JP2021031544A - Thermally conductive polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition excellent in moldability, 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) 5-60 pts.wt. of talc (component C), (D) 5-30 pts.wt. of a bromine-based flame retardant (component D), (E) 0.1-5 pts.wt. of a fluorine-containing drip inhibitor (component E), (F) 5-50 pts.wt. of a liquid crystal polyester resin (component F), (G) 0.1-5 pts.wt. of an acid-modified olefin resin (component G), and (H) 0.1-5 pts.wt. of a silane coupling agent (component H).SELECTED DRAWING: None

Description

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

Polycarbonate resin is widely used in the fields of automobile interior and exterior parts, OA equipment, electrical and electronic equipment, etc. because it has excellent heat resistance, flame retardancy, and mechanical strength. In recent years, in order to efficiently dissipate the generated heat to the outside, a thermoplastic resin composition having excellent resin molding processability, heat resistance, flame retardancy, rigidity, and insulating property while improving the thermal conductivity of the polycarbonate resin. The demand for plastics is increasing. In particular, it is technically difficult to achieve both thermal conductivity and moldability.

As a method for further improving the thermal conductivity of these polymer compositions, a thermally conductive polymer material in which a carbon-based material having high thermal conductivity is filled in the polymer material has been proposed. For example, a method of adding graphitized carbon fibers to a polymer material (see Patent Documents 1 to 3) and a method of adding pitch-based carbon fibers and scaly graphite to a thermoplastic resin are known, but the insulating property is deteriorated and difficult. There were various problems such as a decrease in flammability, and the decrease in molding processability was particularly remarkable.

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

JP-A-2002-88250 JP-A-2002-339171 Japanese Unexamined Patent Publication No. 2003-112915 Japanese Unexamined Patent Publication No. 2010-195890 Japanese Unexamined Patent Publication No. 2008-239899 Japanese Unexamined Patent Publication No. 2008-270709 Japanese Unexamined Patent Publication No. 2011-12193 Japanese Unexamined Patent Publication No. 2012-188579 Japanese Unexamined Patent Publication No. 2013-203770

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

As a result of diligent studies to solve the above problems, the present inventor has found polycarbonate resin, glass fiber, talc, brominated flame retardant, fluorine-containing drip inhibitor, liquid crystal polyester resin, acid-modified olefin resin and silane coupling agent. We have found a method for obtaining a thermally conductive polycarbonate resin composition having excellent molding processability, thermal conductivity, heat resistance, flame retardancy, rigidity and insulating property and a molded product thereof by blending them in a ratio of characteristics, and have found the present invention. Has been completed.

According to the present invention, the above problems are (A) 100 parts by weight of polycarbonate resin (A component), (B) 20 to 60 parts by weight of glass fiber (B component), and (C) 5 to 5 parts by weight of talc (C component). 60 parts by weight, (D) brominated flame retardant (D component) 5 to 30 parts by weight, (E) fluorine-containing dripping inhibitor (E component) 0.1 to 5 parts by weight, (F) liquid crystal polyester resin (F component) ) 5 to 50 parts by weight, (G) acid-modified olefin resin (G component) 0.1 to 5 parts by weight, and (H) silane coupling agent (H component) 0.1 to 5 parts by weight. It is achieved by the heat conductive polycarbonate resin composition.

Hereinafter, the details of the present invention will be described.
(Component A: Polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a molten transesterification method, a solid phase 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 are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as 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) Pentan, 4,4'-(p-phenylenediisopropyridene) 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) ketone Hydroxyphenyl) esters, bis (4-hydroxy-3-methylphenyl) sulfides, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Be done. A preferable divalent phenol is a bis (4-hydroxyphenyl) alkane, and among them, bisphenol A is particularly preferable from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to the bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, a special polycarbonate produced by using other divalent phenols can be used as the A component.

For example, 4,4'-(m-phenylenediisopropyridene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis (4-hydroxy) as a part or all of the divalent phenol component. Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis (4-hydroxyphenyl) Polycarbonates (monopolymers or copolymers) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "BCF") have dimensions due to water absorption. Suitable for applications with particularly stringent requirements for change and morphological stability. It is preferable to use these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is the following copolymerized polycarbonates (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) and BCF in 100 mol% of the divalent phenol component constituting the polycarbonate. Copolymerized polycarbonate in an amount of 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, further preferably 60 to 85 mol%) and BCF in 100 mol% of the divalent phenol component constituting the polycarbonate. A copolymerized polycarbonate having a content of 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, further preferably 45 to 65 mol%) and Bis in 100 mol% of the divalent phenol component constituting the polycarbonate. -A copolymerized polycarbonate having a TMC of 20-80 mol% (more preferably 25-60 mol%, even more preferably 35-55 mol%).

These special polycarbonates may be used alone or in admixture of two or more. Further, these can also be used by mixing them with a widely 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, JP-A-2002-117580 and the like. ing.

Among the various polycarbonates described above, those in which the copolymerization composition and the like are adjusted so that the water absorption rate and Tg (glass transition temperature) are within the following ranges have good hydrolysis resistance of the polymer itself and. Since it is remarkably excellent in low warpage after molding, it is particularly suitable in fields 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) Tg of 160 to 250 ° C. Polycarbonate preferably at 170 to 230 ° C. and having a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

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

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

In producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc. are used. You may use it. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. , A copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including an alicyclic type), and a polyester carbonate resin copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. Further, it may 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 polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) hepten-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) Etan, 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, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 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 structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from divalent phenol and the structural unit derived from such a polyfunctional aromatic compound. It is 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, still more preferably 0.05 to 0.8 mol%.

Further, particularly in the case of the molten transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably 100 mol% in total including the structural unit derived from divalent phenol. It is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, still more preferably 0.01 to 0.8 mol%. The ratio of such a branched structure ^{can be calculated by 1 1} H-NMR measurement.

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

Reaction formats such as the interfacial polymerization method, the molten transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the methods for producing the polycarbonate resin of the present invention, are described in various documents and patent publications. This 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 even more preferably 18,000. ~ 26,000. A polycarbonate resin having a viscosity average molecular weight of less than 12,500 may not have good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight of more than 32,000 may be inferior in flame retardancy.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution of 0.7 g of polycarbonate in 100 ml of methylene chloride at 20 ° C. _{for the specific viscosity (η SP) calculated by the following formula.}
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight M is calculated by the following formula.
η _SP / c = [η] + 0.45 × ^{[η] 2} c (however, [η] is the ultimate 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 the weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. The solvent in the resulting solution is then removed. The solid after removing the solvent is sufficiently dried to obtain a solid having a component that dissolves in methylene chloride. From a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is obtained in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described 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.

[In the above general formula (1), R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 18 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 2 to 10 carbon atoms alkenyl groups, 6 to 14 carbon atoms aryl groups, 6 to 14 carbon atoms aryloxy groups, carbon atoms Represents a group selected from the group consisting of an arylyl group having a number of 7 to 20, an arylyloxy group having a carbon atom number of 7 to 20, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2). ]

[In the above general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an alkoxy group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkoxy group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of ~ 14, an aryloxy group having 6 to 10 carbon atoms, an alkoxy group having 7 to 20 carbon atoms, an alkoxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from the group, and if there are a plurality of groups, they may be the same or different, and g is an integer of 1 to 10 and h is an integer of 4 to 7. ]

[In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups 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 divalent phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and the like. 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'-dihydroxydiphenyl ether, 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'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 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, 3-adamantandiyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantan and the like can be mentioned.

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, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used individually or in combination of 2 or more types.

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

The hydroxyaryl-terminated polydiorganosiloxane (II) prescribes phenols having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol. It is easily produced by subjecting the terminal of a polysiloxane chain having the degree of polymerization of the above to a hydrosilylation reaction. Of these, (2-allylphenol) -terminal polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminal polydiorganosiloxane are preferable, and (2-allylphenol) -terminal polydimethylsiloxane and (2-methoxy-4) are particularly preferable. -Allylphenol) -terminated polydimethylsiloxane is preferred. 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 low temperature impact property during high temperature molding. If the upper limit of such a suitable range is exceeded, the amount of outgas generated during high-temperature molding is large, and the low-temperature impact resistance may be inferior.

Further, in order to realize high impact resistance, the degree of polymerization (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The degree of polymerization of diorganosiloxane (p + q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of the suitable range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited, and when the upper limit of the suitable range is exceeded, poor appearance appears.

The content of polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer used in 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 the suitable range, impact resistance and flame retardancy are excellent, and below the upper limit of the suitable range, a stable appearance that is not easily affected by molding conditions can be easily obtained. The degree of polymerization of polydiorganosiloxane and the content of polydiorganosiloxane can be calculated by 1H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

Further, as long as it does not interfere with the present invention, a comonomer other than the above divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) is added in a range 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 in advance by a reaction of a dihydric phenol (I) and a carbonic acid ester-forming compound in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. To do.

In producing the oligomer of divalent phenol (I), the entire amount of divalent phenol (I) used in the method of the present invention may be made into an oligomer at a time, or a part thereof may be used as a post-added monomer at the subsequent interface. It may be added as a reaction raw material to the polycondensation reaction. The post-added monomer is added to allow the polycondensation reaction in the subsequent stage to proceed rapidly, and it is not necessary to add it when it is not necessary.

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

The ratio 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 preferably adopted.

As the acid binder, for example, 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 are used. Similarly to the above, the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of divalent phenol (I) used for forming the oligomer (usually 1 mol corresponds to 2 equivalents). ..

As the solvent, a solvent inert to various reactions such as those used for producing a known 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. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The reaction pressure for forming the oligomer is not particularly limited and may be normal pressure, pressurization, 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 during polymerization, so it is desirable to cool with water or ice. The reaction time depends on other conditions and cannot be unconditionally defined, but is usually 0.2 to 10 hours. The pH range of the oligomer-forming reaction is the same as the known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

In the present invention, after obtaining a mixed solution containing an oligomer of divalent phenol (I) having a terminal chloroformate group, the molecular weight distribution (Mw / Mn) is up to 3 or less while stirring the mixed solution. The highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) is added to the divalent phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are polycondensed. Thereby, a polycarbonate-polydiorganosiloxane copolymer is obtained.

(In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, and R ⁹ and R ¹⁰ are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, and alkoxy groups 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.)

In carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid binder, for example, 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 are used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the divalent phenol (I) as described above is added as a post-addition monomer to this reaction step, the post-addition amount is two. It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of the valent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mol corresponds to 2 equivalents).

Polycondensation by the intercondensation polycondensation reaction between the oligomer of divalent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

In such a polymerization reaction, a terminal terminator 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 phenols, p-tert-butylphenols, p-cumylphenols, tribromophenols, etc., long-chain alkylphenols and aliphatic carboxylic acids Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenyl alkyl acid ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, with respect to 100 mol of all the divalent phenolic compounds used, and it is naturally possible to use two or more kinds of compounds in combination. is there.

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

The reaction time of such a 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 divalent phenolic compound to obtain a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate-polydiorganosiloxane copolymer resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl). ) Hepten-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, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxy) Examples thereof include phenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 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, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. It is 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 1 1} H-NMR measurement.

The reaction pressure can be reduced pressure, normal pressure, or pressurized pressure, but usually, normal pressure or the self-pressure of the reaction system can be preferably used. The reaction temperature is selected from the range of -20 to 50 ° C., and in many cases, heat is generated during polymerization, so it is desirable to cool with water or ice. The reaction time varies depending on other conditions such as the reaction temperature and cannot be unconditionally specified, but 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, cross-linking treatment, partial decomposition treatment, etc.) to reduce the desired amount. 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 subjecting various post-treatments such as a known separation and purification method.

The average size of the polydiorganosiloxane domain 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, still more preferably 5 to 25 nm. If it is less than the lower limit of such a suitable range, impact resistance and flame retardancy may not be sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, impact resistance may not be stably exhibited. This provides a polycarbonate resin composition having excellent impact resistance and appearance.

The average domain size and standardized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded product 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, if there are regions having different electron densities having a size of about 1 to 100 nm in a substance, diffuse scattering of X-rays is measured by the difference in electron densities. The particle size of the object to be measured 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 the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. The average size and particle size distribution (standardized dispersion) of the polydiorganosiloxane domain are obtained by performing a simulation using commercially available analysis software from the temporary particle size and the temporary particle size distribution model. According to the small-angle X-ray scattering method, the average size and particle size distribution of polydiorganosiloxane domains dispersed in a matrix of polycarbonate polymer, which cannot be measured accurately by observation with a transmission electron microscope, can be accurately, easily, and reproducibly measured. Can be measured. The average domain size means the number average of individual domain sizes. Normalized 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 with the average domain size, and is represented by the following formula (1).

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 are to measure a thickness of 1.0 mm of a three-stage plate produced by the method described in Examples by such a small angle X-ray scattering method. The measured value 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 the glass fiber, and is generally used as a reinforcing material for synthetic resins. The glass fiber is preferably a glass fiber having an average fiber length of 30 to 900 μm in the resin composition and an average L / D of 10 to 300. Here, L is the average length of the glass fiber, D is the average diameter in the case of the glass fiber having a round cross section, and is the average value of the major axis in the cross section in the case of the flat cross section glass fiber. The average fiber length is more preferably 30 to 500 μm, and the L / D is more preferably 10 to 200. If the L / D is less than 10, heat resistance may not be exhibited, and if it is more than 300, the appearance and moldability of the molded product may be deteriorated, which is not preferable. Further, if the average fiber length is smaller than 30 μm, heat resistance may not be exhibited, and if it is larger than 900 μm, the appearance and moldability of the molded product may be deteriorated. Further, the diameter of the glass fiber does not need to be particularly limited, but is preferably in the range of 3 to 50 μm. 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 flat cross section is more preferable.

The glass composition of the glass fiber is not particularly limited as various glass compositions typified by A glass, C glass, T glass, NCR glass, HME glass, E glass and the like are applied.

The content of the B component is 20 to 60 parts by weight, preferably 20 to 55 parts by weight, and more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the A component. When the content of the B component is less than 20 parts by weight, the heat resistance and rigidity are insufficient, and the flame retardancy is also lowered. On the other hand, if the amount is more than 60 parts by weight, the extrusion processability is lowered.

(C component: talc)
Talc used in this invention is referred to as hydrated magnesium silicate, a typical chemical formula thereof is represented by _{4SiO 2 · 3MgO · H 2 O} . The chemical composition varies slightly depending on the production area, but is generally SiO ₂ 64.4%, MgO 31.8%, and ignition loss (moisture) 3.8%.

The average particle size of the talc used in the present invention is preferably 5 μm or less. More preferably, the average particle size is 3 μm or less, and particularly preferably 2 μm or less. As the lower limit, 0.05 μm can be mentioned. Here, the average particle size of talc refers to D50 (median diameter of particle size distribution) measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods. Specific examples of the device for performing such measurement include Sedigrap 5100 manufactured by Micromeritix.

Talc is preferably used in granulated form. As a granulation method, there are cases where a binder is used and cases where a binder is substantially not used. Those that do not use a binder are more preferable. As a granulation method when a binder is not used, a degassing compression method (for example, a method of roller compression with a briquetting machine while degassing in a vacuum state), and a rolling granulation method or a cohesive granulation method. And so on.

The content of the C component is 5 to 60 parts by weight, preferably 5 to 55 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the A component. When the content of the C component is less than 5 parts by weight, the rigidity, thermal conductivity and heat resistance are low, and when it exceeds 60 parts by weight, the extrusion processability is lowered.

(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 in which a part or all of the terminal glycidyl group thereof is blocked. Examples thereof include brominated diphenyl ether flame retardants, brominated imide flame retardants, and brominated polystyrene flame retardants.

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, tetrabrombisphenol S, tris (2,3-dibromopropyl-1) Isocyanurate, tribromophenol, tribromophenylallyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabrombisphenol A, tetrabrombisphenol A derivative, tetrabrombisphenol A-epoxy oligomer or polymer, tetrabrom Bisphenol A-carbonate oligomers or polymers, brominated epoxy resins such as brominated phenol novolac epoxy, tetrabrom bisphenol A-bis (2-hydroxydiethyl ether), tetrabrom bisphenol A-bis (2,3-dibromopropyl ether), Tetrabrombisphenol A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneopentyl glycol , Pentabromobenzyl polyacrylate, dibromocredyl glycidyl ether, N, N'-ethylene-bis-tetrabromophthalimide and the like. Among them, tetrabrombisphenol A-epoxy oligomer, tetrabrombisphenol A-carbonate oligomer, brominated epoxy resin and the like can be mentioned.

As the brominated flame retardant of the present invention, brominated polycarbonate (including oligomers) 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 (4) is at least 60 mol%, preferably at least 80 mol% of all the structural units, and particularly preferably substantially the following general formula. It is a brominated polycarbonate compound composed of the structural unit represented by (4).

(In the formula (4), 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 such formula (4), preferably R is a methylene group, an ethylene group, an isopropylidene group, -SO 2 - shows a _particularly preferably isopropylidene group.

The brominated polycarbonate has a small amount of residual chlorohomate group terminals, and the amount of terminal chlorine is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. To determine the amount of terminal chlorine, dissolve the sample in methylene chloride, add 4- (p-nitrobenzyl) pyridine to react with terminal chlorine (terminal chlorohomet), and use this as an ultraviolet visible spectrophotometer (U, manufactured by Hitachi, Ltd.). It can be obtained by measuring according to -3200). 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 molding processability is provided.

Further, the brominated polycarbonate preferably has few remaining hydroxyl group terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, and more preferably 0.0003 mol or less, with respect to 1 mol of the constituent 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 1} H-NMR method. Such an 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 in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate was 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 with respect 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 extrusion processability is lowered.

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

Polytetrafluoroethylene (fibrillated PTFE) having a fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to bond PTFE to each other to form a fibrous form due to an external action such as shearing force. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. Such a number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in Japanese Patent Application Laid-Open No. 6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in such publication in ^{the range of 10 7} to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

As the PTFE, not only a solid form but also an aqueous dispersion form can be used. Further, the 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 another resin in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in Japanese Patent Application Laid-Open No. 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 of Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Chemical Industry Co., Ltd. Commercially available aqueous dispersions of fibrillated PTFE include Fluon AD-1, AD-936 manufactured by Asahi IC Eye Fluoropolymers Co., Ltd., Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., and Mitsui. Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd. can be mentioned as a representative.

Examples of the fibrillated PTFE in the mixed form include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coaggregating mixture (Japanese Patent Laid-Open No. 60-258263). (A method described in Japanese Patent Application Laid-Open No. 63-154744, etc.), (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). The method described), (3) A method of uniformly mixing an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution and simultaneously removing each medium from such a mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 06-220210). 08-188653, etc.), (4) A method for polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (Japanese Patent Laid-Open No. 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-based monomer is further polymerized in the mixed dispersion to obtain a mixture (Japanese Patent Laid-Open No. 11-). The one obtained by the method described in No. 29679 or the like) can be used. Commercially available products of these mixed forms of fibrillated PTFE include "Metabrene A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals, and "Blendex B449" (trade name) manufactured by Pacific Interchem Corporation. "POLY TS AD001" (trade name) and the like are exemplified.

Since the fibrillated PTFE does not reduce the mechanical strength, it is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the fibrillated PTFE in the mixed form is advantageous. Further, a method of directly supplying the aqueous dispersion in the form of a melt-kneader to the 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 with respect 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: liquid crystal polyester resin)
The liquid crystal polyester resin used as the F component of the present invention is a thermotropic liquid crystal polyester resin, and has a property of arranging polymer molecular chains in a certain direction in a molten state. The form of such an arrangement state may be any form of nematic type, smetic type, cholesteric type, and discotic type, and may exhibit two or more kinds of forms. Further, the structure of the liquid crystal polyester resin may be any of a main chain type, a side chain type, a rigid main chain bent side chain type, and the like, but the main chain type liquid crystal polyester resin is preferable.

The form of the arrangement state, that is, the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element. More specifically, the anisotropic molten phase can be confirmed by observing the molten sample placed on the Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. The polymer of the present invention transmits polarized light and is optically anisotropy when inspected between orthogonal polarizers, even in a molten and resting state.

The heat resistance of the liquid crystal polyester resin may be in any range, but the one that melts at a portion close to the processing temperature of the polycarbonate resin to form a liquid crystal phase is suitable. In this respect, it is more preferable that the deflection temperature under load of the liquid crystal polyester resin is 150 to 280 ° C., preferably 180 to 250 ° C. Such a liquid crystal polyester resin belongs to the so-called heat resistance category type II. When it has such heat resistance, it is excellent in molding processability as compared with type I having higher heat resistance, and good flame retardancy is achieved as compared with type III having lower heat resistance.

The liquid crystal polyester resin used as the F component of the present invention preferably contains a polyester unit and a polyesteramide unit, preferably an aromatic polyester resin and an aromatic polyesteramide resin, and contains an aromatic polyester unit and an aromatic polyesteramide unit. A liquid crystal polyester resin partially contained in the same molecular chain is also a preferable example.

Particularly preferably, a total aromatic polyester resin or a total aromatic polyesteramide having as a unit component derived from one or more compounds selected from the group of aromatic hydroxycarboxylic acid, aromatic hydroxyamine, and aromatic diamine. It is a resin. More specifically, 1) a liquid crystal polyester resin synthesized mainly from one or more compounds selected from the group consisting mainly of aromatic hydroxycarboxylic acids and derivatives thereof, 2) mainly a) aromatic hydroxycarboxylic acids and One or more compounds selected from the group consisting of the derivatives, b) One or more compounds selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and c) A liquid crystal polyester resin synthesized from one or more compounds selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof, 3) mainly a) aromatic hydroxycarboxylic acids and their derivatives. One or more compounds selected from the group consisting of derivatives, b) one or more compounds selected from the group consisting of aromatic hydroxyamines, aromatic diamines and derivatives thereof, and c) aromatic dicarboxylic acids. Liquid crystal polyesteramide resin synthesized from one or more compounds selected from the group consisting of acids, alicyclic dicarboxylic acids and derivatives thereof, 4) mainly a) from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof. One or more compounds selected, b) One or more compounds selected from the group consisting of aromatic hydroxyamines, aromatic diamines and derivatives thereof, c) Aromatic dicarboxylic acids, alicyclic dicarboxylic acids One or more compounds selected from the group consisting of acids and derivatives thereof, and d) one or more compounds selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof. Examples thereof include a liquid crystal polyesteramide resin synthesized from a compound. 1) A liquid crystal polyester resin synthesized mainly from one or more compounds selected from the group consisting mainly of aromatic hydroxycarboxylic acids and derivatives thereof is preferable.

Further, a molecular weight adjusting agent may be used in combination with the above-mentioned constituent components, if necessary.

Preferred examples of specific compounds used in the synthesis of the liquid crystal polyester resin used as the F component of the present invention are 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy. Naphthalene compounds such as -2-naphthoic acid, biphenyl compounds such as 4,4'-diphenyldicarboxylic acid and 4,4'-dihydroxybiphenyl, p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p-phenylene. Para-substituted benzene compounds such as diamine and their nuclear-substituted benzene compounds (substituents are selected from chlorine, bromine, methyl, phenyl, 1-phenylethyl), meta-substituted benzene compounds such as isophthalic acid and resorcin, Further, it is a compound represented by the following general formula [5], [6] or [7]. Of these, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are particularly preferable, and a liquid crystal polyester resin obtained by mixing both is preferable. The ratio of both is preferably in the range of 90 to 50 mol% for the former, more preferably in the range of 80 to 65 mol%, and more preferably in the range of 10 to 50 mol% for the latter, and more preferably in the range of 20 to 35 mol%.

(However, Y is a group selected from the group consisting of an alkylene group having 1 to 4 carbon atoms and an alkylidene group, -O-, -SO-, -SO _2- , -S-, and -CO-, and Z is a group. A group selected from the group consisting of − (CH ₂ ) _n − (n = 1-4) and −O (CH ₂ ) _{n O− (n = 1-4).}
Further, in the liquid crystal polyester resin used as the B component of the present invention, in addition to the above-mentioned constituent components, a polyalkylene terephthalate-derived unit that does not partially exhibit an anisotropic molten phase may be present in the same molecular chain. .. In this case, the alkylene group has 2 to 4 carbon atoms.

The content of the F component is 5 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the A component. When the content of the F component is less than 5 parts by weight, the molding processability is lowered. If it exceeds 50 parts by weight, flame retardancy, heat resistance and thermal conductivity are lowered.

(G component: acid-modified olefin resin)
As the acid-modified polyolefin resin used as the G component of the present invention, an olefin wax having a carboxyl group and / or a derivative group thereof is preferably used. Examples of the carboxyl group derivative include a carboxylic acid anhydride group, a metal salt of a carboxylic acid, an alkyl ester of a carboxylic acid, an aryl ester and the like. The carboxyl group and / or its derivative group may be bonded to any portion of the olefin wax, and the concentration thereof is not particularly limited, but the range is 0.1 to 6 meq / g per 1 g of the olefin wax. preferable. If it is less than 0.1 meq / g, the improvement of rigidity and impact resistance may be insufficient, and if it is more than 6 meq / g, the thermal stability of the olefin wax itself may be deteriorated, which is not preferable.

Commercially available products of such olefin wax include, for example, Diacarna-DC30M (manufactured by Mitsubishi Kasei Co., Ltd.), Licorub CE 2 TP (manufactured by Clariant Co., Ltd.), high wax acid treatment type 2203A, 1105A (Mitsui Petrochemical Industry Co., Ltd.) (Manufactured by Co., Ltd.), EXL3808 manufactured by Dow Chemical Co., Ltd., paraffin oxide (manufactured by Nippon Seiro Co., Ltd.) and the like. In the present invention, the olefin wax can be used alone or as a mixture of two or more kinds.

The content of the G component is 0.1 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the A component. If the content of the G component 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.

(H component: silane coupling agent)
The silane coupling agent used as the H component of the present invention is, for example, an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group and a ureido group. Can be mentioned. Specific examples thereof include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxycisilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxycisilane, γ- (2-ureidoethyl) amino Ureido group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyl ethyldimethoxysilane, γ-isocyanatopropyl ethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ Amino group-containing alkoxysilane compounds such as-(2-aminoethyl) aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Examples include compounds, among which epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxycisilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Γ-Ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxycisilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane and other ureido group-containing alkoxysilane compounds, γ-isocyanatopropyltriethoxysilane, γ -Isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanato An isocyanato group-containing alkoxysilane compound such as propyltrichlorosilane is preferable. Particularly preferred are epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysisilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. ..

The content of the H component is 0.1 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the A component. When the content of the H component is less than 0.1 parts by weight, the flame retardancy is lowered, and when it is 5 parts by weight or more, the extrusion processability is lowered.

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

(Manufacturing of resin composition)
Any method is adopted for preparing the resin composition of the present invention. For example, a method of premixing A component, B component, C component, D component, E component, F component, G component, H component and optionally other components, and then melt-kneading and pelletizing can be mentioned. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the premixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like, if necessary. As another method, for example, when a substance having a powder form is included, a masterbatch of the additive diluted with the powder is produced by blending a part of the powder and the additive to be blended, and the masterbatch is used. There is a way to do it. After pre-mixing, melt-kneading is performed with a melt-kneader typified by a bent twin-screw extruder, and pelletization is performed with equipment such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant heat stirring vessel, but a vent type twin-screw extruder is preferable.

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

As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign substances and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder 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 (disc filter, etc.) and the like.

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

The resin extruded as described above is directly cut and pelletized, or the strands are cut with a pelletizer after forming the strands and pelletized. When it is necessary to reduce the influence of external dust and 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 discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. , And bubbles (vacuum bubbles) generated inside the strands and pellets can be appropriately reduced. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more 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, still more preferably 2.5 to 3.5 mm.

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

Further, the resin composition of the present invention can also be used in the form of various deformed extrusion-molded products, sheets, films and the like by extrusion molding. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be made into a molded product by rotary molding, blow molding or the like.

Molded products using the resin composition of the present invention include various electronic / electrical equipment parts, camera parts, OA equipment parts, precision mechanical parts, mechanical parts, vehicle parts (particularly interior / exterior parts for vehicles), and other agricultural materials. It is useful for various purposes such as transport containers, play equipment, and miscellaneous goods, and its industrial effect is exceptional.

Further, the molded product made of the resin composition of the present invention can be subjected to various surface treatments. 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 ordinary thermoplastic resins can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metallizing (evaporation, etc.). Hard coat is a particularly preferred and required surface treatment. In addition, since the resin composition of the present invention has improved metal adhesion, it is also preferable to apply a vapor deposition treatment and a plating treatment. The molded product provided with the metal layer in this way can be used for an electromagnetic wave shielding component, a conductive component, an antenna component, and the like. Such parts are particularly preferably in the form of sheets and films.

Specific examples of molded products in which the resin composition of the present invention is used are suitable for application to internal parts and housings of living materials, building materials, interior goods, OA equipment, home appliances, and the like. These products include, for example, personal computers, laptop computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording medium (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs (registered trademarks) / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, suitcases And living materials such as cleaning tools, and resin products formed from the thermoplastic resin composition of the present invention can be used for various parts such as these housings. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, car stereo parts, charging infrastructure parts, and automobile interior / exterior parts.

Since the polycarbonate resin composition of the present invention is excellent in molding processability, thermal conductivity, heat resistance, flame retardancy, rigidity and insulation, it is not limited to outdoor / indoor use, but also for automobile use, infrastructure equipment use, and housing equipment. It is widely useful in various fields such as applications, building materials, living materials, OA / EE, outdoor equipment, and so on. Therefore, the industrial effect of the present invention is extremely large.

The form of the invention that the present inventor considers to be the best at present is a collection of preferable ranges of each of the above requirements. For example, a representative example 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 below with reference to examples. The evaluation was carried out by the following method.
(Evaluation of Thermally Conductive Polycarbonate Resin Composition)
(I) Thermal conductivity The central part of the tensile dumbbell piece (ISO standard ISO527-1 and 2 compliant) obtained by the following method is cut to a predetermined size (100 mm × 10 mm × 3 mmt), and a laser flash device (NETZSCH) is used. The thermal diffusivity in the flow direction of the sample was measured using a Xenon laser flash analyzer (LFA447 type) manufactured by the same company, and the thermal conductivity was calculated.
(Ii) Deflection temperature under load Using the 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 ISO75-1 and ISO2.
(Iii) Bending elastic modulus Using an ISO bending test piece obtained by the following method, the bending elastic modulus was measured according to ISO178.
(Iv) Flame Retardance Using the UL test piece obtained by the following method, a V test (vertical flame retardancy test) at a thickness of 2.8 mm was carried out according to UL94.
(V) Extrusion workability The stability during extrusion was evaluated according to the following criteria.
No shoot-up occurs during extrusion and the strands are stable. : 〇 Shoot-up does not occur during extrusion, but the strands are unstable and pelletization is difficult. : △
Shoot-up occurs during extrusion and pelletization is not possible. : ×
(Vi) Insulation The surface resistivity was measured according to IEC60250, and the evaluation was carried out according to the following criteria.
Surface resistivity is 1 × 10 ¹⁵ or more: 〇 Surface resistivity is 1 × 10 less than ^{15: ×}
(Vii) Moldability Using a spiral flow mold having a flow path thickness of 3 mmt and a flow path width of 8 mmt, the flow length was measured when the cylinder temperature was 300 ° C., the mold temperature was 90 ° C., and the injection pressure was 100 MPa.

[Examples 1 to 14, Comparative Examples 1 to 14]
A mixture consisting of the components shown in Tables 1 and 2 excluding the glass fiber of the component B was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. The glass fiber of the component B was supplied from the second supply port using a side feeder. For extrusion, a vent type twin-screw extruder with a diameter of 30 mmφ (Japan Steel Works, Ltd. TEX30α-38.5BW-3V) is used, and melt kneading is performed at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum degree of 3 kPa. And obtained pellets. The extrusion temperature was 300 ° C. from the first supply port to the die portion. A part of the obtained pellets is dried at 120 ° C. for 6 hours in a hot air circulation type dryer, and then a tensile dumbbell piece for evaluation is used at a cylinder temperature of 300 ° C. and a mold temperature of 90 ° C. using an injection molding machine. (ISO 527-1 and 2 compliant), ISO bending test pieces (ISO 178 and ISO 179 compliant) and UL test pieces were molded.

The components of the symbolic notation in Tables 1 and 2 are as follows.
(Component A)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder with 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 Limited)
A-2: Aromatic polycarbonate resin (polycarbonate resin pellets with a viscosity average molecular weight of 22,200 made from bisphenol A and phosgene by a conventional method, Panlite L-1225Y manufactured by Teijin Limited (product name))
(B component)
B-1: Glass fiber (CSG 3PE-455 (trade name) manufactured by Nitto Boseki Co., Ltd., fiber diameter 13 μm, cut length 3 mm, urethane-based sizing agent)
(C component)
C-1: Talc (Victory Light TK-RC (trade name) manufactured by Katsumitsuyama Mining Co., Ltd.)
(D component)
D-1: Brominated flame retardant (Fireguard FG8500 (trade name) manufactured by Teijin Limited)
(E component)
E-1: Fluorine-containing dripping inhibitor (Polyflon MPA FA500H (trade name) manufactured by Daikin Industries, Ltd.)
(F component)
F-1: Liquid crystal polyester resin (manufactured by Polyplastics Co., Ltd .: Vectra A-950 (trade name))
(G component)
G-1: Acid-modified olefin resin (Diacarna 30 (trade name) manufactured by Mitsubishi Chemical Corporation)
(H component)
H-1: Silane coupling agent (KBM-3103 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.)

Claims (2)

(A) Polycarbonate resin (A component) 100 parts by weight, (B) glass fiber (B component) 20 to 60 parts by weight, (C) talc (C component) 5 to 60 parts by weight, (D) bromine-based 5 to 30 parts by weight of flame retardant (D component), (E) 0.1 to 5 parts by weight of fluorine-containing dripping inhibitor (E component), (F) 5 to 50 parts by weight of liquid crystal polyester resin (F component), (G) A thermally conductive polycarbonate resin composition containing 0.1 to 5 parts by weight of an acid-modified olefin resin (G component) and 0.1 to 5 parts by weight of a (H) silane coupling agent (H component). .. A molded product comprising the thermally conductive polycarbonate resin composition according to claim 1.