Thermoplastic resin composition and composite molded body in which metal molded body and resin molded body are joined

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]

[0001] The present invention relates to a thermoplastic resin composition suitable for molding a composite molded article in which a metal molded article and a resin molded article are bonded together, and to a composite molded article in which a metal molded article and a resin molded article are bonded together. More specifically, the present invention relates to a thermoplastic resin composition that has excellent adhesion to metals, has little decrease in bond strength after a heat cycle test, and is excellent in durability, and to a composite molded article in which a metal molded article and a resin molded article are bonded together. [Background technology]

[0002] Metal materials are used in various fields, including automobiles, electrical engineering, and electronics. Resin molded bodies are sometimes used as metal substitutes to reduce the weight of various parts. However, it is often difficult to replace all metal parts with resin. In such cases, new composite parts can be manufactured by integrally joining metal molded bodies with resin molded bodies. A technology that can integrate metal molded bodies and resin molded bodies in an industrially advantageous manner with high joining strength is needed. Patent Document 1 describes an invention for a laser processing method for metal surfaces to join dissimilar materials (resins), including a step of laser scanning the metal surface in one scanning direction and a step of laser scanning in a cross-scanning direction. Regarding the dissimilar materials, a thermoplastic resin containing glass fiber is also described. Patent Document 2 demonstrates that a composite molded body of a specific structure and a metal has high joining strength. Patent Documents 3 and 4 demonstrate high joining strength between metal molded bodies and resin molded bodies, and describe resin molded bodies made from thermoplastic resins, thermosetting resins, and thermoplastic elastomers blended with carbon fiber, inorganic fiber, metal fiber, or organic fiber. However, these methods are still insufficient in terms of adhesion between metal and resin under environmental temperature changes expected in actual use. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent No. 4020957 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 2020-066652 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2013-52669 [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2014-18995 [Summary of the Invention] [Problems to be Solved by the Invention]

[0004] An object of the present invention is to provide a thermoplastic resin composition having excellent adhesion to a metal, little reduction in bonding strength after a heat cycle test, and excellent durability, and a resin-metal composite formed body comprising the same. [Means for Solving the Problems]

[0005] As a result of intensive studies to solve such problems, the present inventors have found that in a composite formed body in which a resin formed body and a metal formed body are joined, which is formed from a thermoplastic resin composition obtained by blending an appropriate amount of graphite subjected to an expansion treatment with a thermoplastic resin, a thermoplastic resin composition having excellent adhesion between the resin formed body and the metal formed body, little reduction in bonding strength after a heat cycle test, and excellent durability can be obtained, and thus the present invention has been achieved.

[0006] Hereinafter, the present invention will be specifically described.

[0007] <Component A: 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 fluoride resin, ethylene-tetrafluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, vinyl chloride resin, vinylidene chloride resin, polyethylene, polypropylene, chlorinated polyolefin, water-crosslinked polyolefin, modified polyolefin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polystyrene, ABS resin, polyamide, methacrylic resin, polyacetal, polycarbonate resin, cellulose-based resin, polyvinyl alcohol, polyurethane elastomer, polyimide, polyetherimide, polyamideimide, ionomer resin, polyphenylene oxide, methylpentene polymer, polyarylsulfone, polyaryl ether, polyether ketone, polyphenylene sulfide, polysulfone, wholly aromatic polyester, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, and blends of various other polymeric substances. Among these, polycarbonate resins are preferred from the viewpoint of good mechanical properties.

[0008] The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0009] 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-phenylene) Examples of suitable dihydric phenols include 4,4'-(m-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. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among these, bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0010] 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, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as part or all of the dihydric phenol component are suitable for applications where dimensional change due to water absorption and shape stability are particularly strict requirements. 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 suitable that component A constituting the resin composition is a copolymer polycarbonate resin of the following (1) to (3).

[0011] (1) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and BCF accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol components constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, and even more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, and even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and Bis-TMC accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%).

[0012] These special polycarbonate resins may be used alone or in a suitable mixture of two or more. They may also be used in a mixture with a commonly used bisphenol A polycarbonate resin. The production methods and properties 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.

[0013] Among the various polycarbonate resins mentioned above, those in which the copolymer composition and the like are adjusted to bring the water absorption rate and Tg (glass transition temperature) into the ranges described below have good hydrolysis resistance of the polymer itself and are remarkably excellent in terms of low warpage after molding, and are therefore particularly suitable in fields where dimensional stability is required. (i) a polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C; or (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0014] Here, the water absorption rate of polycarbonate resin is a value measured by using a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm and immersing it in water at 23°C for 24 hours in accordance with ISO 62-1980, and then measuring the moisture content. Also, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0015] Carbonate precursors that can be used include carbonyl halides, carbonic acid diesters, and haloformates, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0016] When producing a polycarbonate resin by interfacial polymerization of the dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant to prevent oxidation of the dihydric phenol, etc. may be used as needed. The polycarbonate resin of the present invention also includes branched polycarbonate resins copolymerized with a trifunctional or higher polyfunctional aromatic compound, polyester carbonate resins copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, copolymerized polycarbonate resins copolymerized with a bifunctional alcohol (including alicyclic), and polyester carbonate resins copolymerized with such bifunctional carboxylic acid and bifunctional alcohol. A mixture of two or more of the obtained polycarbonate resins may also be used.

[0017] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)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.

[0018] The structural units derived from polyfunctional aromatic compounds in the branched polycarbonate resin are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols and the structural units derived from such polyfunctional aromatic compounds. In particular, in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols. The proportion of such branched structures is 1 It can be calculated by H-NMR measurement.

[0019] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The bifunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0020] The reaction modes of the methods for producing the polycarbonate resin of the present invention, such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of a cyclic carbonate compound, are well known in various literatures and patent publications.

[0021] 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 ~4.0×10 4 and more preferably 2.0 × 10 4 ~3.5×10 4 , and more preferably 2.2 × 10 4 ~3.0×10 4 The viscosity average molecular weight is 1.8 × 10 4 Polycarbonate resins with a viscosity average molecular weight of less than 4.0 × 10 may not provide good mechanical properties. 4 Resin compositions obtained from polycarbonate resins exceeding this range are inferior in terms of fluidity during injection molding and therefore are inferior in versatility.

[0022] The polycarbonate resin may be obtained by mixing resins having a viscosity average molecular weight outside the above range. 4), the entropy elasticity of the resin is improved. As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in molding processability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, component A has a viscosity average molecular weight of 7×10 4 ~3×10 5 Polycarbonate resin A-1-1 component), and viscosity average molecular weight 1 × 10 4 ~3×10 4 The aromatic polycarbonate resin (component A-1-2) has a viscosity average molecular weight of 1.6 × 10 4 ~3.5×10 4 A polycarbonate resin (component A-1) (hereinafter, sometimes referred to as a "polycarbonate resin containing a high molecular weight component") having the formula:

[0023] In such a polycarbonate resin containing a high molecular weight component (component A-1), the molecular weight of component A-1-1 is 7 × 10 4 ~2×10 5 is preferable, and more preferably 8×10 4 ~2×10 5 , and more preferably 1 × 10 5 ~2×10 5 , particularly preferably 1 × 10 5 ~1.6×10 5 The molecular weight of component A-1-2 is 1 × 10 4 ~2.5×10 4 is preferable, and more preferably 1.1 × 10 4 ~2.4×10 4 , and more preferably 1.2 × 10 4 ~2.4×10 4 , particularly preferably 1.2 × 10 4 ~2.3×10 4 is.

[0024] 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 ratios and adjusting the ratio to satisfy a predetermined molecular weight range. Preferably, the component A-1-1 accounts for 2 to 40% by weight, more preferably 3 to 30% by weight, even more preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight, of 100% by weight of component A-1.

[0025] Methods for preparing component A-1 include: (1) a method in which component A-1-1 and component A-1-2 are polymerized independently and then mixed; (2) a method in which an aromatic polycarbonate resin that shows multiple polymer peaks in a molecular weight distribution chart obtained by GPC, as typified by the method disclosed in Japanese Patent Laid-Open No. 5-306336, is produced in the same system, and the aromatic polycarbonate resin is produced so as to satisfy the conditions for component A-1 of the present invention; and (3) a method in which an aromatic polycarbonate resin obtained by such a production method (production method (2)) is mixed with component A-1-1 and / or component A-1-2 that have been produced separately.

[0026] The viscosity average molecular weight in the present invention is determined by first calculating the specific viscosity (η SP ) was measured using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and calculate the viscosity average molecular weight M using 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

[0027] The viscosity average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is calculated as follows: The composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve the soluble components in the composition. The soluble components are collected by filtration through Celite. The solvent in the resulting solution is then removed. The solid obtained after solvent removal is thoroughly dried to obtain a solid of components soluble in methylene chloride. 0.7 g of this solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined in the same manner as above. The viscosity average molecular weight M is then calculated from the specific viscosity in the same manner as above.

[0028] The polycarbonate resin of the present invention may be a polycarbonate-polydiorganosiloxane copolymer resin, which is preferably 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):

[0029] [ka]

[0030] [In the above general formula (1), R 1 and R 2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 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, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; a and b each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2):

[0031] [ka]

[0032] (In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 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, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, and d is an integer of 4 to 7.

[0033] [ka]

[0034] [In the above 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 or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; e and f are each an integer 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.

[0035] Examples of the dihydric phenol (I) from which the carbonate structural unit represented by 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- 4,4'-Dihydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-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,Examples include 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, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0036] Among these, 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, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0037] 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, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and are particularly preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 and R 10are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) from which the carbonate structural unit represented by the above general formula (3) is derived, for example, a compound represented by the following general formula (I) is suitably used.

[0038] [ka]

[0039] p+q is preferably 4 to 120, more preferably 30 to 120, further preferably 30 to 100, and most preferably 30 to 60.

[0040] Next, a method for producing the above-mentioned preferred polycarbonate-polydiorganosiloxane copolymer resin will be described below. A mixed solution of chloroformate compounds containing the chloroformate of dihydric phenol (I) and / or carbonate oligomers of dihydric phenol (I) having terminal chloroformate groups is prepared by reacting dihydric phenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of dihydric phenol (I) in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution. Phosgene is preferred as the chloroformate-forming compound.

[0041] When producing a chloroformate compound from a dihydric phenol (I), the entire amount of dihydric phenol (I) from which the carbonate structural unit represented by the general formula (1) is derived may be converted into the chloroformate compound at once, or a portion of it may be added as a post-added monomer as a reaction raw material to the subsequent interfacial polycondensation reaction. The post-added monomer is added to facilitate the subsequent polycondensation reaction and need not be added if not necessary. The method for this chloroformate compound production reaction is not particularly limited, but it is typically carried out in a solvent in the presence of an acid binder. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added, and this addition is preferred. The proportion of the chloroformate-forming compound used may be adjusted appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction. When using phosgene, a preferred chloroformate-forming compound, a method of blowing gasified phosgene into the reaction system is preferably used.

[0042] 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, and organic bases such as pyridine, or mixtures thereof. Similarly, the proportion of the acid binder used can be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder per mole of the dihydric phenol (I) used to form the chloroformate compound of the dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents).

[0043] The solvent may be any of various inert solvents used in the production of known polycarbonates, either singly or in combination. Typical 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.

[0044] The pressure in the reaction to produce chloroformate compounds is not particularly limited, and may be normal, elevated, or reduced pressure, although it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C, and since the reaction often generates heat, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range in the reaction to produce chloroformate compounds can be determined using known interfacial reaction conditions, and the pH is usually adjusted to 10 or higher.

[0045] In producing the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, after preparing a mixed solution of chloroformate compounds containing a chloroformate of dihydric phenol (I) and a carbonate oligomer of dihydric phenol (I) having terminal chloroformate groups in the above manner, the mixed solution is stirred and a dihydroxyaryl-terminated polydiorganosiloxane (II) from which the carbonate structural unit represented by general formula (3) is derived is added at a rate of 0.01 mol / min or less per mol of dihydric phenol (I) charged in preparing the mixed solution, thereby causing interfacial polycondensation between the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound, thereby obtaining a polycarbonate-polydiorganosiloxane copolymer resin.

[0046] Polycarbonate-polydiorganosiloxane copolymer resins can be made into branched polycarbonate-polydiorganosiloxane copolymer resins by using a branching agent in combination with a dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)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.

[0047] The method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin may be a method in which a branching agent is included in the mixed solution during the production reaction of a chloroformate compound, or a method in which a branching agent is added during the interfacial polycondensation reaction after the completion of the production reaction. The proportion 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 %, and particularly preferably 0.05 to 1.0 mol %, of the total amount of carbonate structural units constituting the copolymer resin. The amount of branched structures is 1 It can be calculated by H-NMR measurement.

[0048] The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but usually it can be preferably carried out at normal pressure or about the autogenous pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 °C. Since heat is usually generated during polymerization, it is desirable to carry out water cooling or ice cooling. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally specified, but usually it is carried out for 0.5 to 10 hours. In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate-polydiorganosiloxane copolymer resin with a desired reduced viscosity SP / c]. The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (degree of purification) by subjecting it to various post-treatments such as known separation and purification methods.

[0049] The content of the polydiorganosiloxane block represented by the following general formula (4) contained in the above general formula (3) is preferably 1.0 to 10.0% by weight, more preferably 1.0 to 8.0% by weight, still more preferably 1.0 to 5.0% by weight, and most preferably 1.0 to 3.0% by weight based on the total weight of the polycarbonate resin composition.

[0050] [Chemical formula]

[0051] (In the above general formula (4), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, 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.)

[0052] [[ID= The resin composition of the present invention contains thermally expanded graphite as component B. The thermally expanded graphite used in the present invention is artificial graphite obtained by heat-treating natural graphite, petroleum coke, petroleum pitch, amorphous carbon, or other mineral produced in nature, at 2000°C or higher to artificially orient irregularly arranged micrographite crystals. The artificial graphite is then immersed in concentrated sulfuric acid, concentrated nitric acid, or the like, and further treated with an oxidizing agent such as hydrogen peroxide or hydrochloric acid to form a graphite intercalation compound. The resulting graphite is then washed with water and rapidly heated to 800-1000°C to expand the graphite in the C-axis direction of the raw graphite. When graphite that has not been thermally expanded is used, it disperses poorly in the resin, resulting in a significant decrease in the bond strength between the resin and metal after a heat cycle test. Natural graphite is particularly preferred as the graphite to be thermally expanded.

[0053] The thermally expanded graphite is preferably prepared by subjecting the graphite to the thermal expansion treatment and then pulverizing the resultant graphite. Furthermore, the thermally expanded graphite is in a cocoon-like expanded form, and generally has a specific volume of 100 cc / g or more. While it is possible to pulverize the cocoon-like expanded graphite in this form using various known pulverizers, it is more preferable to compress the cocoon-like expanded graphite using a roll, press, or the like to form a sheet, and then pulverize the sheet using various known pulverizers.

[0054] The thermally expanded graphite is classified as needed and then washed and dried as needed to reduce the amount of residual acid components. Its average particle size is preferably 0.1 to 1000 μm, more preferably 25 to 1000 μm. If the average particle size is less than 0.1 μm, extrusion stability during resin composition production may be poor, resulting in reduced productivity. If the average particle size exceeds 1000 μm, the appearance of the molded product surface may be poor.

[0055] The surface of the graphite subjected to the thermal expansion treatment in the present invention may be subjected to surface treatment, such as epoxy treatment, urethane treatment, silane coupling treatment, oxidation treatment, etc., in order to increase the affinity with the aromatic polycarbonate resin as long as the properties of the composition of the present invention are not impaired. Further, the apparent bulk density of the graphite subjected to the thermal expansion treatment of the present invention is preferably 0.01 to 0.50 g / cc, more preferably 0.05 to 0.30 g / cc, and still more preferably 0.10 to 0.25 g / cc. When the apparent bulk density exceeds 0.50 g / cc, the expansion ratio of the expanded graphite is low, and thus the thermal conductivity may be poor. When the apparent bulk density is less than 0.01 g / cc, the extrusion stability during the production of the resin composition may be poor and the productivity may decrease.

[0056] The content of component B is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of component A. When the content of component B is less than 1 part by weight, the retention rate of the bonding strength between the resin and the metal after the heat cycle test is significantly reduced. Further, when it exceeds 80 parts by weight, the fluidity of the resin decreases, and thus the resin does not sufficiently enter the groove portion on the metal surface during metal insert molding, and thus a sufficient bonding strength between the resin and the metal cannot be obtained. <*

[0057] <Component C: fibrous filler> The resin composition of the present invention preferably contains a fibrous filler as component C. Examples of fibrous fillers include glass fiber, carbon fiber, milled carbon fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whiskers, boron whiskers, aluminum borate whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, xonotlite, palygorskite (attapulgite), and sepiolite, and other fibrous inorganic fillers; fibrous heat-resistant organic fillers, such as aramid fiber, polyimide fiber, and polybenzthiazole fiber, are also examples. These fillers are also surface-coated with a different material, such as a metal or metal oxide. Examples of fillers surface-coated with a different material include metal-coated glass fiber and metal-coated carbon fiber. The surface coating method for dissimilar materials is not particularly limited, and examples include various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD methods (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering. Among these fibrous fillers, glass fiber, carbon fiber, carbon milled fiber, and aramid fiber are preferred, with glass fiber and carbon fiber being more preferred. The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 18 μm, more preferably 15 μm. Meanwhile, the lower limit of the fiber diameter is more preferably 1 μm, even more preferably 6 μm. The fiber diameter here refers to the number-average fiber diameter. The number-average fiber diameter is a value calculated from images obtained by scanning electron microscopy of the residue collected after dissolving a molded product in a solvent or decomposing a resin with a basic compound, and the ashing residue collected after ashing in a crucible.

[0058] When the fibrous filler is glass fiber, the glass composition of the glass fiber is not particularly limited, and may be any of various glass compositions, such as A-glass, C-glass, and E-glass. Such glass fillers may contain components such as TiO2, SO3, and P2O5, as necessary. Among these, E-glass (alkali-free glass) is more preferred. Glass fibers that have been surface-treated with known surface treatment agents, such as silane coupling agents, titanate coupling agents, or aluminate coupling agents, are preferred in terms of improving mechanical strength. Furthermore, glass fibers that have been bundled with olefin-based resins, styrene-based resins, acrylic-based resins, polyester-based resins, epoxy-based resins, and urethane-based resins are preferred, with epoxy-based resins and urethane-based resins being particularly preferred in terms of mechanical strength. The amount of sizing agent attached to the bundled glass fibers is preferably 0.1 to 3 wt %, more preferably 0.2 to 1 wt %, based on 100 wt % of the glass fibers. Flat cross-section glass fibers can also be used as the fibrous filler. The flat cross-section glass fiber is a glass fiber having an average major axis of the fiber cross-section of preferably 10 to 50 μm, more preferably 15 to 40 μm, and even more preferably 20 to 35 μm, and an average major axis to minor axis ratio (major axis / minor axis) of preferably 1.5 to 8, more preferably 2 to 6, and even more preferably 2.5 to 5. When flat cross-section glass fibers having an average major axis to minor axis ratio within this range are used, the anisotropy is significantly improved compared to when non-circular cross-section fibers having a cross-section of less than 1.5 are used. Furthermore, examples of the flat cross-sectional shape include, in addition to flat, non-circular cross-sectional shapes such as elliptical, cocoon-shaped, and trilobal shapes, as well as shapes similar to these. Among these, a flat shape is preferred from the viewpoints of improving 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 fibers is preferably 2 to 120, more preferably 2.5 to 70, and even more preferably 3 to 50. If the ratio of the fiber length to the average fiber diameter is less than 2, the effect of improving mechanical strength may be small, and if the ratio of the fiber length to the average fiber diameter exceeds 120, anisotropy may increase and the appearance of the molded article may also deteriorate. The average fiber diameter of such flat cross section glass fibers refers to the number average fiber diameter when the flat cross section shape is converted into a perfect circle of the same area.The average fiber length refers to the number-average fiber length in the reinforced polycarbonate resin composition of the present invention. This number-average fiber length is calculated by an image analyzer from an optical microscope image of the filler residue collected after high-temperature incineration of a molded article, dissolution with a solvent, or chemical decomposition. This value is calculated using the fiber diameter as a guide, excluding fibers with lengths shorter than the diameter.

[0059] The content of component C is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, and 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, peeling may occur during insert molding, and if it exceeds 100 parts by weight, sufficient bonding strength between the resin and metal may not be obtained.

[0060] (Other additives) In order to improve the thermal stability and designability of the thermoplastic resin composition of the present invention, additives used for these purposes can be advantageously used. These additives will be specifically described below.

[0061] (I) Heat stabilizer The thermoplastic resin composition of the present invention may contain various known stabilizers, such as phosphorus-based stabilizers and hindered phenol-based antioxidants.

[0062] (i) Phosphorus-based stabilizers The thermoplastic resin composition of the present invention preferably contains a phosphorus-based stabilizer to the extent that it does not promote hydrolysis. Such a phosphorus-based stabilizer improves thermal stability during production or molding processing, and improves mechanical properties, color, and molding stability. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, as well as tertiary phosphines. Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, and tris(di-n-butylphenyl)phosphite. bis(2,6-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol 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, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, etc. Furthermore, as other phosphite compounds, those which react with dihydric phenols to have a cyclic structure 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, and the like can be mentioned. Examples of the phosphate compound 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, and diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

[0063] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl ... Examples of suitable phosphonite compounds include (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, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Preferred are tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. These phosphonite compounds can be used in combination with phosphite compounds having an aryl group substituted with two or more alkyl groups, which is preferred. Examples of suitable phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine.A particularly preferred tertiary phosphine is triphenylphosphine. The above phosphorus-based stabilizers can be used alone or in combination of two or more. Among the above phosphorus-based stabilizers, it is preferable to use an alkyl phosphate compound, such as trimethyl phosphate. In addition, it is also a preferred embodiment to use such an alkyl phosphate compound in combination with a phosphite compound and / or a phosphonite compound.

[0064] (ii) Hindered phenol antioxidants The thermoplastic resin composition of the present invention may contain a hindered phenol-based antioxidant. Such incorporation is effective in suppressing deterioration of color during molding and over extended use. Examples of hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)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, and 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'-ethyl 2,2'-butylidene-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-te rt-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'-dithiobis(2,6-di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[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 Examples include 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-tris2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. All of these are readily available. The above hindered phenol-based antioxidants can be used alone or in combination of two or more. The amounts of the phosphorus-based stabilizer and the hindered phenol-based antioxidant to be added are each preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight, and even more preferably 0.005 to 0.3 parts by weight, per 100 parts by weight of Component A.

[0065] (iii) Heat stabilizers other than those mentioned above The thermoplastic resin composition of the present invention can also contain heat stabilizers other than the phosphorus-based stabilizer and hindered phenol-based antioxidant. Suitable examples of such heat stabilizers include lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Details of such stabilizers are described in Japanese Patent Application Laid-Open No. 7-233160. This compound is commercially available under the trade name Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers containing this compound in combination with various phosphite compounds and hindered phenol compounds are commercially available. A suitable example is Irganox HP-2921 manufactured by the same company. The amount of lactone-based stabilizer added 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 examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. The amount of such sulfur-containing stabilizers added 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. An epoxy compound can be added to the thermoplastic resin composition of the present invention as needed. Such epoxy compounds are added for the purpose of inhibiting mold corrosion, and essentially any compound having an epoxy functional group can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, copolymer of methyl methacrylate and glycidyl methacrylate, copolymer of styrene and glycidyl methacrylate, etc. The amount of such epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and even more preferably 0.005 to 0.1 parts by weight, per 100 parts by weight of Component A.

[0066] (II) Flame retardants The thermoplastic resin composition of the present invention can be blended with a flame retardant. The incorporation of such compounds not only improves flame retardancy, but also, depending on the properties of each compound, improves antistatic properties, fluidity, rigidity, and thermal stability. Examples of such flame retardants include (i) organometallic salt-based flame retardants (e.g., organic alkali (earth) metal sulfonates, organic metal borate-based flame retardants, and organic metal stannate-based flame retardants), (ii) organophosphorus-based flame retardants (e.g., organic group-containing monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) silicone-based flame retardants consisting of silicone compounds, and (iv) fibrillated PTFE. Of these, organometallic salt-based flame retardants and organophosphorus-based flame retardants are preferred. These may be used singly or in combination.

[0067] (i) Organic metal salt flame retardants The organic metal salt compound is preferably an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, and preferably an alkali (earth) metal salt of an organic sulfonate. Examples of the alkali (earth) metal salt of an organic sulfonate include metal salts of fluorine-substituted alkylsulfonic acids, such as metal salts of perfluoroalkylsulfonic acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, with alkali metals or alkaline earth metals, 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. Examples of alkali metals constituting the metal salt include lithium, sodium, potassium, rubidium, and cesium, while examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Alkali metals are more preferred. Among these alkali metals, rubidium and cesium, which have a larger ionic radius, are preferred when higher transparency is required. However, these metals are not widely used and are difficult to purify, which can result in cost disadvantages. On the other hand, metals with smaller ionic radii, such as lithium and sodium, may be disadvantageous in terms of flame retardancy. Taking these factors into consideration, the alkali metals in the alkali metal sulfonates can be selected appropriately, but potassium sulfonates, which have an excellent balance of properties in all respects, are most suitable. Such potassium salts can also be used in combination with alkali metal sulfonates of other alkali metals.

[0068] Specific examples of alkali metal salts of perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctane sulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. Here, the number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8.

[0069] Among these, potassium perfluorobutanesulfonate is particularly preferred. Perfluoroalkylsulfonic acid alkali (earth) metal salts made from alkali metals usually contain a certain amount of fluoride ions (F-). The presence of such fluoride ions can reduce flame retardancy, so it is preferable to reduce their content as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The fluoride ion content is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. For production efficiency, it is preferable that the fluoride ion content be 0.2 ppm or more. Such alkali (earth) metal perfluoroalkylsulfonate salts with reduced fluoride ion content can be produced by known methods, including reducing the amount of fluoride ions contained in the raw materials used to produce the fluorine-containing organometallic salt, removing hydrogen fluoride and other products obtained by the reaction by heating or using gases generated during the reaction, and reducing the amount of fluoride ions by purifying the fluorine-containing organometallic salt using recrystallization, reprecipitation, or other purification methods. Because organometallic flame retardants are relatively soluble in water, they are preferably produced using ion-exchanged water, particularly water with an electrical resistance of 18 MΩ cm or more, i.e., an electrical conductivity of approximately 0.55 μS / cm or less, by dissolving and washing the product at a temperature higher than room temperature, followed by cooling and recrystallization.

[0070] Specific examples of the alkali (earth) metal salts of aromatic sulfonates include disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, and benzenesulfonic acid Examples of suitable sulfonates include strontium, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfone-3,4'-disulfonate, 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 benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, a formalin condensate of sodium naphthalenesulfonate, and a formalin condensate of sodium anthracenesulfonate. Of these alkali (earth) metal salts of aromatic sulfonic acid, 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 (with a weight ratio of the former to the latter of 15 / 85 to 30 / 70) are particularly preferred.

[0071] Suitable examples of organic metal salts other than alkali(earth) metal sulfonates include alkali(earth) metal salts of sulfates and alkali(earth) metal salts of aromatic sulfonamides. Examples of alkali(earth) metal salts of sulfates include alkali(earth) metal salts of sulfates of monohydric and / or polyhydric alcohols. Examples of sulfates of monohydric and / or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, sulfates of polyoxyethylene alkylphenyl ethers, mono-, di-, tri-, and tetrasulfates of pentaerythritol, sulfates of lauric acid monoglyceride, sulfates of palmitic acid monoglyceride, and sulfates of stearic acid monoglyceride. Examples of alkali(earth) metal salts of these sulfates include alkali(earth) metal salts of lauryl sulfate. Examples of alkali (earth) metal salts of aromatic sulfonamides include saccharin, N-(p-tolylsulfonyl)-p-toluenesulfonimide, N-(N'-benzylaminocarbonyl)sulfanilimide, and alkali (earth) metal salts of N-(phenylcarboxyl)sulfanilimide. The content of the organic metal salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, even more preferably 0.01 to 0.3 parts by weight, and particularly preferably 0.03 to 0.15 parts by weight, per 100 parts by weight of component A.

[0072] (ii) Organophosphorus flame retardants As the organic phosphorus flame retardant, an aryl phosphate compound or a phosphazene compound is preferably used. These organic phosphorus flame retardants have a plasticizing effect, which is advantageous in that they can improve molding processability. As the aryl phosphate compound, various phosphate compounds known as conventional flame retardants can be used, but more preferably, one or more phosphate compounds represented by the following general formula (5) can be used.

[0073] [ka]

[0074] (In the above formula, M represents a divalent organic group derived from a dihydric phenol, and Ar 1 , Ar 2 , Ar 3 , and Ar 4 each represents a monovalent organic group derived from a monohydric phenol. a, b, c, and d each independently represent 0 or 1, and m is an integer of 0 to 5. In the case of a mixture of phosphate esters with different degrees of polymerization m, m represents the average value thereof and is a value of 0 to 5.

[0075] The phosphate compound of the above formula may be a mixture of compounds having different m numbers, and in the case of such a mixture, the average m number is preferably in the range of 0.5 to 1.5, more preferably 0.8 to 1.2, even more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

[0076] Specific preferred examples of the dihydric phenol 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, and among these, resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.

[0077] The above Ar 1 , Ar2 , Ar 3 , and Ar 4 Specific preferred examples of the monohydric phenol from which the formula (I) is derived include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol, and among these, phenol and 2,6-dimethylphenol are preferred.

[0078] Such monohydric phenols may be substituted with halogen atoms, and specific examples of phosphate compounds having a group derived from such monohydric phenols include tris(2,4,6-tribromophenyl)phosphate, tris(2,4-dibromophenyl)phosphate, and tris(4-bromophenyl)phosphate.

[0079] 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, as well as phosphate oligomers based on resorcinol bis(di(2,6-xylyl)phosphate), phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphoric acid ester oligomers based on bisphenol A bis(diphenyl phosphate) (here, "based on" means that it may contain small amounts of other components with different degrees of polymerization, and more preferably, the component in formula (5) where m=1 accounts for 80% by weight or more, more preferably 85% by weight or more, and even more preferably 90% by weight or more).

[0080] As the phosphazene compound, various phosphazene compounds known as flame retardants can be used, but phosphazene compounds represented by the following general formulas (6) and (7) are preferred.

[0081] [ka]

[0082] [ka]

[0083] (In the formula, X 1 , X 2 , X 3 , X 4 represents an organic group that does not contain hydrogen, a hydroxyl group, an amino group, or a halogen atom, and r represents an integer of 3 to 10.

[0084] In the above formulas (6) and (7), X 1 , X 2 , X 3 , X 4 Examples of the halogen-free organic group represented by the formula (6) include an alkoxy group, a phenyl group, an amino group, an allyl group, etc. Among these, the cyclic phosphazene compound represented by the formula (6) is preferred, and further, X 1 , X 2 Cyclic phenoxyphosphazenes in which is a phenoxy group are particularly preferred.

[0085] The content of the organophosphorus 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 organophosphorus flame retardant is less than 1 part by weight, it is difficult to obtain a flame-retardant effect, and if it exceeds 50 parts by weight, problems such as strand breakage and surging may occur during kneading and extrusion, resulting in reduced productivity.

[0086] (iii) Silicone flame retardants Silicone compounds used as silicone flame retardants improve flame retardancy through a chemical reaction during combustion. Various compounds previously proposed as flame retardants for aromatic polycarbonate resins can be used as such compounds. Silicone compounds are thought to impart a high flame retardant effect, particularly when used with polycarbonate resins, by bonding with themselves or with components derived from the resin during combustion to form a structure, or by a reduction reaction during the formation of this structure.

[0087] Therefore, it is preferable that the silicone compound contains a group that is highly active in such a reaction, and more specifically, it is preferable that the silicone compound contains a predetermined amount of at least one group selected from alkoxy groups and hydrogen (i.e., Si-H groups). The content of such groups (alkoxy groups, Si-H groups) is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably 0.12 to 1 mol / 100 g, and even more preferably 0.15 to 0.6 mol / 100 g. This ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound using an alkaline decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and a methoxy group is particularly suitable.

[0088] Generally, the structure of a silicone compound is composed of any combination of the following four types of siloxane units: M unit: (CH3)3SiO 1 / 2 , H(CH3)2SiO 1 / 2 , H2(CH3)SiO 1 / 2 , (CH3)2(CH2=CH)SiO 1 / 2 , (CH3)2(C6H5)SiO 1 / 2 , (CH3)(C6H5)(CH2=CH)SiO 1 / 2 D units: (CH3)2SiO, H(CH3)SiO, H2SiO, H(C6H5)SiO, (CH3)(CH2=CH)SiO, (C6H5)2SiO and other difunctional siloxane units; T units: (CH3)SiO 3 / 2 , (C3H7)SiO 3 / 2 , HSiO 3 / 2 , (CH2=CH)SiO 3 / 2 , (C6H5)SiO 3 / 2 Q unit: a tetrafunctional siloxane unit represented by SiO2.

[0089] Specific examples of the structure of the silicone compound used in the silicone flame retardant include rational formulas Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and more preferred structures are MmDn and MmDnTp.

[0090] Here, the coefficients m, n, p, and q in the rational formula are integers of 1 or greater that represent the degree of polymerization of each siloxane unit, and the sum of the coefficients in each rational formula represents the average degree of polymerization of the silicone compound. This average degree of polymerization is preferably in the range of 3 to 150, more preferably 3 to 80, even more preferably 3 to 60, and particularly preferably 4 to 40. The more preferable the range, the better the flame retardancy. Furthermore, as described below, silicone compounds containing a predetermined amount of aromatic groups also exhibit excellent transparency and hue. As a result, good reflected light can be obtained. Furthermore, when any of m, n, p, and q is a value of 2 or greater, the siloxane unit with that coefficient can be two or more types of siloxane units that have different hydrogen atoms or organic residues bonded to them.

[0091] The silicone compound may have a linear or branched structure. The organic residue bonded 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, ethyl, propyl, butyl, hexyl, and decyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; and aralkyl groups such as tolyl. An alkyl group, alkenyl group, or aryl group having 1 to 8 carbon atoms is even more preferred. As the alkyl group, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, and propyl, are particularly preferred. Furthermore, silicone compounds used as silicone flame retardants preferably contain aryl groups. Meanwhile, silane and siloxane compounds used as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone flame retardants in their preferred embodiments in that they exhibit better effects when free of aryl groups. The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and alkoxy group. Examples of such reactive groups include an amino group, a carboxy group, an epoxy group, a vinyl group, a mercapto group, and a methacryloxy group.

[0092] 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, and even more preferably 1 to 5 parts by weight, per 100 parts by weight of component A.

[0093] (iv) Polytetrafluoroethylene with fibril-forming ability (fibrillated PTFE) The fibrillated PTFE may be fibrillated PTFE alone or may be a mixed form of fibrillated PTFE, i.e., a polytetrafluoroethylene-based mixture consisting of fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has an extremely high molecular weight and tends to bond PTFE molecules together to form fibers under external action such as shear force. Its number-average molecular weight is in the range of 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number-average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380°C, as disclosed in, for example, JP-A-6-145520. That is, fibrillated PTFE has a melt viscosity at 380°C of 10 7 ~10 13 poise range, preferably 10 8 ~10 12 The PTFE is in the range of poise. In addition to the solid form, the PTFE can also be used in the form of an aqueous dispersion. Furthermore, the fibrillated PTFE improves dispersibility in resins, and it is also possible to use a PTFE mixture with other resins to obtain better flame retardancy and mechanical properties.

[0094] Furthermore, as disclosed in Japanese Patent Application Laid-Open No. 6-145520, a structure having such fibrillated PTFE as a core and low molecular weight polytetrafluoroethylene as a shell is also preferably used.

[0095] Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui-DuPont Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L from Daikin Chemical Industries, Ltd.

[0096] The mixed form of fibrillated PTFE can be prepared by (1) mixing an aqueous dispersion of fibrillated PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitation to obtain a co-aggregated mixture (methods described in Japanese Patent Laid-Open Nos. 60-258263 and 63-154744, etc.), (2) mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (method described in Japanese Patent Laid-Open No. 4-272957), or (3) uniformly mixing an aqueous dispersion of fibrillated PTFE with an organic polymer particle solution and extracting the co-aggregated mixture from the mixture. (4) a method of simultaneously removing the media (methods described in JP-A-06-220210, JP-A-08-188653, etc.), (5) a method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, and then polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (methods described in JP-A-11-29679, etc.).

[0097] Commercially available products of these mixed forms of fibrillated PTFE include the Metablen A series, represented by Mitsubishi Rayon Co., Ltd.'s "Metablen A3000" (trade name), "Metablen A3700" (trade name), and "Metablen A3800" (trade name), Shine Polymer's SN3300B7 (trade name), and GE Specialty Chemicals' "BLENDEX B449" (trade name).

[0098] The proportion of fibrillated PTFE in the mixed form is preferably 1 to 95% by weight, more preferably 10 to 90% by weight, and most preferably 20 to 80% by weight, of 100% by weight of the mixture.

[0099] When the proportion of fibrillated PTFE in the mixed form is within this range, good dispersibility of the fibrillated PTFE can be achieved. 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 even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of component A.

[0100] (III) Dyes and pigments The thermoplastic resin composition of the present invention can further contain various dyes and pigments to provide molded articles with diverse design properties. Examples of dyes and pigments that can be 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, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the thermoplastic resin composition of the present invention can be blended with a metallic pigment to achieve better metallic colors. Aluminum powder is a suitable metallic pigment. Furthermore, blending with a fluorescent brightener or other fluorescent dye that emits light can provide even better design effects that take advantage of the emitted light color.

[0101] (IV) Fluorescent whitening agents 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. Examples include stilbene-based, benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, Eastman Chemical Company's EASTOBRITE OB-1, and Showa Chemical Co.'s Hakkol PSR. The fluorescent brightener absorbs ultraviolet energy from light and radiates 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 the content exceeds 0.1 part by weight, the effect of improving the color tone of the composition is small.

[0102] (V) Compounds with heat absorbing properties The thermoplastic resin composition of the present invention may contain a compound capable of absorbing heat rays. Suitable examples of such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide, immonium oxide, and titanium oxide, various metal compounds with excellent near-infrared absorption capabilities, such as metal boride-based and tungsten oxide-based near-infrared absorbers such as lanthanum boride, cerium boride, and tungsten boride, and carbon fillers. Examples of such phthalocyanine-based near-infrared absorbers include MIR-362 manufactured by Mitsui Chemicals, Inc., and are readily available commercially. Examples of carbon fillers include carbon black, graphite (both natural and synthetic), and fullerenes, with carbon black and graphite being preferred. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and even more preferably 0.001 to 0.07 parts by weight, relative to 100 parts by weight of Component A. The contents of the metal oxide-based near-infrared absorber, metal boride-based near-infrared absorber, and carbon filler in the thermoplastic resin composition of the present invention are preferably in the range of 0.1 to 200 ppm (weight ratio), and more preferably 0.5 to 100 ppm.

[0103] (VI) Light diffusing agent The thermoplastic resin composition of the present invention can 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 polymeric fine particles are already known as light diffusing agents for polycarbonate resins. More preferred examples include acrylic crosslinked particles with a particle size of several micrometers and silicone crosslinked particles such as polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include spherical, discoidal, cylindrical, and irregular shapes. Such spherical shapes do not necessarily need to be perfect spheres and include deformed ones, and such cylindrical shapes include cubes. Preferred light diffusing agents are spherical, and the more uniform their 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 even more preferably 0.01 to 3 parts by weight, per 100 parts by weight of Component A. Two or more light diffusing agents can be used in combination.

[0104] (VII) Highly reflective white pigment The thermoplastic resin composition of the present invention can be blended with a highly light-reflecting white pigment to impart a light-reflecting 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 such highly light-reflecting white pigment 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 types of highly light-reflecting white pigments can be used in combination.

[0105] (VIII) UV absorbers The thermoplastic resin composition of the present invention can be blended with an ultraviolet absorber to impart weather resistance. Specific examples of such ultraviolet absorbers include benzophenone-based ones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 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-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.Specific examples of the ultraviolet absorber include benzotriazole-based ones, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 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, Examples of the 2-hydroxyphenyl-2H-benzotriazole skeleton include 2-(2-hydroxy-5-acryloxyethylphenyl)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, as well as polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomers, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomers.Specific examples of hydroxyphenyltriazine-based ultraviolet absorbers include 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. Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Specific examples of cyclic iminoester-based ultraviolet absorbers include 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). Specific examples of cyanoacrylate-based ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene. Furthermore, the ultraviolet absorber may be a polymeric ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a photostable monomer with a monomer such as an alkyl (meth)acrylate by adopting a structure of a radically polymerizable monomer compound. Suitable examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.Among these, benzotriazole-based and hydroxyphenyltriazine-based compounds are preferred in terms of UV absorption ability, and cyclic iminoester-based and cyanoacrylate-based compounds are preferred in terms of heat resistance and color. Specific examples include "Chemisorb 79" from Chemipro Kasei Co., Ltd. and "Tinuvin 234" from BASF Japan Ltd. The UV absorbents may be used alone or in combination of two or more.

[0106] 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, and particularly preferably 0.05 to 0.5 part by weight, per 100 parts by weight of component A.

[0107] (IX) Antistatic agents The thermoplastic resin composition of the present invention may require antistatic properties. In such cases, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonate phosphonium salts, such as arylsulfonate phosphonium salts (e.g., dodecylbenzenesulfonate phosphonium salt) and alkylsulfonate phosphonium salts, as well as borate phosphonium salts, such as tetrafluoroborate phosphonium salt. The content of the phosphonium salt is preferably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably 1.5 to 3 parts by weight, per 100 parts by weight of Component A. Examples of antistatic agents include (2) alkali (earth) metal organic sulfonates, such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. As mentioned above, such metal salts are also used as flame retardants. More specifically, examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the alkali (earth) metal organic sulfonate is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight, per 100 parts by weight of component A. In particular, alkali metal salts such as potassium, cesium, and rubidium are suitable.

[0108] Examples of antistatic agents include (3) organic ammonium sulfonates such as ammonium alkylsulfonates and ammonium arylsulfonates. The amount of the ammonium salt is suitably 0.05 parts by weight or less per 100 parts by weight of the components A and B. Examples of antistatic agents include (4) polymers containing a poly(oxyalkylene) glycol component as a constituent, such as polyetheresteramide. The amount of the polymer is suitably 5 parts by weight or less per 100 parts by weight of component A.

[0109] (X) Filler The thermoplastic resin composition of the present invention can be blended with various fillers known as reinforcing fillers other than fibrous fillers. Various plate-like fillers and granular fillers can be used as such fillers. Here, plate-like fillers are fillers that have a plate-like shape (including those with an uneven surface and curved plates). Granular fillers are fillers with shapes other than these, including irregular shapes.

[0110] Preferred examples of plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-like fillers coated with a different material such as a metal or metal oxide. The particle size is preferably in the range of 0.1 to 300 μm. This particle size refers to the median diameter (D50) of the particle size distribution measured by X-ray transmission, a type of liquid-phase precipitation method, in the range up to about 10 μm. In the range of 10 to 50 μm, this refers to the median diameter (D50) of the particle size distribution measured by laser diffraction / scattering. In the range of 50 to 300 μm, this refers to the value measured by the vibrating sieve method. These particle sizes are those in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based, or may be in the form of a granule that has been bundled or compressed with various resins such as olefin-based resins, styrene-based resins, acrylic resins, polyester-based resins, epoxy-based resins, and urethane-based resins, or higher fatty acid esters.

[0111] (XI) Other resins and elastomers In the thermoplastic resin composition of the present invention, a small proportion of other resins or elastomers can be used in place of part of the resin component, provided that the effects of the present invention are not impaired. The amount of other resins or elastomers added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even 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, 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 core-shell elastomers such as MBS (methyl methacrylate / styrene / butadiene) rubber, MB (methyl methacrylate / butadiene) rubber, and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

[0112] (XII) Other additives The thermoplastic resin composition of the present invention may also contain other flow improvers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents, and the like.

[0113] <Production of Resin Composition> Any method can be used to produce the resin composition of the present invention. For example, components A, B, and optionally other components can be thoroughly mixed using a premixing device such as a V-type blender, Henschel mixer, mechanochemical device, or extrusion mixer, followed by granulation using an extrusion granulator or briquetting machine, if necessary, followed by melt-kneading using a melt mixer such as a vented twin-screw extruder, and pelletization using a pelletizer or other device. Other methods include feeding components A, B, and optionally other components independently to a melt mixer such as a vented twin-screw extruder, or premixing a portion of component A and the other components and then feeding the premixer separately from the remaining components. If some of the components to be blended are liquid, a liquid injection device or liquid addition device can be used to feed the components to the melt mixer.

[0114] <Metal molded body> The metal material forming the resin-metal composite molded body of the present invention is preferably a metal material having a joint with a groove formed therein, and more preferably a metal material in which the groove is formed by irradiation with continuous wave laser light or pulse wave laser light. The metal constituting the metal material is not particularly limited and can be appropriately selected from known metals depending on the application. Examples include iron, various stainless steels, aluminum or its alloys, copper, magnesium, and alloys containing these. Among these, aluminum (aluminum alone) and aluminum alloys are preferred, and aluminum alloys are more preferred, in terms of light weight and high strength. Metal molded bodies are formed by cutting, plastic processing such as pressing, punching, grinding, polishing, electrical discharge machining, and other thinning processes, into shapes such as flat plates, curved plates, rods, cylinders, and blocks. The surface of the metal molded body preferably has a large surface area to improve adhesion to the resin, and specifically, a roughened surface is preferred. The method for roughening the surface of a metal component is preferably a method of roughening the surface by a means selected from a chemical etching method using a known etching agent, irradiation with laser light, etching processing, press processing, and blast processing, and more preferably a method of roughening the surface by irradiation with continuous wave laser light or pulse wave laser light.

[0115] <Creating a resin-metal composite molding> The resin-metal composite molded product of the present invention is a composite molded product characterized by the metal material and the resin molded body being bonded together by the resin molded body entering the grooves of the metal material. The method for producing the composite molded product is not particularly limited, and examples include resin molding methods such as injection molding, extrusion molding, hot press molding, compression molding, transfer molding, laser welding molding, reaction injection molding (RIM), rim molding (LIM), and thermal spray molding. Among these, a manufacturing method including a step of irradiating a joining surface of a metal molded body with continuous wave laser light or pulse wave laser light and a step of injection molding a thermoplastic resin composition in a mold, in which the portion of the metal molded body irradiated with continuous wave laser light or pulse wave laser light in the previous step, including the joining surface, is preferred from the standpoint of flexibility in shape and productivity. Furthermore, when producing a composite comprising an aluminum resin composition coating in which an aluminum surface is coated with a resin composition coating, examples include a coating method in which the resin composition is dissolved or dispersed in a solvent and applied, as well as various other painting methods. Other painting methods include baking coating, electrodeposition coating, electrostatic coating, powder coating, and UV-curable coating.

[0116] <Electronic control device> The resin-metal composite molded product of the present invention is preferably used in a control device having a circuit board on which electronic components are mounted, a base having protrusions for installing the circuit board, and a cover formed of resin and covering the circuit board and the base. Furthermore, it is more preferable that the protrusions of the base consist solely of the thermoplastic resin composition of the present application. Furthermore, it is preferable that the base have protrusions and the cover have multiple holes in order to suppress heat generation in the electronic circuit board. [Effects of the Invention]

[0117] The thermoplastic resin composition of the present invention, which contains an appropriate amount of expanded graphite, is a thermoplastic resin composition that, when bonded to a metal, has excellent adhesion to the metal and exhibits excellent durability with little decrease in bond strength after a heat cycle test. These technologies are not available in conventional resin-metal bonding technologies, and are extremely useful in various industrial applications such as office automation equipment and electrical and electronic equipment, with extremely significant industrial effects. DETAILED DESCRIPTION OF THE INVENTION

[0118] The present inventors currently consider the best embodiment of the present invention to be a combination of the preferred ranges of the above-mentioned requirements, and representative examples thereof are described in the following examples, although the present invention is not limited to these embodiments. [Example]

[0119] The present invention will be further explained below with reference to examples, but is not limited thereto. The evaluation was carried out on the following items.

[0120] (i) Adhesion strength Pellets obtained from each composition in the examples were dried in a hot air dryer at 100°C for 5 hours and then molded into specimens for resin-metal adhesion tests conforming to ISO 19095-2 using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U-SM IV) at a cylinder temperature of 310°C and a mold temperature of 110°C (170mm length x 10mm width x 4mm thickness: butt joint type). The metal molded body used was an aluminum plate (thickness: 4mm) of alloy number 5052 specified in JIS H4000 cut to dimensions of 85mm x 10mm, and then laser-cut to form grooves on the metal surface. The grooves had a diameter of 40-80µm, a depth of 75-125µm, and a spacing of 90-120µm. The obtained test piece was conditioned at 23°C and 50% RH for 24 hours, and then the resin-metal adhesion strength (tensile strength using butt-jointed test pieces) was measured in accordance with ISO 19095-3. The adhesion strength is preferably 20 MPa or more.

[0121] (ii) Strength retention rate after heat cycle test The composite molded article used in "(i) Adhesion strength" was subjected to a heat cycle test (2000 cycles, each cycle consisting of heating at 80°C for 30 minutes, followed by cooling at -40°C for 30 minutes), and then the resin-metal adhesion strength (tensile strength of butt-jointed test pieces) was measured and the strength retention rate was calculated using the following formula (1). The strength retention rate is preferably 80% or more.

[0122]

number

[0123] [Examples 1 to 12, Comparative Examples 1 to 5] Resin compositions containing the components listed in Table 1 were prepared as follows. The components were weighed and mixed uniformly using a tumbler, excluding the fibrous filler. The mixture was then fed into an extruder to prepare the resin compositions. The extruder used was a vented twin-screw extruder (TEX-30XSST, fully intermeshing, co-rotating, double-start screws) manufactured by The Japan Steel Works, Ltd. The extrusion conditions were a throughput of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 280 to 320°C. The fibrous filler was fed into the extruder through the second feed port using a side feeder, while the remaining polycarbonate resin and additives were fed into the extruder through the first feed port. The first feed port is the feed port farthest from the die, and the second feed port is the feed port located between the extruder die and the first feed port. The resulting pellets were then molded into test specimens for evaluation using an injection molding machine as described above. The evaluation results are shown in Table 1. The symbols used in Table 1 represent the following components:

[0124] (Component A) A-1: Aromatic polycarbonate resin, Teijin Ltd. 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, 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 Industries Co., Ltd. (C component) C-1: Glass fiber, Nittobo Co., Ltd. Chopped strand CS3PE455FB (product name) C-2: Carbon fiber, Teijin Limited HTC422 (product name) (Other ingredients) D-1: Stabilizer, Johoku Chemical Industry Co., Ltd. JC-224 (product name) D-2: Weatherproofing agent, Tinuvin 234 (product name) manufactured by BASF Japan Ltd. D-3: Release agent, Riken Vitamin Co., Ltd. Rikemal SL-900 (product name) D-4: Colorant, Koshigaya Chemical Industry Co., Ltd. RB90003S (product name)

[0125] [Table 1]

Claims

1. 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, characterized in that the thermoplastic resin composition contains 1 to 80 parts by weight of (B) expanded graphite (component B) and 1 to 100 parts by weight of (C) a fibrous filler (component C) per 100 parts by weight of (A) a thermoplastic resin (component A).

2. 2. The thermoplastic resin composition according to claim 1, wherein component C is glass fiber and / or carbon fiber.

3. A composite molded body in which a metal molded body having a groove portion on its surface and a resin molded body made of the thermoplastic resin composition described in claim 1 or 2 are joined together, characterized in that the metal molded body and the resin molded body are joined together by the resin molded body entering the groove portion.

4. 4. The composite molding according to claim 3, wherein the grooves on the surface of the metal molding are formed by irradiating the surface of the metal molding with a continuous wave laser beam or a pulse wave laser beam.

5. A method for producing a composite molded body according to claim 3 or 4, characterized in that it comprises a step of irradiating a joining surface of the metal molded body with continuous wave laser light or pulse wave laser light, and a step of placing a portion of the metal molded body including the joining surface irradiated with continuous wave laser light or pulse wave laser light in a mold and injection molding the thermoplastic resin composition according to claim 1 or 2.

6. 5. An electronic control device comprising: a circuit board on which electronic components are mounted; a base portion having protrusions for installing said circuit board; and a cover portion formed of resin and covering said circuit board and said base portion, wherein said base portion is the composite molded product according to claim 3 or 4.

7. 7. The electronic control device according to claim 6, wherein the protrusions on the base are made of the thermoplastic resin composition according to claim 1 or 2.

8. 8. The electronic control device according to claim 6, wherein the cover portion has a plurality of holes.

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