JP6480120B2 - Thermally conductive polycarbonate resin composition and molded article - Google Patents

Description

  The present invention relates to a thermally conductive polycarbonate resin composition and a molded article, and more particularly to a thermally conductive polycarbonate resin composition and a molded article excellent in thermal conductivity, rigidity and flame retardancy.

  Polycarbonate resins are excellent in impact resistance, heat resistance, electrical insulation, dimensional stability, etc., and the balance of these properties is also good, so electric and electronic equipment parts, OA equipment parts, precision machine parts, parts for vehicles It is widely used in fields such as

  However, polycarbonate resins can cause various faults due to static electricity because they have high electrical resistivity and are easily charged. Also, in the above fields, most devices are equipped with components that generate heat, but in recent years, with the advancement of devices with higher performance, the amount of power consumption per component tends to increase, and the amount of heat generated from components tends to increase. There is a need for polycarbonate resin materials that exhibit higher thermal conductivity.

  As a method of imparting thermal conductivity to a polycarbonate resin material, methods of blending various thermal conductive fillers are known, and Patent Documents 1 to 4 show polycarbonate resin compositions having good thermal conductivity. ing. However, although these polycarbonate resin compositions can exhibit appropriate good thermal conductivity, they have the disadvantage that the rigidity is deteriorated, and they are excellent in thermal conductivity and also excellent in rigidity. Polycarbonate resin compositions are desired.

Japanese Patent Application Publication No. 2007-238917 Japanese Patent Application Publication No. 2008-163270 Unexamined-Japanese-Patent No. 2009-161582 JP, 2011-16936, A

In recent years, in the field of parts (such as housings and covers) of various electric and electronic devices represented by portable terminals, the required specifications for thermal conductivity and rigidity become increasingly sophisticated and difficult. It is essential to have excellent flammability. However, until now, it has been the case that no high level polycarbonate resin material has been proposed in which the thermal conductivity, rigidity and flame retardancy are all improved in a well-balanced manner.
An object (problem) of the present invention is to provide a thermally conductive polycarbonate resin composition having particularly excellent rigidity while having high thermal conductivity and high degree of flame retardancy.

The inventors of the present invention conducted intensive studies to achieve the above problems, and as a result, a polycarbonate resin containing boron nitride, a phosphorus-based flame retardant, a fluoropolymer and a silicate compound in specific amounts, respectively, It has been found that the problems are solved, and in particular, the rigidity is further improved, and the present invention has been completed.
The present invention is as follows.

[1] Containing 15 to 50 parts by mass of boron nitride, 3 to 30 parts by mass of phosphorus-based flame retardant, 0.001 to 10 parts by mass of fluoropolymer, and 15 to 50 parts by mass of silicate compound with respect to 100 parts by mass of polycarbonate resin Thermally conductive polycarbonate resin composition characterized by the above-mentioned.
[2] The thermally conductive polycarbonate resin composition according to the above [1], wherein the phosphorus-based flame retardant is a phosphoric acid ester compound or a phosphazene compound.
[3] The thermally conductive polycarbonate resin composition according to the above [1] or [2], wherein the silicate compound is talc.
[4] The thermally conductive polycarbonate resin composition according to any one of the above [1] to [3], further containing 7 to 20 parts by mass of a siloxane-based elastomer with respect to 100 parts by mass of the polycarbonate resin.
[5] Furthermore, the organic phosphate compound represented by the following general formula (1) is contained in an amount of 0.2 to 1 part by mass with respect to 100 parts by mass of a polycarbonate resin, according to any one of the above [1] to [4] Thermally conductive polycarbonate resin composition.
O = P (OH) _m (OR) _3-m (1)
(In the general formula (1), R represents an alkyl group or an aryl group, which may be the same or different, and m is an integer of 0 to 2)
[6] A molded article obtained by molding the thermally conductive polycarbonate resin composition according to any one of the above [1] to [5].

  According to the polycarbonate resin composition of the present invention, it is possible to provide a thermally conductive polycarbonate resin composition which exhibits particularly excellent rigidity while having excellent thermal conductivity and a high degree of flame retardancy.

  Hereinafter, the present invention will be described in detail with reference to embodiments and exemplifications, etc., but the present invention is not limited to the embodiments and exemplifications shown below, and so forth without departing from the scope of the present invention. It can be implemented with any change.

  The thermally conductive polycarbonate resin composition of the present invention comprises 15 to 50 parts by mass of boron nitride, 3 to 30 parts by mass of a phosphorus-based flame retardant, 0.001 to 10 parts by mass of a fluoropolymer and 100 parts by mass of a polycarbonate resin. It is characterized by containing 15-50 mass parts of compounds.

[Polycarbonate resin]
There is no restriction on the type of polycarbonate resin used in the present invention, and one type of polycarbonate resin may be used, or two or more types may be used in combination in an arbitrary ratio and an arbitrary ratio.

  A polycarbonate resin is a polymer of a basic structure having a carbonate bond represented by [—O—X—O—CO—], and X is generally a hydrocarbon, but a hetero atom for imparting various characteristics, Heterocyclic X introduced may be used.

  Further, polycarbonate resins can be classified into aromatic polycarbonate resins in which carbon directly bonded to carbonic bonds is aromatic carbon and aliphatic polycarbonate resins in which aliphatic carbon is directly bonded, but any of them can be used. Among them, aromatic polycarbonate resins are preferable from the viewpoint of heat resistance, mechanical physical properties, electrical characteristics and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer which makes a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, carbon dioxide may be reacted with cyclic ether as a carbonate precursor. The polycarbonate polymer may be linear or branched. Furthermore, the polycarbonate polymer may be a homopolymer comprising one kind of repeating unit, or may be a copolymer having two or more kinds of repeating units. At this time, as the copolymer, various copolymer forms such as a random copolymer and a block copolymer can be selected. In general, such polycarbonate polymers are thermoplastic resins.

  Among the monomers used as the raw material of the aromatic polycarbonate resin, to cite an example of the aromatic dihydroxy compound,

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (that is, 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, 1 , Dihydroxynaphthalenes such as 7-dihydroxynaphthalene, 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 (that is, 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-naphthyl ethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Etc. bis (hydroxyaryl) alkanes such as

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Etc. bis (hydroxyaryl) cycloalkanes;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardo-structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4'-dihydroxydiphenyl sulfide,
Dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide;

Dihydroxy diaryl sulfoxides such as 4,4'-dihydroxy diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide;

4,4'-dihydroxydiphenyl sulfone,
Dihydroxy diaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone;
Etc.

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

In addition, as an example of a monomer that is a raw material of aliphatic polycarbonate resin,
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkane diols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol and decane-1,10-diol;

  Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4,4, Cycloalkane diols 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 -Cyclic ethers such as 1,2-epoxycyclohexane, 2,3-epoxy norbornane, and 1,3-epoxypropane; and the like.

  Among the monomers used as the raw materials of polycarbonate resins, carbonyl halides, carbonate esters and the like are used as examples of carbonate precursors. 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 the carbonyl halide include phosgene; bischloroformates of dihydroxy compounds, haloformates such as monochloroformates of dihydroxy compounds, and the like.

  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; biscarbonates of dihydroxy compounds; monocarbonates of dihydroxy compounds; cyclic carbonates And carbonates of dihydroxy compounds such as

-Manufacturing method of polycarbonate resin The manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods 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.
Among these methods, particularly preferred ones will be specifically described below.

.. Interfacial polymerization method First, the case where polycarbonate resin is manufactured by the interfacial polymerization method will be described.
In the interfacial polymerization method, after the dihydroxy compound is reacted with a carbonate precursor (preferably phosgene) in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, the pH is usually maintained at 9 or more. The polycarbonate resin is obtained by performing interfacial polymerization in the presence. In addition, in the reaction system, a molecular weight modifier (end stopper) may be present if necessary, and an antioxidant may be present to prevent oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Among the carbonate precursors, it is preferable to use phosgene, and a method using phosgene is particularly called phosgene method.

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

  Examples of the alkali compound contained in the aqueous alkali solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium hydrogencarbonate and alkaline earth metal compounds, among which sodium hydroxide and water Potassium oxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although the concentration of the alkali compound in the aqueous alkali solution is not limited, it is usually used at 5 to 10% by mass in order to control the pH in the aqueous alkali solution of the reaction to 10 to 12. For example, when blowing in phosgene, the molar ratio of the bisphenol compound to the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. It is preferable to set it as 1: 2.0 or more, usually 1: 3.2 or less, and in particular 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine and trihexylamine; and alicyclic resins such as N, N'-dimethylcyclohexylamine and N, N'-diethylcyclohexylamine Aromatic amines such as tertiary amines; N, N'-dimethylaniline, N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzyl ammonium chloride, tetramethyl ammonium chloride, triethyl benzyl ammonium chloride, etc. Pyridine; guanine; salts of guanidine; and the like. The polymerization catalyst may be used alone, or two or more may be used in any combination and ratio.

  Examples of the molecular weight modifier include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptan; phthalimide and the like, among which aromatic phenols are preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenols. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight modifier may be used 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the molecular weight modifier used is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the dihydroxy compound. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin can be obtained, and the appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be mixed at any time between the time of the reaction between the dihydroxy compound and phosgene (phosgenation) and the time of the polymerization reaction start.
The reaction temperature is usually 0 to 40 ° C., and the reaction time is usually several minutes (eg, 10 minutes) to several hours (eg, 6 hours).

··· Melt transesterification method Next, the case of producing a polycarbonate resin by a melt transesterification method will be described.
In the melt transesterification method, for example, a transesterification reaction of carbonic acid diester with a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, as a carbonic diester, for example, dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like; diphenyl carbonate; substituted diphenyl carbonates such as ditolyl carbonate and the like can be mentioned. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable, and particularly diphenyl carbonate is more preferable. One carbonic diester may be used, or two or more carbonic diesters may be used in any combination and ratio.

  The ratio between the dihydroxy compound and the carbonic diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equal molar amount or more of the carbonic diester with respect to 1 mol of the dihydroxy compound, and more preferably 1.01 mol or more Is more preferred. The upper limit is usually 1.30 moles or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In polycarbonate resins, the amount of terminal hydroxyl groups tends to greatly affect the thermal stability, hydrolysis stability, color tone and the like. Therefore, the amount of terminal hydroxyl groups may be adjusted as necessary by any known method. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can usually be obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of pressure reduction at the time of the transesterification reaction. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the mixing ratio of carbonic diester and dihydroxy compound to adjust the amount of terminal hydroxyl groups, the mixing ratio is as described above.
Further, as a more positive adjustment method, a method of mixing an end terminator separately at the time of reaction may be mentioned. Examples of the terminal stopper at this time include monohydric phenols, monohydric carboxylic acids, carbonic diesters and the like. In addition, 1 type may be used for end terminator and 2 or more types may be used together by arbitrary combinations and a ratio.

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

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. Moreover, the pressure at the time of reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be carried out while removing by-products such as aromatic hydroxy compounds under the above conditions.

  The melt polycondensation reaction can be carried out either batchwise or continuously. When carrying out by a batch system, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, and what is necessary is just to set an appropriate order arbitrarily. However, in consideration of the stability of the polycarbonate resin, it is preferable to carry out the melt polycondensation reaction continuously.

  In the melt transesterification method, if necessary, a catalyst deactivator may be used. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be optionally used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. The catalyst deactivator may be used alone or in combination of two or more at any ratio and ratio.

  The amount of catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, with respect to the alkali metal or alkaline earth metal contained in the above-mentioned transesterification catalyst. Preferably, it is 5 equivalents or less. Furthermore, it is usually 1 ppm or more, and usually 100 ppm or less, preferably 20 ppm or less, relative to the polycarbonate resin.

-Other matters concerning polycarbonate resin The molecular weight of the polycarbonate resin may be appropriately selected and determined, but the viscosity average molecular weight [Mv] is usually 10000 or more, preferably 16000 or more, more preferably 17000 or more, more preferably 18000 or more Also, it is usually 40000 or less, preferably 30000 or less.

In addition, with viscosity average molecular weight [Mv], using methylene chloride as a solvent, the intrinsic viscosity [ロ ー] (unit dl / g) at a temperature of 20 ° C. is determined using a Ubbelohde viscometer, and Schnell's viscosity formula, ie, , = 1 = 1.23 × 10 ⁻⁴ Mv ^0.83 . In addition, the intrinsic viscosity [η] is a value calculated by measuring the specific viscosity [で_sp ] at each solution concentration [C] (g / dl) according to the following equation.

  The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. This can further improve the retention heat stability and color tone of the polycarbonate resin. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and 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 property of a resin composition can be improved more.

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

  Polycarbonate resin is not limited to an embodiment including polycarbonate resin alone (polycarbonate resin alone is not limited to one including only one kind of polycarbonate resin, for example, it is used in a sense including an embodiment including plural kinds of polycarbonate resins different in monomer composition and molecular weight from each other) And may be used in combination with alloys (mixtures) of polycarbonate resins and other thermoplastic resins. Furthermore, for example, in order to further enhance flame retardancy and impact resistance, polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; phosphorus atom for the purpose of further enhancing thermal oxidation stability and flame retardancy Copolymers with monomers, oligomers or polymers having the formula; Copolymers with monomers, oligomers or polymers having the dihydroxyanthraquinone structure for the purpose of improving the thermal oxidation stability; polystyrene etc. to improve the optical properties Copolymer with an oligomer or polymer having an olefin structure; copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; or even a copolymer based on a polycarbonate resin Good.

  The polycarbonate resin may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded article. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9000 or less. Furthermore, the content of the polycarbonate oligomer is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Furthermore, 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). The above-mentioned used products include, for example, optical recording media such as optical discs; light guide plates; automobile window glass, automobile head lamp lenses, vehicle transparent members such as windshields; containers such as water bottles; Examples include building members such as glass windows and corrugated sheets. In addition, nonconforming products, crushed products obtained from sprues, runners, etc. or pellets obtained by melting them can also be used.
However, it is preferable that it is 80 mass% or less among polycarbonate resin, and it is more preferable that it is 50 mass% or less among regenerated polycarbonate resin. Since the recycled polycarbonate resin is highly likely to be degraded due to thermal degradation, aging degradation, etc., when such polycarbonate resin is used more than the above range, it is possible to lower the hue and mechanical properties. It is because there is sex.

[Boron nitride]
The polycarbonate resin composition of the present invention contains boron nitride. By containing boron nitride in a proportion of 15 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate resin, the thermal conductivity of the obtained polycarbonate resin composition can be greatly improved, and a phosphorus-based flame retardant, By combining a fluoropolymer and a silicate compound in a specific amount, a thermally conductive polycarbonate resin composition exhibiting excellent rigidity can be obtained while having excellent thermal conductivity and high flame retardancy. .

  The shape of the boron nitride used in the present invention is not particularly limited, and any desired one can be used. Specifically, spherical shape, linear shape (fiber shape), flat plate shape (scale shape), curved plate shape, needle shape, etc. are mentioned. And, it may be used as a single particle or in the form of granules (aggregate of single particles). In the present invention, using a scale-like one is preferable because a resin composition having excellent thermal conductivity can be obtained and mechanical properties are improved.

  Boron nitride is known to have multiple stable structures such as c-BN (zinc blende structure), w-BN (wurtzite structure), h-BN (hexagonal structure), r-BN (rhombohedral structure), etc. It is done. In the present invention, any boron nitride may be used. Among them, using a boron nitride having a hexagonal crystal structure provides sufficient thermal conductivity and wear of a molding machine or a mold used when obtaining a resin molded product. Is preferable because it can be reduced.

  The average particle size of boron nitride is not limited, but is preferably 1 to 300 μm, more preferably 2 to 200 μm, and particularly preferably 5 to 100 μm.

  As boron nitride, the thermal conductivity at 25 ° C. is preferably 30 W / (m · K) or more, and more preferably 50 W / (m · K) or more.

  The content of boron nitride in the thermally conductive polycarbonate resin composition of the present invention is 15 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate resin. If the content of boron nitride is less than 15 parts by mass, the thermal conductivity is insufficient, and if it exceeds 50 parts by mass, the rigidity tends to be insufficient. The content of boron nitride is preferably 18 parts by mass or more, more preferably 20 parts by mass or more, and preferably 45 parts by mass or less, more preferably 40 parts by mass or less.

[Phosphorous flame retardant]
The polycarbonate resin composition of the present invention contains a phosphorus-based flame retardant in an amount of 3 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Thus, the flame retardance of the polycarbonate resin composition of this invention can be improved by containing a phosphorus base flame retardant.

  The phosphorus-based flame retardant may be a compound containing phosphorus in the molecule, and may be a low molecular weight, an oligomer or a polymer, but from the viewpoint of heat stability, for example, The phosphoric acid ester compounds represented by 2) and the phosphazene compounds represented by the following formulas (3) and (4) are particularly preferable.

-Phosphate ester compound The phosphate ester compound represented by the above general formula (2) may be a mixture of compounds having different numbers of k, and in the case of a mixture of condensed phosphate esters having different k, k is the average value of those mixtures. 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, still more preferably Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

And 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, Divalent compounds 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. Among these, in particular, divalent groups derived from resorcinol, bisphenol A and 3,3'-dihydroxybiphenyl are preferable.

  Further, p, q, r and s in the general formula (2) each represent 0 or 1, and among them, 1 is preferable.

Moreover, R < ¹ >, R < ² >, R < ³ > and R < ⁴ > show a C6-C20 aryl group which may be substituted by a C1-C6 alkyl group or an alkyl group, respectively. Examples of such an aryl group include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, p-cumylphenyl group and the like. Groups, cresyl groups and xylyl groups are more preferred.

Specific examples of the phosphoric acid ester compound represented by the general formula (2) are
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- (bis- (bis) aromatic phosphate esters such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphoric 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 phosphoric acid ester compound represented by the general formula (2) is preferably 0.2 mg KOH / g, more preferably 0.15 mg KOH / g or less, still more preferably 0.1 mg KOH or less, particularly preferably Is less than 0.05 mg KOH / g. The lower limit of the acid value may be substantially zero.

  As the phosphoric acid ester compounds used in the present invention, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3), in addition to the above-mentioned ones. -Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphoric acid Naturally, polyester resins containing ester sites, polycarbonate resins or epoxy resins are also included.

Phosphazene Compounds Examples of the phosphazene compounds represented by the above general formulas (3) and (4) include phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p- Cyclics such as tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc., (poly) xylyloxy phosphazene, etc. and / or or linear _{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- Toriruokishiho Fazen, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene etc.), (poly) phenoxy xylyloxy phosphazenes And cyclic and / or linear C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazenes such as (poly) phenoxy tolyloxy _xylyloxy phosphazene and the like.
Among these, preferably cyclic and / or linear phenoxy phosphazenes, cyclic and / or linear C _1-3 alkyl C _6-20 aryloxy phosphazenes, C _{6 20} aryloxy C _1-3 alkyl C _6-20 Aryloxy phosphazenes (eg, cyclic and / or linear tolyloxy phosphazenes, cyclic and / or linear phenoxy tolyl phenoxy phosphazenes, etc.).

The cyclic phosphazene compound represented by the general formula (3), R ⁵ and R ⁶ may be the same or different, 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 phenoxy phosphazene in which R ⁵ and R ⁶ are a phenyl group is particularly preferable.
As such cyclic phenoxy phosphazene compounds, for example, hexachlorocyclotriphosphazene, octachloro, and cyclochlorophosphazenes can be obtained from a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, etc. obtained by taking out cyclic chlorphosphazenes such as cyclotetraphosphazenes, decachlorocyclopentaphosphazenes and substituting them with a phenoxy group can be mentioned. .

  Further, in the general formula (3), 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 different in t may be used. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10-40% by mass, and t = 5 or more in total is 30% by mass or less.

In the general formula (4), R ⁷ and R ⁸ may be the same or different, and represent 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 a phenyl group is particularly preferable.
Such a linear phenoxy phosphazene compound is obtained, for example, by ring-loop polymerization of hexachlorocyclotriphosphazene obtained by the above method at a temperature of 220 to 250 ° C. The compound obtained by substituting phosphazene with a phenoxy group is mentioned.

And R ⁹ is selected from the group consisting of -N = P (OR ⁷ ) ₃ , -N = P (OR ⁸ ) ₃ , -N = P (O) OR ⁷ and -N = P (O) OR ⁸ R ¹⁰ represents at least one selected, and R ¹⁰ represents a group of -P (OR ⁷ ) ₄ , -P (OR ⁸ ) ₄ , -P (O) (OR ⁷ ) ₂ , -P (O) (OR ⁸ And _b ) at least one selected from _two groups.

  In the general formula (4), u is an integer of 3 to 10,000, preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

The phosphazene compound may be a crosslinked phosphazene compound partially crosslinked. The heat resistance tends to be improved by having such a crosslinked structure.
As such a crosslinked phosphazene compound, a compound having a crosslinked structure represented by the following general formula (5), for example, a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, bisphenol S residue), Compounds having a crosslinked structure of 4,4'-diphenylene) isopropylidene group, compounds having a crosslinked structure of 4,4'-oxydiphenylene group, compounds having a crosslinked structure of 4,4'-thiodiphenylene group, etc. And compounds having a crosslinked structure of 4,4'-diphenylene group.

Wherein (5), ^{X 3} is _{-C (CH 3) 2 -,} - SO 2 -, - S-, or a -O-, v is 0 or 1. ]

Moreover, as a crosslinked phosphazene compound, a crosslinked phenoxy phosphazene compound in which a cyclic phenoxy phosphazene compound in which R ⁵ and R ⁶ in the general formula (3) are a phenyl group is crosslinked by a crosslinking group represented by the above general formula (5) Alternatively, a cross-linked phenoxy phosphazene compound in which the chain-like phenoxy phosphazene compound in which R ⁷ and R ⁸ in the general formula (4) are a phenyl group is crosslinked by the cross-linking group represented by the general formula (5) is flame retardant In view of the above, a crosslinked phenoxy phosphazene compound in which the cyclic phenoxy phosphazene compound is crosslinked by the crosslinking group represented by the general formula (5) is more preferable.

  In addition, the content of phenylene group in the crosslinked phenoxy phosphazene compound is the total phenyl group in the cyclic phosphazene compound represented by the general formula (3) and / or the chained phenoxy phosphazene compound represented by the general formula (4) It is usually 50 to 99.9%, preferably 70 to 90%, based on the number of phenylene groups. The crosslinked phenoxy phosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a cyclic phenoxy phosphazene compound represented by the general formula (3) and a crosslinked phenoxy formed by crosslinking the cyclic phenoxy phosphazene compound represented by the general formula (4) by a crosslinking group. It is preferable from the viewpoint of flame retardancy and mechanical properties that it is at least one selected from the group consisting of phosphazene compounds.

  As described above, the content of the phosphorus-based flame retardant is 3 to 30 parts by mass, preferably 3.5 parts by mass or more, and more preferably 4 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin. 25 parts by mass or less is preferable, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.

[Fluoropolymer]
The polycarbonate resin composition of the present invention contains a fluoropolymer as an anti-dripping agent.
The fluoropolymer includes, for example, fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin and the like. Among them, tetrafluoroethylene resin is particularly preferable. As this fluoroethylene resin, the fluoroethylene resin which has fibril formation ability is mentioned.

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

Furthermore, fluoroethylene polymers having a multilayer structure formed by polymerizing vinyl monomers can also be used, and as such fluoroethylene polymers, polystyrene-fluoroethylene complex, polystyrene-acrylonitrile-fluoroethylene Complexes, polymethyl methacrylate-fluoroethylene complex, polybutyl methacrylate-fluoroethylene complex, etc., and specific examples include “Metabrene A-3800” manufactured by Mitsubishi Rayon Co., Ltd. “Brendex manufactured by GE Specialty Chemical Co., Ltd.” 449 "and the like.
In addition, 1 type may contain fluoropolymer, and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the fluoropolymer is 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin. It is not less than 10 parts by mass, preferably not more than 8 parts by mass, and more preferably not more than 7 parts by mass. When the content of the fluoropolymer is less than the lower limit of the above range, the effect of the flame retardancy improvement by the fluoropolymer becomes insufficient, and when the content of the fluoropolymer exceeds the upper limit of the above range, the polycarbonate resin composition It is easy to produce the appearance defect and the fall of mechanical strength of the molded article which shape | molded.

[Silicate compound]
The polycarbonate resin composition of the present invention contains a silicate compound. The silicate compound is a compound having a chemical composition and a chemical composition of SiO ₂ units. Specific examples of the silicate compound include talc, mica, magnesium silicate, aluminum silicate, calcium silicate, kaolin, diatomaceous earth, smectite and the like, and may be either a natural product or a synthetic product. In addition, it may be a calcined product or an uncalcined product, and may be a hydrate or an anhydrate.
As a plate-like silicate compound, talc and mica are excellent in the effect of enhancing the flame retardancy of the resin composition, and also excellent in the effect of preventing hardness and warpage, and the effect of improving heat resistance and mechanical strength, and further thermally stable. It is preferable because talc is also excellent, and talc is particularly preferable.

  The average particle diameter of the silicate compound is preferably 0.5 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 2 to 10 μm. If it is less than 0.5 μm, handling becomes difficult, and if it exceeds 100 μm, the impact resistance tends to decrease.

  The silicate compound 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 treating agent is not particularly limited, and conventionally known ones can be used, but hydrogen siloxane compounds such as methyl hydrogen siloxane and epoxy group-containing silane coupling agents such as epoxysilane, and amino silane such as aminosilane The group-containing silane coupling agent is preferable because it hardly reduces the physical properties of the polycarbonate resin. Besides, polyoxyethylene silane or the like can be used.

  There is no limitation in particular in the method of processing a silicate compound with a surface treating agent, and it can carry out by a usual method. For example, it can be carried out by adding a surface treatment agent to a silicate compound and stirring or mixing in a solution or while heating.

  The above-mentioned silicate compounds may be used alone or in combination of two or more different in average particle diameter, type, surface treating agent and the like.

  The content of the silicate compound is 15 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate resin. In addition to the effect of improving the flame retardancy of molded articles obtained when the content is less than 15 parts by mass, the effect of improving heat resistance and mechanical strength tends to be inferior. If the amount is more than 50 parts by mass, impact resistance, thermal stability and surface properties of the obtained molded article are lowered, and further, workability such as kneading with a resin at the time of melt kneading becomes difficult. The content of the silicate compound is preferably 20 parts by mass or more, in particular 25 parts by mass or more, preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and particularly 35 parts by mass or less.

[Siloxane based elastomer]
The polycarbonate resin composition of the present invention preferably contains a siloxane-based elastomer. Examples of the siloxane elastomer include silicone rubber such as polyorganosiloxane rubber, and in particular, a graft copolymer obtained by graft copolymerization of a polysiloxane rubber component and a monomer component copolymerizable therewith is preferable. The method for producing the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The copolymerization system may be a single-step graft or multi-step graft.

  Specific examples of monomer components that can be graft-copolymerized with the polyorganosiloxane rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) Epoxy group-containing (meth) acrylic acid ester compounds such as acrylates; maleimide compounds such as maleimide, N-methyl maleimide, N-phenyl maleimide, etc .; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, itaconic acid, etc. The anhydride (for example, maleic anhydride etc.) etc. are mentioned. 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 in terms of mechanical properties and surface appearance, and more preferably (meth) acrylic acid esters It is a compound. Specific examples of (meth) acrylic acid ester compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate and the like be able to.

  The graft copolymer obtained by copolymerizing the polyorganosiloxane rubber component is preferably a core / shell type graft copolymer from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from IPN type composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and is formed by copolymerizing (meth) acrylic acid ester around the core layer. Particularly preferred are core / shell graft copolymers consisting of a shell layer. The core / shell type graft copolymer preferably contains 40 to 80% by mass of the polyorganosiloxane rubber component, and more preferably 50 to 70% by mass.

  The content of the siloxane-based elastomer is preferably 7 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Thus, the impact resistance of a polycarbonate resin composition can be improved by containing a siloxane-type elastomer. If the content of the siloxane-based elastomer is less than 7 parts by mass, the effect of improving the impact resistance by the siloxane-based elastomer tends to be insufficient, and if it exceeds 20 parts by mass, appearance defects of the molded article and heat resistance deterioration easily occur. The lower limit of the content is preferably 7.5 parts by mass or more, and the upper limit of the content is preferably 15 parts by mass or less, and more preferably 13 parts by mass or less.

[Organic phosphate compound]
The polycarbonate resin composition of the present invention preferably further contains an organic phosphate compound represented by the following general formula (1) as a stabilizer.
O = P (OH) _m (OR) _3-m (1)
(In the general formula (1), R represents an alkyl group or an aryl group, which may be the same or different, and m is an integer of 0 to 2)
The organic phosphate compounds may be used alone or in combination of two or more.

  In the above general formula (1), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 1 to 30 carbon atoms. is there. M is preferably 1 or 2.

  In the above general formula (1), R is preferably an alkyl group having 1 to 30 carbon atoms, and among them, an alkyl group having 8 to 30 carbon atoms is preferable. Specifically, for example, n-octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl It is preferable that it is a group, trian cotyl group etc.

  In the above general formula (1), monoalkyl acid phosphate in which m is 2 or dialkyl acid phosphate in which m is 1 or a mixture thereof can also be preferably used in the present invention. As a specific commercial product of such a phosphate compound, for example, octadecyl acid phosphate (a mixture of a monoalkyl compound and a dialkyl compound) can be mentioned under the trade name “AX-71” manufactured by ADEKA Corporation.

[Release agent]
The polycarbonate resin composition of the present invention preferably contains a release agent.
As a mold release agent, aliphatic carboxylic acid, ester of aliphatic carboxylic acid and alcohol, aliphatic hydrocarbon compound, polysiloxane silicone oil etc. are mentioned, for example.

  Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic monohydric, divalent or trivalent carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are C6-C36 monohydric or dihydric carboxylic acids, and C6-C36 aliphatic saturated monohydric carboxylic acids are more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, cerotic acid, melotic acid, tetraliacontanic acid, montanic acid and adipin. Acid, azelaic acid and the like.

  As an 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, as the alcohol, for example, saturated or unsaturated monohydric or polyhydric alcohol can be mentioned. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols having 30 or less carbon atoms or aliphatic saturated polyhydric alcohols are more preferable. In addition, with an aliphatic here, an alicyclic compound is also contained.

  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. Can be mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Also, the above-mentioned ester may be a pure substance, but may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which are combined to constitute one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (mixture mainly composed of myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of aliphatic hydrocarbon compounds include liquid paraffin, paraffin wax, micro wax, polyethylene wax, Fischer-Tropsch wax, α-olefin oligomers having 3 to 12 carbon atoms, and the like. In addition, as an aliphatic hydrocarbon here, an alicyclic hydrocarbon is also contained. Also, these hydrocarbons may be partially oxidized. Further, the number average molecular weight of the aliphatic hydrocarbon compound is preferably 200 to 15,000, and more preferably 5,000 or less.

  Among these, paraffin wax, polyethylene wax or partial oxides of polyethylene wax are preferable, paraffin wax and polyethylene wax are more preferable, and polyethylene wax is particularly preferable.

In addition, 1 type may be contained in the mold release agent, and 2 or more types may be contained by arbitrary combinations and ratios.
The content of the releasing 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 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin. It is. When the content of the release agent is less than the lower limit of the above range, the effect of the releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

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

-Other resins Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate and polybutylene terephthalate resin;
Polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin) Styrene-based resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; Resin; polysulfone resin etc. are mentioned.

In addition, 1 type may contain other resin and 2 or more types may be contained by arbitrary combinations and ratios.
When it contains other resin, it is preferable that it is 40 mass parts or less in a total of 100 mass parts of polycarbonate resin and other resins, It is more preferable that it is 30 mass parts or less, and it is 20 mass parts or less Is more preferred.

Resin Additives As resin additives, for example, heat stabilizers other than those described above, antioxidants, titanium oxide, glass fibers, UV absorbers, dyes and pigments (including carbon black), antistatic agents, antifogging agents Lubricants, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents and the like. In addition, 1 type may be contained in the resin additive, and 2 or more types may be contained by arbitrary combinations and ratios.
Hereinafter, examples of additives suitable for the polycarbonate resin composition of the present invention will be specifically described.

· · Thermal stabilizer Examples of the thermal stabilizer include phosphorus compounds, and phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid and polyphosphoric acid; sodium acid pyrophosphate, potassium acid pyrophosphate, Acid pyrophosphate metal salts such as calcium acid pyrophosphate; phosphates of Group 1 or 2 B metals such as potassium phosphate, sodium phosphate, cesium phosphate, zinc phosphate; organic phosphite compounds, organic phosphonite compounds, etc. Of these, organic phosphite compounds are particularly preferred.

Examples of 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-dibis- tert-Butylphenyl) octyl phosphite etc. are mentioned.
In addition, 1 type may contain the heat stabilizer and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the heat 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, relative to 100 parts by mass of the polycarbonate resin. It is not more than mass part, preferably not more than 0.7 mass part, more preferably not more than 0.5 mass part. If the content of the heat stabilizer is less than the lower limit value of the above range, the heat stabilization effect may be insufficient, and if the content of the heat stabilizer exceeds the upper limit value of the above range, the effect is hit off And may not be economical.

· · Antioxidant The antioxidant includes, for example, hindered phenolic antioxidants. As a specific example thereof, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-Butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl [Methyl] phosphonate, 3,3 ′, 3 ′ ′, 5,5 ′, 5 ′ ′-hexa-tert-butyl-a, a ′, a ′ ′- Styrene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-4 Hydroxy-m-triyl) propionate], hexamethylene bis [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 are preferred. preferable.
In addition, 1 type may contain antioxidant and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the antioxidant is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Part or less. If the content of the antioxidant is less than the lower limit of the above range, the effect as the antioxidant may be insufficient. If the content of the antioxidant exceeds the upper limit of the above range, The effect may have plateaued and may not be economical.

· Titanium oxide titanium oxide, light-shielding molded article obtained from the polycarbonate resin composition, whiteness, and functions so as to improve and light reflection characteristics. The titanium oxide is not particularly limited in its production method, crystal form and average particle size.

Although there are a sulfuric acid method and a chlorine method as a manufacturing method of titanium oxide, any may be sufficient.
In addition, although there are rutile type and anatase type as the crystal form, a rutile type crystal form is preferable from the viewpoint of light resistance. The average particle size of the titanium oxide based additive is usually 0.1 to 0.7 μm, preferably 0.1 to 0.4 μm.

  The titanium oxide is preferably pretreated with an alumina-based surface treatment agent before the surface treatment with an organosiloxane-based surface treatment agent described later. Alumina hydrate is suitably used as the alumina-based surface treatment agent. Further, it may be pretreated with silica hydrate together with alumina hydrate. The method of pretreatment is not particularly limited, and any method can be used. The pretreatment with alumina hydrate and, if necessary, silicic acid hydrate is preferably carried out in the range of 1 to 15% by weight with respect to titanium oxide.

  Alumina hydrate and, if necessary, silicic acid hydrate pretreated titanium oxide may be further improved in thermal stability by surface treating the surface with an organosiloxane-based surface treatment agent. In addition to the above, the uniform dispersion in the polycarbonate resin composition and the stability of the dispersed state are improved. As the organosiloxane-based surface treatment agent, polyorganohydrogensiloxane compounds are preferable.

  There are a wet method and a dry method in the surface treatment method with the surface treatment agent of the organosiloxane type of titanium oxide. In the wet method, alumina hydrate and, if necessary, titanium oxide pretreated with silicic acid hydrate are added to a mixture of an organosiloxane-based surface treatment agent and a solvent, the solvent is removed after stirring, Furthermore, it is the method of heat-processing at 100-300 degreeC after that. The dry method is a method of mixing titanium oxide and polyorganohydrogensiloxanes pretreated in the same manner as described above with a Henschel mixer etc., and spraying an organic solution of polyorganohydrogensiloxanes onto the pretreated titanium oxide. C., and heat-treated at 100 to 300.degree. C., and the like. The amount of the siloxane-based surface treatment agent is not particularly limited, but in view of the reflectivity of titanium oxide, the moldability of the resin composition, etc., it is usually in the range of 1 to 5% by weight based on titanium oxide. is there.

  The content of titanium oxide is preferably in the range of 3 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Here, the mass of titanium oxide means the total mass including the surface treatment agent of the alumina hydrate, the silica hydrate, and the organosiloxane type surface treatment including these treatment agents, when it is surface-treated.

· · Glass fiber As glass fiber, as long as it is usually used for thermoplastic resin, A glass, E glass, alkali resistant glass composition containing a zirconia component, chopped strand, roving glass, thermoplastic resin Any known glass fiber can be used regardless of the form of the glass fiber at the time of blending such as a (long fiber) master batch of and glass fiber. Among them, alkali-free glass (E glass) is preferable as the glass fiber used in the present invention for the purpose of improving the thermal stability of the polycarbonate resin composition of the present invention.

  The number average fiber length of the glass fiber is preferably 1 mm or more and 10 mm or less, more preferably 1.5 to 6 mm, and still more preferably 2 to 5 mm. If the number average fiber length is more than 10 mm, the glass fibers are likely to come off from the surface of the molded article, and the productivity is likely to be reduced. If the number average fiber length is less than 1 mm, the improvement in mechanical strength tends to be insufficient because the aspect ratio of the glass fiber is small.

  It is preferable that the diameter of glass fiber is 3 micrometers or more and 20 micrometers or less. These can be produced by grinding strands of glass fibers, specifically, for example, with a hammer mill or a ball mill, according to any conventionally known method. If the diameter of the glass fiber is less than 3 μm, the mechanical strength is not sufficiently improved, and if it exceeds 20 μm, the appearance is likely to be deteriorated. The diameter of the glass fiber is more preferably 5 μm or more and 15 μm or less, still more preferably 6 μm or more and 14 μm or less.

  The glass fiber can be surface-treated with a silane coupling agent such as aminosilane and epoxysilane for the purpose of improving the adhesion to the polycarbonate resin.

In addition, it is preferable to use, as a glass fiber, a chopped strand (chopped glass fiber) which is usually a bundle of a large number of these fibers and cut into a predetermined length, and at this time, a glass fiber is blended with a focusing agent. Is preferred. In addition to the advantage that the production stability of the polycarbonate resin composition of the present invention is enhanced by blending a focusing agent, good mechanical properties can be obtained.
The focusing agent is not particularly limited, and examples thereof include urethane, epoxy and acrylic focusing agents. Among them, as a focusing agent for glass fiber used in the present invention, a urethane based or epoxy based focusing agent is more preferable, and an epoxy based focusing agent is more preferable.

  The cut length of the chopped strand (chopped glass fiber) is not particularly limited, but is usually 1 to 10 mm, preferably 1.5 to 6 mm, and more preferably 2 to 5 mm.

  As preferable content of glass fiber, it is 10-100 mass parts with respect to 100 mass of polycarbonate resin. When the content of the glass fiber is less than 10 parts by mass, the effect of improving the elastic modulus is insufficient, and conversely, when it exceeds 100 parts by mass, the impact resistance and the flowability tend to be insufficient. The content of the glass fiber is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and preferably 80 parts by mass or less, more preferably 65 parts by mass or less.

[Method of producing polycarbonate resin composition]
There is no limitation on the method for producing the thermally conductive polycarbonate resin composition of the present invention, and any known method for producing a polycarbonate resin composition can be widely adopted, and polycarbonate resin, boron nitride, phosphorus based flame retardant, fluoropolymer and silicate compound, In addition, after mixing in advance other components to be blended if necessary using various mixers such as tumblers and Henschel mixers, for example, Banbury mixers, rolls, brabenders, single-screw kneading extruders, twin-screw kneading extruders And melt kneading using a mixer such as a kneader.
The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Molding]
Pellets obtained by pelletizing the above-described polycarbonate resin composition are molded by various molding methods to be molded articles. Alternatively, the resin melt-kneaded by the extruder may be directly molded into a molded article without passing through the pellets.
There is no restriction | limiting in particular as a shape of a molded article, According to the use of a molded article, and the objective, it can select suitably, For example, plate shape, plate shape, rod shape, rod shape, sheet shape, film shape, cylindrical shape, cyclic | annular, A circular shape, an elliptical shape, a polygonal shape, a deformed product, a hollow product, a frame shape, a box shape, a panel shape and the like can be mentioned.

  The method for molding the molded body is not particularly limited, and conventionally known molding methods can be adopted. For example, injection molding method, injection compression molding method, extrusion molding method, profile extrusion method, transfer molding method, hollow molding method, Gas-assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And pressure molding methods.

  The polycarbonate resin composition of the present invention is a resin material of high thermal conductivity excellent in thermal conductivity (heat dissipation), rigidity and flame retardancy, so a molded article obtained by molding the composition is a personal computer, digital camera or various kinds. It is particularly suitable for components and housings of portable terminals, LED mounting substrates or heat sink members in LED lighting, components, battery charging equipment components, battery covers and the like.

Hereinafter, the present invention will be more specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily changed and implemented without departing from the scope of the present invention.
Each raw material component used for the following example and comparative example is as Table 1 below.

(Examples 1 to 6, Comparative Examples 1 to 6)
The components listed in Table 1 above are compounded in proportions (all expressed in mass parts) shown in Table 3 and Table 4 below and uniformly mixed with a tumbler mixer, and then a twin-screw extruder (made by Japan Steel Using a product manufactured by TEX30HSST), feed it to the extruder from the barrel at the upstream part of the extruder at a cylinder temperature of 280 ° C, a screw rotation speed of 200 rpm and a discharge rate of 20 kg / hr to melt and knead to obtain pellets of polycarbonate resin composition. The

[Evaluation of tensile properties]
The resin composition pellet obtained by the above method is dried at 100 ° C. for 5 hours, and then using an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.), cylinder setting temperature 270 to 290 ° C., mold temperature Injection molding was carried out under the conditions of 100 ° C., injection time of 2 seconds, and molding cycle of 40 seconds, and ISO multipurpose test pieces (4 mm thick) were injection molded.
The tensile elastic modulus (unit: MPa) and the breaking point strength (unit: MPa) were measured at a temperature of 23 ° C. according to ISO standard 527-1 and ISO 527-2 using the obtained ISO test piece.

[Evaluation of bending characteristics]
Using a bending test piece (thickness 4 mm) manufactured in the same manner as in the above tensile property evaluation, according to ISO 178, the bending elastic modulus (unit: MPa) and bending stress (unit: MPa) are measured at a temperature of 23 ° C. It was measured.

[Heat resistance evaluation: DTUL (deflection temperature under load, unit: ° C.)]
Using the ISO multi-purpose test piece obtained above, according to ISO 75-1 & 2, the measurement was performed under the condition of 1.80 MPa load (method A). In the table, it is written as "DTUL".

[Measurement of thermal conductivity (unit: W / m · K)]
The ISO multipurpose test piece obtained above is cut into slices of 0.15 to 0.5 mm thickness, and this is used as a sample, using thermal wave thermal analyzer “ai-Phase Mobile 1” manufactured by Eyephase Inc. It measured about MD direction (resin flow direction at the time of shaping | molding), and thickness direction.

[Evaluation of flammability: UL94 test]
The above pellets were dried at 100 ° C. for 5 hours and then injection molded using an injection molding machine (“J55-60H” manufactured by Japan Steel Works, Ltd.) under the conditions of a cylinder setting temperature of 340 ° C., a mold temperature of 120 ° C. and a molding cycle of 30 seconds. A UL test specimen having a length of 125 mm and a width of 13 mm and a thickness of 1.5 mm was formed.
The obtained test pieces are conditioned for 48 hours in a constant temperature room at a temperature of 23 ° C. and a humidity of 50%, and the UL 94 test prescribed by Underwriters Laboratories (UL) in the United States (combustion of plastic materials for parts of equipment It carried out according to the test. UL 94 V is a method to evaluate the flammability from the remaining flame time and dripping property after indirectly heating a burner flame for 10 seconds to a test piece of a predetermined size held vertically, V-0, V-1 In order to have the flammability of V2 and V-2, it is necessary to satisfy the criteria shown in Table 2 below.

Here, the afterflame time is the length of time that the flame burning of the test piece continues after the ignition source is moved away. In addition, cotton ignition by drip is determined depending on whether the marking cotton located about 300 mm below the lower end of the test piece is ignited by a drip from the test piece. Furthermore, when one or more of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) as not satisfying V-2.
Tables 3 and 4 show the above evaluation results.

  According to the thermally conductive polycarbonate resin composition of the present invention, a thermally conductive thermoplastic resin material excellent in thermal conductivity, rigidity, and flame retardancy can be obtained. Therefore, parts of personal computers, digital cameras or various portable terminals and the like It can be particularly suitably used for a housing, a substrate for LED mounting or a heat sink member in LED lighting, parts, battery charging equipment parts, battery covers and the like, and the industrial applicability is very high.

Claims (3)

15 to 50 parts by mass of boron nitride, 3 to 30 parts by mass of phosphorus-based flame retardant, 0.001 to 10 parts by mass of fluoropolymer, 15 to 50 parts by mass of talc, and the following general formula (1) with respect to 100 parts by mass of polycarbonate resin A thermally conductive polycarbonate resin composition comprising 0.2 to 1 part by mass of the organic phosphate compound represented by and 7 to 20 parts by mass of a siloxane-based elastomer .
O = P (OH) _m (OR) _3-m (1)
(In the general formula (1), R represents an alkyl group or an aryl group, which may be the same or different, and m is an integer of 0 to 2)   The thermally conductive polycarbonate resin composition according to claim 1, wherein the phosphorus-based flame retardant is a phosphoric acid ester compound or a phosphazene compound. The molded article formed by shape | molding the heat conductive polycarbonate resin composition of Claim 1 or 2 .