JP2020094137A - Thermally conductive polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition excellent in thermal conductivity, heat resistance, flame retardancy, rigidity and insulating properties.SOLUTION: The thermally conductive polycarbonate resin composition contains, based on (A) 100 pts.wt. of a polycarbonate resin (component A), (B) 20-60 pts.wt. of glass fibers (component B), (C) 5-40 pts.wt. of boron nitride (component C) having an average particle diameter of 15-28 μm and a tap density of 0.5 g/mL or more, (D) 5-30 pts.wt. of a bromine-based flame retardant (component D), and (E) 0.1-5 pts.wt. of a fluorine-containing drip inhibitor (component E).SELECTED DRAWING: None

Description

The present invention relates to a heat conductive polycarbonate resin composition and a molded article thereof. More specifically, the present invention relates to a thermoplastic resin composition having excellent thermal conductivity, heat resistance, flame retardancy, rigidity and insulating properties, and a molded product thereof.

BACKGROUND OF THE INVENTION Polycarbonate resins are widely used in the fields of interior and exterior parts of automobiles, OA equipment, electric and electronic equipment, etc. because they have excellent heat resistance and flame retardancy and mechanical strength. In recent years, in order to efficiently radiate the generated heat to the outside, there has been a demand for a thermoplastic resin composition having excellent heat resistance, flame retardancy, rigidity and insulation of the resin while enhancing the thermal conductivity of the polycarbonate resin. It is rising.

As a method for further improving the thermal conductivity of these polymer compositions, a thermally conductive polymer material obtained by filling a polymer material with a carbon-based material having high thermal conductivity has been proposed. For example, a method of adding graphitized carbon fiber to a polymer material (see Patent Documents 1 to 3) and a method of adding pitch-based carbon fiber and scaly graphite to a thermoplastic resin are known, but insulation deterioration or difficulty There were various problems such as deterioration of flammability.

On the other hand, in order to improve the thermal conductivity while maintaining the insulating property, metal oxides such as aluminum oxide, boron nitride, aluminum nitride, silicon nitride, magnesium oxide, zinc oxide, silicon carbide, quartz, and aluminum hydroxide, metal It is known to add fillers such as nitrides, metal carbides, and metal hydroxides, but it is difficult to obtain a thermoplastic resin having improved thermal conductivity and high flame retardancy. (See Patent Documents 4 to 7). Further, it is known to use a specific boron nitride or to add an amine-based silane coupling agent in order to improve thermal conductivity, flame retardancy and the like while maintaining the insulating property of the polycarbonate resin. At present, the conductivity, heat resistance, flame retardancy, and rigidity are not sufficient (see Patent Documents 8 and 9).

JP, 2002-88250, A JP 2002-339171 A JP, 2003-112915, A JP, 2010-195890, A JP, 2008-239899, A JP, 2008-270709, A JP, 2011-12193, A JP 2012-188579 A JP, 2013-203770, A

In view of the above, an object of the present invention is to provide a polycarbonate resin composition excellent in thermal conductivity, heat resistance, flame retardancy, rigidity and insulation, and a molded product thereof.

The present inventor has conducted diligent studies to solve the above problems, and by combining a polycarbonate resin, glass fiber, a specific boron nitride, a brominated flame retardant and a fluorine-containing anti-dripping agent in a ratio of characteristics, thermal conduction The present invention has been completed by finding a method for obtaining a thermally conductive polycarbonate resin composition excellent in heat resistance, heat resistance, flame retardancy, rigidity and insulation and a molded article thereof.

According to the present invention, the above-mentioned problems are (A) polycarbonate resin (A component) 100 parts by weight, (B) glass fiber (B component) 20 to 60 parts by weight, and (C) average particle diameter 15 μm to 28 μm. , 5 to 40 parts by weight of boron nitride (C component) having a tap density of 0.5 g/ml or more, 5 to 30 parts by weight of (D) brominated flame retardant (D component) and (E) fluorine-containing anti-dripping agent ( Component E) 0.1 to 5 parts by weight is contained in the heat conductive polycarbonate resin composition.

Hereinafter, details of the present invention will be described.

(A component: polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-state transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)- 1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl) Pentane, 4,4'-(p-phenylenediisopropylidene)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane , Bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-) Hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Be done. A preferred dihydric phenol is bis(4-hydroxyphenyl)alkane, and among them, bisphenol A is particularly preferred and widely used from the viewpoint of impact resistance.

In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced by using other dihydric phenols as the A component.

For example, 4,4′-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis(4-hydroxy) as a part or all of the dihydric phenol component. Phenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis(4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") has a dimension due to water absorption. It is suitable for applications in which changes and morphological stability are particularly demanding. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more, based on the whole dihydric phenol component constituting the polycarbonate.

Particularly, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is the following copolycarbonate (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF. Is 20 to 80 mol% (more preferably 25 to 60 mol%, further preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, further preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF. Is from 5 to 90 mol% (more preferably from 10 to 50 mol%, further preferably from 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate having TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, further preferably 35 to 55 mol%).

These special polycarbonates may be used alone or in combination of two or more kinds. Further, these can be used as a mixture with a commonly used bisphenol A type polycarbonate.

The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

In addition, among the various polycarbonates described above, those having a water absorption rate and a Tg (glass transition temperature) within the following ranges by adjusting the copolymerization composition and the like have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where morphological stability is required.
(I) Polycarbonate having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13% and a Tg of 120 to 180°C, or (ii) a Tg of 160 to 250°C, A polycarbonate having a temperature of 170 to 230° C. and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption of the polycarbonate is a value obtained by measuring the water content after dipping in water at 23° C. for 24 hours according to ISO62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Further, Tg (glass transition temperature) is a value obtained by a differential scanning calorimeter (DSC) measurement based on JIS K7121.

As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

In producing a polycarbonate resin by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, if necessary, a catalyst, an end terminating agent, an antioxidant for preventing the dihydric phenol from being oxidized, and the like. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher functional polyfunctional aromatic compound, and a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. , A copolymerized polycarbonate resin copolymerized with a difunctional alcohol (including an alicyclic group), and a polyester carbonate resin copolymerized with such a difunctional carboxylic acid and a difunctional alcohol. It may also be a mixture of two or more of the obtained polycarbonate resins.

The branched polycarbonate resin can impart drip prevention performance and the like to the polycarbonate resin composition of the present invention. Examples of the trifunctional or higher-functional polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phlorogluside, or 4,6-dimethyl-2,4,6-tris(4-hydrodiphenyl)heptene-2,2. ,4,6-Trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl) Ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[ 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other trisphenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, Examples thereof include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, and among them, 1,1,1-tris(4-hydroxy) Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferable, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferable.

The constituent unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably 100 mol% in total of the constituent unit derived from the dihydric phenol and the constituent unit derived from the polyfunctional aromatic compound, preferably It is 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, and further preferably 0.05 to 0.8 mol %.

Further, particularly in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is also preferably 100 mol% in total with the structural unit derived from the dihydric phenol, preferably. It is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, and further preferably 0.01 to 0.8 mol %. The ratio of the branched structure can be calculated by 1H-NMR measurement.

The aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as An alicyclic diol is more preferable as the difunctional alcohol, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

The reaction modes such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the production methods of the polycarbonate resin of the present invention, include various documents and patent publications. Is a well known method.

In producing the polycarbonate resin composition of the present invention, the viscosity average molecular weight of the polycarbonate resin is preferably 12,500 to 32,000, more preferably 16,000 to 28,000, and further preferably 18,000. ~26,000. With a polycarbonate resin having a viscosity average molecular weight of less than 12,500, good mechanical properties may not be obtained in some cases. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight of more than 32,000 may have poor flame retardancy.

The viscosity average molecular weight as used in the present invention is obtained by first using a Ostwald viscometer to calculate a specific viscosity (η _SP ) calculated by the following formula from a solution prepared by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20° C.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[T ₀ is the number of seconds of methylene chloride drop, t is the number of seconds of drop of sample solution]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following mathematical formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η]=1.23×10 ⁻⁴ M ^0.83
c=0.7

The viscosity average molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. The soluble matter is collected by Celite filtration. After that, the solvent in the obtained solution is removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of a component soluble in methylene chloride. A specific viscosity at 20° C. is obtained from a solution prepared by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is a copolymer prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). It is preferably a resin.

［上記一般式（１）において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式（２）で表される基からなる群より選ばれる少なくとも一つの基である。］

[In the general formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 aryloxy group, carbon atom Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are a plurality of groups, they may be the same or different. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). ]

［上記一般式（２）においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数６〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１〜１０の整数、ｈは４〜７の整数である。］

[In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^17, and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, wherein R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 18; Alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms From an aryl group having 14 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. It represents a group selected from the group consisting of two or more, and when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

［上記一般式（３）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０〜３００の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。］

[In the general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbons or a substituent having 6 to 12 carbons. Alternatively, it is an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. , Q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1 -Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropyl) Phenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2 ,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl) Propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy) -3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenylether, 4,4' -Dihydroxy-3,3'-dimethyldiphenylether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4, 4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4' -Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis{2-(4-hydroxyphenyl) )Propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydro) Xyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1, Examples thereof include 3-adamantanediyl)diphenol and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{ 2-(4-hydroxyphenyl)propyl}benzene is preferred, especially 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4′-. Sulfonyldiphenol and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Of these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most suitable. These may be used alone or in combination of two or more.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3), for example, the following compounds are preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by subjecting the end of the polysiloxane chain having the degree of polymerization of 1 to a hydrosilation reaction. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferable, and particularly (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4). Preferred are allylphenol)-terminated polydimethylsiloxanes. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. The molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to exhibit more excellent low outgassing property and high temperature impact resistance during high temperature molding. When the amount exceeds the upper limit of the preferable range, the amount of outgas generated during high temperature molding is large and the low temperature impact resistance may be poor.

Further, in order to realize a high degree of impact resistance, the degree of polymerization (p+q) of diorganosiloxane of hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, still more preferably 14 to 100. If it is less than the lower limit of the preferred range, the impact resistance, which is a characteristic of the polycarbonate-polydiorganosiloxane copolymer, is not effectively exhibited, and if it exceeds the upper limit of the preferred range, poor appearance appears.

The content of the polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component A is preferably 0.1 to 50% by weight. The content of the polydiorganosiloxane component is more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight. Above the lower limit of this preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of this preferred range, a stable appearance that is less susceptible to molding conditions is likely to be obtained. The polydiorganosiloxane polymerization degree and the polydiorganosiloxane content can be calculated by 1H-NMR measurement.

In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

Further, other than the above dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II), a comonomer other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is contained in an amount of 10% by weight or less based on the total weight of the copolymer. It can also be used together.

In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared by previously reacting a dihydric phenol (I) with a carbonic acid ester-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution. To do.

In producing the oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into the oligomer at one time, or a part of the dihydric phenol (I) may be used as a post-added monomer to form a post-stage interface. You may add as a reaction raw material to a polycondensation reaction. The post-addition monomer is added in order to accelerate the subsequent polycondensation reaction, and it is not necessary to intentionally add it when it is not necessary.

The method of this oligomer formation reaction is not particularly limited, but a method performed in a solvent in the presence of an acid binder is usually preferable.

The proportion of the carbonic acid ester forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When a gaseous carbonic acid ester-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably adopted.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. The proportion of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent weight) of the reaction, similarly to the above. Specifically, it is preferable to use 2 equivalents or slightly excess amount of the acid binder with respect to the number of moles of dihydric phenol (I) used for forming the oligomer (usually 1 mole corresponds to 2 equivalents). ..

As the solvent, solvents that are inert to various reactions such as those used in the known production of polycarbonate may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Particularly, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The reaction pressure for oligomer formation is not particularly limited and may be normal pressure, increased pressure or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of −20 to 50° C., and in many cases, heat is generated with the polymerization, so water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified unconditionally, but is usually 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

According to the present invention, a mixed solution containing an oligomer of a dihydric phenol (I) having a terminal chloroformate group is thus obtained, and then the mixed solution is stirred to have a molecular weight distribution (Mw/Mn) of 3 or less. The highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (4) is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. Thus, a polycarbonate-polydiorganosiloxane copolymer is obtained.

（上記一般式（４）において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは１０〜３００の自然数である。Ｘは炭素数２〜８の二価脂肪族基である。）

(In the above general formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbons or a substituent having 6 to 12 carbons. Alternatively, it is an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. , Q is 0 or a natural number, p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

When carrying out the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent amount) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction step, the amount of the post-added component It is preferable to use 2 equivalents or an excess of alkali with respect to the total number of moles of the polyhydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

Polycondensation by an interfacial polycondensation reaction between an oligomer of dihydric phenol (I) and a hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixed solution.

In such a polymerization reaction, a terminal stopper or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols and aliphatic carboxylic acids. Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to accelerate the polycondensation reaction.

The reaction time of the polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

A branching agent can be used in combination with the above dihydric phenol compound to give a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher-functional polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydrodiphenyl). ) Heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris (4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, Trisphenol such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy) Phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among others, 1,1,1 -Tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferable, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferable. . The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9, in the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. Mol%, more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%. The amount of the branched structure can be calculated by 1H-NMR measurement.

The reaction pressure may be any of reduced pressure, normal pressure and increased pressure, but normally, it can be preferably carried out at normal pressure or at about the self pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50° C., and in many cases, heat is generated with the polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as reaction temperature and therefore cannot be specified unconditionally, but it is usually 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _SP /c].

The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purification degree) by performing various post-treatments such as a known separation and purification method.

The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 40 nm. The average size is more preferably 1 to 30 nm, further preferably 5 to 25 nm. If it is less than the lower limit of the preferable range, impact resistance and flame retardancy may not be sufficiently exhibited, and if it exceeds the upper limit of the preferable range, impact resistance may not be stably exhibited. This provides a polycarbonate resin composition excellent in impact resistance and appearance.

The average domain size and normalized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded article in the present invention were evaluated by the small angle X-ray scattering method (SAXS). The small angle X-ray scattering method is a method for measuring diffuse scattering/diffraction occurring in a small angle region within a scattering angle (2θ)<10°. In this small-angle X-ray scattering method, when there are regions having different electron densities of about 1 to 100 nm in the substance, diffuse scattering of X-rays is measured due to the difference in electron density. The particle size of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregated structure in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer, diffuse scattering of X-rays occurs due to a difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10° is measured to measure a small angle X-ray scattering profile, and the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there exists, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model, and the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain are obtained. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the matrix of the polycarbonate polymer, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, easily, and with good reproducibility. Can be measured. The average domain size means the number average of individual domain sizes. The standardized dispersion means a parameter in which the spread of the particle size distribution is standardized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size by the average domain size, and is represented by the following formula (1).

上記式（１）において、δはポリジオルガノシロキサンドメインサイズの標準偏差、Ｄａｖは平均ドメインサイズである。

In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.

The terms "average domain size" and "normalized dispersion" used in connection with the present invention refer to measurement of a 1.0-mm-thick portion of a three-stage plate prepared by the method described in Examples by such a small-angle X-ray scattering method. The measured values obtained by In addition, the analysis was performed using an isolated particle model that does not consider the interaction between particles (interference between particles).

(B component: glass fiber)
The glass fiber used in the present invention is obtained by cutting or crushing glass fiber and is generally used as a reinforcing material for synthetic resin. The glass fiber is preferably a glass fiber having an average fiber length in the resin composition of 30 to 900 μm and an average L/D of 10 to 300. Here, L is the average length of the glass fibers, D is the average diameter in the case of glass fibers having a round cross section, and in the case of flat cross-section glass fibers, it is the average value of the major axis of the cross section. The average fiber length is more preferably 30 to 500 μm, and the L/D is more preferably 10 to 200. When L/D is less than 10, heat resistance may not be exhibited, and when it is more than 300, the appearance and moldability of the molded product may be deteriorated, which is not preferable. If the average fiber length is less than 30 μm, heat resistance may not be exhibited, and if it exceeds 900 μm, the appearance and moldability of the molded product may be deteriorated. Further, the diameter of the glass fiber is not particularly limited, but the range of 3 to 50 μm is preferable. If it exceeds 50 μm, the appearance of the molded product may be impaired, which is not preferable.

As the glass fiber, a glass fiber having a round cross section and a glass fiber having a flat cross section are preferable, and a glass fiber having a round cross section is more preferable.

Various glass compositions represented by A glass, C glass, T glass, NCR glass, HME glass, E glass and the like are applied to the glass composition of the glass fiber, and are not particularly limited.

The content of the component B is 20 to 60 parts by weight, preferably 20 to 55 parts by weight, and more preferably 20 to 50 parts by weight, based on 100 parts by weight of the component A. When the content of the component B is less than 20 parts by weight, sufficient heat resistance cannot be obtained and the rigidity is insufficient, and when it exceeds 60 parts by weight, the moldability is deteriorated.

(C component: boron nitride)
Examples of boron nitride include cubic boron nitride and hexagonal boron nitride, with hexagonal boron nitride being preferred. Further, boron nitride includes spheres, scales, and aggregates thereof, and any of them can be used in the present invention. Among them, it is preferable to use a scaly or scaly aggregate because a composition having better thermal conductivity can be obtained and mechanical properties can be improved.

The average particle diameter (D50) of boron nitride is 15 to 28 μm, preferably 15 to 25 μm, and more preferably 17 to 25 μm, as measured by a laser diffraction/scattering method. If the average particle size is less than 15 μm, the extrusion stability during the production of the resin composition is poor and the productivity is reduced. If the average particle size exceeds 28 μm, the thermal conductivity will decrease.

The tap density of boron nitride is 0.5 g/ml or more, preferably 0.52 g/ml or more, more preferably 0.55 g/ml or more. The upper limit is not particularly limited, but is preferably 1.0 g/ml or less, more preferably 0.9 g/ml or less. If the tap density is less than 0.5 g/ml, extrusion stability will be poor and productivity will be reduced.

The content of the component C is 5 to 40 parts by weight, preferably 5 to 35 parts by weight, and more preferably 10 to 30 parts by weight, relative to 100 parts by weight of the component A. When the content of the C component is less than 5 parts by weight, the rigidity is low and the thermal conductivity is low, and when it exceeds 40 parts by weight, the extrudability is deteriorated.

(D component: brominated flame retardant)
Examples of the brominated flame retardant used in the present invention include a brominated bisphenol A type polycarbonate flame retardant having a bromine content of 20% by weight or more, a brominated bisphenol A type epoxy resin, and a modification obtained by blocking a part or all of the terminal glycidyl group. Compounds, brominated diphenyl ether flame retardants, brominated imide flame retardants, brominated polystyrene flame retardants and the like.

Specific examples include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis(2,4,6-tribromophenoxy)ethane, ethylenebistetrabromophthalimide, Hexabromobenzene, 1,1-sulfonyl[3,5-dibromo-4-(2,3-dibromopropoxy)]benzene, polydibromophenylene oxide, tetrabromobisphenol S, tris(2,3-dibromopropyl-1) Isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol A, tetrabromobisphenol A derivative, tetrabromobisphenol A-epoxy oligomer or polymer, tetrabromo Bisphenol A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol A-bis(2-hydroxydiethyl ether), tetrabromobisphenol A-bis(2,3-dibromopropyl ether), Tetrabromobisphenol A-bis(allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris(tribromoneopentyl)phosphate, poly(pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneopentylglycol , Pentabromobenzyl polyacrylate, dibromocresyl glycidyl ether, N,N′-ethylene-bis-tetrabromophthalimide and the like. Among them, tetrabromobisphenol A-epoxy oligomer, tetrabromobisphenol A-carbonate oligomer, brominated epoxy resin and the like can be mentioned.

As the brominated flame retardant of the present invention, brominated polycarbonate (including oligomer) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can significantly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (5) is at least 60 mol%, preferably at least 80 mol% of all structural units, particularly preferably substantially the following general formula It is a brominated polycarbonate compound consisting of the structural unit represented by (5).

（式（５）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）
また、かかる式（５）において、好適にはＲはメチレン基、エチレン基、イソプロピリデン基、−ＳＯ_２−、特に好ましくはイソプロピリデン基を示す。

(In the formula (5), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO ₂ -.)
Further, in the formula (5), R is preferably a methylene group, an ethylene group, an isopropylidene group or -SO ₂ -, and particularly preferably an isopropylidene group.

The brominated polycarbonate has few residual chloroformate group terminals, and the amount of terminal chlorine is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of such terminal chlorine is obtained by dissolving the sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine, and reacting with terminal chlorine (terminal chloroformate), and then using this with an ultraviolet-visible spectrophotometer (U, Hitachi, Ltd.). -3200) to measure and obtain. When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition having more excellent moldability is provided.

Further, it is preferable that the brominated polycarbonate has few residual hydroxyl groups. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less, relative to 1 mol of the structural unit of the brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving the sample in deuterated chloroform and measuring by ¹ H-NMR method. This amount of terminal hydroxyl groups is preferable because the thermal stability of the resin composition is further improved.

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-mentioned specific viscosity calculation formula used in calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention.

The content of the D component is 5 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 5 to 20 parts by weight, relative to 100 parts by weight of the A component. If the content is less than 5 parts by weight, the flame retardancy is not improved, and if it exceeds 30 parts by weight, the extrudability is deteriorated.

(Component E: Fluorine-containing dripping inhibitor)
The resin composition of the present invention contains a fluorine-containing anti-dripping agent. By using such a fluorine-containing anti-dripping agent together with the above flame retardant, better flame retardancy can be obtained. Examples of such a fluorine-containing anti-dripping agent include a fluorine-containing polymer having a fibril forming ability, and examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene/hexafluoropropylene copolymer). Polymers, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc., but preferably polytetrafluoroethylene (hereinafter referred to as PTFE). Sometimes referred to).

Polytetrafluoroethylene (fibrillated PTFE) capable of forming fibrils has an extremely high molecular weight, and tends to bond PTFEs to each other by an external action such as shearing force to form a fibrous form. Its number average molecular weight is in the range of 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380° C. measured by the method described in this publication of 107 to 1013 poise, preferably 108 to 1012 poise.

In addition to the solid form, such PTFE may be used in the form of an aqueous dispersion. In addition, PTFE having such a fibril-forming ability improves the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell is also preferably used.

Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L manufactured by Daikin Chemical Industries, Ltd., and the like. Examples of commercially available aqueous dispersions of fibrillated PTFE include Fluon AD-1 and AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., Mitsui. Representative examples thereof include Teflon (registered trademark) 30J manufactured by DuPont Fluorochemicals Co., Ltd.

As the fibrillated PTFE in a mixed form, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (JP-A-60-258263). JP-A No. 63-154744, etc.), and (2) a method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (JP-A-4-272957). Described method), (3) a method of uniformly mixing an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles, and simultaneously removing the respective media from the mixture (JP-A 06-220210, JP-A 06-220210). 08-188653) and (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of fibrillated PTFE (described in JP-A-9-95583). Method) and (5) a method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is polymerized in the mixed dispersion, and then a mixture is obtained (JP-A-11- Those obtained by the method described in No. 29679) can be used. Commercially available products of fibrillated PTFE in the form of a mixture thereof include "Metabrene A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals, and "Blendex B449" manufactured by Pacific Interchem Corporation. POLY TS AD001” (trade name) and the like are exemplified.

Since the fibrillated PTFE does not lower the mechanical strength, it is preferably dispersed as finely as possible. As a means for achieving such fine dispersion, the fibrillated PTFE in the mixed form is advantageous. Further, a method of directly supplying an aqueous dispersion form to a melt-kneader is also advantageous for fine dispersion. However, it is necessary to consider that the hue of the aqueous dispersion form is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, based on 100% by weight of the mixture. When the proportion of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.

The content of the E component is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, and more preferably 0.2 to 0.8 parts by weight, relative to 100 parts by weight of the A component. .. If the content is less than 0.1 parts by weight, the flame retardancy is lowered, and if it exceeds 5 parts by weight, the extrusion processability is lowered.

(F component: phosphate compound)
The resin composition of the present invention may contain a phosphate compound. Examples of the phosphate compound include monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, mono. Lauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono(4-dodecyl)phenyl phosphate, mono(4-methylphenyl)phosphate, mono(4-ethylphenyl)phosphate, mono(4 -Propylphenyl)phosphate, mono(4-dodecylphenyl)phosphate, monotolylphosphate, monoxylylphosphate, monobiphenylphosphate, mononaphthylphosphate, and monoanthrylphosphate, and other monoalkylphosphates and monoarylphosphates However, these may be used alone or as a mixture of two or more kinds, for example, as a mixture of a monoalkyl phosphate and a monoaryl phosphate. However, when the above phosphorus compounds are used as a mixture of two or more kinds, the proportion of monoalkyl phosphate is preferably 50% or more, more preferably 90% or more, and particularly preferably 100%. Is more preferable.

The content of the F component is preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.8 part by weight, relative to 100 parts by weight of the A component. If the content is less than 0.01 part by weight, the molding heat stability may be poor, and if it exceeds 1 part by weight, the moist heat resistance may decrease.

(About other additives)
In addition, various known additives described in JP-A-2016-160278 can be added to the composition of the present invention as necessary.

(Production of resin composition)
Any method may be used to prepare the resin composition of the present invention. For example, there may be mentioned a method in which the A component, the B component, the C component, the D component, the E component and optionally other components are premixed, and then melt-kneaded and pelletized. Examples of the premixing means include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the pre-mixing, granulation can be performed by an extrusion granulator or a briquetting machine, if necessary. As another method, for example, when a powder having a form of powder is contained, a part of the powder is blended with an additive to prepare a master batch of the additive diluted with the powder, and the master batch is used. There is a method of doing. After pre-mixing, the mixture is melt-kneaded by a melt-kneader typified by a vented twin-screw extruder, and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring container, but a vented twin-screw extruder is preferable.

In addition, a method of independently supplying each component to a melt-kneader typified by a twin-screw extruder can be used without premixing. In addition, there is a method in which some components are premixed and then fed to the melt-kneader independently of the remaining components. Particularly when an inorganic filler is blended, it is preferable to supply the inorganic filler into the molten resin from a supply port in the middle of the extruder by using a supply device such as a side feeder. The pre-mixing means and granulation are the same as above. When the components to be blended are liquid, a so-called liquid injection device or liquid addition device can be used to supply the components to the melt-kneader.

As the extruder, an extruder having a vent capable of degassing water in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump for efficiently discharging generated water and volatile gas from the vent to the outside of the extruder is preferably installed. It is also possible to install a screen for removing foreign substances mixed in the extrusion raw material in the zone in front of the extruder die part to remove the foreign substances from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disc filter).

Examples of the melt kneader include a twin screw extruder, a Banbury mixer, a kneading roll, a single screw extruder, and a multi-screw extruder having three or more screws.

The resin extruded as described above is directly cut into pellets, or after forming a strand, the strand is cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust or the like during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical disks are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. Moreover, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to realize a high molding cycle and reduce the rate of occurrence of defects such as silver. The shape of the pellet may be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and further preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and further preferably 2.5 to 3.5 mm.

The resin composition of the present invention can be manufactured into various products by injection molding the pellets manufactured as described above to obtain molded products. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples include mold molding, rapid heating and cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultra-high speed injection molding. Further, either cold runner method or hot runner method can be selected for molding.

The resin composition of the present invention can also be used in the form of various shaped extrusion molded articles, sheets, films and the like by extrusion molding. Further, an inflation method, a calendar method, a casting method or the like can be used for forming a sheet or a film. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

Molded articles using the resin composition of the present invention include various electronic/electrical equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts (particularly interior/exterior parts for vehicles), other agricultural materials, It is useful for various uses such as transport containers, play equipment, and miscellaneous goods, and the industrial effects it produces are exceptional.

Further, various kinds of surface treatments can be applied to the molded article made of the resin composition of the present invention. Surface treatment here means a new layer on the surface layer of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dip plating, etc.), painting, coating, printing, etc. It is formed, and the method used for a usual thermoplastic resin can be applied. Specific examples of the surface treatment include various surface treatments such as a hard coat, a water-repellent/oil-repellent coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (vapor deposition). Hardcoats are a particularly preferred and required surface treatment. In addition, since the resin composition of the present invention has improved metal adhesion, it is preferable to apply vapor deposition treatment and plating treatment. The molded product thus provided with the metal layer can be used as an electromagnetic wave shield component, a conductive component, an antenna component and the like. Such parts are particularly preferably sheet-shaped and film-shaped.

Specific examples of molded articles in which the resin composition of the present invention is used are suitable for application to internal parts and housings of daily life materials/building materials/interior products, OA equipment/home electric appliances. Examples of these products include personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, drives for recording media (CD, CD-ROM, DVD, PD, FDD, etc.), parabolic antennas, electric motors. Tools, VTR, TV, iron, hair dryer, rice cooker, microwave oven, audio equipment, audio equipment such as audio/laser disk (registered trademark)/compact disk, lighting equipment, refrigerator, air conditioner, typewriter, word processor, suitcase Living goods such as cleaning tools and cleaning tools can be cited, and the resin product formed from the thermoplastic resin composition of the present invention can be used for various parts such as these housings. Other resin products include vehicle parts such as deflector parts, car navigation parts, car stereo parts, charging infrastructure parts, and automobile interior/exterior parts.

INDUSTRIAL APPLICABILITY The polycarbonate resin composition of the present invention has excellent thermal conductivity, heat resistance, flame retardancy, rigidity, and insulation properties, and therefore is not limited to outdoor/indoor use, but is also used for automobiles, infrastructure equipment, housing equipment, and building materials. It is widely useful in various fields such as household appliances, OA/EE applications, outdoor equipment applications, etc. Therefore, the industrial effect of the present invention is extremely large.

The present invention, which is considered to be the best by the present inventor, is a compilation of preferable ranges of the above-mentioned requirements. For example, representative examples thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described with reference to examples. The evaluation was carried out by the following method.
(Evaluation of heat conductive polycarbonate resin composition)
(I) Thermal conductivity A central part of a tensile dumbbell piece (according to ISO standard ISO527-1 and 2) obtained by the following method was cut into a predetermined size (100 mm x 10 mm x 3 mmt), and a laser flash device (NETZSCH) was used. The thermal diffusivity in the flow direction of the sample was measured using a Xenon laser flash analyzer LFA447 type manufactured by Co., Ltd., and the thermal conductivity was calculated.
(Ii) Deflection temperature under load Using an ISO bending test piece obtained by the following method, the deflection temperature under load was measured under a load of 1.80 MPa according to ISO 75-1 and 2.
(Iii) Flexural modulus The flexural modulus was measured according to ISO178 using the ISO bending test piece obtained by the following method.
(Iv) Flame retardancy Using a UL test piece obtained by the following method, a V (vertical flame retardancy test) test was performed at a thickness of 2.8 mm according to UL94.
(V) Extrudability The stability during extrusion was evaluated according to the following criteria.
Shoot-up does not occur during extrusion and the strands are stable: ○ Shoot-up does not occur during extrusion, but the strands are unstable and pelletization is difficult: △
Shoot-up occurs during extrusion, making pelletization difficult: ×
(Vi) Insulation The surface resistivity was measured according to IEC60250, and the evaluation was performed according to the following criteria.
Surface resistivity of 1×10 ¹⁵ or more: ○ Surface resistivity of less than 1×10 ¹⁵ : ×

[Examples 1 to 10, Comparative Examples 1 to 10]
A mixture having the composition shown in Tables 1 and 2 and composed of components other than the component B glass fiber was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing with a V type blender. The component B glass fiber was supplied from the second supply port using a side feeder. For extrusion, a bent twin-screw extruder with a diameter of 30 mmφ (TEX30α-38.5BW-3V, Japan Steel Works, Ltd.) was used, and the melt was kneaded at a screw rotation speed of 230 rpm, a discharge rate of 25 kg/h, and a vent vacuum degree of 3 kPa. And pellets were obtained. The extrusion temperature was 300° C. from the first supply port to the die portion. A part of the obtained pellets was dried at 120°C for 6 hours with a hot air circulation dryer, and then using an injection molding machine, a tensile dumbbell piece for evaluation at a cylinder temperature of 300°C and a mold temperature of 90°C. (ISO527-1 and 2 compliant), ISO bending test pieces (ISO178 and ISO179 compliant) and UL test pieces were molded.

The components represented by symbols in Tables 1 and 2 are as follows.
(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX (product name) manufactured by Teijin Ltd.)
A-2: Aromatic polycarbonate resin (polycarbonate resin pellets having a viscosity average molecular weight of 22,200 made from bisphenol A and phosgene by a conventional method, Panlite L-1225Y (product name) manufactured by Teijin Ltd.)
(B component)
B-1: Glass fiber (manufactured by Nitto Boseki Co., Ltd., CSG 3PE-455 (trade name), fiber diameter 13 μm, cut length 3 mm, urethane sizing agent)
(C component)
C-1: Boron nitride (HS (product name) manufactured by Dandong Chemical Engineering Institute, plate-like average particle diameter (D50) measured by laser diffraction/scattering method: 20 μm, tap density: 0.6 g/ml)
C-2: Boron Nitride (HN (product name) manufactured by Dandong Chemical Engineering Institute, plate-shaped average particle diameter (D50) measured by laser diffraction/scattering method: 10 μm, tap density: 0.3 g/ml)
C-3: Boron nitride (HSL (product name) manufactured by Dandong Chemical Engineering Institute, plate-shaped average particle diameter (D50) measured by laser diffraction/scattering method: 30 μm, tap density: 0.6 g/ml)
(D component)
D-1: Brominated flame retardant (Teijin Co., Ltd. Fireguard FG8500 (trade name))
(E component)
E-1: Fluorine-containing anti-dripping agent (Polyflon MPA FA500H (trade name) manufactured by Daikin Industries, Ltd.)
(F component)
F-1: Phosphate compound (TMP (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)

Claims (3)

(A) Polycarbonate resin (A component) 100 parts by weight, (B) glass fiber (B component) 20 to 60 parts by weight, (C) average particle diameter 15 to 28 μm, tap density 0.5 g/ml. 5 to 40 parts by weight of boron nitride (C component), 5 to 30 parts by weight of (D) brominated flame retardant (D component) and 0.1 to 5 parts by weight of (E) fluorine-containing anti-dripping agent (E component). A thermally conductive polycarbonate resin composition, characterized in that it contains a part. The heat conductive polycarbonate resin composition according to claim 1, which comprises 0.01 to 1 part by weight of the (F) phosphate compound (F component) with respect to 100 parts by weight of the component A. A molded article comprising the thermally conductive polycarbonate resin composition according to claim 1.