Thermoplastic resin composition, and molding comprising the same

Abstract

To provide a thermoplastic resin composition excellent in releasability and dimension stability even under severe processing conditions, small in impact property reduction, and excellent also in recyclability, and a molding comprising the same.SOLUTION: A thermoplastic resin composition includes: (A) 100 pts.wt. of a thermoplastic resin (component A); (B) 0.01 to 1 pt.wt. of a fatty acid ester resin (component B) containing a constitutional unit derived from at least one alcohol selected from the group consisting of 1-docosanol, and 1-octacosanol; (C) 1 to 150 pts.wt. of an inorganic filler (component C); and (D) 0.001 to 1 pt.wt. of at least one phosphoric acid ester (component D) selected from the group consisting of a phosphonic acid ester (component D-1) having an acid value of 0.01 to 0.30 mgKOH / g, an acidic phosphoric acid ester (component D-2) having an acid value of 10 to 200 mgKOH / g, a trialkyl phosphate (component D-3), and a stearyl phosphate zinc salt (component D-4).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin composition that is excellent in mold release properties and dimensional stability, has little decrease in impact characteristics, and is excellent in recyclability even under severe processing conditions, and a molded article made thereof.

Background Art

[0002] Thermoplastic resin compositions are used in a wide range of fields such as casings and parts of electric, electronic, and OA equipment, interior and exterior parts for automobiles, furniture, musical instruments, and miscellaneous goods. In particular, in recent years, in order to realize a sustainable society, high recyclability is desired for thermoplastic resin compositions. On the other hand, it is widely known to use phosphorus-based compounds as heat stabilizers in thermoplastic resin compositions. Patent Document 1 discloses adding a specific phosphorus-based compound to a resin component composed of a polycarbonate-based resin and a polyester resin. Patent Document 2 discloses using phosphorus-based compounds in combination. However, with existing methods, the thermal stability during molding is still insufficient, and in particular, in applications where thin-wall and weight reduction are required, the molding conditions tend to be high temperature and the cases of insufficient thermal stability are increasing. Furthermore, the demand for recycling and reusing products is also high, and there is an increasing need to propose materials that can satisfy the requirements for a thermoplastic resin composition with little deterioration in physical properties and excellent recyclability even under severe processing conditions.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

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 mold release properties and dimensional stability, little reduction in impact properties, and excellent recyclability even under severe processing conditions, and a molded article made therefrom.

Means for Solving the Problems

[0005] As a result of intensive studies to solve such problems, the present inventors have found that by blending a fatty acid ester resin having a specific alcohol component, an inorganic filler, and a specific phosphate ester with a thermoplastic resin, even under severe processing conditions, it is possible to provide a thermoplastic resin composition having excellent mold release properties and dimensional stability, little reduction in impact properties, and excellent recyclability, and a molded article made therefrom, and thus have reached the present invention.

[0006] That is, the present invention is as follows. 1. A thermoplastic resin composition containing 0.01 to 1 part by weight of a fatty acid ester resin (component B) containing a structural unit derived from at least one alcohol selected from the group consisting of (B) 1-docosanol and 1-octacosanol, 1 to 150 parts by weight of an inorganic filler (component C), and 0.001 to 1 part by weight of at least one phosphate ester (component D) selected from the group consisting of a phosphonic acid ester (component D-1) having an acid value of 0.01 to 0.30 mgKOH / g, an acidic phosphate ester (component D-2) having an acid value of 10 to 200 mgKOH / g, a trialkyl phosphate (component D-3), and a zinc stearyl phosphate salt (component D-4) per 100 parts by weight of the thermoplastic resin (component A). 2. The thermoplastic resin composition according to item 1 above, wherein the component A is at least one thermoplastic resin selected from the group consisting of (A-1) a polycarbonate resin (component A-1), (A-2) an ABS resin (component A-2), (A-3) a polyester resin excluding component B (component A-3), (A-4) an AS resin (component A-4), (A-5) a PS resin (component A-5), and (A-6) an AAS resin (component A-6). 3. The thermoplastic resin composition according to item 1 or 2 above, wherein the content of the component A-1 is 40 to 100 parts by weight in 100 parts by weight of the component A. 4. The thermoplastic resin composition according to any one of the preceding items 1 to 3, wherein the C component is at least one inorganic filler selected from the group consisting of (C-1) glass fiber (C-1 component), (C-2) plate-like glass filler (C-2 component), (C-3) fibrous carbon filler (C-3 component), (C-4) non-fibrous carbon filler (C-4 component), and (C-5) silicate mineral (C-5 component). 5. The thermoplastic resin composition according to any one of the preceding items 1 to 4, wherein the D component is triethyl phosphonoacetate. 6. The thermoplastic resin composition according to any one of the preceding items 1 to 4, wherein the D component is trimethyl phosphate. 7. The thermoplastic resin composition according to any one of the preceding items 1 to 6, wherein the melting point of the B component is 80 to 95 °C. 8. The thermoplastic resin composition according to any one of the preceding items 1 to 7, wherein the acid value of the B component is 50 mgKOH / g or less. 9. A molded article comprising the thermoplastic resin composition according to any one of the preceding items 1 to 8.

[0007] Hereinafter, the present invention will be specifically described.

[0008] <Component A: Thermoplastic Resin Composition> The thermoplastic resin used as the A component of the present invention is preferably a polycarbonate resin, an ABS resin, a polyester resin excluding the B component, an AS resin, a PS resin, an AAS resin, an AES resin, a polyamide resin, a polyolefin resin, a fluororesin, a PPS resin, a PEEK resin, a polyarylate resin, a polyacetal resin, etc., and more preferably at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, an ABS resin, a polyester resin excluding the B component, an AS resin, a PS resin, and an AAS resin.

[0009] <Component A-1: Polycarbonate Resin> The polycarbonate resin used as Component A-1 of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

[0010] Typical examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylenediisopropylidene)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. A preferred dihydric phenol is bis(4-hydroxyphenyl)alkane, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance and is widely used.

[0011] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is possible to use, as component A-1, special polycarbonate resins produced using other dihydric phenols. For example, as part or all of the dihydric phenol component, 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-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") are used. Polycarbonate resins (homopolymers or copolymers) are suitable for applications where requirements for dimensional changes due to water absorption and morphological stability are particularly strict. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more, based on the total amount of the dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is one of the copolymer polycarbonate resins of the following (1) to (3). (1) A copolymer polycarbonate resin in which, in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%) and BCF is 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%). (3) In 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%), and Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%) of the copolymerized polycarbonate resin.

[0012] These special polycarbonate resins may be used alone or may be appropriately mixed and used in two or more kinds. Further, they can also be used in mixture with the commonly used bisphenol A type polycarbonate resin. The production methods and characteristics of these special polycarbonate resins are described in detail, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580, and the like.

[0013] Among the various polycarbonate resins described above, those in which the water absorption rate and Tg (glass transition temperature) are within the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance of the polymer itself and are also extremely excellent in low warpage property after molding, and thus are particularly suitable in fields where form 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 rate 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 the polycarbonate resin is a value obtained by measuring the moisture content after immersing a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm in water at 23°C for 24 hours in accordance with ISO62-1980. The Tg (glass transition temperature) is a value obtained by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0015] As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate, etc. are used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, etc. are mentioned.

[0016] When producing a polycarbonate resin from the dihydric phenol and the carbonate precursor by an interfacial polymerization method, a catalyst, a terminal stopper, an antioxidant for preventing oxidation of the dihydric phenol, etc. may be used as necessary. Further, the polycarbonate resin of the present invention includes a branched polycarbonate resin copolymerized with a polyfunctional aromatic compound having three or more functional groups, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) dicarboxylic acid, a copolymerized polycarbonate resin copolymerized with a dihydric alcohol (including alicyclic), and a polyester carbonate resin copolymerized with such a dicarboxylic acid and a dihydric alcohol together. Further, a mixture obtained by mixing two or more of the obtained polycarbonate resins may also be used.

[0017] The branched polycarbonate resin can impart properties such as drip prevention performance to the thermoplastic resin composition of the present invention. Examples of the polyfunctional aromatic compound having three or more functional groups used in such a branched polycarbonate resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other triphenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, etc. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and particularly 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

[0018] The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and still more preferably 0.05 to 0.8 mol% in the total 100 mol% of the structural unit derived from the divalent phenol and the structural unit derived from such a polyfunctional aromatic compound. Further, particularly in the case of the melt transesterification method, branched structural units may be generated as side reactions. Also for the amount of such branched structural units, it is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and still more preferably 0.01 to 0.8 mol% in the total 100 mol% with the structural unit derived from the divalent phenol. The ratio of such a branched structure can be calculated by 1 1H-NMR measurement.

[0019] Aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. More preferred as the bifunctional alcohol are alicyclic diols, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0020] Reaction forms such as the interfacial polymerization method, melt transesterification method, carbonate prepolymer solid-phase transesterification method, and ring-opening polymerization method of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are well-known methods in various literatures and patent gazettes.

[0021] In producing the thermoplastic resin composition of the present invention, the viscosity-average molecular weight of the polycarbonate resin is preferably from 12,500 to 32,000, more preferably from 16,000 to 28,000, and still more preferably from 18,000 to 26,000. With a polycarbonate resin having a viscosity-average molecular weight of less than 12,500, good mechanical properties may not be obtained. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity-average molecular weight exceeding 32,000 may be inferior in molding processability.

[0022] The viscosity-average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from the specific viscosity (η SP ) calculated by the following formula in a solution of 0.7 g of polycarbonate dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t - t0) / t0 [t0 is the dropping time of methylene chloride, t is the dropping time of the sample solution] The viscosity-average molecular weight M is calculated from the obtained specific viscosity (η SP ) by the following mathematical formula. η SP / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23×10 -4 M 0.83 c = 0.7

[0023] Furthermore, the viscosity-average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble components in the composition. The soluble components are collected by filtration through Celite. Thereafter, the solvent in the obtained solution is removed. The solid after solvent removal is thoroughly dried to obtain a solid of the component soluble in methylene chloride. From a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride, the specific viscosity at 20°C is determined in the same manner as above, and the viscosity-average molecular weight M is calculated from the specific viscosity in the same manner as above.

[0024] As the polycarbonate resin of the present invention, a polycarbonate-polydiorganosiloxane copolymer resin can also be used. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0025] [Chemical formula]

[0026] [In the above general formula (1), R 1 and R 2each 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 a plurality of them, they may be the same or different. e and f are each an integer from 1 to 4, and W is at least one group selected from the group consisting of a single bond and a group represented by the following general formula (2).

[0027] [Chemical formula]

[0028] [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 them, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0029] [Chemical formula]

[0030] In the general formula (3) above, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are 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. p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 350 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms.]

[0031] Examples of the divalent phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl 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, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the like can be mentioned.,

[0032] Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferable, and particularly 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferable. Among them, 2,2-bis(4-hydroxyphenyl)propane having excellent strength and good durability is most suitable. Further, these may be used alone or in combination of two or more kinds.,

[0033] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, compounds shown below are preferably used.,

[0034]

Chemical formula

[0035] Hydroxyaryl-terminated polydiorganosiloxane (II) can be easily produced by subjecting phenols having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol, to a hydrosilylation reaction at the terminals of a polysiloxane chain having a predetermined degree of polymerization. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and particularly (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are preferred. Hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. In order to exhibit more excellent low outgassing property and low temperature impact property during high temperature molding, such molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and still more preferably 2 or less. When exceeding the upper limit of such a suitable range, the amount of outgas generated during high temperature molding is large, and the low temperature impact property may be inferior.

[0036] Also, in order to achieve a high degree of impact resistance, the degree of polymerization (p + q) of the diorganosiloxane of hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. Such degree of polymerization (p + q) of the diorganosiloxane is more preferably 10 to 200, still more preferably 12 to 150, and particularly preferably 14 to 100. When less than the lower limit of such a suitable range, the impact resistance, which is a characteristic of the polycarbonate-polydiorganosiloxane copolymer, is not effectively exhibited, and when exceeding the upper limit of such a suitable range, poor appearance appears.

[0037] The content of the polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in Component A-1 is preferably 0.1 to 50% by weight. Such a polydiorganosiloxane component content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. Above the lower limit of such a preferred range, it is excellent in impact resistance and flame retardancy, and below the upper limit of such a preferred range, a stable appearance that is not easily affected by molding conditions is easily obtained. Such a polydiorganosiloxane degree of polymerization and polydiorganosiloxane content can be calculated by 1 H-NMR measurement.

[0038] In the present invention, only one kind of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more kinds may be used. Also, within a range not interfering with the present invention, other comonomers other than the above-mentioned dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) can be used in combination within a range of 10% by weight or less based on the total weight of the copolymer.

[0039] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an aqueous alkali solution.

[0040] In generating the oligomer of the dihydric phenol (I), the total amount of the dihydric phenol (I) used in the method of the present invention may be made into an oligomer at once, or a part thereof may be added as a post-added monomer to the interfacial polycondensation reaction in the subsequent stage as a reaction raw material. The post-added monomer is added to accelerate the polycondensation reaction in the subsequent stage, and there is no need to add it deliberately if it is not necessary. The method of this oligomer formation reaction is not particularly limited, but usually, a method of performing it in a solvent in the presence of an acid binder is preferred.

[0041] The usage ratio of the carbonic ester-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When using a gaseous carbonic ester-forming compound such as phosgene, a method of blowing it into the reaction system can be preferably adopted.

[0042] As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof are used. The usage ratio of the acid binder may also be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, it is preferable to use 2 equivalents or a slightly excessive amount of the acid binder with respect to the number of moles of the divalent phenol (I) used for the formation of the oligomer (usually 1 mole corresponds to 2 equivalents).

[0043] As the solvent, various solvents inert to the reaction, such as those used in the production of known polycarbonates, may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

[0044] The reaction pressure for oligomer formation is not particularly limited and may be any of normal pressure, increased pressure, and reduced pressure. However, 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. In many cases, since heat is generated during polymerization, it is desirable to cool with water or ice. The reaction time depends on other conditions and cannot be generally specified, but it is usually carried out for 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

[0045] Thus, the present invention obtains a mixed solution containing an oligomer of a dihydric phenol (I) having a terminal chloroformate group, and then adds a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) which is highly purified to a molecular weight distribution (Mw / Mn) of 3 or less while stirring the mixed solution to the dihydric phenol (I), and interfacially polycondenses the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0046]

Chemical formula

[0047] (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 10 are 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, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 350 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

[0048] When performing an interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof are used. Specifically, when using the hydroxyaryl-terminated polydiorganosiloxane (II), or when adding a part of the above-mentioned divalent phenol (I) as a post-added monomer at this reaction stage, it is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of the post-added divalent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0049] The polycondensation by the interfacial polycondensation reaction of the oligomer of the divalent phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above-mentioned mixed solution.

[0050] In such a polymerization reaction, a terminal terminator or a molecular weight regulator is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid, alkyl ester of hydroxybenzoic acid, alkyl ester of hydroxyphenylalkanoic acid, alkyl ether phenol, etc. are exemplified. The amount used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all the divalent phenol-based compounds used, and it is of course possible to use two or more compounds in combination.

[0051] In order to promote the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added.

[0052] The reaction time of such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0053] The branching agent can be used in combination with the above-mentioned divalent phenolic compound to form a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other tris-phenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, etc. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and particularly 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, still more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol% in the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. Regarding the amount of such a branched structure 1 It can be calculated by H-NMR measurement.

[0054] The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually, it can be preferably carried out at normal pressure or at about the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 °C. Since heat is generated during polymerization in many cases, 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.

[0055] Optionally, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (such as mixing, fractionation, etc.) and / or chemical treatment (such as polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate-polydiorganosiloxane copolymer resin with a desired reduced viscosity [η SP / c].

[0056] The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods and recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (degree of purification).

[0057] The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. Such an average size is more preferably 1 to 30 nm, and even more preferably 5 to 25 nm. If it is less than the lower limit of such a preferred range, the impact resistance and flame retardancy are not sufficiently exhibited. If it exceeds the upper limit of such a preferred range, the impact resistance may not be stably exhibited.

[0058] The average domain size and normalized dispersion of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article according to the present invention were evaluated by the small angle X-ray scattering method (SAXS). The small angle X-ray scattering method is a method for measuring diffuse scattering and diffraction that occurs in a small angle region where the scattering angle (2θ) is less than 10°. In this small angle X-ray scattering method, when there are regions with different electron densities on the order of 1 to 100 nm in size in a substance, diffuse scattering of X-rays is measured due to the difference in electron density. Based on this scattering angle and scattering intensity, the particle size of the object to be measured is determined. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregated structure in which polydiorganosiloxane domains are dispersed in the matrix of a polycarbonate polymer, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10° is measured to measure the small angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical domains and there is a variation in the particle size distribution, a simulation is performed using commercially available analysis software from a hypothetical particle size and a hypothetical particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domains. According to the small angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domains dispersed in the matrix of the polycarbonate polymer, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, simply, and reproducibly. The average domain size means the number average of the individual domain sizes. The normalized dispersion means a parameter obtained by normalizing the spread of the particle size distribution by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size by the average domain size, and is represented by the following formula (1).

[0059]

Number

[0060] The terms "average domain size" and "normalized dispersion" used in connection with the present invention indicate measured values obtained by measuring the 1.0 mm thick portion of the three-layer plate prepared by the method described in the Examples by such small-angle X-ray scattering method. Further, the analysis was performed using an isolated particle model that does not consider the particle-particle interaction (particle-particle interference).

[0061] <A-2 component: ABS resin> The ABS resin used as Component A-2 of the present invention is a copolymer obtained by graft-polymerizing acrylonitrile and styrene onto polybutadiene. As the styrene, styrene and α-methylstyrene are particularly preferably used. The proportion of the components grafted onto such polybutadiene is preferably 95 to 20% by weight, more preferably 90 to 50% by weight, based on 100% by weight of the ABS resin component. Further, with respect to 100% by weight of the total amount of such acrylonitrile and styrene, acrylonitrile is preferably 5 to 50% by weight and styrene is preferably 95 to 50% by weight. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc. can be mixed and used for a part of the components graft-polymerized onto the above polybutadiene, and their content ratios are preferably 15% by weight or less in the ABS resin component. Further, various conventionally known initiators, chain transfer agents, emulsifiers, etc. used in the reaction can be used as necessary. In the ABS resin of the present invention, the particle diameter of the polybutadiene is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and even more preferably 0.3 to 1.5 μm. The particle size distribution of such polybutadiene can be either a single distribution or one having two or more peaks, and further, in its morphology, even if the particles form a single phase, or it may have a salami structure by containing an occluded phase around the particles. Also, it is well known that the ABS resin contains a copolymer composed of acrylonitrile and styrene that is not grafted to the diene rubber component, and the ABS resin of the present invention may also contain such free polymer components generated during such polymerization. The reduced viscosity of the copolymer composed of such free acrylonitrile and styrene is preferably such that the reduced viscosity (30 °C) is 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g. Also, the proportion of grafted acrylonitrile and styrene is preferably 20 to 200% in terms of grafting rate (weight%) with respect to polybutadiene, more preferably 20 to 70%. Such ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization methods, but those produced by bulk polymerization are particularly preferred.In the case of bulk polymerization, since it substantially does not contain alkali metal salts and the like derived from emulsifiers and the like, it is possible to better maintain the thermal stability of the thermoplastic resin composition. Also, the copolymerization method may be carried out in one stage or in multiple stages. Further, a blend of a vinyl compound polymer obtained by separately copolymerizing acrylonitrile and styrene with the ABS resin obtained by such a production method can also be preferably used.

[0062] <A-3 component: Polyester resin excluding B component> The polyester resin excluding the B component used as the A-3 component of the present invention is preferably a polyester resin in which 70 mol% or more, more preferably 90 mol% or more, and still more preferably 99 mol% or more of 100 mol% of the dicarboxylic acid component forming the polyester resin is an aromatic dicarboxylic acid.

[0063] Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, and the like. These dicarboxylic acids can be used alone or in admixture of two or more. In the polyester resin of the present invention, in addition to the above aromatic dicarboxylic acids, an aliphatic dicarboxylic acid component of less than 30 mol% can be copolymerized. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like.

[0064] Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether), and the like. These can be used alone or in combination of two or more. In addition, the content of the diphenol in the diol component is preferably 30 mol% or less.

[0065] Specific examples of the polyester resin include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, and copolymer polyester resins such as polyethylene isophthalate / terephthalate copolymer and polybutylene terephthalate / isophthalate copolymer.

[0066] The terminal group structure of the polyester resin used in the present invention is not particularly limited, and it may be the case where the ratio of the hydroxyl group to the carboxyl group in the terminal group is approximately the same, or the ratio of one of them may be large. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

[0067] Regarding the method for producing the polyester resin used in the present invention, in accordance with a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., the dicarboxylic acid component and the diol component are polymerized while heating, and the by-produced water or lower alcohol is discharged out of the system. For example, as the germanium-based polymerization catalyst, oxides, hydroxides, halides, alcoholates, phenolates of germanium, etc. can be exemplified, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxy germanium, etc. can be exemplified. In the present invention, compounds such as manganese, zinc, calcium, magnesium, etc. used in the transesterification reaction, which is the previous stage of the conventionally known polycondensation, can also be used in combination, and after the transesterification reaction is completed, it is also possible to deactivate such a catalyst with a compound such as phosphoric acid or phosphorous acid compound and then perform polycondensation. Furthermore, the method for producing the polyester resin can be either a batch type or a continuous polymerization type method.

[0068] Furthermore, among the above polyester resins, polyethylene terephthalate is particularly preferred. The polyethylene terephthalate of the present invention is a polymer obtained by a polycondensation reaction from terephthalic acid or its derivative and 1,4-ethanediol or its derivative, and includes those copolymerized with other dicarboxylic acid components and other alkylene glycol components as described above.

[0069] The terminal group structure of polyethylene terephthalate is not particularly limited as described above, but those with fewer terminal carboxyl groups compared to terminal hydroxyl groups are more preferred. Regarding the production method, the above various methods can be adopted, but a continuous polymerization type is preferred. This is because its quality stability is high and it is also cost-effective. Furthermore, it is preferable to use an organic titanium compound as the polymerization catalyst. This is because it tends to have little influence on transesterification reactions and the like. Specific preferred examples of such organic titanium compounds include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, and the reaction product of tetrabutyl titanate and trimellitic anhydride. The usage amount of the organic titanium compound is preferably in a ratio such that the titanium atom is 3 to 12 mg atoms% relative to the acid component constituting polyethylene terephthalate.

[0070] The molecular weight of the polyester resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 35 °C using o-chlorophenol as a solvent is preferably 0.5 to 1.5, more preferably 0.6 to 1.2.

[0071] <A-4 component: AS resin> The AS resin used as the A-4 component of the present invention is a copolymer of acrylonitrile and styrene. The AS resin may have high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during its production. Furthermore, in some cases, it is also possible to use polymers and copolymers with a narrow molecular weight distribution, block copolymers, and polymers and copolymers with high stereoregularity obtained by methods such as anionic living polymerization and radical living polymerization.

[0072] <A-5 component: PS resin> The PS resin used as the A-5 component of the present invention is a polymer of styrene.

[0073] <A-6 component: AAS resin> The AAS resin used as the A-6 component of the present invention is a copolymer composed of acrylonitrile, styrene, and an acrylic rubber component.

[0074] <Component B: Fatty acid ester resin> The thermoplastic resin composition of the present invention contains, as the B component, a fatty acid ester resin containing a structural unit derived from at least one alcohol selected from the group consisting of 1-docosanol and 1-octacosanol. When a fatty acid ester resin other than the above is used as the B component, the recyclability (release load) deteriorates. The fatty acid ester resin refers to an ester of one carboxylic acid selected from the group consisting of aliphatic monocarboxylic acids and aliphatic dicarboxylic acids and one alcohol selected from the group consisting of aliphatic saturated monohydric alcohols and aliphatic saturated polyhydric alcohols.

[0075] The content of the structural unit derived from at least one alcohol selected from the group consisting of 1-docosanol and 1-octacosanol is preferably 30 mol% or more, more preferably 40 mol% or more, of all the structural units derived from the alcohol in the fatty acid ester resin. The upper limit of the content of the above structural unit is preferably 70 mol% or less, more preferably 60 mol% or less.

[0076] The acid component of the fatty acid ester resin is not particularly limited, but saturated fatty acids having 10 to 30 carbon atoms are preferred, and saturated fatty acids having 16 to 27 carbon atoms are more preferred. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, henicosylic acid, behenic acid, etc., and it is particularly preferred to contain stearic acid and henicosylic acid.

[0077] The acid value of the B component is preferably 50 mgKOH / g or less, more preferably 10 mgKOH / g or less. When the acid value exceeds 50 mgKOH / g, the strength retention rate after retention and the recyclability may deteriorate. The lower limit of the acid value is not particularly limited, but it is preferably 1 mgKOH / g.

[0078] The melting point of component B is preferably 80°C to 95°C, more preferably 83°C to 93°C. If the melting point is less than 80°C, the recyclability may deteriorate, and if it exceeds 95°C, the mold release property may deteriorate.

[0079] The content of component B is 0.01 to 1 part by weight, preferably 0.05 to 0.9 part by weight, more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of component A. If the content of component B is less than 0.01 part by weight, the mold release property deteriorates, and if it exceeds 1 part by weight, the recyclability deteriorates.

[0080] <Component C: Inorganic filler> As the inorganic filler, conventionally known inorganic fillers can be used, and among them, at least one inorganic filler selected from the group consisting of (C-1) glass fiber (C-1 component), (C-2) plate-shaped glass filler (C-2 component), (C-3) fibrous carbon filler (C-3 component), (C-4) non-fibrous carbon filler (C-4 component), and (C-5) silicate mineral (C-5 component) is preferable.

[0081] <C-1 component: Glass fiber> As the glass fibers used in the present invention, the glass compositions such as A glass, C glass, and E glass are not particularly limited, and may optionally contain components such as TiO2, SO3, and P2O5. However, E glass (alkali-free glass) is more preferable when blended with a thermoplastic resin. Furthermore, it is also possible to use two or more of these glass fibers in combination. The glass fibers are obtained by rapidly cooling molten glass while stretching it by various methods to form a predetermined fibrous or milled shape. The rapid cooling and stretching conditions in such cases are not particularly limited either. In addition to a circular cross-section, shapes other than circular, such as elliptical, may-shaped, and three-lobed, may also be used. Furthermore, a mixture of circular glass fibers and glass fibers with a non-circular shape may also be used. Among these, more preferable are circular glass fibers. Also, it is preferable to pretreat these glass fibers with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, and an epoxy compound, or with an organicized onium ion in a swelling layered silicate in order to obtain more excellent mechanical strength. The glass fibers used in the present invention preferably have a diameter (D) in the range of 6 to 13 μm, a cut length (L) in the range of 30 μm to 9 mm, and an L / D in the range of 2.3 to 1500.

[0082] <C-2; Plate-shaped glass filler> Examples of the plate-shaped glass filler include glass flakes, metal-coated glass flakes, and metal oxide-coated glass flakes.

[0083] Glass flakes are plate-shaped glass fillers manufactured by methods such as the cylindrical blowing method and the sol-gel method. The size of the raw materials for such glass flakes can be selected in various ways depending on the degree of grinding and classification. The average particle size of the glass flakes is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and even more preferably 30 to 300 μm. Those within the above range may be excellent in terms of both handleability and moldability. Usually, plate-shaped glass fillers crack during melt-kneading processing with a resin, and their average particle size becomes smaller. The number average particle size of the plate-shaped glass filler in the thermoplastic resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and even more preferably 20 to 80 μm. Incidentally, such a number average particle size is a value calculated by an image analyzer from an image obtained by observing the residue of the plate-shaped glass filler collected by treatments such as high-temperature ashing of the molded product, dissolution with a solvent, and decomposition with a chemical, using an optical microscope. Also, when calculating such a value, it is a value obtained by a method of not counting those with a length less than the thickness as a reference. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1.5 to 6 μm. The plate-shaped glass filler having the above number average particle size and thickness may achieve good mechanical strength, appearance, and moldability.

[0084] For the glass composition of the plate-shaped glass filler, various glass compositions typified by A glass, C glass, and E glass are applicable and not particularly limited. Such a plate-shaped glass filler may contain components such as TiO2, SO3, and P2O5 as necessary. Among these, E glass (alkali-free glass) is more preferable. Also, the plate-shaped glass filler is preferably surface-treated with a well-known surface treatment agent, such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent, from the viewpoint of improving mechanical strength. Further, the plate-shaped glass filler is preferably used as one that has been subjected to a bundling treatment with an olefin-based resin, a styrene-based resin, an acrylic-based resin, a polyester-based resin, an epoxy-based resin, a urethane-based resin, or the like. The amount of the bundling agent adhered to the bundled plate-shaped glass filler is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight, in 100% by weight of the plate-shaped glass filler.

[0085] Furthermore, the plate-shaped glass filler includes those coated with different materials on the surface. Suitable examples of such different materials include metals and metal oxides. Examples of the metal include silver, copper, nickel, and aluminum. Examples of the metal oxide include titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide. The method for surface coating of such different materials is not particularly limited, and examples thereof include various known plating methods (e.g., electroplating, electroless plating, hot dip plating, etc.), vacuum deposition method, ion plating method, CVD methods (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD method, and sputtering method.

[0086] <C-3 component: fibrous carbon filler> Examples of the fibrous carbon filler include carbon fiber, metal-coated carbon fiber, carbon milled fiber, vapor-grown carbon fiber, and carbon nanotube. The carbon nanotube may have a fiber diameter of 0.003 to 0.1 μm and may be single-layer, double-layer, or multi-layer, with multi-layer (so-called MWCNT) being preferred. Among these, carbon fiber and metal-coated carbon fiber are preferred in terms of excellent mechanical strength and the ability to impart good electrical conductivity. Incidentally, good electrical conductivity has become one of the important properties required for resin materials in recent digital precision equipment (represented by digital still cameras, for example).

[0087] As the carbon fiber, any of cellulose-based, polyacrylonitrile-based, pitch-based, etc. can be used. Also, those obtained by a method of spinning without going through an infusibilization process typified by a method of spinning a raw material composition composed of a polymer of aromatic sulfonic acids or their salts by a methylene-type bond and a solvent, followed by carbonization, etc. can be used. Furthermore, any of general-purpose type, medium elastic modulus type, and high elastic modulus type can be used. Among these, the high elastic modulus type of polyacrylonitrile-based is particularly preferable. Also, the average fiber diameter of the carbon fiber is not particularly limited, but is usually 3 to 15 μm, preferably 5 to 13 μm. Carbon fibers having an average fiber diameter within such a range may be able to exhibit good mechanical strength and fatigue characteristics without impairing the appearance of the molded article. Also, the preferable fiber length of the carbon fiber is preferably 60 to 500 μm, more preferably 80 to 400 μm, and even more preferably 100 to 300 μm as the number average fiber length in the thermoplastic resin composition. Incidentally, such a number average fiber length is a value calculated by an image analysis device from an optical microscope observation, etc. from the residue of the carbon fiber collected by treatments such as high-temperature ashing of the molded article, dissolution by a solvent, and decomposition by a chemical. Also, when calculating such a value, it is a value obtained by a method of not counting those having a length less than the fiber length. The aspect ratio of the carbon fiber is preferably in the range of 10 to 200, more preferably in the range of 15 to 100, and even more preferably in the range of 20 to 50. The aspect ratio refers to the value obtained by dividing the average fiber length by the average fiber diameter.

[0088] Furthermore, the surface of the carbon fiber is preferably oxidized for the purpose of enhancing the adhesion to the matrix resin and improving the mechanical strength. The oxidation treatment method is not particularly limited, but for example, (1) a method of treating the fibrous carbon filler with an acid, an alkali, their salts, or an oxidizing gas, (2) a method of firing a fiber capable of being made into a fibrous carbon filler or a fibrous carbon filler at a temperature of 700 °C or higher in the presence of an inert gas containing an oxygen-containing compound, and (3) a method of heat-treating the fibrous carbon filler after oxidation treatment in the presence of an inert gas, etc. are preferably exemplified.

[0089] The metal-coated carbon fiber is obtained by coating a metal layer on the surface of a carbon fiber. Examples of the metal include silver, copper, nickel, and aluminum, among which nickel is preferable from the viewpoint of the corrosion resistance of the metal layer. As the method of metal coating, various methods described above for surface coating with different materials in the plate-shaped glass filler can be adopted. Among them, the plating method is preferably used. Further, as the original carbon fiber for such a metal-coated carbon fiber, those mentioned as the above carbon fiber can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm, and still more preferably 0.2 to 0.35 μm.

[0090] Such carbon fibers and metal-coated carbon fibers are preferably those subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, fibrous carbon fillers treated with a urethane resin or an epoxy resin are suitable in the present invention because of their excellent mechanical strength.

[0091] <C-4 component: non-fibrous carbon filler> Examples of the non-fibrous carbon filler include carbon black, graphite, and fullerenes. Among these, carbon black and graphite are preferable from the viewpoints of mechanical strength, moisture and heat resistance, and thermal stability. As the carbon black, carbon black having a DBP oil absorption of 100 ml / 100 g to 500 ml / 100 g is preferable from the viewpoint of conductivity. Such carbon black is generally acetylene black or ketjen black. Specifically, for example, Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd., Vulcan XC-72 and BP-2000 manufactured by Cabot Corporation, Ketjen Black EC and Ketjen Black EC-600JD manufactured by Lion Corporation, etc. can be mentioned.

[0092] As the graphite, either natural graphite known as graphite in mineral name or various artificial graphites can be used. As the natural graphite, any of earthy graphite, scaly graphite (Vein Graphite also referred to as massive graphite), and flaky graphite can be used. Further, artificial graphite is obtained by heat-treating amorphous carbon to artificially orient micro graphite crystals in an irregular arrangement, and includes, in addition to artificial graphite used for general carbon materials, kish graphite, decomposed graphite, and pyrolytic graphite. Artificial graphite used for general carbon materials is usually produced by graphitization treatment using petroleum coke or coal-based pitch coke as the main raw material.

[0093] The graphite of the present invention may include expandable graphite made expandable by a treatment typified by acid treatment or the graphite after the expansion treatment. The particle size of the graphite is preferably in the range of 2 to 300 μm. Such a particle size is more preferably 5 to 200 μm, still more preferably 7 to 100 μm, and particularly preferably 7 to 50 μm. By satisfying such a range, good mechanical strength and the appearance of the molded product may be achieved. On the other hand, when the average particle size is less than 2 μm, the effect of improving rigidity may be small, and when the average particle size exceeds 300 μm, the impact resistance is significantly reduced, and so-called floating of graphite may become conspicuous on the surface of the molded product, which is not preferable.

[0094] The fixed carbon content of the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98% by weight or more. Further, the volatile content of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less.

[0095] The average particle size of the graphite in the present invention refers to the particle size of the graphite itself before it becomes a resin composition, and such a particle size is determined by the laser diffraction / scattering method.

[0096] Also, as long as the properties of the composition of the present invention are not impaired, the surface of the graphite may be subjected to surface treatment, such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment, etc., in order to increase its affinity with the thermoplastic resin.

[0097] <C-5 Component: Silicate Mineral> As the silicate mineral, orthosilicate, disilicate, cyclic silicate, chain silicate, etc. are suitable. The silicate mineral takes a crystalline state, and further, the crystal may be in any form that each silicate mineral can take, and the shape of the crystal can also take various shapes such as fibrous and plate-like.

[0098] The silicate mineral may be any of a composite oxide, an oxygen acid salt (consisting of an ionic lattice), and a solid solution. Further, the composite oxide may be either a combination of two or more single oxides and a combination of two or more single oxides and oxygen acid salts. Further, in the solid solution, it may be either a solid solution of two or more metal oxides or a solid solution of two or more oxygen acid salts. It may also be a hydrate. The form of the crystal water in the hydrate may be any of those that enter as hydrogen silicate ions as Si-OH, those that enter ionically as hydroxide ions (OH - ) with respect to metal cations, and those that enter as H2O molecules in the gaps of the structure.

[0099] As the silicate mineral, an artificial synthetic product corresponding to a natural product can also be used. As the artificial synthetic product, silicate minerals obtained from various conventionally known methods, such as various synthetic methods using solid reaction, hydrothermal reaction, and ultrahigh pressure reaction, etc., can be used.

[0100] Specific examples of the silicate mineral in each metal oxide component are as follows. Here, the notation in parentheses is the name of a mineral or the like having such a silicate mineral as the main component, and it means that the compound in parentheses can be used as the exemplified metal salt.

[0101] Examples of those containing K2O as a component include K2O·SiO2, K2O·4SiO2·H2O, K2O·Al2O3·2SiO2 (calcilite), K2O·Al2O3·4SiO2 (leucite), and K2O·Al2O3·6SiO2 (orthoclase), etc.

[0102] Examples of those containing Na2O as a component include Na2O·SiO2 and its hydrates, Na2O·2SiO2, 2Na2O·SiO2, Na2O·4SiO2, Na2O·3SiO2·3H2O, Na2O·Al2O3·2SiO2, Na2O·Al2O3·4SiO2 (jadeite), 2Na2O·3CaO·5SiO2, 3Na2O·2CaO·5SiO2, and Na2O·Al2O3·6SiO2 (albite), etc.

[0103] Examples of those containing Li2O as a component include Li2O·SiO2, 2Li2O·SiO2, Li2O·SiO2·H2O, 3Li2O·2SiO2, Li2O·Al2O3·4SiO2 (petalite), Li2O·Al2O3·2SiO2 (eucryptite), and Li2O·Al2O3·4SiO2 (spodumene), etc.

[0104] Examples of those containing BaO as a component include BaO·SiO2, 2BaO·SiO2, BaO·Al2O3·2SiO2 (celsian), and BaO·TiO2·3SiOx2 (bentorite), etc.

[0105] Examples of materials containing CaO in their components include 3CaO·SiO2 (alite, a cement clinker mineral), 2CaO·SiO2 (belite, a cement clinker mineral), 2CaO·MgO·2SiO2 (okermanite), 2CaO·Al2O3·SiO2 (gehlenite), a solid solution of okermanite and gehlenite (merrillite), CaO·SiO2 (wollastonite (including both α-type and β-type)), CaO·MgO·2SiO2 (diopside), CaO·MgO·SiO2 (larnite), 3CaO·MgO·2SiO2 (merwinite), CaO·Al2O3·2SiO2 (anorthite), 5CaO·6SiO2·5H2O (tobermorite, and other tobermorite group hydrates such as 5CaO·6SiO2·9H2O), 2CaO·SiO2·H2O (hillebrandite) and other wollastonite group hydrates, 6CaO·6SiO2·H2O (xonotlite) and other xonotlite group hydrates, 2CaO·SiO2·2H2O (gyrolite) and other gyrolite group hydrates, CaO·Al2O3·2SiO2·H2O (lawsonite), CaO·FeO·2SiO2 (hedenbergite), 3CaO·2SiO2 (tilleyite), 3CaO·Al2O3·3SiO2 (grossular), 3CaO·Fe2O3·3SiO2 (andradite), 6CaO·4Al2O3·FeO·SiO2 (preocroite), as well as clinzoisite, piemontite, allanite, vesuvianite, onyx, scawtite, and augite, etc.

[0106] Furthermore, Portland cement can be cited as a silicate mineral containing CaO in its components. The type of Portland cement is not particularly limited, and any type such as ordinary, early strength, ultra-early strength, moderate heat, sulfate-resistant, white, etc. can be used. Additionally, various blended cements, such as blast furnace cement, silica cement, fly ash cement, etc. can also be used as component B. Also, blast furnace slag, ferrite, etc. can be cited as other silicate minerals containing CaO in their components.

[0107] Examples of ZnO-containing compounds include ZnO·SiO2, 2ZnO·SiO2 (troostite), and 4ZnO·2SiO2·H2O (hemimorphite). Examples of MnO-containing compounds include MnO·SiO2, 2MnO·SiO2, CaO·4MnO·5SiO2 (rhodonite), and cosrite. Examples of FeO-containing compounds include FeO·SiO2 (ferrosilite), 2FeO·SiO2 (ferroolivine), 3FeO·Al2O3·3SiO2 (almandine), and 2CaO·5FeO·8SiO2·H2O (tetactinocene).

[0108] CoO-containing compounds include CoO·SiO2 and 2CoO·SiO2. Examples include:

[0109] Materials containing MgO include MgO·SiO2 (steatite, enstatite), 2MgO·SiO2 (forsterite), 3MgO·Al2O3·3SiO2 (byrope), 2MgO·2Al2O3·5SiO2 (cordierite), 2MgO·3SiO2·5H2O, 3MgO·4SiO2·H2O (talc), 5MgO·8SiO2·9H2O (attapulgite), 4MgO·6SiO2·7H2O (sepiolite), and Examples include 3MgO·2SiO2·2H2O (chrysolite), 5MgO·2CaO·8SiO2·H2O (tremolite), 5MgO·Al2O3·3SiO2·4H2O (chlorite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), Na2O·3MgO·3Al2O3·8SiO2·H2O (lanthusite), as well as magnesium tourmaline, anthosphite, cummingtonite, vermiculite, and smectite.

[0110] Examples of materials that contain Fe2O3 include Fe2O3·SiO2.

[0111] Examples of materials that contain ZrO2 include ZrO2·SiO2 (zircon) and AZS refractories.

[0112] Examples of minerals containing Al2O3 include Al2O3·SiO2 (sillimanite, andalusite, kyanite), 2Al2O3·SiO2, Al2O3·3SiO2, 3Al2O3·2SiO2 (mullite), Al2O3·2SiO2·2H2O (kaolinite), Al2O3·4SiO2·H2O (pyrophyllite), Al2O3·4SiO2·H2O (bentonite), K2O·3Na2O·4Al2O3·8SiO2 (nepheline), K2O·3Al2O3·6SiO2·2H2O (muscovite, sericite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), as well as various zeolites, fluorphlogopite, and biotite.

[0113] Among the silicate minerals mentioned above, talc, mica, and wollastonite are particularly suitable because they have an excellent balance between rigidity and impact resistance, are excellent in moist heat resistance, thermal stability, and appearance, and are easily available.

[0114] The content of component C is 1 to 150 parts by weight, preferably 3 to 140 parts by weight, and more preferably 5 to 130 parts by weight, per 100 parts by weight of component A. If the content of component C is less than 1 part by weight, sufficient dimensional stability cannot be obtained, and if it exceeds 150 parts by weight, recyclability deteriorates.

[0115] <D成分:リン酸エステル> The thermoplastic resin composition of the present invention contains at least one phosphate ester selected from the group consisting of a phosphonate ester (component D-1) having an acid value of 0.01 to 0.30 mgKOH / g, an acidic phosphate ester (component D-2) having an acid value of 10 to 200 mgKOH / g, a trialkyl phosphate (component D-3), and a zinc salt of stearyl phosphate (component D-4). The content of component D is 0.001 to 1 part by weight, preferably 0.01 to 0.1 part by weight, and more preferably 0.01 to 0.07 part by weight, per 100 parts by weight of component A. When the content of component D is less than 0.001 part by weight or more than 1 part by weight, strength during molding processing is significantly reduced and recyclability is also impaired.

[0116] <Component D-1: Phosphonic Acid Ester> The phosphonic acid esters used in the present invention may be phosphonic acid monoesters, phosphonic acid diesters, or phosphonic acid triesters, with phosphonic acid triesters being preferred. Various combinations of esters with carbon numbers ranging from 1 to 22 can be used, but triethyl phosphonoacetate is most preferred. The acid value of the phosphonic acid ester is 0.01 - 0.30 mgKOH / g, preferably 0.01 - 0.20 mgKOH / g, and more preferably 0.05 - 0.15 mgKOH / g. Those with an acid value less than 0.01 mgKOH / g are not practical in production, and when the acid value is greater than 0.30 mgKOH / g, the strength during molding processing decreases significantly, and the recyclability also deteriorates. The acid value was measured using a potentiometric titration apparatus, and an alcohol solution of the phosphonic acid ester was titrated with a KOH alcohol solution.

[0117] <Component D-2: Acidic Phosphate Ester> The acidic phosphate esters used in the present invention may be phosphate monoesters, phosphate diesters, phosphate triesters, and mixtures thereof, with a mixture of monoester and diester being preferred. Various combinations of esters with carbon numbers ranging from 1 to 22 can be used, but stearyl acid phosphate is most preferred. The acid value of the acidic phosphate ester is 10 - 200 mgKOH / g, preferably 120 - 180 mgKOH / g, and more preferably 150 - 170 mgKOH / g. When the acid value is less than 10 mgKOH / g, it is not practical in production as an acidic phosphate ester, and when the acid value is greater than 200 mgKOH / g, the strength during molding processing decreases significantly, and the recyclability also deteriorates. The acid value was measured using a potentiometric titration apparatus, and an alcohol solution of the acidic phosphate ester was titrated with a KOH alcohol solution.

[0118] <Component D-3: Trialkyl Phosphate> Examples of the trialkyl phosphate used in the present invention include tributyl phosphate, triisopropyl phosphate, triethyl phosphate, and trimethyl phosphate, etc., and trimethyl phosphate is preferred.

[0119] <Component D: Zinc stearyl phosphate> Examples of the zinc stearyl phosphate used in the present invention include zinc distearyl phosphate, zinc monostearyl phosphate, and mixtures thereof, etc. When using the mixture, the mixing ratio (molar ratio) of zinc distearyl phosphate and zinc monostearyl phosphate is preferably 1:2.

[0120] (Other additives) For the improvement of the thermal stability and designability of the thermoplastic resin composition of the present invention, the additives used for these improvements are advantageously used. These additives will be specifically described below.

[0121] (I) Heat stabilizer The thermoplastic resin composition of the present invention can be blended with various known stabilizers other than component D. Examples of the stabilizer include hindered phenol antioxidants.

[0122] (i) Hindered phenol antioxidant 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'-thiobis(ethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris(2-[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl) isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane, etc. are exemplified. All of these are readily available. The above hindered phenol antioxidants can be used alone or in combination of two or more. The content of the hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, and still more preferably 0.005 to 0.3 part by weight with respect to 100 parts by weight of Component A.,

[0123] (ii) Heat stabilizers other than hindered phenol antioxidants The thermoplastic resin composition of the present invention can also contain heat stabilizers other than Component D and the 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 content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of Component A. Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. The content of such sulfur-containing stabilizers 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 blended into the thermoplastic resin composition of the present invention as needed. Such epoxy compounds are blended for the purpose of inhibiting mold corrosion, and basically 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 content of such epoxy compounds 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.

[0124] (II) Anti-drip agent As the anti-dripping agent, a fibrillation-type fluoropolymer is preferably used, and polytetrafluoroethylene (fibrillated PTFE) is particularly preferred. The fibrillated PTFE may be fibrillated PTFE alone or 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 a fibrous form under external influences 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 fibrillated PTFE is in the range of poise. In addition to a solid form, such fibrillated PTFE can also be used in the form of an aqueous dispersion. Furthermore, such fibrillated PTFE can be used in a mixed form with other resins to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties.

[0125] 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.

[0126] 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.

[0127] Examples of the mixed form of fibrillated PTFE include: (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (methods described in JP-A-60-258263 and JP-A-63-154744, etc.); (2) a method in which an aqueous dispersion of fibrillated PTFE and dried organic polymer particles are mixed (method described in JP-A-4-272957); (3) a method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from such a mixture (methods described in JP-A-06-220210, JP-A-08-188653, etc.); (4) a method in which a monomer for forming an organic polymer is polymerized in an aqueous dispersion of fibrillated PTFE (method described in JP-A-9-95583); and (5) a method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, then a vinyl monomer is polymerized in the mixed dispersion, and then a mixture is obtained (method described in JP-A-11-29679, etc.). Those obtained by such methods can be used.

[0128] Examples of commercially available products of these mixed forms of fibrillated PTFE include the Metablen A series represented by "Metablen A3000" (trade name), "Metablen A3700" (trade name), and "Metablen A3800" (trade name) of Mitsubishi Rayon Co., Ltd., SN3300B7 (trade name) of Shine Polymer Co., Ltd., and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals Co., Ltd.

[0129] Regarding the proportion of fibrillated PTFE in the mixed form, in 100% by weight of such a mixture, the fibrillated PTFE is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and most preferably 20% to 80% by weight.

[0130] 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 0.005 to 20 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. If the content is less than 0.005 part by weight, it is difficult to achieve the flame retardant effect, and if it exceeds 20 parts by weight, the thermal shock resistance (electromagnetic shielding properties) may decrease.

[0131] (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.

[0132] (IV) Fluorescent whitening agents The fluorescent brightener used in the thermoplastic resin composition of the present invention 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 and radiates it 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 amount exceeds 0.1 part by weight, the effect of improving the color tone of the composition may be small.

[0133] (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), more preferably 0.5 to 100 ppm.

[0134] (VI) Light diffusing agent In the thermoplastic resin composition of the present invention, a light diffusing agent can be blended to impart a light diffusing effect. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for thermoplastic resins. More preferably, examples include acrylic crosslinked particles with a particle size of several μm and silicone crosslinked particles typified by polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include spherical, disk-shaped, columnar, and irregular shapes. Such spherical shapes do not necessarily have to be perfect spheres and include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform its particle size, the more preferable. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of component A. Incidentally, two or more kinds of light diffusing agents can be used in combination.

[0135] (VII) White pigment for high light reflection In the thermoplastic resin composition of the present invention, a white pigment for high light reflection can be blended to impart a light reflection effect. As such a white pigment, titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferable. The content of such a white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight with respect to 100 parts by weight of component A. Incidentally, two or more kinds of white pigments for high light reflection can be used in combination.

[0136] (VIII) Ultraviolet absorber An ultraviolet absorber can be blended into the thermoplastic resin composition of the present invention 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-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.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 the ultraviolet absorber include, in the case of hydroxyphenyltriazines, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol. Further, examples include compounds in which the phenyl group of the above-exemplified compounds, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, is a 2,4-dimethylphenyl group. Specific examples of the ultraviolet absorber in the case of cyclic iminoesters include, for example, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazin-4-one). Specific examples of the ultraviolet absorber in the case of cyanoacrylates include, for example, 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. Further, the above ultraviolet absorber may be a polymer-type ultraviolet absorber obtained by copolymerizing such an ultraviolet-absorbing monomer and / or a light-stabilizing monomer with a monomer such as an alkyl (meth)acrylate by taking the structure of a monomer compound capable of radical polymerization. Preferred examples of the ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of 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.

[0137] 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.

[0138] (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.

[0139] 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.

[0140] (X) Elastomer The thermoplastic resin composition of the present invention may contain a small amount of elastomer, provided that the effects of the present invention are not impaired. The amount of elastomer 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 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.

[0141] (XI) 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.

[0142] <Production of Resin Composition> The thermoplastic resin composition of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. When preparing such pellets, the above-mentioned various reinforcing fillers and additives can also be blended.

[0143] <Regarding the manufacturing of molded products> The thermoplastic resin composition of the present invention can be injection-molded into various molded articles using pellets prepared as described above. Furthermore, the resin composition can be melt-kneaded in an extruder and directly molded into sheets, films, profile extrusions, direct blow moldings, and injection-molded articles without first passing through the pelletizing process. Injection molding can be performed using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including supercritical fluid injection), insert molding, in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these molding methods are well known. Molding can be performed using either a cold runner or hot runner system. The resin composition of the present invention can also be extrusion-molded into various profile extrusions, sheets, films, and other forms. Sheets and films can also be molded using inflation, calendaring, casting, and other methods. Furthermore, heat-shrinkable tubing can be molded by a specific stretching procedure. The resin composition of the present invention can also be formed into a molded article by rotational molding, blow molding, or the like. [Effects of the Invention]

[0144] The thermoplastic resin composition of the present invention is a thermoplastic resin composition that exhibits excellent mold releasability and dimensional stability, little deterioration in impact properties, and excellent recyclability even under severe processing conditions. Therefore, the composition is useful in applications requiring thin-walled, lightweight products under high-temperature molding conditions, as well as in cases where products are recycled and reused, and the industrial effects it offers are extremely significant. [Brief explanation of the drawings]

[0145]

Figure 1

Figure 2

[0146] The embodiments of the present invention are those that summarize 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]

[0147] The present invention will be further explained below with reference to examples, but is not limited thereto. Evaluation was carried out on the following items.

[0148] (i) Demolding ability (mold release load) Pellets obtained from each composition in the examples were dried in a hot air dryer at 100°C for 5 hours. Then, using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U-SM IV) under the conditions of the temperature and injection pressure shown in the table, box-shaped molded articles (100 mm wide, 150 mm long, 30 mm high, and 2 mm thick) were continuously molded. The average demolding load after 10 to 15 molding shots was measured. A load cell was installed behind the ejector pin to measure the maximum load required to demold the box-shaped molded article from the mold. The demolding load should be 180 N or less.

[0149] (ii) Thermal stability (retention rate of physical properties after retention) Pellets obtained from each composition in the examples were dried in a hot air dryer at 100°C for 5 hours and then continuously molded into ISO test specimens (compliant with ISO 179) using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U SM IV) at the temperatures listed in the table. The molding machine operation was then stopped, and the resin was allowed to dwell in the cylinder. After 15 minutes, test specimens were molded again, and Charpy impact tests (notched, compliant with ISO 179) were performed before and after the dwell. The property retention rate before and after the dwell was calculated using the following formula. The property retention rate must be 80% or higher. Property retention rate during dwell (%) = [Charpy impact value after dwell / Charpy impact value before dwell] x 100

[0150] (iii) Dimensional stability (coefficient of linear expansion) After annealing the ISO test specimens used for “(ii) Thermal stability” (drying at 100 °C for 1 hour), test specimens with a size of 5 mm square were cut out. Taking the direction of measuring the resin flow direction during injection molding as the measurement direction, using the linear expansion coefficient measuring device “TMA4000SE” manufactured by NETZSCH, the linear expansion coefficient of the test specimens at 23 °C to 55 °C was measured at a heating rate of 2 °C / min. The linear expansion coefficient should be -4 0.5×10

[0151] (iv) Recyclability (Physical property retention rate) The ISO test specimens used for “(ii) Thermal stability” were horizontally placed outdoors in Midori-ku, Chiba City for one year, then pulverized and formed into ISO test specimens. The Charpy impact values of the ISO test specimens before placement and the regenerated ISO test specimens were measured in the same manner as in “(ii) Thermal stability”. The Charpy impact value of the regenerated ISO test specimen was taken as the “Charpy impact value after recycling”, and the physical property retention rate was measured from the following formula. The physical property retention rate after recycling should be 60% or more. Physical property retention rate after recycling (%) = [Charpy impact value after recycling / Charpy impact value before placement] × 100

[0152] (v) Recyclability (Increase rate of demolding load) The box-shaped molded products used for “(i) Demolding property” were horizontally placed outdoors in Midori-ku, Chiba City for one year, then pulverized and continuously formed into box-shaped molded products again. The average value of the demolding load when 10 to 15 shots were molded was taken as the “demolding load after recycling”, and the increase rate of the demolding load was measured from the following formula. The increase rate of the demolding load after recycling should be 130% or less. Increase rate of demolding load after recycling (%) = [Demolding load after recycling / Demolding load before placement] × 100

[0153] [Examples 1 to 25, Comparative Examples 1 to 10] A resin composition consisting of the compounding ratios in Tables 1 and 2 was prepared as follows. The explanations will be made according to the symbols in the following tables. Each component in the ratios in the table was weighed and uniformly mixed using a tumbler, and such a mixture was put into an extruder to prepare the resin composition. As the extruder, a vent-type twin-screw extruder manufactured by Japan Steel Works, Ltd.: TEX-30XSST (fully meshing, co-rotating, 2-flight screw) was used. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vacuum degree of the vent of 3 kPa, and the extrusion temperature was the temperature shown in the table. Using the obtained pellets, test pieces for evaluation were molded using an injection molding machine by the above method. Each evaluation result is shown in Tables 1 and 2. The components with symbol notations in Tables 1 and 2 are as follows.

[0154] (Component A: Thermoplastic resin) A-1-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 20,700 made from bisphenol A and phosgene by a conventional method, manufactured by Teijin Ltd., Panlite L-1225WS (product name)) A-1-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity-average molecular weight 19,800, PDMS content 4.2%, PDMS degree of polymerization 37) A-2: ABS resin (manufactured by Nippon A&L Co., Ltd., Santa Tack AT-07 (product name), butadiene rubber component about 17.5% by weight, weight-average rubber particle diameter 1.2 μm, manufactured by bulk polymerization) A-3: Polyethylene terephthalate resin (manufactured by Teijin Ltd., TRN-8550FF (product name)) A-4: AS resin (manufactured by Nippon A&R Co., Ltd., Lite Tack ABS-207 (product name)) A-5: PS resin (manufactured by IRPC Public Company Limited, GP-110 (product name)) A-6: AAS resin (manufactured by INEOS, 777K (product name))

[0155] (Component B: Fatty acid ester resin) B-1: Esters of 1-docosanol and 1-octacosanol with aliphatic carboxylic acids (TOWAX-374, manufactured by Toa Kasei Co., Ltd., acid value 4 mg KOH / g, melting point 90°C) B-2: Esters of 1-docosanol and 1-octacosanol with aliphatic carboxylic acids (manufactured by Toa Kasei Co., Ltd., X1-220322-1, acid value 66 mg KOH / g, melting point 83°C) B-3 (Comparative Example): Ester of ethylene glycol and aliphatic carboxylic acid (Licowax E powder, manufactured by Clariant Japan Co., Ltd., melting point 81°C) B-4 (Comparative Example): Ester of pentaerythritol and aliphatic carboxylic acid (Rikestar EW-400 (trade name), manufactured by Riken Vitamin Co., Ltd., acid value 9 mg KOH / g, melting point 73°C)

[0156] (Component C: inorganic filler) C-1: Glass fiber (product name: 3PE455FB, manufactured by Nitto Boseki Co., Ltd.) C-2: Glass flakes (product name: MEG160FYX, manufactured by Nippon Sheet Glass Co., Ltd.) C-3: Carbon fiber (Teijin Limited, HT C422 (product name)) C-4: Non-fibrous carbon filler (product name: EN-250HT, manufactured by Nishimura Graphite Co., Ltd.) C-5: Talc (Victorite TK-RC (product name) manufactured by Shokoyama Mining Co., Ltd.)

[0157] (D component) (D-1 component: phosphonate ester) D-1-1: Triethyl phosphonoacetate (JC-224 (trade name), manufactured by Johoku Chemical Industry Co., Ltd., acid value 0.08 mg KOH / g) D-1-2 (Comparative Example): Triethyl phosphonoacetate (Solvay, acid value 0.39 mg KOH / g) D-1-3: Triethyl phosphonoacetate (mixture of D-1-1 and D-1-2 (weight ratio 1:1), acid value 0.23 mg KOH / g) (D-2 component: acidic phosphate ester) D-2-1: Stearyl acid phosphate (AX-71 (trade name) manufactured by ADEKA Corporation, acid value 158 mg KOH / g) D-2-2 (comparative example): Stearyl acid phosphate (A-18F (trade name) manufactured by SC Organic Chemicals Co., Ltd., acid value 215 mg KOH / g) D-2-3: Stearyl acid phosphate (mixture of D-2-1 and D-2-2 (weight ratio 1:1), acid value 187 mg KOH / g) (D-3 component: Trialkyl phosphate) D-3-1: Trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.) (D-4 component: Zinc stearyl phosphate) D-4-1: Zinc stearyl phosphate (mixture of zinc distearyl phosphate and zinc monostearyl phosphate, JP-518Zn manufactured by Johoku Chemical Industry Co., Ltd.)

[0158]

Table 1

[0159]

Table 2

Claims

1. A thermoplastic resin composition containing, per 100 parts by weight of a thermoplastic resin (Component A), 0.01 to 1 part by weight of a fatty acid ester resin (Component B) containing a structural unit derived from at least one alcohol selected from the group consisting of 1-docosanol and 1-octacosanol, 1 to 150 parts by weight of an inorganic filler (Component C), and 0.001 to 1 part by weight of at least one phosphate ester (Component D) selected from the group consisting of a phosphonate ester (Component D-1) having an acid value of 0.01 to 0.30 mg KOH / g, an acidic phosphate ester (Component D-2) having an acid value of 10 to 200 mg KOH / g, a trialkyl phosphate (Component D-3), and a zinc stearyl phosphate salt (Component D-4).

2. The thermoplastic resin composition according to Claim 1, wherein Component A is at least one thermoplastic resin selected from the group consisting of (A-1) a polycarbonate resin (Component A-1), (A-2) an ABS resin (Component A-2), (A-3) a polyester resin excluding Component B (Component A-3), (A-4) an AS resin (Component A-4), (A-5) a PS resin (Component A-5), and (A-6) an AAS resin (Component A-6).

3. The thermoplastic resin composition according to Claim 1 or 2, wherein the content of Component A-1 is 40 to 100 parts by weight in 100 parts by weight of Component A.

4. The thermoplastic resin composition according to Claim 1 or 2, wherein Component C is at least one inorganic filler selected from the group consisting of (C-1) glass fiber (Component C-1), (C-2) plate-like glass filler (Component C-2), (C-3) fibrous carbon filler (Component C-3), (C-4) non-fibrous carbon filler (Component C-4), and (C-5) silicate mineral (Component C-5).

5. The thermoplastic resin composition according to Claim 1 or 2, wherein Component D is triethyl phosphonoacetate.

6. The thermoplastic resin composition according to Claim 1 or 2, wherein Component D is trimethyl phosphate.

7. The thermoplastic resin composition according to Claim 1 or 2, wherein the melting point of Component B is 80 to 95 °C.

8. The thermoplastic resin composition according to Claim 1 or 2, wherein the acid value of Component B is 50 mg KOH / g or less.

9. A molded article comprising the thermoplastic resin composition according to Claim 1 or 2.

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