JP2023083765A - Thermoplastic resin composition and composite molding comprising metal molding and resin molding joined together - Google Patents

Abstract

To provide a thermoplastic resin composition that has excellent adhesion to metal, is less prone to a deterioration of bonding strength after a heat cycle test, and has excellent durability.SOLUTION: A thermoplastic resin composition is for producing a resin molding in a composite molding, which comprises the resin molding joined to a metal molding, the thermoplastic resin composition comprising (A) a thermoplastic resin (A component) and (B) expanded graphite (B component) of 1-80 pts.wt. relative to the A component 100 pts.wt.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition suitable for forming a composite molded article in which a metal molded article and a resin molded article are joined, and a composite molded article in which a metal molded article and a resin molded article are joined. More particularly, the present invention relates to a thermoplastic resin composition having excellent adhesion to metals, less reduction in bonding strength after a heat cycle test and excellent durability, and a composite molded article in which a metal molded article and a resin molded article are joined.

Metal materials used in various fields such as automobiles, electrics, and electronics are sometimes replaced with resin molded products from the viewpoint of weight reduction of various parts, but all metal parts are replaced with resin. It is often difficult to do so. In such a case, it is conceivable to manufacture a new composite part by joining and integrating a metal molded body and a resin molded body. There is a demand for a technology capable of joining and integrating with high joining strength. Patent Document 1 describes laser processing of a metal surface for bonding with a different material (resin), which includes a step of laser scanning the metal surface in one scanning direction and a step of laser scanning in the scanning direction crossing it. A method invention is described. As for the heterogeneous material, a thermoplastic resin to which glass fiber is added is also described. Patent Document 2 discloses that a composite molded body of polycarbonate having a specific structure and metal has high bonding strength. Patent Documents 3 and 4 indicate that the bonding strength between the metal molded body and the resin molded body is high. It describes a mixture of fibers, inorganic fibers, metal fibers, and organic fibers. However, all of these are still inadequate for adhesion between metal and resin under environmental temperature changes expected in actual use.

Japanese Patent No. 4020957 JP 2020-066652 A JP 2013-52669 A JP 2014-18995 A

An object of the present invention is to provide a thermoplastic resin composition which has excellent adhesion to metals, little reduction in bonding strength after a heat cycle test, and excellent durability, and a resin-metal composite molded article formed therefrom.

The present inventors have made intensive studies to solve such problems, and found that a resin molded article formed from a thermoplastic resin composition obtained by blending an appropriate amount of graphite that has been subjected to expansion treatment to a thermoplastic resin. To obtain a thermoplastic resin composition having excellent adhesion between a resin molded body and a metal molded body, less decrease in bonding strength after a heat cycle test, and excellent durability in a composite molded body in which the metal molded body is joined. The present invention was achieved by discovering that

The present invention will be specifically described below.

<A component: thermoplastic resin>
The thermoplastic synthetic resin is not particularly limited, and examples thereof include urethane resin, chlorotrifluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, Vinylidene resin, ethylene-tetrafluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, vinyl chloride resin, nylidene chloride resin, polyethylene, polypropylene, chlorinated polyolefin, water-crosslinked polyolefin, modified polyolefin, ethylene-vinyl acetate copolymer coalescence, ethylene-ethyl acrylate copolymer, polystyrene, ABS resin, polyamide, methacrylic resin, polyacetal, polycarbonate resin, cellulosic resin, polyvinyl alcohol, polyurethane elastomer, polyimide, polyetherimide, polyamideimide, ionomer resin, polyphenylene oxide, Examples include methylpentene polymer, polyallyl sulfone, polyallyl ether, polyether ketone, polyphenylene sulfide, polysulfone, wholly aromatic polyester, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, and blends of various high molecular substances. can do. Among these, polycarbonate resins are preferred from the viewpoint of good mechanical properties.

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

Representative examples of dihydric phenols used herein include 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) 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. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, of which bisphenol A is particularly preferred from the standpoint of impact resistance and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, special polycarbonate resins produced using other dihydric phenols can be used as component A. For example, as part or all of the dihydric phenol component, 4,4′-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis(4-hydroxy phenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl) Polycarbonate resin (homopolymer or copolymer) using fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as “BCF”) Suitable for applications with particularly strict requirements for dimensional change and shape stability. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is the following copolymerized polycarbonate resins (1) to (3). is.

(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, and A copolymer polycarbonate resin having a BCF 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%, still more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, and A copolymer polycarbonate resin having a BCF 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%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, and A copolymer polycarbonate resin containing 20 to 80 mol % (more preferably 25 to 60 mol %, still more preferably 35 to 55 mol %) of Bis-TMC.

These special polycarbonate resins may be used alone or in combination of two or more. Moreover, these can also be used by mixing with a widely used bisphenol A type polycarbonate resin. The manufacturing method and characteristics of these special polycarbonate resins are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435 and JP-A-2002-117580. It is

Among the various polycarbonate resins described above, those having the water absorption rate and Tg (glass transition temperature) within the following range by adjusting the copolymer composition etc. have good hydrolysis resistance of the polymer itself, In addition, since it is remarkably excellent in low warpage properties after molding, it is particularly suitable in fields where shape stability is required.
(i) a polycarbonate resin having a water absorption 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 , preferably 170 to 230° C., and 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 the polycarbonate resin is obtained by measuring the water content after immersing a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in water at 23 ° C. for 24 hours in accordance with ISO62-1980. is. Further, Tg (glass transition temperature) is a value determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

Carbonate precursors include carbonyl halides, diesters of carbonic acid and haloformates, and specific examples include phosgene, diphenyl carbonate and dihaloformates of dihydric phenols.

In producing a polycarbonate resin by interfacial polymerization of the dihydric phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, an antioxidant for preventing oxidation of the dihydric phenol, and the like are added. may be used. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. , copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Moreover, the mixture which mixed 2 or more types of obtained polycarbonate resin may be sufficient.

The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)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-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Structural units derived from a polyfunctional aromatic compound in the branched polycarbonate resin preferably account for 100 mol% of the total of structural units derived from a dihydric phenol and structural units derived from such a polyfunctional aromatic compound. is 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, still more preferably 0.05 to 0.8 mol %. In addition, particularly in the case of the melt transesterification method, branched structural units may occur as a side reaction. 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 branched structures can be calculated by ¹ H-NMR measurement.

Aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as are preferably exemplified. Alicyclic diols are more suitable as bifunctional alcohols, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of a cyclic carbonate compound, which are methods for producing the polycarbonate resin of the present invention, can be found in various literatures and patent publications. It is a well-known method in

In producing the thermoplastic resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ , more preferably 2.0×10 ⁴ to 3.5×10 ⁴ , more preferably 2.2×10 ⁴ to 3.0×10 ⁴ . Polycarbonate resins having a viscosity-average molecular weight of less than 1.8×10 ⁴ may not provide good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity-average molecular weight exceeding 4.0×10 ⁴ is inferior in versatility due to poor fluidity during injection molding.

The polycarbonate resin may be obtained by mixing substances having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity-average molecular weight exceeding the above range (5×10 ⁴ ) has improved entropy elasticity. As a result, good moldability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in moldability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, component A is a polycarbonate resin having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ (component A-1-1) and an aromatic polycarbonate having a viscosity average molecular weight of 1×10 ⁴ to 3×10 ⁴ . A polycarbonate resin (component A-1) consisting of a resin (component A-1-2) and having a viscosity average molecular weight of 1.6×10 ⁴ to 3.5×10 ⁴ (hereinafter referred to as “polycarbonate resin containing a high molecular weight component ”) can also be used.

In such a high-molecular-weight component-containing polycarbonate resin (component A-1), the molecular weight of component A-1-1 is preferably 7×10 ⁴ to 2×10 ⁵ , more preferably 8×10 ⁴ to 2×10 5 , and further preferably 8×10 4 to 2×10 ⁵ . It is preferably 1×10 ⁵ to 2×10 ⁵ , particularly preferably 1×10 ⁵ to 1.6×10 ⁵ . The molecular weight of component A-1-2 is preferably 1×10 ⁴ to 2.5×10 ⁴ , more preferably 1.1×10 ⁴ to 2.4×10 ⁴ , still more preferably 1.2×10 ⁴ . to 2.4×10 ⁴ , particularly preferably 1.2×10 ⁴ to 2.3×10 ⁴ .

The high-molecular-weight component-containing polycarbonate resin (component A-1) can be obtained by mixing the components A-1-1 and A-1-2 in various proportions and adjusting the mixture to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of A-1 component, A-1-1 component is 2 to 40% by weight, more preferably A-1-1 component is 3 to 30% by weight, still more preferably The content of component A-1-1 is 4 to 20% by weight, and the content of component A-1-1 is particularly preferably 5 to 20% by weight.

In addition, as a method for preparing the A-1 component, (1) a method in which the A-1-1 component and the A-1-2 component are polymerized independently and then mixed, and (2) JP-A-5-306336. Using a method for producing an aromatic polycarbonate resin showing multiple polymer peaks in a molecular weight distribution chart by GPC method in the same system, represented by the method shown in JP-A-2003-120002, such an aromatic polycarbonate resin is produced by the A- of the present invention. A method of manufacturing to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a manufacturing method (manufacturing method of (2)), separately manufactured A-1-1 component and / or A method of mixing with the A-1-2 component can be mentioned.

The viscosity-average molecular weight referred to in the present invention is obtained by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20° C. to determine the specific viscosity (η _SP ) calculated by the following formula.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
The viscosity-average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following 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

Calculation of the viscosity-average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is performed in the following manner. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble matter in the composition. Such soluble matter is collected by celite filtration. The solvent in the resulting solution is then removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of the component soluble in methylene chloride. From a solution obtained by dissolving 0.7 g of this 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 resin containing dihydric phenol units represented by the following general formula (1) and hydroxyaryl-terminated polydiorganosiloxane units represented by the following general formula (3). is preferred.

[In the above 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, cycloalkyl group having 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, 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 carboxy group; a and b 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 general formula (2) above, 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, a carbon 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; R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a halogen atom, or a an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms. an aryl group of up to 14, an aryloxy group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxy group represents a group selected from the group consisting of, when there are more than one, they may be the same or different, c is an integer of 1 to 10, and d is an integer of 4 to 7.)

[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 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or 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, e and f are integers of 1 to 4, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 4 or more and 150 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) from which the carbonate constitutional unit represented by the general formula (1) is derived 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-isopropylphenyl)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- ter, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 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'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2 -(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4- hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4′-(1,3-adamantanediyl)diphenol, 1,3- bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the like.

Among others, 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 are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used alone or in combination of two or more.

In the carbonate structural unit represented by the general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, with a hydrogen atom or an alkyl group having 1 to 4 carbon atoms being particularly preferred. As the dihydroxyaryl-terminated polydiorganosiloxane (II) from which the carbonate structural unit represented by the general formula (3) is derived, for example, compounds represented by the following general formula (I) are preferably used.

p+q is preferably 4 to 120, more preferably 30 to 120, even more preferably 30 to 100, and most preferably 30 to 60.

Next, a method for producing the above preferred polycarbonate-polydiorganosiloxane copolymer resin will be described below. By reacting dihydric phenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of dihydric phenol (I) in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution, A mixed solution of chloroformate compounds is prepared comprising a chloroformate of dihydric phenol (I) and/or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group. Phosgene is preferred as the chloroformate-forming compound.

In producing the chloroformate compound from the dihydric phenol (I), the total amount of the dihydric phenol (I) that induces the carbonate constitutional unit represented by the general formula (1) may be converted into the chloroformate compound at once. Alternatively, a part thereof may be added as a post-addition monomer to the subsequent interfacial polycondensation reaction as a reaction raw material. The post-addition monomer is added in order to facilitate the subsequent polycondensation reaction, and it is not necessary to add it unless necessary. Although the method of this chloroformate compound-producing reaction is not particularly limited, a method of conducting the reaction in a solvent in the presence of an acid binder is usually preferred. Furthermore, if desired, a small amount of antioxidant such as sodium sulfite and hydrosulfide may be added, preferably. The ratio of the chloroformate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalents) of the reaction. When phosgene, which is a suitable chloroformate-forming compound, is used, a method of blowing gasified phosgene into the reaction system can be suitably employed.

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. is used. The ratio of the acid binder to be used may also be appropriately determined in consideration of the stoichiometric ratio (equivalents) of the reaction in the same manner as described above. Specifically, per 1 mol of dihydric phenol (I) used to form a chloroformate compound of dihydric phenol (I) (usually 1 mol corresponds to 2 equivalents), 2 equivalents or a slightly excess amount thereof It is preferred to use an acid binding agent.

As the solvent, a solvent inert to various reactions, such as those used in the production of known polycarbonates, may be used singly or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

The pressure in the reaction for producing the chloroformate compound 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°C to 50°C. In many cases, the reaction generates heat, so cooling with water or ice is desirable. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. Known interfacial reaction conditions can be used for the pH range in the production reaction of the chloroformate compound, and the pH is usually adjusted to 10 or higher.

In the preparation of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, a chloroformate of dihydric phenol (I) and a chloroformate containing a carbonate oligomer of dihydric phenol (I) having terminal chloroformate groups are thus used. After preparing the mixed solution of the formate compound, while stirring the mixed solution, dihydroxyaryl-terminated polydiorganosiloxane (II) that induces the carbonate structural unit represented by the general formula (3) is charged for preparing the mixed solution. by adding at a rate of 0.01 mol/min or less per 1 mol of the dihydric phenol (I) added, and interfacial polycondensation of the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound , to obtain a polycarbonate-polydiorganosiloxane copolymer resin.

The polycarbonate-polydiorganosiloxane copolymer resin can be made into a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent together with a dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)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-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Even if the method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin includes a branching agent in the mixed solution during the production reaction of the chloroformate compound, interfacial polycondensation after the production reaction is completed. A method in which a branching agent is added during the reaction may be used. The ratio of carbonate structural units derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, in the total amount of carbonate structural units constituting the copolymer resin, Especially preferred is 0.05 to 1.0 mol %. The amount of such branched structures can be calculated by ¹ H-NMR measurement.

The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure. The reaction temperature is selected from the range of −20 to 50° C. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally defined, 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 achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin with a viscosity of [η _SP /c]. The resulting reaction product (crude product) is subjected to various post-treatments such as known separation and purification methods, and can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purity).

The content of the polydiorganosiloxane block represented by the following general formula (4) contained in the above general formula (3) is 1.0 to 10.0% by weight based on the total weight of the polycarbonate resin composition. 1.0 to 8.0% by weight is more preferred, 1.0 to 5.0% by weight is even more preferred, and 1.0 to 3.0% by weight is most preferred.

(In general formula (4) above, 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 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or an unsubstituted aryl group, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 4 to 150.)

<B component: expanded graphite>
The resin composition of the present invention contains thermally expanded graphite as the B component. The thermally expanded graphite used in the present invention is obtained by heat-treating natural graphite, petroleum coke, petroleum pitch, amorphous carbon, etc., which are naturally produced as minerals, at a temperature of 2000 ° C. or higher to form irregularly arranged fine graphite crystals. The artificial graphite that has been artificially processed is immersed in concentrated sulfuric acid, concentrated nitric acid, etc., and further treated by adding an oxidizing agent such as hydrogen peroxide or hydrochloric acid to generate a graphite intercalation compound, and then washed with water. This graphite is expanded in the C-axis direction of raw material graphite by rapid heating at 800 to 1000°C. When graphite that has not undergone thermal expansion treatment is used, its dispersibility in resin is poor, and the joint strength between resin and metal after a heat cycle test is remarkably lowered. Natural graphite is particularly preferable as the graphite to be thermally expanded.

The thermally expanded graphite is desirably graphite prepared by pulverizing after the thermal expansion treatment. Furthermore, the expanded graphite subjected to the above thermal expansion treatment has a shape expanded like a cocoon, and generally has a specific volume of 100 cc/g or more. However, it is more preferable to compress the cocoon-shaped expanded graphite with a roll, a press, or the like to form a sheet, which is then pulverized by various known pulverizers.

The thermally expanded graphite is classified and used as required, and further washed with water and dried as required in order to reduce the residual acid component. The average particle size is preferably 0.1-1000 μm, more preferably 25-1000 μm. If the average particle size is less than 0.1 μm, the extrusion stability during production of the resin composition may be poor, resulting in a decrease in productivity. If the average particle size exceeds 1000 μm, the appearance of the surface of the molded product may deteriorate.

The surface of the graphite subjected to thermal expansion treatment in the present invention may be subjected to surface treatment such as epoxy treatment, urethane treatment, silane treatment, etc. in order to increase affinity with the aromatic polycarbonate resin as long as the properties of the composition of the present invention are not impaired. Coupling treatment, oxidation treatment, or the like may be performed. Furthermore, the apparent bulk specific gravity of the thermally expanded graphite of the present invention is preferably 0.01 to 0.50 g/cc, more preferably 0.05 to 0.30 g/cc, and more preferably 0.10 to 0.25 g/cc. cc is more preferred. If the apparent bulk specific gravity exceeds 0.50 g/cc, the thermal conductivity may be poor due to the low expansion ratio of the expanded graphite. If the apparent bulk specific gravity is less than 0.01 g/cc, the extrusion stability during production of the resin composition may be poor, resulting in a decrease in productivity.

The content of component B is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 40 parts by weight, per 100 parts by weight of component A. If the content of the B component is less than 1 part by weight, the retention of the bond strength between the resin and the metal is significantly reduced after the heat cycle test. Moreover, if the amount exceeds 80 parts by weight, the fluidity of the resin is lowered, so that the resin does not sufficiently penetrate into the grooves on the metal surface during metal insert molding, and sufficient bonding strength between the resin and the metal cannot be obtained. .

<C component: fibrous filler>
The resin composition of the present invention preferably contains a fibrous filler as the C component. Fibrous fillers are, for example, glass fibers, carbon fibers, carbon milled fibers, metal fibers, asbestos, rock wool, ceramic fibers, slag fibers, potassium titanate whiskers, boron whiskers, aluminum borate whiskers, calcium carbonate whiskers, oxide fibrous inorganic fillers such as titanium whiskers, wollastonite, xonotlite, palygorskite (attapulgite) and sepiolite; heat-resistant organic fibrous fillers such as aramid fibers, polyimide fibers and polybenzthiazole fibers; Examples of these fillers include fibrous fillers whose surfaces are coated with different materials such as metals and metal oxides. Examples of the filler whose surface is coated with a different material include metal-coated glass fiber and metal-coated carbon fiber. The method of coating the surface of the dissimilar material is not particularly limited. For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, and the like can be mentioned. Among these fibrous fillers, glass fiber, carbon fiber, carbon milled fiber and aramid fiber are preferable, and glass fiber and carbon fiber are more preferable. The fibrous filler preferably has a fiber diameter in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 18 µm, still more preferably 15 µm. On the other hand, the lower limit of the fiber diameter is more preferably 1 μm, still more preferably 6 μm. The fiber diameter referred to here refers to the number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after dissolving the molded product in a solvent or decomposing the resin with a basic compound, and the residue collected after incineration in a crucible. It is a value calculated from an image observed with an electron microscope.

When the fibrous filler is glass fiber, the glass composition of the glass fiber is not particularly limited, and various glass compositions represented by A glass, C glass, E glass, and the like are applied. Such glass fillers may contain components such as TiO ₂ , SO ₃ and P ₂ O ₅ as necessary. Among these, E glass (alkali-free glass) is more preferable. Such glass fibers are preferably surface-treated with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like, from the viewpoint of improving mechanical strength. In addition, it is preferable to use olefin-based resin, styrene-based resin, acrylic-based resin, polyester-based resin, epoxy-based resin, urethane-based resin, or the like for convergence treatment. Especially preferred. The amount of the sizing agent attached to the sizing-treated glass fibers is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, based on 100% by weight of the glass fibers. A flat cross-section glass fiber can also be used as a fibrous filler. The flat cross-section glass fiber preferably has an average long diameter of 10 to 50 μm, more preferably 15 to 40 μm, still more preferably 20 to 35 μm, and a ratio of long diameter to short diameter (long diameter/short diameter). Glass fibers having an average value of preferably 1.5 to 8, more preferably 2 to 6, still more preferably 2.5 to 5. The use of flat cross-section glass fibers having an average major axis to minor axis ratio of less than 1.5 greatly improves the anisotropy compared to the use of non-circular cross-section fibers having an average major axis to minor axis ratio of less than 1.5. The flattened cross-sectional shape includes not only a flattened shape, but also non-circular cross-sectional shapes such as elliptical, cocoon-shaped, trefoil-shaped, or similar shapes. Among them, a flat shape is preferable from the viewpoint of improvement in mechanical strength and low anisotropy. The ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross-section glass fiber is preferably 2 to 120, more preferably 2.5 to 70, and still more preferably 3 to 50. If the diameter ratio is less than 2, the effect of improving the mechanical strength may be reduced, and if the ratio of the fiber length to the average fiber diameter exceeds 120, the anisotropy will increase and the appearance of the molded product may deteriorate. There is The average fiber diameter of such flat cross-section glass fibers means the number average fiber diameter when the flat cross-section shape is converted into a perfect circle with the same area. The average fiber length refers to the number average fiber length in the reinforced polycarbonate resin composition of the present invention. The number-average fiber length is a value calculated by an image analysis device from an optical microscope image of the residue of the filler collected by processing such as high-temperature incineration of the molded product, dissolution with a solvent, and decomposition with chemicals. is. In addition, when calculating such a value, the value is based on a method in which the fiber diameter is used as a guideline, and fibers with a length smaller than that are not counted.

The content of component C is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, even more preferably 10 to 50 parts by weight, per 100 parts by weight of component A. If the content of component C is less than 1 part by weight, separation may occur during insert molding, and if it exceeds 100 parts by weight, sufficient bonding strength between resin and metal may not be obtained.

(Other additives)
In order to improve the thermal stability and design properties of the thermoplastic resin composition of the present invention, the additives used for these improvements are advantageously used. These additives will be specifically described below.

(I) Thermal Stabilizer The thermoplastic resin composition of the present invention may contain various known stabilizers. Examples of stabilizers include phosphorus stabilizers and hindered phenol antioxidants.

(i) Phosphorus-Based Stabilizer The thermoplastic resin composition of the present invention preferably contains a phosphorus-based stabilizer to the extent that it does not promote hydrolyzability. Such phosphorus-based stabilizers improve thermal stability during production or molding, and improve mechanical properties, color, and molding stability. Phosphorous stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphines. Specific examples of phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenyl Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, tris( diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2, 6-di-tert-butylphenyl)phosphite, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl -4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)penta Erythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like. Furthermore, as other phosphite compounds, those having a cyclic structure which react with dihydric phenols can also be used. For example, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert- butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2′-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite , 2,2′-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite. Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate and the like can be mentioned, and triphenyl phosphate and trimethyl phosphate are preferred.

Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenedi Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite , tetrakis(2,6-di-tert-butylphenyl)-4,3′-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di -n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2, 4-di-tert-butylphenyl)-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable. Phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like. Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus-based stabilizers may be used singly or in combination of two or more. Among the above phosphorus-based stabilizers, it is preferable to incorporate an alkyl phosphate compound represented by trimethyl phosphate. In addition, the combination use of such an alkyl phosphate compound with a phosphite compound and/or a phosphonite compound is also a preferred embodiment.

(ii) Hindered phenol antioxidant The thermoplastic resin composition of the present invention may contain a hindered phenol antioxidant. Such blending exhibits an effect of suppressing deterioration of hue during molding and deterioration of hue during long-term use, for example. Examples of hindered phenol antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfer ) propionate, 2-tert-butyl-6-(3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-( N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2′ -methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2 , 2′-dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-butylidene-bis(4 -methyl-6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5 -methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-( 3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- 1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6-tert-butyl-m-cresol), 4,4′- thiobis(3-methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4′-di-thiobis(2,6-di-tert-butylphenol), 4,4′-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3′,5′-di-tert-butylanilino) -1,3,5-triazine, N,N′-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N′-bis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2 , 4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5- Di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2 [3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate and tetrakis[methylene-3-(3′,5′-di-tert-butyl-4-hydroxyphenyl) propionate]methane and the like are exemplified. All of these are readily available. The above hindered phenol-based antioxidants can be used alone or in combination of two or more. The amount of the phosphorus stabilizer and the hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, with respect to 100 parts by weight of component A, respectively. More preferably, it is 0.005 to 0.3 parts by weight.

(iii) Other heat stabilizers The thermoplastic resin composition of the present invention may contain other heat stabilizers than the phosphorus stabilizer and hindered phenol antioxidant. Such other heat stabilizers are preferably lactone-based stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is available commercially as Irganox HP-136 (trademark, CIBA SPECIALTY CHEMICALS). Further, stabilizers obtained by mixing said compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. The amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of component A. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. exemplified. The amount of the sulfur-containing stabilizer to be blended is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A. The thermoplastic resin composition of the present invention may optionally contain an epoxy compound. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically all those having epoxy functional groups can be applied. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexylcarboxylate, 2,2-bis(hydroxymethyl)-1-butanol of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, copolymers of styrene and glycidyl methacrylate, and the like. The amount of the epoxy compound to be added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, still more preferably 0.004 to 0.15 parts by weight, based on 100 parts by weight of component A. 005 to 0.1 parts by weight.

(II) Flame Retardant The thermoplastic resin composition of the present invention may contain a flame retardant. Incorporation of such compounds provides improved flame retardancy, but also provides, depending on the properties of each compound, improved antistatic properties, fluidity, stiffness, and thermal stability, for example. Examples of such flame retardants include (i) organic metal salt flame retardants (e.g., organic sulfonic acid alkali (earth) metal salts, organic borate metal salt flame retardants, and organic stannate metal salt flame retardants), ( ii) organic phosphorus-based flame retardants (e.g., organic group-containing monophosphate compounds, phosphate oligomeric compounds, phosphonate oligomeric compounds, phosphonitrile oligomeric compounds, phosphonic acid amide compounds, etc.), (iii) silicone-based flame retardants consisting of silicone compounds and (iv) fibrillated PTFE, among which organic metal salt-based flame retardants and organic phosphorus-based flame retardants are preferred. These may be used alone or in combination of two.

(i) Organometallic salt-based flame retardant The organometallic salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkali (earth) metal organic sulfonate. is preferred. The organic sulfonic acid alkali (earth) metal salts include fluorine-substituted alkyl sulfones such as metal salts of perfluoroalkyl sulfonic acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and alkali metals or alkaline earth metals. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, with alkali metals or alkaline earth metals are included. Alkali metals that make up the metal salt include lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. Alkali metals are more preferred. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are suitable when the demand for transparency is higher. It may be disadvantageous. On the other hand, metals with smaller ionic radii, such as lithium and sodium, may be disadvantageous in terms of flame retardancy. Although the alkali metal in the alkali metal sulfonate can be properly used in consideration of these factors, the potassium sulfonate is most preferable because of its well-balanced properties in all respects. Such potassium salts and alkali metal sulfonate salts of other alkali metals can also be used in combination.

Specific examples of perfluoroalkylsulfonic acid alkali metal salts include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, rubidium perfluorohexanesulfonate, and the like can be mentioned, and these can be used alone or in combination of two or more. The perfluoroalkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.

Among these, potassium perfluorobutanesulfonate is particularly preferred. The alkali (earth) metal salt of perfluoroalkylsulfonate, which is an alkali metal, usually contains not a small amount of fluoride ions (F-). Since the presence of such fluoride ions can be a factor in deteriorating flame retardancy, it is preferable to reduce them as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. In addition, it is preferable that the concentration is 0.2 ppm or more in terms of production efficiency. Such an alkali (earth) metal perfluoroalkylsulfonate having a reduced amount of fluoride ions is produced by a known production method and is contained in raw materials for producing a fluorine-containing organic metal salt. A method of reducing the amount of fluoride ions, a method of removing hydrogen fluoride and the like obtained by the reaction by gas generated during the reaction or by heating, and a purification method such as recrystallization and reprecipitation for the production of fluorine-containing organometallic salts. can be produced by a method of reducing the amount of fluoride ions using In particular, since organometallic salt-based flame retardants are relatively soluble in water, ion-exchanged water, especially water satisfying an electrical resistance value of 18 MΩ·cm or more, that is, an electrical conductivity of about 0.55 μS / cm or less, is used. It is also preferable to manufacture by a step of dissolving at a temperature higher than room temperature, washing, and then cooling to recrystallize.

Specific examples of the alkali (earth) metal aromatic sulfonate include disodium diphenylsulfide-4,4′-disulfonate, dipotassium diphenylsulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly(2,6-dimethylphenylene oxide) polysodium polysulfonate , poly(1,3-phenylene oxide) polysodium polysulfonate, poly(1,4-phenylene oxide) polysodium polysulfonate, poly(2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly(2-fluoro- 6-Butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl -3,3'-calcium disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, diphenylsulfone-3,4'-disulfonic acid dipotassium, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, Calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracene sulfonate. can. Of these alkali (earth) metal salts of aromatic sulfonates, potassium salts are particularly preferred. Among these alkali (earth) metal salts of aromatic sulfonates, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferred, and mixtures thereof (the former and the latter weight ratio of 15/85 to 30/70).

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfate esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfate esters, mention may be made in particular of alkali (earth) metal salts of sulfate esters of monohydric and/or polyhydric alcohols, such monohydric and/or polyhydric alcohols Sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, lauric acid monoglyceride sulfate esters, palmitate monoglyceride sulfates, stearate monoglyceride sulfates, and the like. The alkali (earth) metal salts of these sulfate esters are preferably alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N-(p-tolylsulfonyl)-p-toluenesulfimide, N-(N'-benzylaminocarbonyl)sulfanilimide, and N-( and alkali (earth) metal salts of phenylcarboxyl)sulfanilimide. The content of the organometallic salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and still more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of component A. 0.3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(ii) Organic Phosphorus Flame Retardant As the organic phosphorus flame retardant, aryl phosphate compounds and phosphazene compounds are preferably used. Since these organic phosphorus flame retardants have a plasticizing effect, they are advantageous in terms of improving moldability. As the aryl phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (5) can be mentioned.

(However, M in the above formula represents a divalent organic group derived from a dihydric phenol, and Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each a monovalent organic group derived from a monohydric phenol. a, b, c and d are each independently 0 or 1, m is an integer of 0 to 5, and in the case of a mixture of phosphate esters with different polymerization degrees m, m is the average value and values from 0 to 5.)

The phosphate compound of the above formula may be a mixture of compounds having different m numbers, and in such mixtures the average m number is preferably between 0.5 and 1.5, more preferably between 0.8 and 1.5. 2, more preferably 0.95 to 1.15, particularly preferably 1 to 1.14.

Suitable specific examples of dihydric phenols from which M is derived include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4 -hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.

Preferable specific examples of monohydric phenols from which Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are derived include phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol. is phenol, and 2,6-dimethylphenol.

Such monohydric phenol may be substituted with a halogen atom, and specific examples of phosphate compounds having a group derived from the monohydric phenol include tris(2,4,6-tribromophenyl)phosphate and tris(2,4,6-tribromophenyl)phosphate. Examples include (2,4-dibromophenyl)phosphate, tris(4-bromophenyl)phosphate and the like.

On the other hand, specific examples of phosphate compounds not substituted with halogen atoms include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl)phosphate, and resorcinol bisdi(2,6-xylyl)phosphate). Preferred are phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphate ester oligomers based on bisphenol A bis(diphenyl phosphate). indicates that a small amount of other components with different polymerization degrees may be included, more preferably the component of m = 1 in the formula (5) is 80% by weight or more, more preferably 85% by weight or more, and even more preferably 90% by weight or more).

Various phosphazene compounds known as conventional flame retardants can be used as the phosphazene compound, but phosphazene compounds represented by the following general formulas (6) and (7) are preferable.

(Wherein, X ¹ , X ² , X ³ and X ⁴ represent hydrogen, hydroxyl group, amino group, or an organic group containing no halogen atom, and r represents an integer of 3 to 10.)

Examples of the halogen-free organic groups represented by X ¹ , X ² , X ³ and X ⁴ in the formulas (6) and (7) include an alkoxy group, a phenyl group, an amino group and an allyl group. is mentioned. Among them, a cyclic phosphazene compound represented by the above formula (6) is preferable, and a cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula (6) are phenoxy groups is particularly preferable.

The content of the organic phosphorus flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and even more preferably 5 to 20 parts by weight, per 100 parts by weight of component A. If the amount of the organic phosphorus flame retardant is less than 1 part by weight, it is difficult to obtain the flame retardant effect. may occur.

(iii) Silicone Flame Retardant A silicone compound used as a silicone flame retardant improves flame retardancy through a chemical reaction during combustion. As the compound, various compounds that have been proposed as flame retardants for aromatic polycarbonate resins can be used. When the silicone compound is burned, it combines with itself or with a component derived from the resin to form a structure, or through a reduction reaction during the formation of the structure. considered to be effective.

Therefore, it preferably contains a group that is highly active in such reactions, and more specifically, it preferably contains a predetermined amount of at least one group selected from alkoxy groups and hydrogen (that is, Si—H groups). preferable. The content ratio of such groups (alkoxy group, Si—H group) is preferably in the range of 0.1 to 1.2 mol/100 g, more preferably in the range of 0.12 to 1 mol/100 g, and more preferably 0.15 to 0.15 mol/100 g. A range of 6 mol/100 g is more preferred. Such a ratio can be obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline decomposition method. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group is particularly preferable.

Generally, the structure of a silicone compound is constructed by arbitrarily combining the four types of siloxane units shown below. That is, M units: ( _CH3 )3SiO1 _{/ 2} , H( _CH3 ) _{2SiO1/ 2} , _H2 ( _CH3 )SiO1 _/2 , ( _CH3 ) ₂ ( _CH2 =CH) _{SiO1 /2 ,} ( _CH3 ) ₂ ( _C6H5 )SiO1 _/ 2, ( _CH3 )( _C6H5 )( _CH2 =CH)SiO1 _{/ 2} , and other monofunctional siloxane units, D units: 2 such as ( _CH3 ) _2SiO , _H ( _CH3 )SiO, _{H2SiO ,} H( _C6H5 )SiO, ( _CH3 )( _CH2 =CH) _SiO , ( _C6H5 )2SiO; Functional siloxane units, T units: ( _CH3 )SiO3 _/2 , ( _C3H7 )SiO3 _{/ 2} , HSiO3 _/2 , ( _CH2 =CH)SiO3 _{/2 ,} ( _C6H5 ) Trifunctional siloxane units such as SiO _3/2 , and Q units: tetrafunctional siloxane units represented by SiO ₂ .

Specifically, the structures of silicone compounds used in silicone-based flame retardants include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compounds are MmDn, MmTp, MmDnTp and MmDnQq, and more preferred structures are MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . The average degree of polymerization is preferably in the range of 3-150, more preferably in the range of 3-80, still more preferably in the range of 3-60, and most preferably in the range of 4-40. It comes to be excellent in flame retardance, so that it is such a suitable range. Furthermore, as described later, silicone compounds containing a predetermined amount of aromatic groups are excellent in transparency and hue. As a result, good reflected light can be obtained. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with that coefficient can be two or more siloxane units having different bonding hydrogen atoms and organic residues. .

The silicone compound may be linear or branched. Also, the organic residue that bonds to the silicon atom preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as tolyl groups. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group and propyl group is particularly preferred. Furthermore, the silicone compound used as the silicone-based flame retardant preferably contains an aryl group. On the other hand, silane compounds and siloxane compounds used as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone-based flame retardants in their preferred aspects in that they exhibit favorable effects when they do not contain aryl groups. . Silicone compounds used as silicone flame retardants may contain reactive groups other than the Si—H groups and alkoxy groups. Examples of such reactive groups include amino groups, carboxy groups, epoxy groups, vinyl groups, mercapto groups, and methacryloxy groups.

The content of the silicone flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 1 to 5 parts by weight, per 100 parts by weight of component A.

(iv) polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or mixed fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture comprising fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has a very high molecular weight and tends to bind PTFE together by an external action such as a shearing force to form a fibrous form. Its number average molecular weight ranges from 1.5 million to tens of millions. Such a lower limit is more preferably 3 million. Such number-average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380° C., as disclosed in JP-A-6-145520, for example. That is, the fibrillated PTFE has a melt viscosity of 10 ⁷ to 10 ¹³ poise, preferably 10 ⁸ to 10 ¹² poise at 380° C. measured by the method described in the publication. Such PTFE can be used not only in a solid form but also in an aqueous dispersion form. In addition, such fibrillated PTFE improves its dispersibility in resins, and it is also possible to use PTFE mixtures in the form of mixtures with other resins in order to obtain better flame retardancy and mechanical properties.

Further, as disclosed in JP-A-6-145520, those having such a fibrillated PTFE as a core and a low-molecular-weight polytetrafluoroethylene as a shell are also preferably used.

Commercially available products of such fibrillated PTFE include, for example, 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.

Mixed forms of fibrillated PTFE include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer to co-precipitate to obtain a co-aggregated mixture (JP-A-60-258263; (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (described in JP-A-4-272957). (3) A method in which an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles are uniformly mixed, and the respective media are simultaneously removed from the mixture (JP-A-06-220210, JP-A-06-220210; 08-188653, etc.), (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (described in JP-A-9-95583, method), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (JP-A-11- 29679) can be used.

Commercial products of fibrillated PTFE in a mixed form include METABLEN represented by "METABLEN A3000" (trade name), "METABLEN A3700" (trade name), and "METABLEN A3800" (trade name) of Mitsubishi Rayon Co., Ltd. A series, Shine Polymer's SN3300B7 (trade name), and GE Specialty Chemicals' "BLENDEX B449" (trade name) are exemplified.

The ratio of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and 20% by weight, based on 100% by weight of the mixture. Weight percent to 80 weight percent is most preferred.

Good dispersibility of the fibrillated PTFE can be achieved when the proportion of the fibrillated PTFE in the mixed form is in this range. The content of fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, and 0.1 to 0.5 parts by weight, per 100 parts by weight of component A. 5 parts by weight is more preferred.

(III) Dyes and Pigments The thermoplastic resin composition of the present invention further contains various dyes and pigments to provide molded articles exhibiting various design properties. The dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, Examples include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the thermoplastic resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is suitable as the metallic pigment. Further, by blending a fluorescent brightening agent or other fluorescent dye that emits light, it is possible to impart a better design effect by making use of the luminescent color.

(IV) Fluorescent brightener In the thermoplastic resin composition of the present invention, the fluorescent brightener is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white. , benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Co., Ltd., and "Hakkor PSR" manufactured by Showa Chemical Co., Ltd., and the like. Here, the fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy in the visible region. The content of the fluorescent brightener is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of component A. Even if it exceeds 0.1 part by weight, the effect of improving the color tone of the composition is small.

(V) Compound Having Ability to Absorb Heat Rays The thermoplastic resin composition of the present invention can contain a compound having ability to absorb heat rays. Examples of such compounds include phthalocyanine near-infrared absorbers, metal oxide near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide and titanium oxide, lanthanum boride, cerium boride and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity, such as metal boride-based and tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near-infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and readily available. Examples of carbon fillers include carbon black, graphite (both natural and artificial) and fullerenes, preferably carbon black and graphite. These can be used singly or in combination of two or more. The content of the phthalocyanine-based near-infrared absorbent is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and 0.001 to 0 0.07 parts by weight is more preferred. The content of the metal oxide near-infrared absorber, the metal boride near-infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the thermoplastic resin composition of the present invention. A range of 0.5 to 100 ppm is more preferred.

(VI) Light diffusing agent The thermoplastic resin composition of the present invention may be blended with a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymeric fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer microparticles are already known microparticles as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane are exemplified. The shape of the light diffusing agent is exemplified by a spherical shape, a discoidal shape, a columnar shape, and an amorphous shape. Such spheres do not have to be perfect spheres and include deformed ones, and such cylinders include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of component A. . Two or more light diffusing agents can be used in combination.

(VII) High Light Reflection White Pigment The thermoplastic resin composition of the present invention may be blended with a high light reflection white pigment to impart a light reflection effect. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, per 100 parts by weight of component A. Two or more kinds of the high light reflection white pigment can be used in combination.

(VIII) Ultraviolet absorber The thermoplastic resin composition of the present invention may be blended with an ultraviolet absorber to impart weather resistance. Specific examples of such UV absorbers include benzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzene oxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy -4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like. Specific examples of benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole. , 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′- methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl ) benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole- 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl ) benzotriazole, 2,2′-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2 -hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, and a copolymer of said monomer and a vinyl-based monomer copolymerizable with said monomer, or a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and said monomer and a vinyl-based monomer copolymerizable with said monomer; Examples thereof include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as polymers. Specifically, the ultraviolet absorber is hydroxyphenyltriazine-based, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4, 6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol , 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl )-5-butyloxyphenol and the like. Furthermore, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc., in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl A compound having a phenyl group is exemplified. Specifically, cyclic iminoester-based UV absorbers include, for example, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-m-phenylenebis(3,1 -benzoxazin-4-one), and 2,2′-p,p′-diphenylenebis(3,1-benzoxazin-4-one). Further, as the ultraviolet absorber, specifically in the cyanoacrylate type, for example, 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2- Examples include cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene. Further, the above ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and/or photostable monomer and a monomer such as alkyl (meth)acrylate It may be a polymer-type ultraviolet absorber obtained by copolymerizing with a body. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester. be. Among them, benzotriazole and hydroxyphenyltriazine are preferred in terms of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferred in terms of heat resistance and hue. Specific examples thereof include "Chemisorb 79" manufactured by Chemipro Kasei Co., Ltd., "TINUVIN 234" manufactured by BASF Japan Ltd., and the like. The ultraviolet absorbers may be used singly or as a mixture of two or more.

The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 1 part by weight, with respect to 100 parts by weight of component A, especially It is preferably 0.05 to 0.5 parts by weight.

(IX) Antistatic Agent The thermoplastic resin composition of the present invention may be required to have antistatic performance, and in such cases, it preferably contains an antistatic agent. Examples of such antistatic agents include (1) arylsulfonic acid phosphonium salts typified by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and tetrafluoroborate phosphonium salts. Phosphonium borate salts are mentioned. The content of the phosphonium salt is appropriately 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, still more preferably 1 part by weight with respect to 100 parts by weight of component A. .5 to 3 parts by weight. Examples of antistatic agents include (2) organic lithium sulfonate, organic sodium sulfonate, organic potassium sulfonate, organic cesium sulfonate, organic rubidium sulfonate, organic calcium sulfonate, organic magnesium sulfonate, and organic barium sulfonate. organic sulfonic acid alkali (earth) metal salts such as Such metal salts are also used as flame retardants, as described above. More specific examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the organic alkali (earth) metal sulfonate is appropriately 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably 0 parts by weight, per 100 parts by weight of component A. 0.005 to 0.2 parts by weight. Especially preferred are alkali metal salts such as potassium, cesium and rubidium.

Examples of antistatic agents include (3) organic sulfonate ammonium salts such as alkylsulfonate ammonium salts and arylsulfonate ammonium salts. The amount of the ammonium salt is appropriately 0.05 parts by weight or less per 100 parts by weight of the component A and B. The antistatic agent includes, for example, (4) a polymer containing a poly(oxyalkylene) glycol component such as polyetheresteramide as its constituent component. The amount of the polymer is suitably 5 parts by weight or less per 100 parts by weight of component A.

(X) Filler The thermoplastic resin composition of the present invention may contain various fillers known as reinforcing fillers other than fibrous fillers. Various plate-like fillers and granular fillers can be used as such fillers. Here, the plate-like filler is a filler having a plate-like shape (including those having irregularities on the surface and those having curved plates). Particulate fillers are fillers of shapes other than these, including irregularly shaped fillers.

Plate-shaped fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and plate-shaped fillers obtained by coating these fillers with different materials such as metals and metal oxides. Materials and the like are preferably exemplified. Its particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods, in the region up to about 10 μm, and laser diffraction in the region of 10 to 50 μm.・A value based on the median diameter (D50) of the particle size distribution measured by the scattering method, and in the range of 50 to 300 μm, the value obtained by the vibratory sieving method. Such particle size is the particle size in the resin composition. The plate-like fillers may be surface-treated with various silane-based, titanate-based, aluminate-based, and zirconate-based coupling agents. , epoxy resins, urethane resins, and other resins, higher fatty acid esters, and the like, or may be granules subjected to compression.

(XI) Other Resins and Elastomers In the thermoplastic resin composition of the present invention, other resins and elastomers can be used in place of a part of the resin component to exhibit the effects of the present invention within a range that does not impair the effects of the present invention. It can also be used in a small proportion within the range. The amount of other resins and elastomers is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and most preferably 3 parts by weight or less per 100 parts by weight of component A. . Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. , phenolic resins, and epoxy resins. Examples of elastomers include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and MBS (methyl methacrylate/sterene/butadiene), which is a core-shell type elastomer. rubber, MB (methyl methacrylate/butadiene) rubber, MAS (methyl methacrylate/acrylonitrile/styrene) rubber, and the like.

(XII) Other Additives The thermoplastic resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents, and the like. .

<Regarding the production of the resin composition>
Any method may be employed to produce the resin composition of the present invention. For example, components A and B and optionally other components are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and optionally an extrusion granulator. or a briquetting machine, followed by melt-kneading with a melt-kneader typified by a vent-type twin-screw ruder, and pelletization with a device such as a pelletizer. Alternatively, A component, B component and optionally other components are supplied independently to a melt kneader typified by a vented twin screw Ruder, after premixing a part of A component and other components , and a method of supplying to a melt-kneader independently of the remaining components. When the components to be blended include liquid components, a so-called liquid injection device or liquid addition device can be used for supplying the components to the melt-kneader.

<Metal compact>
The metal material forming the resin-metal composite molded article of the present invention is preferably a metal material in which a joint portion having a groove is formed, and the groove is formed by irradiation with a continuous wave laser beam or a pulse wave laser beam Materials are more preferred. The metal constituting the metal material is not particularly limited, and can be appropriately selected from known metals depending on the application. Examples thereof include those selected from iron, various stainless steels, aluminum or its alloys, copper, magnesium and alloys containing them. Among these, from the viewpoint of light weight and high strength, aluminum (single aluminum) and aluminum alloys are preferred, and aluminum alloys are more preferred. A metal compact is processed into, for example, a flat plate shape, a curved plate shape, a rod shape, a cylindrical shape, a block shape, etc., by cutting a metal material, plastic working by pressing, etc., punching, cutting, polishing, and thinning work such as electrical discharge machining. be. The surface of the metal compact preferably has a large surface area in order to improve the adhesion to the resin, and more specifically, the surface is preferably roughened. The method for roughening the surface of the metal member is preferably a chemical etching method using a known etchant, a method of roughening by a means selected from laser light irradiation, etching, pressing, and blasting, and a continuous wave laser beam. Alternatively, a method of roughening by irradiating a pulse wave laser beam is more preferable.

<Preparation of resin-metal composite molded body>
The resin-metal composite molded article of the present invention is a composite molded article characterized in that the metal material and the resin molded article are joined and integrated by inserting the resin molded article into the grooves of the metal material. The method for producing the composite molded body is not particularly limited, and injection molding, extrusion molding, hot press molding, compression molding, transfer molding, laser welding molding, reaction injection molding (RIM molding), rim molding (LIM molding) ), and resin molding methods such as thermal spray molding. Among them, the step of irradiating the joint surface of the metal compact with a continuous wave laser beam or a pulse wave laser beam and the part including the joint surface of the metal compact irradiated with the continuous wave laser beam or the pulse wave laser beam in the previous step is placed in a mold and the thermoplastic resin composition is injection-molded, from the viewpoint of flexibility of shape and productivity. In the case of producing a composite body composed of an aluminum resin composition film in which a resin composition film is coated on an aluminum surface, a coating method of dissolving or dispersing the resin composition in a solvent and applying it, and other various coating methods are mentioned. be able to. Other coating methods include baking coating, electrodeposition coating, electrostatic coating, powder coating, and ultraviolet curing coating.

<Electronic control unit>
The resin-metal composite molded article of the present invention includes a circuit board on which electronic components are mounted, a base portion having protrusions for mounting the circuit board, and a cover portion formed of a resin covering the circuit board and the base portion. is preferably used for the base part in a control device having Furthermore, it is more preferable that the protrusions of the base portion are made only of the thermoplastic resin composition of the present invention. In order to suppress heat generation of the electronic circuit board, it is preferable that the base portion has projections and the cover portion has a plurality of holes.

The thermoplastic resin composition containing an appropriate amount of the expanded graphite of the present invention has excellent adhesion to the metal in the composite molded article bonded to the metal, and the bonding strength does not decrease after the heat cycle test. It is a thermoplastic resin composition with a small amount and excellent durability. These techniques do not exist in the conventional resin-to-metal adhesion techniques, are extremely useful in various industrial applications such as the field of OA equipment and electrical and electronic equipment, and have a very large industrial effect.

The best mode of the present invention, which the present inventors consider to be the best, summarizes the preferred ranges of the above requirements, and representative examples thereof are 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 below, but the present invention is not limited thereto.
In addition, it implemented about the following items as evaluation.

(i) Adhesion strength Pellets obtained from each composition of Examples were dried at 100°C for 5 hours in a hot air dryer, and injection molding machine [Sumitomo Heavy Industries Co., Ltd. SG150U SM IV] At a cylinder temperature of 310°C and a mold temperature of 110°C, a test piece for a resin-to-metal adhesion test conforming to ISO 19095-2 was molded. (Length: 170 mm x Width: 10 mm, Thickness: 4 mm: butt type) After cutting an aluminum plate material (thickness: 4 mm) of alloy number 5052 specified in JIS H4000 as a metal compact into a size of 85 mm x 10 mm. A metal molded body was used in which a joining portion having grooves was formed on the metal surface by a laser. The grooves had a diameter of 40 to 80 μm, a depth of 75 to 125 μm, and an interval between grooves of 90 to 120 μm. After the obtained test piece was conditioned at 23° C. and 50% RH for 24 hours, the resin-to-metal adhesion strength (tensile strength of butt test piece) was measured according to ISO 19095-3. Adhesion strength is preferably 20 MPa or more.

(ii) Strength retention rate after heat cycle test Heat cycle test using the composite molded body used in “(i) Adhesion strength” (heated and treated at 80 ° C. for 30 minutes, cooled and treated at -40 ° C. for 30 minutes After 2,000 cycles of a test in which one cycle was treated for 1 minute, the resin-to-metal adhesion strength (tensile strength by butt test piece) was measured, and the strength retention rate was calculated by the following formula (1). The strength retention rate is preferably 80% or more.

[Examples 1 to 12, Comparative Examples 1 to 5]
A resin composition having the compounding ratio shown in Table 1 was prepared in the following manner. The description will be made according to the symbols in the table below. Each component in the ratio shown in the table was weighed, mixed uniformly using a tumbler except for the fibrous filler, and the mixture was put into an extruder to prepare a resin composition. The extruder used was a vented twin-screw extruder manufactured by The Japan Steel Works, Ltd.: TEX-30XSST (perfect meshing, co-rotating, double screw). The extrusion conditions were a discharge rate of 20 kg/h, a screw rotation speed of 150 rpm, a vent vacuum degree of 3 kPa, and an extrusion temperature of 280 to 320°C. The fibrous filler was supplied from the second supply port using the side feeder of the extruder, and the remaining polycarbonate resin and additives were supplied to the extruder from the first supply port. The first feed port here is the feed port farthest from the die, and the second feed port is the feed port located between the die and the first feed port of the extruder. The obtained pellets were used to mold test pieces for evaluation using an injection molding machine as described above. Each evaluation result is shown in Table 1. In addition, each component of symbol notation in Table 1 is as follows.

(A component)
A-1: Aromatic polycarbonate resin, manufactured by Teijin Limited Panlite L-1225WX (product name)
A-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 23,500, PDMS content 8.4%, PDMS polymerization degree 37)
A-3: Polyphenylene sulfide resin, manufactured by Polyplastics, C0202C7 (product name)
(B component)
B-1: Expanded graphite, manufactured by Nishimura Graphite Co., Ltd., E-40 (product name)
B-2 (for comparison): flake graphite, SC-120 (product name) manufactured by Fuji Graphite Industry Co., Ltd.
(C component)
C-1: glass fiber, chopped strand CS3PE455FB (product name) manufactured by Nittobo Co., Ltd.
C-2: Carbon fiber, manufactured by Teijin Limited HTC422 (product name)
(Other ingredients)
D-1: Stabilizer, Johoku Chemical Industry Co., Ltd. JC-224 (product name)
D-2: weathering agent, BASF Japan Co., Ltd. Tinuvin234 (product name)
D-3: Release agent, Rikemal SL-900 (product name) manufactured by Riken Vitamin Co., Ltd.
D-4: Colorant, RB90003S (product name) manufactured by Koshigaya Kasei Kogyo Co., Ltd.

Claims (9)

A thermoplastic resin composition for producing a resin molded body in a composite molded body in which a metal molded body and a resin molded body are joined, ) A thermoplastic resin composition characterized by containing 1 to 80 parts by weight of expanded graphite (component B). The thermoplastic resin composition according to claim 1, characterized by containing 1 to 100 parts by weight of (C) a fibrous filler (component C) with respect to 100 parts by weight of component A. 3. The thermoplastic resin composition according to claim 2, wherein the C component is glass fiber and/or carbon fiber. A composite molded body in which a metal molded body having a groove on the surface and a resin molded body made of the thermoplastic resin composition according to any one of claims 1 to 3 are joined, wherein the groove is in the groove A composite molded article characterized in that a metal molded article and a resin molded article are joined and integrated by inserting the resin molded article. 5. The composite compact according to claim 4, wherein the grooves on the surface of the metal compact are formed by irradiating the surface of the metal compact with a continuous wave laser beam or a pulse wave laser beam. 6. The method for producing a composite compact according to claim 4, wherein in the step of irradiating a continuous wave laser beam or a pulse wave laser beam to the joint surface of the metal compact and in the pre-step, continuous wave laser beam or pulse wave laser beam A step of inject-molding the thermoplastic resin composition according to any one of claims 1 to 3 by arranging in a mold a portion including the bonding surface of the metal molded body irradiated with the wave laser light. A method for producing a composite molded body, characterized in that An electronic control device comprising a circuit board on which electronic components are mounted, a base portion having protrusions for installing the circuit board, and a cover portion formed of resin covering the circuit board and the base portion, An electronic control device, wherein the base portion is the composite molded article according to claim 4 or 5. 8. The electronic control device according to claim 7, wherein the protrusion of the base portion is made only of the thermoplastic resin composition according to any one of claims 1 to 3. 9. The electronic control device according to claim 7, wherein said cover portion has a plurality of holes.