JP2018145397A - 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 excellent in rigidity, bending strength, impact strength, and weld strength, and is reduced in weight.SOLUTION: A polycarbonate resin composition contains, with respect to 100 pts.mass of a polycarbonate resin (A), 5 to 120 pts.mass of a carbon fiber (B), 1 to 15 pts.mass of a scaly inorganic mineral filler (C), and 15 to 50 pts.mass of a phosphorous flame retardant (D), where a ratio of the scaly inorganic mineral filler (C) is 3 to 30 mass% with respect to the carbon fiber (B).SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded product. Specifically, even when it is a thin-walled molded product, it has extremely high flame retardancy, and further has excellent rigidity, bending strength, impact strength, weld strength, and light weight. The present invention relates to a 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 to 3).
However, since the glass fiber reinforced polycarbonate resin has a high specific gravity, it has not been possible to obtain a light, thin, small and high strength molded product as required recently.

On the other hand, for example, Patent Documents 4 to 6 propose carbon fiber-reinforced polycarbonate resins in which carbon fibers and organic phosphate esters are blended.
However, the above-described carbon fiber reinforced polycarbonate resin has a problem of reduction in flame retardancy and impact resistance.

Japanese Patent Laid-Open No. 10-46017 Japanese Patent Laid-Open No. 10-30056 JP 2014-156588 A Japanese Patent Laid-Open No. 9-48912 JP 2000-226508 A JP 2002-265767 A

  The present invention was devised in view of the above problems, and has extremely high flame retardancy even when formed into a thin-walled molded article, and further has excellent rigidity, bending strength, impact strength, weld strength, and light weight. An object (problem) is to provide a material that can be made into a material.

As a result of intensive studies in order to solve the above problems, the inventor contains carbon fiber, a flaky inorganic mineral filler, and a phosphorus-based flame retardant in a polycarbonate resin, and a ratio of the flaky inorganic mineral filler to the carbon fiber. It was found that a polycarbonate resin composition that is light in weight, excellent in impact strength and weld strength, and excellent in rigidity, bending strength, and flame retardancy can be obtained by combining a specific amount of the above.
The present invention provides the following polycarbonate resin composition and molded article.

[1] Carbon fiber (B) 5 to 120 parts by mass, scale-like inorganic mineral filler (C) 1 to 15 parts by mass and phosphorus flame retardant (D) 15 to 50 parts by mass with respect to 100 parts by mass of polycarbonate resin (A) The polycarbonate resin composition is characterized in that the ratio of the scaly inorganic mineral filler (C) to the carbon fiber (B) is 3 to 30% by mass.
[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 scaly inorganic mineral filler (C) is talc and / or mica.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the phosphorus-based flame retardant (D) is a condensed phosphate ester compound.
[5] The core / shell graft copolymer (F) according to any one of [1] to [4], further containing 3 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Polycarbonate resin composition.
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the core / shell type graft copolymer (F) is a graft copolymer having a silicone-acrylate composite rubber as a core.
[7] The above [1] to [1], wherein the mass ratio (C) / (F) of the content of the scale-like inorganic mineral filler (C) and the core / shell type graft copolymer (F) is 0.1-2. 6] The polycarbonate resin composition according to any one of the above.
[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 0.8 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 polycarbonate resin composition has extremely high flame retardancy even in the case of a thin molded article, and is excellent in rigidity, bending strength, impact strength, weld strength, and reduced in weight. Things are 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.

  The polycarbonate resin composition of the present invention comprises 5 to 120 parts by mass of carbon fiber (B), 1 to 15 parts by mass of a flaky inorganic mineral filler (C) and a phosphorus flame retardant (100 parts by mass of polycarbonate resin (A). D) It contains 15 to 50 parts by mass, and the ratio of the scaly inorganic mineral filler (C) to the carbon fiber (B) is 3 to 30% by mass.

[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 24000. 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.

[Carbon fiber (B)]
The polycarbonate resin composition of the present invention contains carbon fiber (B). As the carbon fiber (B), any of PAN (polyacrylonitrile), pitch, rayon and the like can be used.

The average fiber diameter of the carbon fiber (B) is preferably 20 μm or less, and most preferably in the range of 5 to 8 μm from the balance of fluidity, impact resistance, dimensional stability and appearance. If the average fiber diameter exceeds 20 μm, the balance between dimensional stability and impact resistance is lowered, which is not preferable.
The average fiber length of the carbon fibers (B) in the resin composition is preferably in the range of 0.1 to 2 mm from the viewpoint of balance between impact resistance, dimensional stability, and appearance.

The carbon fiber (B) is preferably subjected to surface treatment, and the tensile strength and bending strength as the resin composition are improved. Any commonly used surface treating agent can be used, and examples thereof include epoxy sizing agents, urethane sizing agents, epoxy-urentane sizing agents, polyamide sizing agents, and olefin sizing agents. Among these, epoxy-based, polyamide-based, and urethane-based materials are preferable because of their good dispersibility with respect to the polycarbonate resin.
The amount of the surface treatment agent is preferably in the range of 0.5 to 15 parts by mass and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the carbon fiber (B).

  Content of the carbon fiber (B) in the polycarbonate resin composition of this invention is 5-120 mass parts with respect to 100 mass parts of polycarbonate resin (A). If the carbon fiber (B) content is less than 5 parts by mass, the rigidity is insufficient. Conversely, if it exceeds 120 parts by mass, the impact resistance and fluidity are insufficient, and the production becomes difficult. The content of the carbon fiber (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less. is there.

[Scale-like inorganic mineral filler (C)]
The polycarbonate resin composition of the present invention contains a scaly inorganic mineral filler (C). In the present invention, an inorganic mineral filler refers to an inorganic mineral that is contained in a resin component to improve strength and rigidity, and a scale shape is observed from a predetermined angle, such as a flat plate shape, a curved plate shape, etc. The area (when viewed in plan) is a shape larger than the area when observed from an angle orthogonal to the observation direction.

  Examples of the scale-like inorganic mineral filler (C) include talc, mica, kaolin, and the like. Among them, talc and / or mica are preferable, and talc is particularly preferable. The scale-like inorganic mineral filler (C) may be a single type or a mixture of two types.

Talc may be surface-treated with various surface treatment agents such as a silane treatment agent in order to enhance the adhesion to the polycarbonate resin. The surface treatment agent is not particularly limited, and a conventionally known one can be used, but a hydrogen siloxane compound such as methylhydrogen siloxane, an epoxy group-containing silane coupling agent such as epoxy silane, and an amino such as amino silane. A group-containing silane coupling agent is preferable because it hardly reduces the physical properties of the polycarbonate resin. In addition, polyoxyethylene silane or the like can be used.
There is no particular limitation on the method for treating talc with the surface treatment agent, and it can be carried out by a usual method. For example, it can be carried out by adding a surface treatment agent to talc and stirring or mixing in solution or with heating.

  Content of a scale-like inorganic mineral filler (C) is 1-15 mass parts with respect to 100 mass parts of polycarbonate resin (A). If the content is less than 1 part by mass, the effect of improving strength and flame retardancy will be insufficient, and if it exceeds 15 parts by mass, the weld strength will be reduced, which is not suitable. The content of the scale-like inorganic mineral filler (C) is preferably 1.5 parts by mass or more, more preferably 3 parts by mass or more, preferably 10 parts by mass or less, and more preferably 7 parts by mass or less.

And the polycarbonate resin composition of this invention is characterized by the ratio of the scale-like inorganic mineral filler (C) with respect to content of carbon fiber (B) being 3-30 mass%. By setting the content to 3 to 30% by mass, it is possible to provide a material that can effectively reduce the weight with high rigidity, low specific gravity, and improved strength and flame retardancy. The proportion of the scale-like inorganic mineral filler (C) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 12% by mass or more, particularly preferably 13% by mass or more, and preferably 25% by mass or less. More preferably, it is 20 mass% or less, Most preferably, it is 17 mass% or less.
Here, the ratio of the scale-like inorganic mineral filler (C) is a value (%) with respect to 100% by mass of the carbon fiber (B).

[Phosphorus flame retardant (D)]
The supercritical foam molding thermoplastic resin composition of the present invention contains a phosphorus-based flame retardant (D).
The phosphorus-based flame retardant (D) is a compound containing phosphorus in the molecule, and may be a low molecule, an oligomer, or a polymer. The condensed phosphate compound represented by the formula (1) and the phosphazene compounds represented by the general formulas (2) and (3) are particularly preferable.

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

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

  Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.

R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

As a specific example of the condensed phosphate ester compound represented by the general formula (1),
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

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

  As the phosphoric ester compound, in addition to the above, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, containing phosphate ester moiety Naturally, polyester resins, polycarbonate resins or epoxy resins are also included.

<Phosphazene compound>
Examples of the phosphazene compounds represented by the general formulas (2) and (3) 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 (2), R ⁵ and R ⁶ 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 ⁵ and R ⁶ 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 formula (2), t represents an integer of 3 to 25. Among them, a compound in which t is an integer of 3 to 8 is preferable, and a mixture of compounds having different t may be used. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less is preferable.

In formula (3), R ⁷ and R ⁸ 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 ⁷ and R ⁸ 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.

Also, R ⁹ is represented by -N = P (OR ⁷ ) ₃ groups, -N = P (OR ⁸ ) ₃ groups, -N = P (O) OR ⁷ groups, and -N = P (O) OR ⁸ groups. At least one selected is shown, and R ¹⁰ is -P (OR ⁷ ) ₄ group, -P (OR ⁸ ) ₄ group, -P (O) (OR ⁷ ) ₂ group, -P (O) (OR ⁸ ) At least one selected from _two groups.

  Moreover, in Formula (3), u 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.

Further, the phosphazene compound may be a crosslinked phosphazene compound partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
Examples of such crosslinked phosphazene compounds include compounds having a crosslinking structure represented by the following general formula (4), for example, 4,4′-sulfonyldiphenylene (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. Examples thereof include compounds having a crosslinked structure of 4,4′-diphenylene group.

[In Formula (4), X ² is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and 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 ⁵ and R ⁶ are phenyl groups in the general formula (2) with a crosslinking group represented by the general formula (4). Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ⁷ and R ⁸ are phenyl groups in the general formula (3) with a crosslinking group represented by the general formula (4) is flame retardant. From the above point, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) 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 (2) and / or the all phenyl groups in the chain-like phenoxyphosphazene compound represented by the general formula (3) 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 is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (2) and the cyclic phenoxyphosphazene compound represented by the general formula (3) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  As the phosphorus-based flame retardant (D), the above-described condensed phosphate compound is particularly preferable.

  Content of phosphorus flame retardant (D) is 15-50 mass parts with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 20 mass parts or more, Preferably it is 40 mass parts or less. When the blending amount of the phosphorus-based flame retardant (D) is less than 15 parts by mass, the flame retardancy becomes insufficient, and when it exceeds 50 parts by mass, a remarkable decrease in heat resistance and a decrease in mechanical properties are caused.

[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.

[Core / shell type graft copolymer (F)]
The polycarbonate resin composition of the present invention preferably contains a core / shell type graft copolymer (F). As the core / shell type graft copolymer (F), a rubber component is used as a core layer, and a (meth) acrylic acid ester compound, a (meth) acrylic acid compound, an aromatic vinyl compound, and an unsaturated nitrile compound are provided around the core layer. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing at least one monomer component selected from the above is preferred.

  Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate-2-ethylhexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, silicone-acrylate composite rubber, styrene-butadiene rubber, ethylene-α-olefin rubber such as ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, ethylene-acrylic rubber, fluorine rubber And so on. These may be used alone or in admixture of two or more.

  In the present invention, the core / shell type graft copolymer (F) is preferably a graft copolymer having a silicone-acrylate composite rubber as a core, and in particular, an acrylic resin around the core of the silicone-acrylate composite rubber. A core / shell type graft copolymer having a polymer or copolymer component as a shell layer.

  Examples of the silicone-acrylate composite rubber constituting the core layer include polyorganosiloxanes, for example, polymers containing dimethylsiloxane units as constituent units, and acrylics such as (meth) acrylate compounds or unsaturated nitrile compounds such as acrylonitrile. Those composed of system components are preferred.

The shell of the acrylic component can be obtained by polymerizing a (meth) acrylic acid ester compound, a (meth) acrylic acid compound, or the like.
Examples of (meth) acrylic acid ester compounds include (meth) acrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and hexyl methacrylate; aryl (meth) acrylates such as phenyl methacrylate and naphthyl methacrylate; glycidyl acrylate and glycidyl Examples thereof include glycidyl group-containing (meth) acrylates such as methacrylate; among them, methacrylic acid alkyl esters are preferable, and methyl methacrylate is more preferable.
In addition, the said (meth) acrylic acid ester compound can use 1 type (s) or 2 or more types.

  In addition to the (meth) acrylic acid ester compound, other vinyl monomers may be contained. Other vinyl monomers include, for example, aromatic vinyls such as styrene and α-methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; maleimide, N -Maleimide compounds such as methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid, and anhydrides thereof (for example, maleic anhydride); and the like.

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

  The content of the core / shell type graft copolymer (F) is preferably 3 to 10 parts by mass, more preferably 4 parts by mass or more, more preferably 100 parts by mass of the polycarbonate resin (A). 8 parts by mass or less. If the content of the core / shell type graft copolymer (D) is less than 3 parts by mass, the impact resistance improvement effect cannot be sufficiently obtained, and if it exceeds 10 parts by mass, the heat resistance is hardly lowered. Flammability is likely to deteriorate.

  The mass ratio (C) / (F) of the contents of the scale-like inorganic mineral filler (C) and the core / shell type graft copolymer (F) is preferably in the range of 0.1-2. If the mass ratio exceeds 2, the weld bending strength tends to decrease, and if it is less than 0.1, the combustibility tends to be insufficient. The preferred lower limit of the mass ratio (C) / (F) range is 0.2, 0.3, 0.45, 0.6, 0.8, 0.9, and the mass ratio (C) / (F ) Is preferably 1.8, 1.6, 1.4, 1.2, 1.1.

[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.
However, the content when other resins are contained is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). In particular, the amount is preferably 3 parts by mass or less.

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, and fluidity modifiers. , Dispersants, antibacterial agents and the like. 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), scaly inorganic mineral filler (C) and phosphorus-based flame retardant (D), and other components blended as necessary, such as tumblers and Henschel mixers. Examples thereof include a method of premixing using various mixers and then melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. The carbon fiber (B) is preferably side fed.

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.

  The obtained polycarbonate resin composition of the present invention is excellent in flame retardancy, and exhibits a high flame retardance of V-0 at a thickness of 0.8 mm based on the UL94 test.

  In order to produce a molded article from the polycarbonate resin composition of the present invention, a molding method generally adopted 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.

(Examples 1-20, Comparative Examples 1-14)
[Production of resin pellets]
Among each component described in Table 1, after compounding carbon fiber (B) and phosphorus flame retardant (D) other than the amount (parts by mass) described in Tables 3 to 5, and mixing for 20 minutes with a tumbler, Supplyed from an upstream feeder to an extruder “TEX30α” manufactured by Nippon Steel Works with 1 vent, the amount of phosphorus flame retardant (D) shown in Tables 3 to 5 in the middle of the barrel by a liquid injection pump (parts by mass) The carbon fiber (B) is further fed from the middle of the barrel by the side feeder in the amounts (parts by mass) shown in Tables 3 to 5, while the rotation speed is 200 rpm, the discharge rate is 30 kg / h, and the barrel temperature is 260. The molten resin which was kneaded under the condition of ° C. and extruded into a strand shape was cooled in a water tank and pelletized using a pelletizer to obtain a pellet 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 0.8 mm was formed by injection molding under the condition of a mold temperature of 60 ° C.

[specific gravity]
Using the ISO multipurpose test piece (4 mm thickness) obtained by the above method, specific gravity was measured according to ISO1883.

[Fluidity evaluation]
After the pellets obtained by the above-mentioned method were dried at 80 ° C. for 5 hours, the cylinder temperature was 280 ° C., the mold temperature was 60 ° C. using “NEX80III” (clamping force 80 tons) manufactured by Nissei Plastic Industry Co., Ltd. Under the conditions of an injection pressure of 150 MPa, a bar flow molded product having a width of 20 mm and a thickness of 1 mm was injection molded, and the 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 bending 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.
Furthermore, the total burning time (unit: second) in all five was counted and evaluated. A smaller total combustion time means that it has good flame retardancy, and is preferable.
The above evaluation results are shown in Tables 3 to 5 below.

(Comparative Examples 15-19)
[Production of resin pellets]
Among the components listed in Table 1, glass fibers CX1 and CX2 and the flame retardant (D) other than the flame retardant (D) were blended in the amounts (parts by mass) listed in Table 6 and mixed for 20 minutes with a tumbler. Supplied from an upstream feeder to an extruding machine “TEX30α” manufactured by Nippon Steel Works Co., Ltd., and a phosphorus flame retardant (D) was supplied in the amount (part by mass) shown in Table 6 from the middle of the barrel by a liquid injection pump. The glass fibers CX1 and CX2 are kneaded under the conditions of a rotation speed of 200 rpm, a discharge amount of 30 kg / h, and a barrel temperature of 260 ° C. while supplying the glass fibers CX1 and CX2 in the amount (part by mass) shown in Table 6 from the middle of the barrel. The molten resin extruded in a shape was cooled in a water bath and pelletized using a pelletizer to obtain pellets of a polycarbonate resin composition.
Various evaluations were performed in the same manner as described above using the obtained pellets.
The evaluation results are shown in Table 6 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)

  Contains 5 to 120 parts by mass of carbon fiber (B), 1 to 15 parts by mass of a flaky inorganic mineral filler (C) and 15 to 50 parts by mass of a phosphorus-based flame retardant (D) with respect to 100 parts by mass of the polycarbonate resin (A). And the ratio of the scale-like inorganic mineral filler (C) with respect to carbon fiber (B) is 3-30 mass%, The polycarbonate resin composition characterized by the above-mentioned.   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 scaly inorganic filler (C) is talc and / or mica.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the phosphorus-based flame retardant (D) is a condensed phosphate ester compound.   Furthermore, 3-10 mass parts of core / shell type graft copolymers (F) are contained with respect to 100 mass parts of polycarbonate resin (A), The polycarbonate resin composition of any one of Claims 1-4. .   The polycarbonate resin composition according to any one of claims 1 to 5, wherein the core / shell type graft copolymer (F) is a graft copolymer having a silicone-acrylate composite rubber as a core.   The mass ratio (C) / (F) of the content of the scale-like inorganic mineral filler (C) and the core / shell type graft copolymer (F) is 0.1 to 2, 7. The polycarbonate resin composition according to item.   The polycarbonate resin composition according to any one of claims 1 to 7, wherein the flammability based on the UL94 test is V-0 at a thickness of 0.8 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.