone rubber constituting the core layer is preferably a polyorganosiloxane, for example, a polymer containing a dimethylsiloxane unit as a constituent unit or a siloxane containing a vinyl polymerizable functional group as a constituent component.
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.

  The silicone rubber constituting the core layer is preferably a composite rubber containing an acrylic polymer. Examples of the acrylic polymer include polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl acrylate / 2-ethylhexyl acrylate copolymer. These may be used alone or in admixture of two or more. The composite rubber here 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 layer of the graft copolymer (C) include acrylic-based, preferably polyalkyl (meth) acrylate-based, and the like. An alkyl (meth) acrylate unit and a polyfunctional alkyl ( 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 0.1-2.0 mass% in 100 mass% of polyalkyl (meth) acrylate, 0.3- More preferably, it is 1.0 mass%.

  Moreover, as a copolymerization component which comprises the shell layer of a graft copolymer (C), 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.

  In addition, polyfunctional aromatic vinyl compounds such as divinylbenzene and divinyltoluene; 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

  Although there is no restriction | limiting in particular in manufacturing a graft copolymer (C), Usually, in the latex of a polyorganosiloxane component, the said alkyl (meth) acrylate component and a polyfunctional alkyl (meth) acrylate component, or acrylonitrile Ingredient grafting using radical polymerization initiator, preferably redox polymerization initiator such as redox polymerization initiator combining peroxide and azo initiator or oxidizer / reducing agent with addition of styrene component A method of producing by polymerization or the like is preferred.

Further, the Si content (total mass of Si atoms) of the graft copolymer (C) needs to be 4 to 20% by mass, and the upper limit thereof is preferably 17% by mass or less, more preferably 15%. It is preferably at most 13 mass%, particularly preferably at most 12 mass%, more preferably at least 5 mass%, more preferably at least 6 mass%. By making Si content into such a range, a flame retardance can be improved. In addition, impact resistance and heat resistance may 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 graft copolymer (C).
The Si content of the siloxane-based core / shell elastomer (C) is measured as a value detected by inductively coupled plasma emission analysis (ICP / AES method).

Content of a graft copolymer (C) is 0.1-1.5 mass parts with respect to 100 mass parts of polycarbonate resin (A). When the content of the graft copolymer (C) is less than 0.1 parts by mass, the flame retardancy is insufficient, and when the content exceeds 1.5 parts by mass, the flame retardancy is deteriorated.
The content of the graft copolymer (C) is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and preferably 1.3 parts by mass or less, more preferably 1.0 parts by mass. It is preferable that the amount is not more than part by mass, more preferably not more than 0.8 part by mass, particularly preferably not more than 0.6 part by mass.

  As described above, the mass ratio (C / B) of the content of the graft copolymer (C) and the aromatic sulfonic acid metal salt flame retardant (B) is 4 to 15. When C / B is less than 4, the effect of improving the flame retardancy becomes insufficient, and when the content exceeds the upper limit of the above range, the appearance defect or the mechanical strength of the molded product molded from the polycarbonate resin composition is reduced. Is likely to occur. When the ratio exceeds 15, the flame retardancy becomes insufficient. C / B is preferably 5 or more, more preferably 6 or more, preferably 13 or less, more preferably 11 or less, and even more preferably 10 or less.

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

  Examples of the fluoroethylene resin having a fibril-forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J”, “Teflon (registered trademark) 6C” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Daikin Industries, Ltd. “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500H”, and the like are available. Furthermore, as commercially available products of aqueous dispersions of fluoroethylene resin, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon D” manufactured by Daikin Industries, Ltd. -1 "and the like.

Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like.
In addition, 1 type may contain fluoropolymer and 2 or more types may contain it by arbitrary combinations and a ratio.

  Content of a fluoropolymer (D) is 0.05-1 mass part with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 0.1 mass part or more, More preferably, it is 0.15 mass. Part or more, more preferably 0.2 part by weight or more, particularly preferably 0.25 part by weight or more, preferably 0.8 part by weight or less, more preferably 0.6 part by weight or less, further preferably Is 0.5 parts by mass or less, particularly preferably 0.45 parts by mass or less. When the content of the fluoropolymer (D) is less than 0.05 parts by mass, the effect of improving the flame retardancy by the fluoropolymer (D) is insufficient, and when the content exceeds the upper limit of the above range, the polycarbonate Deterioration in appearance and mechanical strength of the molded product obtained by molding the resin composition are likely to occur.

[Phosphorus 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 thermal stability, heat discoloration resistance, weather resistance and the like of the polycarbonate resin composition are 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 phosphorus stabilizer content is less than or equal to the lower limit of the above range, the thermal stability effect will be insufficient, and if the phosphorus stabilizer content exceeds the upper limit value of the above range, the effect will peak and be economical. Not.

[Phenolic antioxidant]
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 ′, 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, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-te t- 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. , Preferably 0.3 parts by mass or less, more preferably 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 is insufficient, and when the content of the phenolic antioxidant exceeds the upper limit of the above range , The effect will end, and it will not be economical.

[Release agent]
Moreover, it is also 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, 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, 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.

  As the aliphatic hydrocarbon, an aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 is preferable. For example, liquid paraffin, paraffin wax, micro wax, polyethylene wax, Fischer-Tropsch wax, α-olefin having 3 to 12 carbon atoms. An oligomer etc. are mentioned. 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 5000 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), aromatic sulfonic acid metal salt flame retardant (B), graft copolymer (C) and fluoropolymer (D), and other compounds blended as necessary. A method in which components are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then melt kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. Is 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.

[Flame retardance]
The polycarbonate resin composition of the present invention has an extremely high flame retardance of 5 VA in the UL94 test at a thickness of 3 mm in the UL94 test defined by US Underwriters Laboratories (UL).
In addition, the polycarbonate resin composition of the present invention preferably has a flame retardance of 5 VA at 3 mm thickness and V-0 of 1.5 mm thickness in UL94 test.
The UL94 test V-0, V-1, and V-2 are also defined in JIS standards, and 5VA and 5VB are defined in JIS C60695-11-10 as JIS C60695-11-10.

[Molding]
As a method for producing a molded article from the polycarbonate resin composition of the present invention, a molding method generally employed for the 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.

  Examples of molded products include parts such as electrical and electronic equipment, information terminal equipment, in-vehicle equipment, OA equipment, home appliances, machine parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, in-vehicle equipment, and home appliances, and is particularly suitable as a housing for liquid crystal display equipment such as personal computers and car navigation systems.

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 1-6, Comparative Examples 1-11)
[Production of resin pellets]
Each component described in 1 above was blended in the proportions (mass ratio) described in Tables 3 to 4 below, mixed for 20 minutes with a tumbler, and then a twin-screw extruder manufactured by Nippon Steel Works, Ltd. equipped with 1 vent ( TEX30HSST), 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 in a strand shape is quenched in a water tank, pelletized using a pelletizer, and polycarbonate A pellet of the resin composition 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 temperature is 280 ° C. and the load is 160 kgf / cm ² using an elevated flow tester in accordance with the method described in JIS K7210 Annex C. The flow rate Q value (unit: × 10 ⁻² cm ³ / sec) per unit time of the composition was measured under the above conditions 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”.

[Flame retardance evaluation]
After drying the pellets obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, injection was performed under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. Molded, 125 mm × 12.5 mm × 1.5 mmt UL94 test specimen, UL94 5V Bar test specimen (125 mm × 12.5 mm × 3.0 mmt) and molded.
Moreover, after drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, using an EC-160 injection molding machine manufactured by Toshiba Machine Co., Ltd. under conditions of a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. A test piece for 5V Plate test (150 mm × 150 mm × 3.0 mmt) was injection molded.

The UL94 test specimen obtained above was molded, and V-0, V-1, and V-2 were determined based on the UL94 standard.
The UL94-5V test uses a 3 mm-thick test piece (two types of rod and plate), the after-flame time of the rod-shaped test piece after 5 seconds × 5 flame contact, the drip property, and the plate-shaped test piece In the method of evaluating flame retardance from the presence or absence of through holes, the determination criteria are as shown in Table 2 below. Those not satisfying any criteria of 5VA and 5VB were expressed as NR.

The above results are shown in Tables 3 to 4 below.

  Since the polycarbonate resin composition of the present invention has extremely high flame retardancy, it can be widely and suitably used for components such as electric and electronic equipment, OA equipment, information terminal equipment, in-vehicle equipment, etc., and industrial applicability is extremely high. Very expensive.

Claims (3)

  From 100 parts by mass of the polycarbonate resin (A), 0.05 to 0.15 parts by mass of the aromatic sulfonic acid metal salt flame retardant (B), from the rubbery polymer component containing the organosiloxane unit and the graft copolymer component And 0.1 to 1.5 parts by mass of the graft copolymer (C) having a Si content of 4 to 20% by mass and 0.05 to 1 part by mass of the fluoropolymer (D), ) And (B) have a mass ratio (C / B) of 4-15.   The polycarbonate resin composition according to claim 1, wherein the aromatic sulfonic acid metal salt-based flame retardant (B) is a paratoluenesulfonic acid alkali metal salt.   The polycarbonate resin composition according to claim 1 or 2, wherein the flame retardancy at 3 mm thickness is 5 VA.