JP2018145304A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which has extremely high flame retardancy even when formed into a thin molding, is also excellent in fluidity, impact strength, weld strength, and heat resistance, and has high rigidity, and a molded article of the same.SOLUTION: A polycarbonate resin composition contains, with respect to 100 pts.mass of a polycarbonate resin (A), 20 to 200 pts.mass of an inorganic filler (B), 10 to 30 pts.mass of a phosphazene compound (C), and 3 to 15 pts.mass of a core/shell type graft copolymer (D) having 5% weight reduction temperature by thermogravimetric analysis of 330°C or higher.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded article, and more specifically, it has extremely high flame retardancy even in the case of a thin molded article, and further has excellent fluidity, impact strength, weld strength, and heat resistance. The present invention relates to a rigid polycarbonate resin composition and a molded product thereof.

Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields.
Among them, the flame retardant polycarbonate resin composition is suitably used as a member for information / mobile devices such as computers, notebook computers, tablet terminals, smartphones, mobile phones, and OA devices such as printers and copiers. Yes.

In recent years, electric and electronic devices such as the above-mentioned information and mobile devices have been reduced in size and thickness. Therefore, even if the material used is thin, it has high flame retardancy and is also rigid. There is also a need for materials that are superior to the above.
Several methods for increasing the rigidity of the polycarbonate resin have been studied, but the method of blending a fibrous reinforcing material such as glass fiber is the most effective for the demand for thin and high rigidity as described above. . As a means for imparting flame retardancy to such a glass fiber reinforced polycarbonate resin, conventionally, a halogen-based flame retardant has been added to the polycarbonate resin. However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were.

Many glass fiber reinforced polycarbonate resin compositions containing organic phosphates have been proposed as alternative methods (see, for example, Patent Documents 1 and 2).
However, a material having high fluidity is required for molding a thin molded body required in recent years. However, the glass fiber reinforced polycarbonate resin composition as described above has insufficient fluidity, and the thin molded body is It could not be obtained, and the impact resistance was insufficient.

  Furthermore, it is difficult to meet the thin-walled flame retardant properties required in recent years with a resin composition containing only the organic phosphate ester flame retardant as described above. When the compounding amount of the acid ester is increased, the impact resistance and heat resistance are also remarkably lowered.

  In Patent Document 3, a resin composition in which a specific graft polymer is further blended with a glass fiber reinforced polycarbonate resin composition in which an organic phosphate ester is blended is proposed, and the improvement in thin flame retardancy and impact resistance is proposed. Although it has been achieved, the electric / electronic housing as described above has insufficient impact resistance to withstand the impact when dropped. Moreover, the polycarbonate which mix | blended organophosphate ester also has the subject that heat resistance is still inadequate.

  Patent Documents 4 and 5 propose a glass fiber reinforced polycarbonate resin composition containing a phosphazene compound, but no mention is made of the strength of an important weld part in a filler reinforced material. Is considered inadequate.

Japanese Patent Laid-Open No. 10-46017 Japanese Patent Laid-Open No. 10-30056 JP 2014-156588 A JP2013-177475A JP2013-189618A

  The present invention was devised in view of the above problems, and has extremely high flame retardancy even in the case of a thin-walled molded body, and further has excellent fluidity, impact strength, weld strength, and heat resistance. It is an object (problem) to provide a rigid material.

As a result of intensive studies to solve the above-mentioned problems, the inventor combined a polycarbonate resin with an inorganic filler, a phosphazene compound, and a specific core / shell type graft copolymer in specific amounts, respectively. In the reinforced polycarbonate resin, a highly rigid polycarbonate resin composition that has extremely high flame retardancy even when it is made into a thin-walled molded body, and also has excellent fluidity, impact strength, weld strength, and heat resistance can be obtained. The present invention was completed.
The present invention provides the following polycarbonate resin composition and molded article.

[1] 20 to 200 parts by mass of the inorganic filler (B), 10 to 30 parts by mass of the phosphazene compound (C) with respect to 100 parts by mass of the polycarbonate resin (A), and a 5% weight reduction temperature by thermogravimetric analysis is 330 ° C. A polycarbonate resin composition comprising 3 to 15 parts by mass of the core / shell type graft copolymer (D) as described above.
[2] The polycarbonate resin composition according to [1], further containing 0.05 to 2 parts by mass of the fluoropolymer (E) with respect to 100 parts by mass of the polycarbonate resin (A).
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the inorganic filler (B) is a glass filler.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the phosphazene compound (C) is a cyclic aromatic phosphazene.
[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the ratio of the core / shell type graft copolymer (D) to the phosphazene compound (C) is 10 to 80% by mass.
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the ratio of the core / shell type graft copolymer (D) to the inorganic filler (B) is 3 to 15%.
[7] The polycarbonate resin composition according to any one of [1] to [6], wherein the polycarbonate resin (A) has a viscosity average molecular weight (Mv) of 17000 to 22000.
[8] The polycarbonate resin composition according to any one of [1] to [7], wherein the combustibility based on the UL94 test is V-0 at a thickness of 1 mm.
[9] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [8].
[10] The molded product according to [9], which is a casing of an electric / electronic device.
[11] The molded article according to [10], wherein the electrical and electronic device is a notebook computer, a tablet terminal, a smartphone, or a mobile phone.

  According to the polycarbonate resin composition of the present invention, the filler-reinforced polycarbonate resin has extremely high flame retardancy even in the case of a thin-walled molded body, and further has fluidity, impact strength, weld strength, and heat resistance. An excellent high-rigidity polycarbonate resin composition becomes possible.

  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 polycarbonate resin composition of the present invention, the inorganic filler (B) is 20 to 200 parts by mass, the phosphazene compound (C) is 10 to 30 parts by mass, and 5% by thermogravimetric analysis with respect to 100 parts by mass of the polycarbonate resin (A). 3-15 mass parts of core / shell type graft copolymers (D) whose weight reduction temperature is 330 degreeC or more are contained.

[Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin used for the polycarbonate resin composition of this invention. In addition, one type of polycarbonate resin may be used, or two or more types may be used in any combination and in any ratio.

  The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond, represented by 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,
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

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

The molecular weight of the polycarbonate resin may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is preferably 17000 to 22000, more preferably 17000 to 20000, still more preferably 17000 to 19000. By setting the viscosity average molecular weight in such a range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by setting the viscosity average molecular weight to be equal to or less than the upper limit of the above range, the polycarbonate of the present invention. The fluidity of the resin composition can be suppressed and improved, and the molding processability can be improved and the thin-wall molding process can be easily performed.
In addition, two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed. The viscosity average molecular weight of the polycarbonate resin mixture is preferably in the above range.

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 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. 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 the polycarbonate resin composition of this invention 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, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[Inorganic filler (B)]
The polycarbonate resin composition of the present invention contains an inorganic filler (B). In the present invention, the inorganic filler refers to an inorganic filler that is contained in a resin component to improve strength and rigidity, and may be in any form such as fibrous, plate-like, granular, and amorphous.

  When the inorganic filler (B) is fibrous, for example, glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, metal fiber, wollastonite, etc. Of inorganic fibers. Of these, glass fiber is particularly preferable. The inorganic filler (B) may be a single type or a mixture of two types.

  When the form of the inorganic filler (B) is fibrous, the average fiber diameter, average fiber length, and cross-sectional shape are not particularly limited, but the average fiber diameter is preferably selected, for example, in the range of 1 to 100 μm, and the average fiber length Is preferably selected within the range of 0.1 to 20 mm. The average fiber diameter is more preferably about 1 to 50 μm, more preferably about 5 to 20 μm. The average fiber length is preferably about 0.12 to 10 mm. In addition, when the fiber cross section is a flat shape such as an oval, an ellipse, or a bowl, the flatness ratio (major axis / minor axis ratio) is preferably 1.4 to 10, more preferably 1.5 to 8, 1.8 to 5 is more preferable. It is preferable to use glass fibers having such an irregular cross section because dimensional stability such as fluidity, appearance, warpage of a molded product and anisotropy of shrinkage is easily improved.

In order to improve the adhesion at the interface between the inorganic filler and the resin component, the surface of the inorganic filler is preferably treated with a sizing agent or a surface treatment agent. Functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, titanate compounds and the like can be mentioned. In particular, in the present invention, the inorganic filler is preferably treated with an epoxy resin such as a bisphenol type epoxy compound or a novolac type epoxy compound, or an isocyanate compound (urethane resin).
The inorganic filler may be surface-treated in advance with the sizing agent or surface treatment agent, and may be surface-treated by adding a sizing agent or surface treatment agent when preparing the resin composition of the present invention.

  As the inorganic filler (B), in addition to the above-described fibrous inorganic filler, other inorganic fillers that are plate-like, granular, or amorphous can also be used. The plate-like inorganic filler exhibits a function of reducing anisotropy and warping, and examples thereof include glass flakes, talc, mica, mica, and kaolin. Among the plate-like inorganic fillers, glass flakes are preferable.

  Other inorganic fillers that are granular or amorphous include ceramic beads, asbestos, clay, zeolite, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide, and the like.

  Content of an inorganic filler (B) is 20-200 mass parts with respect to 100 mass parts of polycarbonate resin (A). If the content is less than 20 parts by mass, the rigidity is insufficient, and if it exceeds 200 parts by mass, sufficient strength cannot be obtained, and production becomes difficult. 50 mass parts or more are preferable, as for content of an inorganic filler (B), 80 mass parts or more are more preferable, 170 mass parts or less are preferable, and 140 mass parts or less are more preferable.

[Phosphazene Compound (C)]
The phosphazene compound (C) contained in the polycarbonate resin composition of the present invention is preferably a phosphazene compound represented by the following general formulas (1) and (2).

Examples of the phosphazene compounds represented by the general formulas (1) and (2) include phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene). O, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xylyloxyphosphazene and / or cyclic and chain C _1-6 alkyl C _6-20 aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- tolyloxy phosphazene, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxysilyloxyphosphazene, (poly ) Cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as _{phenoxytolyloxyxyloxyphosphazene} .
Of these, cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 Aryloxyphosphazenes (eg, cyclic and / or chain tolyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc.).

In the cyclic phosphazene compound represented by the general formula (1), R ¹ and R ² may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among them, cyclic phenoxyphosphazene in which R ¹ and R ² are phenyl groups is particularly preferable.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. .

  Moreover, in general formula (1), although a represents the integer of 3-25, the compound whose a is an integer of 3-8 is preferable especially, and the mixture of the compound from which a differs may be sufficient. Among them, a mixture of compounds in which a = 3 is 50% by mass or more, a = 4 is 10 to 40% by mass, and a = 5 or more is 30% by mass or less is preferable.

In General Formula (2), R ³ and R ⁴ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, a benzyl group, and the like, and a chain phenoxyphosphazene in which R ³ and R ⁴ are phenyl groups is particularly preferable.
Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group.

In addition, R ⁵ is represented by -N = P (OR ³ ) ₃ groups, -N = P (OR ⁴ ) ₃ groups, -N = P (O) OR ³ groups, and -N = P (O) OR ⁴ groups. represents at least one selected, ^{R 6} is, -P ^(OR _{3) 4} group, -P ^(OR ₄₎ 4 ^{group, -P (O) (OR 3} ) 2 group, -P (O) (OR ⁴ ) At least one selected from _two groups.

  Moreover, in general formula (2), b shows the integer of 3-10,000, Preferably it is 3-1,000, More preferably, it is 3-100, More preferably, it is 3-25.

The phosphazene compound (C) may be a crosslinked phosphazene compound that is partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
Examples of such a crosslinked phosphazene compound include a crosslinked structure represented by the following general formula (3), for example, a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, bisphenol S residue), 2,2- ( 4,4′-diphenylene) isopropylidene group-crosslinked structure, 4,4′-oxydiphenylene group-crosslinked structure, 4,4′-thiodiphenylene group-crosslinked structure, etc. And compounds having a crosslinked structure of 4,4′-diphenylene group.

Wherein (3), X is _{-C (CH 3) 2 -,} - SO 2 -, - S-, or a -O-, v is 0 or 1. ]

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹ and R ² are phenyl groups in the general formula (1) with a crosslinking group represented by the general formula (3). Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ³ and R ⁴ are phenyl groups in the general formula (2) with a crosslinking group represented by the general formula (3) is flame retardant. From the viewpoint of properties, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (3) is more preferable.

  The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (1) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (2) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound (C) is obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (1) and the cyclic phenoxyphosphazene compound represented by the general formula (1) with a crosslinking group. The resulting crosslinked phenoxyphosphazene compound is preferred from the viewpoint of flame retardancy and mechanical properties.

  The content of the phosphazene compound (C) is 10 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin, preferably 12 parts by mass or more, more preferably 14 parts by mass or more, and preferably 28 parts by mass or less. More preferably, it is 26 parts by weight or less.

[Core / shell type graft copolymer (D)]
As the core / shell type graft copolymer, a rubber polymer is used as a core layer, and a shell formed by copolymerizing monomer components such as an acrylic ester, a methacrylic ester and an aromatic vinyl compound around the core layer. A core / shell type graft copolymer comprising layers, but in the polycarbonate resin composition of the present invention, a core / shell type graft copolymer (D ).

The 5% weight loss temperature is a value measured by thermogravimetric analysis (TGA). When the temperature is raised from 40 ° C. to 550 ° C. in a nitrogen atmosphere at a rate of temperature increase of 10 ° C./min, By temperature is meant the temperature at which the weight of the sample has been reduced by 5%.
The 5% weight loss temperature of the core / shell type graft copolymer (D) is 330 ° C. or higher, preferably 340 ° C. or higher, more preferably 345 ° C. or higher. The higher the 5% weight loss temperature exceeds 330 ° C., the higher the decomposition temperature of the resin composition and the better the flame retardancy.

  In order to set the 5% weight loss temperature to 330 ° C. or higher, it is preferable to use a diene rubber component as the rubber polymer that is the core of the core / shell type graft copolymer (D).

  The core / shell type graft copolymer (D) is preferably a graft copolymer obtained by graft polymerizing a diene rubber component with a monomer component copolymerizable therewith. Such a graft copolymer may be produced by any production method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be a single-stage graft or a multi-stage graft. Also good.

  The rubber component generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the diene rubber component include polybutadiene rubber, butadiene-acrylic composite rubber, styrene-butadiene rubber, and ethylene-propylene-butadiene rubber. These may be used alone or in admixture of two or more.

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

  The core / shell type graft copolymer (D) used in the present invention is preferably a butadiene-based elastomer from the viewpoint of impact resistance and flame retardancy. Among these, a core / shell type graft copolymer comprising a shell layer formed by copolymerizing a (meth) acrylic acid ester around a polybutadiene-containing rubber component as a core layer is particularly preferable. The core / shell type graft copolymer preferably contains 40% by mass or more of a butadiene rubber component, more preferably 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid components is preferable.

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

  Content of a core / shell type graft copolymer (D) is 3-15 mass parts with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 4 mass parts or more, More preferably, it is 4.5 mass parts It is above, Preferably it is 14 mass parts or less. When the content of the core / shell type graft copolymer (D) is less than 3 parts by mass, the effect of improving the impact resistance and the weld strength cannot be sufficiently obtained. Deteriorates and the effect of improving the weld strength decreases.

[Fluoropolymer (E)]
The polycarbonate resin composition of the present invention preferably further contains a fluoropolymer (E). Thereby, the melting characteristic of a polycarbonate resin composition can be improved, and the dripping prevention property at the time of combustion can be improved.

The apparent density of the fluoropolymer (E) is preferably 0.4 g / ml or more. When the apparent density of the fluoropolymer (E) is 0.4 g / ml or more, the dripping prevention property during combustion is further improved. The apparent density of the fluoropolymer is more preferably 0.45 g / ml or more, and from the viewpoint of handling properties, it is preferably 2.0 g / ml or less, more preferably 1.5 g / ml or less, More preferably, it is 1.0 g / ml or less.
The apparent density of the fluoropolymer is measured using an apparent density measuring device based on JIS K6820.

  The preferable content of the fluoropolymer (E) is 0.05 to 2 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). When the amount is less than 0.05 parts by mass, the effect of improving flame retardancy tends to be insufficient, and when the amount exceeds 2 parts by mass, poor appearance and reduced mechanical strength tend to occur. The content of the fluoropolymer (E) is more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, more preferably 1.5 parts by mass or less, and particularly preferably 1.2 parts by mass or less. It is preferable that

The fluoropolymer is usually a polymer or copolymer containing a polyfluoroethylene structure, and specific examples include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene / hexafluoropropylene copolymer, and the like. Of these, tetrafluoroethylene polymers are preferred.
Moreover, as this fluoropolymer, what has fibril formation ability is preferable, and specifically, fluoropolymer resin which has fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  An organic polymer-coated fluoroolefin resin can also be suitably used as the fluoropolymer. 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 fluoropolymer. More preferred are monomers, (meth) acrylic acid ester monomers, and vinyl cyanide monomers.

[Flowability modifier]
The resin composition of the present invention preferably contains a fluidity modifier. The fluidity modifier is a component that improves the fluidity of the polycarbonate resin, and various low-molecular compounds or polymer compounds can be used. Particularly preferred in the present invention is an acrylonitonyl-styrene copolymer.

The acrylonitrile-styrene copolymer polymerizes at least a styrene monomer and a (meth) acrylonitrile monomer in the presence of rubber, and if necessary, further a styrene monomer and a (meth) acrylonitrile monomer. It is a styrene / (meth) acrylonitrile copolymer obtained by polymerizing other monomers copolymerizable with the monomer. In the styrene / (meth) acrylonitrile-based copolymer, the above two or more types of monomers are not limited to those that are all graft-polymerized with rubber to form a graft copolymer. Rather, it is usually a mixture that contains a large amount of a copolymer obtained by copolymerizing only two or more monomers together with the graft copolymer.
The acrylonitrile-styrene copolymer as the fluidity modifier in the present invention is commercially available, for example, as an AS resin, a SAN resin, an ABS resin, an AES resin, or an AAS resin, depending on the type of rubber and / or monomer constituting the copolymer. And the like.

  When the fluidity modifier is contained, the content is preferably 1 to 20 parts by mass, more preferably 3 parts by mass or more, and further preferably 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, it is 18 parts by mass or less, and more preferably 16 parts by mass or less. If the content of the fluidity modifier is less than the above lower limit, it is difficult to sufficiently obtain the effect of improving the moldability by improving the fluidity due to the incorporation of the fluidity modifier. , Impact resistance and flame retardancy tend to decrease.

[Phosphorus stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer. 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.
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 usually 0.001 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). Moreover, it is 1 mass part or less normally, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part or less. If the content of the phosphorus stabilizer is less than 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 May stop and become economical.

[Phenolic stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phenol-based stabilizer. As a phenol type stabilizer, a hindered phenol type antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionamide], 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 ″-( 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- ert- 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.
In addition, 1 type may be contained for the phenol type stabilizer, and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the phenol-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 100 parts by mass of the polycarbonate resin (A). 0.5 parts by mass or less. When the content of the phenol-based stabilizer is less than the lower limit of the range, the effect as the phenol-based stabilizer may be insufficient, and the content of the phenol-based stabilizer exceeds the upper limit of the range. If this is the case, the effect may reach its peak and not economical.

[Release agent]
Moreover, it is also preferable that the polycarbonate resin composition of this invention contains a mold release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, 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.

  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 other resin additives other than those described above. 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), and acrylonitrile-styrene copolymer (AS). Resin) and the like; polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyether imide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins; .
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and a ratio.

Resin Additives Other resin additives other than those described above include, for example, ultraviolet absorbers, dyes and pigments (including carbon black), antistatic agents, antifogging agents, antiblocking agents, plasticizers, dispersants, and antibacterial agents. Etc. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[Production Method of Polycarbonate Resin Composition]
There is no restriction | limiting in the manufacturing method of 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), inorganic filler (B), phosphazene compound (C), core / shell type graft copolymer (D), and other components blended as necessary. For example, after mixing in advance using various mixers such as a tumbler and a Henschel mixer, a method of melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. .

Also, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and supplied to an extruder using a feeder and melt kneaded to produce the polycarbonate resin composition of the present invention. You can also.
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. The polycarbonate resin composition of the present invention 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.

  As a method for producing the molded article, 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. Of these, injection molding methods such as injection molding, ultra-high speed injection molding, and injection compression molding are preferred.

[Molding]
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 suitable for use in parts such as electrical and electronic equipment, OA equipment, and information terminal equipment. Among them, it is suitable for a housing of an electric / electronic device, and particularly suitable for a casing of a notebook computer, a tablet terminal, a smartphone, or a mobile phone.

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.
The core / shell graft copolymer 5% weight loss temperature was measured using a thermogravimetric analyzer “STA7000” manufactured by Hitachi High-Tech Science Co., Ltd., with a measurement range of 40 to 550 ° C., a temperature increase rate of 10 ° C./min, Under a nitrogen atmosphere of 200 ml / min, thermogravimetry was performed under the condition of a sample amount of 5 mg, and a 5% weight reduction temperature was calculated.

(Examples 1-22, Comparative Examples 1-22)
[Production of resin pellets]
In each component described in Table 1, components other than the inorganic filler (B) and flame retardant (CX1) were blended in the amounts (parts by mass) described in Table 3 and below, and after mixing for 20 minutes with a tumbler, 1 vent was added. It is supplied from the upstream feeder to the extruder “TEX30α” manufactured by Nippon Steel Works, and the flame retardant (CX1) is supplied from the middle of the barrel by the liquid injection pump in the amount described in Table 3 and below. ) Is fed from the middle of the barrel by the side feeder in the amounts (parts by mass) listed in Table 3 and below, kneaded at a rotational speed of 200 rpm, a discharge rate of 30 kg / h, and a barrel temperature of 260 ° C., and extruded into a strand shape. The molten resin thus obtained was cooled in a water tank and pelletized using a pelletizer to obtain pellets of a polycarbonate resin composition.

[Preparation of test piece]
The pellet obtained by the above-mentioned method was dried at 80 ° C. for 5 hours, and then the cylinder temperature was 280 ° C. using an injection molding machine “Si-80-6” (clamping force 80 tons) manufactured by Toyo Machine Metal Co., Ltd. Then, injection molding was performed under the condition of a mold temperature of 60 ° C. to form an ISO multipurpose test piece (4 mm thickness).
After the pellets obtained by the above method were dried at 80 ° C. for 5 hours, the injection molding machine “SE100D” (clamping force 100 tons) manufactured by Sumitomo Heavy Industries, Ltd. was connected to gates at both ends of the test piece. Using the provided mold, injection molding was performed under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 60 ° C., and a weld test piece having a length of 125 mm, a width of 13 mm, a thickness of 1.6 mm and a weld in the center of the test piece was formed.
Furthermore, after the pellets obtained by the above-mentioned method were dried at 80 ° C. for 5 hours, the cylinder temperature was 280 ° C. using an injection molding machine “SE100D” (clamping force 100 tons) manufactured by Sumitomo Heavy Industries, Ltd. A test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1 mm was formed by injection molding under the conditions of a mold temperature of 60 ° C.

[Fluidity evaluation]
After the pellets obtained by the above-mentioned method were dried at 80 ° C. for 5 hours, a cylinder temperature of 280 ° C., a mold temperature of 60 ° C., and an injection pressure using NEX80III (mold clamping force of 80 tons) manufactured by Nissei Plastic Industry Co., Ltd. Under the condition of 150 MPa, a bar flow molded product having a width of 20 mm and a thickness of 1 mm was injection molded, and its flow length (unit: mm) was evaluated.

[Bending characteristics]
Using the ISO multipurpose test piece obtained by the above method, the flexural modulus (unit: GPa) and the flexural strength (unit: MPa) were measured and evaluated in accordance with ISO178.

[Shock resistance]
Using the ISO multi-purpose test piece obtained by the above-described method, notched and unnotched Charpy impact strength (unit: kJ / m ² ) was measured and evaluated in accordance with ISO179.

[Weld strength]
Using the Instron universal testing machine, the weld test piece obtained by the above-described method is made so that the weld part comes into contact with the indenter under the conditions of a fulcrum distance of 26 mm, an indenter radius R of 5 mm, and an indenter descending speed of 1 mm / min. A test piece was placed and subjected to a bending test, and its strength (unit: MPa) was evaluated.
The weld strength measured by this method is preferably 80 MPa or more.

[Heat-resistant]
Using the ISO multipurpose test piece obtained by the above-mentioned method, a deflection temperature under load of 1.8 MPa was measured and evaluated according to ISO75.

[Flame retardancy evaluation UL94 test]
The UL UL test (equipment parts) defined by US Underwriters Laboratories (UL) was conditioned for 48 hours in a temperature-controlled room at 23 ° C and 59% humidity. Plastic material combustion test).
UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in the following table.

Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. Further, the cotton ignition by the drip is determined by whether or not the marking surface that is approximately 300 mm below the lower end of the test piece is ignited by a drip from the test piece.
The above evaluation results are shown in Tables 3 to 7 below.

  Since the polycarbonate resin composition of the present invention is a highly rigid material that has extremely high flame retardancy even when formed into a thin-walled molded article, and further has excellent fluidity, impact strength, weld strength, and heat resistance, It can be used widely and suitably for parts such as electronic equipment, OA equipment, information terminal equipment, home appliances, etc., and industrial applicability is very high.

Claims (11)

  20 to 200 parts by mass of the inorganic filler (B), 10 to 30 parts by mass of the phosphazene compound (C) with respect to 100 parts by mass of the polycarbonate resin (A), and a 5% weight reduction temperature by thermogravimetric analysis is 330 ° C. or higher. A polycarbonate resin composition comprising 3 to 15 parts by mass of a core / shell type graft copolymer (D).   Furthermore, the polycarbonate resin composition of Claim 1 which contains a fluoropolymer (E) 0.05-2 mass parts with respect to 100 mass parts of polycarbonate resin (A).   The polycarbonate resin composition according to claim 1 or 2, wherein the inorganic filler (B) is a glass-based filler.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the phosphazene compound (C) is a cyclic aromatic phosphazene.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein a ratio of the core / shell type graft copolymer (D) to the phosphazene compound (C) is 10 to 80% by mass.   The polycarbonate resin composition according to any one of claims 1 to 5, wherein a ratio of the core / shell type graft copolymer (D) to the inorganic filler (B) is 3 to 15%.   The polycarbonate resin composition according to any one of claims 1 to 6, wherein the polycarbonate resin (A) has a viscosity average molecular weight (Mv) of 17,000 to 22,000.   The polycarbonate resin composition according to any one of claims 1 to 7, wherein the combustibility based on the UL94 test is V-0 at a thickness of 1 mm.   The molded article which shape | molded the polycarbonate resin composition of any one of Claims 1-8.   The molded article according to claim 9, which is a casing of an electric / electronic device.   The molded article according to claim 10, wherein the electric and electronic device is a notebook computer, a tablet terminal, a smartphone, or a mobile phone.