Thermoplastic resin composition and molded article comprising same

Abstract

Provided are: a thermoplastic resin composition which has little discoloration and little decrease in strength even under harsh processing conditions and which has excellent recyclability; and a molded article comprising the thermoplastic resin composition. This composition contains (A) 100 parts by weight of a thermoplastic resin (component A) and (B) 0.001-1 part by weight of a metal phosphate salt (component B) having an acid value of 10-55 mgKOH / g. The composition according to the present invention further contains (C) 1-150 parts by weight of an inorganic filler (component C) and / or (D) 0.01-25 parts by weight of a flame retardant (component D) per 100 parts by weight of component A.

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin composition that exhibits minimal discoloration and strength loss during molding, and a molded article comprising the same. More specifically, the present invention relates to a thermoplastic resin composition that exhibits minimal discoloration and strength loss even under severe processing conditions and exhibits excellent recyclability, and a molded article comprising the same. Background Art

[0002] Thermoplastic resin compositions have been widely used in the fields of housings and parts for electrical, electronic and automated office equipment, interior and exterior parts for automobiles, furniture, musical instruments, sundries, etc. In particular, in recent years, in order to achieve a sustainable society, higher recyclability has been expected from thermoplastic resin compositions. On the other hand, it is well known that phosphorus compounds are used as heat stabilizers in thermoplastic resin compositions. Patent Document 1 discloses the use of specific phosphorus compounds in resins composed of polycarbonate resins and polyester resins. Patent Document 2 discloses the combined use of phosphorus compounds. However, in existing methods, the thermal stability during molding is still insufficient. In particular, in applications requiring thin walls and lightweight, there is a trend for molding conditions to become high temperatures, and the number of cases of insufficient thermal stability is increasing. In addition, there is a high demand for recycling products again, and there is an increasing need to propose a material that can meet the requirements for thermoplastic resin compositions that do not discolor or reduce strength even under harsh processing conditions and have excellent recyclability.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent No. 4983427

[0006] Patent Document 2: Japanese Patent No. 5640734 Summary of the Invention

[0007] An object of the present invention is to provide a thermoplastic resin composition that exhibits minimal discoloration and strength loss even under severe processing conditions and has excellent recyclability, and a molded article comprising the same.

[0008] The present inventors have conducted extensive research to achieve the above-mentioned objectives and have discovered that by adding a phosphate metal salt having a specific acid value to a thermoplastic resin composition, it is possible to provide a thermoplastic resin composition and a molded article comprising the same that exhibit minimal discoloration and strength loss even under harsh processing conditions and excellent recyclability, thereby completing the present invention. In another embodiment, the inventors have discovered that by adding an inorganic filler and / or a flame retardant in addition to the phosphate metal salt having a specific acid value, it is possible to provide a thermoplastic resin composition and a molded article comprising the same that exhibit enhanced rigidity or flame retardancy in addition to preventing discoloration and strength loss.

[0009] That is, the present invention is as follows.

[0010] 1. A thermoplastic resin composition comprising 0.001 to 1 part by weight of (B) a phosphoric acid ester metal salt having an acid value of 10 to 55 mgKOH / g (component B) based on 100 parts by weight of (A) a thermoplastic resin (component A).

[0011] 2. The thermoplastic resin composition according to the above Item 1, further comprising 1 to 150 parts by weight of (C) an inorganic filler (component C) based on 100 parts by weight of component A.

[0012] 3. The thermoplastic resin composition according to the above item 1 or 2, further comprising 0.01 to 25 parts by weight of a flame retardant (component D) based on 100 parts by weight of component A.

[0013] 4. The thermoplastic resin composition according to any one of the above 1 to 3, further comprising 0.05 to 3 parts by weight of an anti-dripping agent (component E) based on 100 parts by weight of component A.

[0014] 5. The thermoplastic resin composition according to any one of the above items 1 to 4, 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 (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).

[0015] 6. The thermoplastic resin composition according to any one of the above items 1 to 5, 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), and (A-3) a polyester resin (component A-3).

[0016] 7. The thermoplastic resin composition according to any one of the above 1 to 6, wherein the content of the component A-1 is 40 to 100 parts by weight based on 100 parts by weight of the component A.

[0017] 8. The thermoplastic resin composition according to any one of the above 1 to 7, wherein the component B is stearyl acid phosphate zinc salt.

[0018] 9. The thermoplastic resin composition according to the above item 2, wherein the component C is at least one inorganic filler selected from the group consisting of (C-1) glass fiber (component C-1), (C-2) plate-shaped 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).

[0019] 10. The thermoplastic resin composition according to the above item 3, wherein the component D is at least one flame retardant selected from the group consisting of (D-1) a halogenated carbonate compound (component D-1), (D-2) a phosphate compound (component D-2), (D-3) a phosphazene compound (component D-3), (D-4) a metal sulfonate (component D-4), and (D-5) an organosilicon compound (component D-5).

[0020] 11. A molded article comprising the thermoplastic resin composition according to any one of 1 to 10 above.

[0021] The thermoplastic resin composition of the present invention exhibits minimal discoloration and strength loss even under severe processing conditions and exhibits excellent recyclability. Therefore, it is useful in applications requiring thin-walled and lightweight molding under high-temperature molding conditions and in applications where products are recycled, and thus has significant industrial benefits. DETAILED DESCRIPTION

[0022] Hereinafter, the present invention will be described in detail.

[0023] <Component A: Thermoplastic resin>

[0024] The thermoplastic resin used as component A in the present invention includes polycarbonate resin, ABS resin, polyester resin, AS resin, PS resin, AAS resin, AES resin, polyamide resin, polyolefin resin, fluorine-based resin, PPS resin, PEEK resin, polyarylate resin, polyoxymethylene resin, and the like. Preferably, it is at least one thermoplastic resin selected from polycarbonate resin, ABS resin, polyester resin, AS resin, PS resin, and AAS resin. Furthermore, component A is at least one thermoplastic resin selected from polycarbonate resin, ABS resin, and polyester resin. The polycarbonate resin content is more preferably 40 to 100 parts by weight per 100 parts by weight of component A. Furthermore, the polycarbonate resin content is more preferably 60 to 100 parts by weight per 100 parts by weight of component A.

[0025] <Component A-1: Polycarbonate resin>

[0026] The polycarbonate resin used as the component A-1 of the present invention is a polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0027] Representative examples of the dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, )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. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes. Among them, bisphenol A is particularly preferred from the perspective of impact resistance and is commonly used.

[0028] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, special polycarbonate resins produced using other dihydric phenols can also be used as component A-1. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylene diisopropylidene)diphenol (sometimes referred to as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (sometimes referred to as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (sometimes referred to as "BCF") as part or all of the dihydric phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly stringent. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, and particularly preferably 10 mol% or more, of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, the component A constituting the resin composition is preferably a copolymerized polycarbonate resin of the following (1) to (3).

[0029] (1) A copolymerized 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%, further preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, further preferably 35 to 55 mol%).

[0030] (2) A copolymerized polycarbonate resin in which, in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, further preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, further preferably 15 to 40 mol%).

[0031] (3) A copolycarbonate resin comprising 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) of BPM and 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%) of Bis-TMC, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin.

[0032] These special polycarbonate resins can be used alone or in combination of two or more. Furthermore, they can be mixed with a general-purpose bisphenol A polycarbonate resin. The preparation methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Application Publication No. 6-172508, Japanese Patent Application Publication No. 8-27370, Japanese Patent Application Publication No. 2001-55435, and Japanese Patent Application Publication No. 2002-117580.

[0033] Among the various polycarbonate resins described above, polycarbonates whose copolymerization composition is adjusted so that the water absorption and Tg (glass transition temperature) are within the following ranges are particularly preferred in fields requiring morphological stability because the polymer itself has good hydrolysis resistance and is also particularly excellent in low bendability after molding.

[0034] (i) a polycarbonate resin having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and a Tg of 120 to 180°C, or

[0035] (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0036] Here, the water absorption of a polycarbonate resin is the value obtained by measuring the moisture content of a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm after immersion in water at 23°C for 24 hours in accordance with ISO 62-1980. Furthermore, Tg (glass transition temperature) is the value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0037] As the carbonate precursor, an acid halide, a carbonic acid diester, a haloformate, or the like is used. Specific examples thereof include phosgene, diphenyl carbonate, and a dihaloformate of a dihydric phenol.

[0038] When utilizing interfacial polymerization to manufacture polycarbonate resin with above-mentioned dihydric phenol and carbonate precursor, also can use catalyzer, terminal terminator, the antioxidant that is used to prevent dihydric phenol oxidation etc. as required.In addition, polycarbonate resin of the present invention comprises the branched polycarbonate resin obtained by the copolymerization of the polyfunctional aromatic compound above trifunctional, the polyester carbonate resin obtained by the copolymerization of the difunctional carboxylic acid of aromatic series or aliphatic series (comprising alicyclic formula), the copolycarbonate resin obtained by the copolymerization of difunctional alcohol (comprising alicyclic formula) and the polyester carbonate resin obtained by the copolymerization of above-mentioned difunctional carboxylic acid and difunctional alcohol.In addition, also can be the mixture that 2 or more of the obtained polycarbonate resin are mixed.

[0039] The branched polycarbonate resin can impart anti-drip properties to the thermoplastic resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucinol, phloroglucinol, 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-methyl Phenol, triphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, trimesic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0040] The content of the structural units 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 even more preferably 0.05 to 0.8 mol%, based on the total 100 mol% of the structural units derived from the dihydric phenol and the structural units derived from the polyfunctional aromatic compound. Furthermore, in the case of the melt transesterification method, branched structural units may be generated as a side reaction. The content of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, based on the total 100 mol% of the structural units derived from the dihydric phenol. 1 It was calculated by H-NMR measurement.

[0041] The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of preferred aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decane dioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid. Difunctional alcohols are more preferably alicyclic diols, examples of which include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0042] Reaction forms such as interfacial polymerization, melt transesterification, carbonate prepolymer solid phase transesterification, and ring-opening polymerization of cyclic carbonate compounds as methods for producing the polycarbonate resin of the present invention are well known in various documents and Japanese Patent Publications.

[0043] When producing the thermoplastic resin composition of the present invention, the viscosity average molecular weight of the polycarbonate resin is preferably 12,500 to 32,000, more preferably 16,000 to 28,000, and even more preferably 18,000 to 26,000. Polycarbonate resins with a viscosity average molecular weight of less than 12,500 may not exhibit good mechanical properties. On the other hand, resin compositions obtained from polycarbonate resins with a viscosity average molecular weight exceeding 32,000 may have poor moldability.

[0044] The viscosity average molecular weight mentioned in the present invention is first determined by using an Ostwald viscometer from a solution of 0.7 g of polycarbonate dissolved in 100 ml of dichloromethane at 20° C. to obtain the specific viscosity (η) calculated from the following formula: SP ),

[0045] Specific viscosity (η SP )=(t-t0) / t0

[0046] [t0 is the dripping time of dichloromethane, t is the dripping time of the sample solution]

[0047] The specific viscosity (ηSP ) The viscosity average molecular weight M is calculated according to the following mathematical formula.

[0048] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0049] [η] = 1.23 × 10 －4 M 0.83

[0050] c=0.7

[0051] The viscosity-average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is calculated according to the following procedure. Specifically, the composition is mixed with 20 to 30 times its weight of dichloromethane to dissolve the soluble components in the composition. The soluble components are collected by filtration using diatomaceous earth. The solvent in the resulting solution is then removed. The solid after solvent removal is thoroughly dried to obtain a solid containing the components soluble in dichloromethane. The specific viscosity at 20°C is determined from a solution prepared by dissolving 0.7 g of the solid in 100 ml of dichloromethane in the same manner as above, and the viscosity-average molecular weight M is calculated from this specific viscosity in the same manner as above.

[0052] A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin of the present invention. 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).

[0053]

[0054] [In the above general formula (1), R 1 and R 2 Each independently represents 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 carboxyl group. When there are plural of each of these groups, they may be the same or different. e and f are each an integer of 1 to 4. W represents at least one group selected from a single bond or a group represented by the following general formula (2).

[0055]

[0056] [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 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, and R 19 and R 20 Each independently represents a group selected from 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 carboxyl group. When a plurality of these groups exist, they may be the same or different. g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0057]

[0058] [In the above general formula (3), R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are 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, R 9 and R 10 Each is 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 from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.]

[0059] Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2 bis(3-tert-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)fluorene (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, etc.

[0060] 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, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane is most preferred due to its excellent strength and good durability.

[0061] As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3), for example, the following compounds are preferably used.

[0062]

[0063] Hydroxyaryl-terminated polydiorganosiloxane (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, with the terminal end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, with (2-allylphenol)-terminated polydimethoxysiloxane and (2-methoxy-4-allylphenol)-terminated polydimethoxysiloxane being particularly preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. To exhibit superior low-outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of the above preferred range is exceeded, the amount of outgassing generated during high-temperature molding may increase, and low-temperature impact resistance may be poor.

[0064] Furthermore, to achieve high impact resistance, the diorganosiloxane polymerization degree (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. If the degree of polymerization is below the lower limit of the preferred range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer cannot be effectively exhibited, while if the degree of polymerization exceeds the upper limit of the preferred range, poor appearance may occur.

[0065] The content of polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A-1 is preferably 0.1 to 50% by weight. The content of the above-mentioned polydiorganosiloxane component is more preferably 0.5 to 30% by weight, and further preferably 1 to 20% by weight. If it is above the lower limit of the above-mentioned preferred range, the impact resistance and flame retardancy are excellent. If it is below the upper limit of the above-mentioned preferred range, it is not easily affected by the molding conditions and a stable appearance is easily obtained. The above-mentioned degree of polymerization of polydiorganosiloxane and content of polydiorganosiloxane can be 1 It was calculated by H-NMR measurement.

[0066] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0067] Furthermore, other comonomers other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) may be used in an amount of 10% by weight or less based on the total weight of the copolymer, within a range not hindering the present invention.

[0068] 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 a water-insoluble organic solvent and an aqueous alkaline solution.

[0069] When producing oligomers of dihydric phenol (I), the entire amount of dihydric phenol (I) used in the method of the present invention can be converted into oligomers at once, or a portion thereof can be added as a post-addition monomer to the subsequent interfacial polycondensation reaction as a reaction raw material. The post-addition monomer is added to accelerate the subsequent polycondensation reaction and does not need to be added specifically unless necessary.

[0070] The method of the oligomer formation reaction is not particularly limited, but is preferably a method in which the reaction is carried out in a solvent in the presence of an acid binder.

[0071] The ratio of the carbonate-forming compound to be used can be appropriately adjusted by taking into account the stoichiometric ratio (equivalent) of the reaction. In addition, when a gaseous carbonate-forming compound such as phosgene is used, it can be preferably blown into the reaction system.

[0072] As above-mentioned acid binding agent, for example, can use organic bases such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, alkali metal carbonate, pyridine or their mixture etc.The usage ratio of acid binding agent also suitably determines as long as the stoichiometric ratio (equivalent) of considering reaction is the same as above-mentioned.Specifically, preferably use 2 equivalents or than its slightly excessive acid binding agent with respect to the mole number (usually 1 mole is equivalent to 2 equivalents) of the dihydric phenol (I) that uses in the formation of oligomer.

[0073] As the solvent, any solvent inert to the reaction, such as solvents used in the production of known polycarbonates, may be used alone or in a mixture. Representative examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as dichloromethane and chlorobenzene. Halogenated hydrocarbon solvents such as dichloromethane are particularly preferred.

[0074] The reaction pressure for oligomer formation is not particularly limited and can be normal pressure, increased pressure, or reduced pressure. It is generally advantageous to conduct the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C. In many cases, water cooling or ice cooling is preferred due to the heat generated by polymerization. The reaction time is affected by other conditions and cannot be generalized, but it is generally 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as that for known interfacial reactions, and the pH is generally adjusted to above 10.

[0075] The present invention obtains a mixed solution containing oligomers of a dihydric phenol (I) having terminal chloroformate groups, and then, while stirring the mixed solution, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3) having a highly purified molecular weight distribution (Mw / Mn) of 3 or less is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer undergo interfacial polycondensation, thereby obtaining a polycarbonate-polydiorganosiloxane copolymer.

[0076]

[0077] (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, R 9and R 10 Each is 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 from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0078] When carrying out interfacial polycondensation reaction, it is possible to consider the stoichiometric ratio (equivalent) of reaction and suitably add an acid binding agent. As acid binding agent, for example, organic bases such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, pyridine or their mixtures etc. can be used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part for dihydric phenol (I) as mentioned above is added to this reaction stage as a post-addition monomer, preferably 2 equivalents or a alkali is used relative to the total molar number (usually 1 mole is equivalent to 2 equivalents) of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) of the post-addition part.

[0079] The polycondensation based on the interfacial polycondensation reaction between the oligomer of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixed solution.

[0080] In the polymerization reaction, a terminal terminator or molecular weight regulator can generally be used. Examples of terminal terminators include compounds having monophenolic hydroxyl groups, such as phenol, p-tert-butylphenol, p-cumylphenol, and tribromophenol. Other examples include long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenyl alkyl esters, and alkyl ether phenols. The amount of terminal terminators used is 100 to 0.5 moles, preferably 50 to 2 moles, based on 100 moles of all diphenolic compounds used. Two or more compounds may also be used in combination.

[0081] In order to promote the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0082] The reaction time of the polymerization reaction is preferably 30 minutes or longer, more preferably 50 minutes or longer. A small amount of an antioxidant such as sodium sulfite or hydrogen sulfide may be added as needed.

[0083] A branching agent can be used in combination with the above-mentioned dihydric phenolic compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucinol, phloroglucinol, 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)ethane, )-4-methylphenol, triphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetrakis(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, trimesic acid, benzophenonetetracarboxylic acid and acid chlorides thereof; among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The ratio 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%, further preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol% based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It was calculated by H-NMR measurement.

[0084] The reaction pressure may be reduced pressure, normal pressure, or increased pressure, and is generally conducted at normal pressure or the autogenous pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C. In many cases, water cooling or ice cooling is preferred due to the generation of heat associated with polymerization. The reaction time is affected by other conditions such as the reaction temperature and cannot be generalized, but is generally 0.5 to 10 hours.

[0085] The obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, classification, etc.) and / or chemical treatment (polymerization reaction, crosslinking treatment, partial decomposition treatment, etc.) as needed to obtain the desired reduced viscosity [η SP / c] polycarbonate-polydiorganosiloxane copolymer resin.

[0086] The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (degree of purification).

[0087] The average size of the polydiorganosiloxane domains in polycarbonate-polydiorganosiloxane copolymer resin molded articles is preferably in the range of 1 to 40 nm. This average size is more preferably 1 to 30 nm, and even more preferably 5 to 25 nm. If the size is below the lower limit of this preferred range, sufficient impact resistance and flame retardancy may not be achieved. If the size exceeds the upper limit of this preferred range, impact resistance may not be stably achieved.

[0088] The average domain size and normalized dispersion of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article of the present invention are evaluated using small-angle X-ray scattering (SAXS). SAXS measures diffuse scattering and diffraction generated in a small-angle region with a scattering angle (2θ) less than 10°. In this SAXS method, if a substance contains regions approximately 1 to 100 nm in size with different electron densities, the difference in electron density is used to measure the diffuse scattering of X-rays. The particle size of the object being measured is determined based on the scattering angle and scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having a condensed structure in which polydiorganosiloxane domains are dispersed within a polycarbonate polymer matrix, diffuse scattering of X-rays is generated by the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) within a range of less than 10° is measured, and the small-angle X-ray scattering distribution is measured. Assuming that the polydiorganosiloxane domain is a spherical domain and that there is a deviation in the particle size distribution, commercially available analytical software is used to simulate the assumed particle size and the assumed particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the matrix of the polycarbonate polymer, which cannot be accurately measured by transmission electron microscopy, can be measured with good accuracy, simplicity, and good reproducibility. The average domain size refers to the number average of the sizes of each domain. The normalized dispersion refers to a parameter that normalizes the width of the particle size distribution to the average size. Specifically, it is a value in which the dispersion of the polydiorganosiloxane domain size is normalized by the average domain size, and is represented by the following formula (1).

[0089] Normalized dispersion (%) = δ / D av …(1)

[0090] In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.

[0091] The terms "average domain size" and "normalized dispersion" used in connection with the present invention represent values measured using the aforementioned small-angle X-ray scattering method on a 1.0 mm thick portion of a three-segment template produced by the method described in the Examples. Furthermore, analysis was performed using an independent particle model that does not consider inter-particle interactions (inter-particle interference).

[0092] <Component A-2: ABS resin>

[0093] The ABS resin used as the A-2 component of the present invention is a copolymer obtained by grafting acrylonitrile and styrene onto polybutadiene. As styrene, styrene and α-methylstyrene are particularly preferably used. The proportion of the above-mentioned component grafted onto the polybutadiene is preferably 95 to 20% by weight, and particularly preferably 90 to 50% by weight, in 100% by weight of the ABS resin component. In addition, with respect to the total amount of 100% by weight of the above-mentioned acrylonitrile and styrene, it is preferred that the acrylonitrile content is 5 to 50% by weight and the styrene content is 95 to 50% by weight. In addition, methyl (meth)acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc. can also be mixed with a portion of the components grafted onto the above-mentioned polybutadiene, and their content ratio in the ABS resin component is preferably 15% by weight or less. Furthermore, various conventionally known substances can be used as the initiator, chain transfer agent, emulsifier, etc. used in the reaction as needed. In the ABS resin of the present invention, the polybutadiene particle size is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. The polybutadiene particle size distribution may be either a single distribution or a distribution with two or more peaks. Morphologically, the particles may form a single phase or have a salami structure with an obscuring phase surrounding the particles. ABS resins are known to contain copolymers of acrylonitrile and styrene that are not grafted onto a diene rubber component. The ABS resin of the present invention may also contain free polymer components generated during such polymerization. The reduced viscosity (at 30°C) of the free copolymer of acrylonitrile and styrene is preferably 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g. The proportion of grafted acrylonitrile and styrene relative to the polybutadiene, expressed as a grafting ratio (weight %), is preferably 20 to 200%, more preferably 20 to 70%. The ABS resin can be manufactured by any of bulk polymerization, suspension polymerization, and emulsion polymerization, with bulk polymerization being particularly preferred. In the case of bulk polymerization, the resin composition is substantially free of alkali metal salts from emulsifiers, etc., and thus can maintain the thermal stability of the resin composition more effectively. Alternatively, the copolymerization method may be a single-step copolymerization or a multi-step copolymerization. Alternatively, a blend of a vinyl compound polymer obtained by copolymerizing acrylonitrile and styrene with the ABS resin obtained by the above-mentioned manufacturing method may be preferably used.

[0094] <Component A-3: Polyester resin>

[0095] The polyester resin used as the component A-3 of the present invention is preferably one in which 70 mol% or more of 100 mol% of the dicarboxylic acid components in the dicarboxylic acid components and diol components forming the polyester is an aromatic dicarboxylic acid, more preferably 90 mol% or more, and most preferably 99 mol% or more.

[0096] Examples of such dicarboxylic acids include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, dibenzoic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, sodium 5-sulfoisophthalate, and ethylene bis(p-terephthalic acid). These dicarboxylic acids may be used alone or as a mixture of two or more. In addition to the aromatic dicarboxylic acids described above, the polyester resin of the present invention may also be copolymerized with an aliphatic dicarboxylic acid component in an amount of less than 30 mol%. Specific examples include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0097] Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 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-xylene glycol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether). These can be used alone or in combination of two or more. The dihydric phenol in the diol component is preferably 30 mol% or less.

[0098] Specific examples of the polyester resin include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis(phenoxy)ethane-4,4′-dicarboxylate, and copolyester resins such as polyethylene isophthalate / polyethylene terephthalate copolymers and polybutylene terephthalate / polybutylene isophthalate copolymers.

[0099] The terminal group structure of the polyester resin used in the present invention is not particularly limited. In addition to the case where the ratio of hydroxyl groups to carboxyl groups in the terminal groups is approximately equal, it is also possible to have a larger ratio of one of the two. In addition, these terminal groups can also be capped by reacting them with reactive compounds.

[0100] The polyester resin production method used in the present invention is carried out by polymerizing a dicarboxylic acid component and the above-mentioned diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., according to a conventional method, and discharging the by-product water or lower alcohol to the outside of the system. For example, as a germanium-based polymerization catalyst, examples include germanium oxides, hydroxides, halides, alkoxides, phenoxides, etc., and more specifically, examples include germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. In addition, in the present invention, compounds such as manganese, zinc, calcium, and magnesium used in the ester exchange reaction, the previous stage of the conventionally known polycondensation, can also be used. After the ester exchange reaction is completed, the above-mentioned catalysts can be deactivated using a phosphoric acid or phosphorous acid compound, and then the polycondensation can be carried out. In addition, the polyester resin production method can also adopt either a batch method or a continuous polymerization method.

[0101] Among the above polyester resins, polyethylene terephthalate is particularly preferred. The polyethylene terephthalate of the present invention is a polymer obtained by polycondensation of terephthalic acid or its derivatives and 1,4-ethanediol or its derivatives, but also includes copolymers obtained by copolymerizing other dicarboxylic acid components and other alkylene glycol components as described above.

[0102] The terminal group structure of polyethylene terephthalate is the same as described above and is not particularly limited. It is more preferred that the terminal carboxyl group is less than the terminal hydroxyl group. In addition, the production method can also adopt the various methods described above, and the continuous polymerization method is preferred. This is because: its quality stability is high and it is also cost-effective. In addition, as a polymerization catalyst, an organic titanium compound is preferably used. The reason is that there is a tendency to have less influence on ester exchange reactions, etc. As the above-mentioned organic titanium compound, as preferred specific examples, titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, the reaction product of tetrabutyl titanate and trimellitic anhydride, etc. can be cited. The amount of the organic titanium compound used is preferably such that the titanium atom is in a ratio of 3 to 12 mg atomic % relative to the acid component constituting polyethylene terephthalate.

[0103] 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, particularly preferably 0.6 to 1.2.

[0104] <Component A-4: AS resin>

[0105] The AS resin used as component A-4 in the present invention is a copolymer of acrylonitrile and styrene. The AS resin can also be a copolymer with high stereoregularity, such as syndiotactic styrene, by using a catalyst such as a metallocene catalyst during its production. Furthermore, depending on the circumstances, polymers and copolymers with narrow molecular weight distributions, block copolymers, and polymers and copolymers with high stereoregularity obtained by methods such as anionic living polymerization and free radical living polymerization can also be used.

[0106] <Component A-5: PS resin>

[0107] The PS resin used as the component A-5 in the present invention is a styrene polymer.

[0108] <Component A-6: AAS resin>

[0109] 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.

[0110] <Component B: Phosphate ester metal salt>

[0111] The metal phosphate salts used in the present invention include those produced by a dry process, obtained by the direct reaction of a fatty acid with a metal oxide or a fatty acid with a metal hydroxide, and those produced by a wet process, in which a sodium salt of a fatty acid reacts with a metal salt in an aqueous solution. The fatty acid can have various combinations of 1 to 22 carbon atoms, with a fatty acid having 18 carbon atoms being more preferred. The most preferred metal phosphate salt is zinc stearyl acid phosphate. The acid value of the metal phosphate salt is 10 to 55 mgKOH / g, preferably 10 to 53 mgKOH / g, and more preferably 30 to 53 mgKOH / g. Acid values less than 10 mgKOH / g are impractical for production, while acid values greater than 55 mgKOH / g cannot prevent discoloration and strength loss during molding. The acid value is measured by indicator titration, titrating a solution of the metal phosphate salt in 2-ethylhexanol with an alcoholic KOH solution at 60°C. Phenolphthalein is used as the indicator.

[0112] The content of component B 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, relative to 100 parts by weight of component A. If the content of component B is less than 0.001 part by weight or exceeds 1 part by weight, discoloration during molding and a decrease in strength cannot be prevented.

[0113] <Other ingredients>

[0114] The thermoplastic resin composition of the present invention may contain the following inorganic filler (component C), flame retardant (component D), anti-dripping agent (component E), and other additives within a range not impairing the purpose of the present invention.

[0115] <Component C: Inorganic filler>

[0116] The inorganic filler of component C can use conventionally known inorganic fillers, among which at least one inorganic filler selected from the group consisting of (C-1) glass fiber (component C-1), (C-2) plate-shaped 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) is preferred.

[0117] The content of component C is preferably 1 to 150 parts by weight, more preferably 3 to 140 parts by weight, and even more preferably 5 to 130 parts by weight relative to 100 parts by weight of component A. If the content of component C is less than 1 part by weight, sufficient rigidity may not be obtained, while if it exceeds 150 parts by weight, the strength and flame retardancy during molding may be reduced.

[0118] <C-1 component: glass fiber>

[0119] As the glass fiber used in the present invention, there is no particular limitation on the glass composition of A glass, C glass, E glass, etc., and they may contain components such as TiO2, SO3, P2O5 according to the circumstances. Among them, E glass (alkali-free glass) is more preferred when combined with a thermoplastic resin. In addition, two or more of these glass fibers may be used in combination. Glass fiber is a fiber made by rapidly cooling molten glass while stretching it using various methods and then forming it into a specified fibrous or ground shape. The rapid cooling and stretching conditions in the above-mentioned cases are also not particularly limited. In addition, the cross-sectional shape may be, in addition to a perfect circle, an elliptical, cocoon-shaped, trilobal, or other shapes other than a perfect circle. In addition, it may be a glass fiber obtained by mixing a perfect circle glass fiber with a glass fiber of a shape other than a perfect circle. Among them, a perfect circle glass fiber is more preferred.

[0120] In order to obtain a better mechanical strength, it is preferable to pre-treat these glass fibers with coupling agents such as isocyanate compounds, organosilane compounds, organotitanate compounds, organoborane compounds and epoxy compounds. The glass fiber used in the present invention preferably has a diameter (D) of 6 to 13 μm, a cut length (L) of 30 μm to 9 mm, and an L / D ratio of 2.3 to 1500.

[0121] <C-2; Plate glass filling material>

[0122] Examples of the plate-shaped glass filler include glass flakes, metal-coated glass flakes, and metal oxide-coated glass flakes.

[0123] The glass flakes that form the base of the plate-shaped glass filler are plate-shaped glass fillers manufactured by methods such as the cylinder blowing method and the sol-gel method. The size of the raw material of the glass flakes can also be selected from various sizes according to the degree of crushing and classification. The average particle size of the glass flakes used in the raw material is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and even more preferably 30 to 300 μm. This is because glass flakes within this range are excellent in both handling and molding processability. Generally, plate-shaped glass fillers break during melt kneading with the resin, resulting in a smaller average particle size. 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. It should be noted that the above number average particle size is a value calculated using an image analyzer from an optical microscope observation of the residue of the plate-shaped glass filler collected during processes such as high-temperature ashing, solvent dissolution, and reagent decomposition of the molded article. This value is calculated by not counting the lengths where the flake thickness is less than the standard value. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1.5 to 6 μm. Sheet glass fillers having the above number average particle size and thickness sometimes achieve excellent mechanical strength, appearance, and moldability.

[0124] The glass composition of the plate glass filling material can be applied to various glass compositions represented by A glass, C glass and E glass, etc., without special limitation. The above-mentioned glass filling material may also contain components such as TiO2, SO3 and P2O5 as needed. Among them, E glass (alkali-free glass) is more preferred. In addition, the plate glass filling material is preferred because the mechanical strength is improved after surface treatment using a well-known surface treatment agent, such as a silane coupling agent, a titanate coupling agent or an aluminate coupling agent. In addition, the plate glass filling material is preferably a plate glass filling material that has been subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin and a polyurethane resin. The amount of the bundling agent attached to the bundled plate glass filling material is preferably 0.5 to 8 weight %, more preferably 1 to 4 weight % in 100 weight % of the plate glass filling material.

[0125] In addition, the plate-shaped glass filling material includes a plate-shaped glass filling material obtained by coating the surface of different types of materials. As the above-mentioned same type of materials, metals and metal oxides can be preferably exemplified. As metals, silver, copper, nickel and aluminum can be exemplified. In addition, as metal oxides, titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide and silicon oxide can be exemplified. The method for coating the surface of the above-mentioned different types of materials is not particularly limited, and for example, various known plating methods (for example, electroplating, electroless plating, hot dip plating, etc.), vacuum evaporation method, ion plating method, CVD method (for example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method and sputtering method can be cited.

[0126] <Component C-3: Fibrous carbon filler>

[0127] Examples of fibrous carbon fillers include carbon fibers, metal-coated carbon fibers, milled carbon fibers, vapor-grown carbon fibers, and carbon nanotubes. Carbon nanotubes may have a fiber diameter of 0.003 to 0.1 μm and may be single-layer, double-layer, or multi-layer, preferably multi-layer (so-called MWCNTs). Carbon fibers and metal-coated carbon fibers are preferred due to their excellent mechanical strength and ability to impart good electrical conductivity. Good electrical conductivity has become one of the important properties required of resin materials in recent digital precision instruments (e.g., digital still cameras).

[0128] As carbon fibers, any of cellulose-based, polyacrylonitrile-based, and pitch-based fibers can be used. In addition, carbon fibers obtained by a method that performs spinning without a non-melting process represented by a method of spinning or molding a raw material composition composed of a polymer based on a methylene bond of an aromatic sulfonic acid or its salt and a solvent, followed by carbonization, can also be used. In addition, any of a general-purpose type, a medium elastic modulus type, and a high elastic modulus type can be used. Among them, a polyacrylonitrile-based high elastic modulus type is particularly preferred. In addition, the average fiber diameter of the carbon fibers is not particularly limited, but is generally 3 to 15 μm, preferably 5 to 13 μm. Carbon fibers that maintain an average fiber diameter within the above range can sometimes exhibit good mechanical strength and fatigue properties without damaging the appearance of the molded article. In addition, the preferred fiber length of the carbon fibers is 60 to 500 μm, preferably 80 to 400 μm, and particularly preferably 100 to 300 μm, based on the number average fiber length in the thermoplastic resin composition. It should be noted that the above-mentioned number average fiber length is a value calculated by optical microscope observation or other image analysis equipment from the carbon fiber residue collected during treatments such as high-temperature incineration of the molded product, dissolution with a solvent, and decomposition with a reagent. Furthermore, this value is calculated by not counting the length values below 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.

[0129] Furthermore, in order to improve adhesion with the matrix resin and mechanical strength, the surface of the carbon fiber is preferably subjected to an oxidation treatment. The oxidation treatment method is not particularly limited, and examples thereof include: (1) a method of treating the fibrous carbon filler with an acid, an alkali, or a salt thereof, or an oxidizing gas; (2) a method of calcining the fiber or fibrous carbon filler that can become the 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 in the presence of an inert gas after the oxidation treatment.

[0130] Metal-coated carbon fibers are carbon fibers having a metal layer coated on the surface of the carbon fibers. Examples of the metal include silver, copper, nickel, and aluminum. Nickel is preferred from the perspective of corrosion resistance of the metal layer. As a method for coating with metal, various methods described above for surface coating of different types of materials in the plate-shaped glass filler can be used. Among them, plating is preferred. In addition, in the case of the above-mentioned metal-coated carbon fibers, the carbon fibers cited as the above-mentioned carbon fibers can be used as the starting raw materials. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably, it is 0.2 to 0.35 μm.

[0131] The carbon fibers and metal-coated carbon fibers are preferably bundled with olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins, polyurethane resins, or the like. In particular, fibrous carbon fillers treated with polyurethane resins or epoxy resins are preferred in the present invention due to their excellent mechanical strength.

[0132] <Component C-4: Non-fibrous carbon filler>

[0133] Examples of non-fibrous carbon fillers include carbon black, graphite, and fullerene. Among these, carbon black and graphite are preferred from the perspectives of mechanical strength, moisture-heat resistance, and thermal stability. Carbon black having a DBP oil absorption of 100 ml / 100 g to 500 ml / 100 g is preferred from the perspective of electrical conductivity. Examples of the aforementioned carbon blacks include acetylene black and Ketjen black. Specifically, examples include DENKA BLACK manufactured by Denki Kagaku Kogyo Co., Ltd., VULCAN XC-72 and BP-2000 manufactured by Cabot Corporation, and Ketjen black EC and Ketjen black EC-600JD manufactured by Lion Corporation.

[0134] As graphite, natural graphite or various artificial graphites of the mineral name graphite can be utilized. As natural graphite, any one of earthy graphite, scaly graphite (also known as Vein Graphite of blocky graphite) and flake graphite (Flake Graphite) can also be used. In addition, artificial graphite is a graphite obtained by artificially orienting irregularly arranged tiny graphite crystals to amorphous carbon by heat treatment. In addition to the artificial graphite generally used in carbon materials, it also includes floating graphite (kish graphite), decomposed graphite and pyrolytic graphite. The artificial graphite generally used in carbon materials is usually manufactured by graphitization treatment with petroleum coke and coal-based pitch coke as main raw materials.

[0135] The graphite of the present invention may include expanded graphite that can be thermally expanded by a treatment such as an acid treatment, or graphite that has undergone the expansion treatment. The particle size of the graphite is preferably in the range of 2 to 300 μm. The above-mentioned particle size is more preferably 5 to 200 μm, further preferably 7 to 100 μm, and particularly preferably 7 to 50 μm. By satisfying the above-mentioned range, good mechanical strength and appearance of the molded product can sometimes be achieved. On the other hand, if the average particle size is less than 2 μm, the effect of improving the rigidity sometimes becomes small, and if the average particle size is greater than 300 μm, the impact resistance is significantly reduced, and sometimes the so-called floating of graphite on the surface of the molded product becomes obvious, which is not preferred.

[0136] 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 even more preferably 98% by weight or more. Furthermore, 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 even more preferably 1% by weight or less.

[0137] The average particle size of graphite in the present invention refers to the particle size of the graphite itself before it becomes a resin composition. The particle size is a value determined by a laser diffraction / scattering method.

[0138] Furthermore, the graphite surface may be subjected to surface treatments such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment to increase affinity with the thermoplastic resin, as long as the properties of the composition of the present invention are not impaired.

[0139] <C-5 component: silicate minerals>

[0140] As the inorganic filler in the present invention, silicate minerals composed of at least a metal oxide component and a SiO2 component can be cited, preferably orthosilicates, disilicates, cyclic silicates, and chain silicates. The silicate minerals are in a crystalline state, and the crystals can be in any form that each silicate mineral can take. In addition, the crystals can also take various shapes such as fibers and plates.

[0141] Silicate minerals can be any compound among composite oxides, oxyacid salts (composed of ionic lattices), and solid solutions. Furthermore, composite oxides can be any combination of two or more single oxides, and any combination of two or more single oxides and oxyacid salts. Furthermore, solid solutions can be any solid solution of two or more metal oxides and any solid solution of two or more oxyacid salts. In addition, they can also be hydrates. The form of crystal water in hydrates can be introduced as hydrosilicate ions in the form of Si-OH, as hydroxide ions (OH － ) is introduced into the metal cation in the form of ions, and is introduced into the gaps in the structure as H2O molecules.

[0142] As silicate minerals, artificially synthesized products corresponding to natural products can also be used. As artificially synthesized products, silicate minerals obtained by various conventionally known methods, such as solid-state reaction, hydrothermal reaction, and ultrahigh pressure reaction, can be used.

[0143] Specific examples of silicate minerals in the metal oxide components include the following: Here, the names of minerals containing the above-mentioned silicate minerals as main components are shown in parentheses, and the compounds in parentheses can be used as the exemplified metal salts.

[0144] Examples of silicate minerals containing K2O include K2O·SiO2, K2O·4SiO2·H2O, K2O·Al2O3·2SiO2 (potassium pyroxene), K2O·Al2O3·4SiO2 (leucite), and K2O·Al2O3·6SiO2 (orthoclase).

[0145] Examples of silicate minerals whose components include Na2O include Na2O·SiO2, and its hydrates, Na2O·2SiO2, 2Na2O·SiO2, Na2O·4SiO2, Na2O·3SiO2·3H2O, Na2O·Al2O3·2SiO2, Na2O·Al2O3·4SiO2 (pyroxene), 2Na2O·3CaO·5SiO2, 3Na2O·2CaO·5SiO2 and Na2O·Al2O3·6SiO2 (albite), etc.

[0146] Examples of silicate minerals containing Li2O include Li2O·SiO2, 2Li2O·SiO2, Li2O·SiO2·H2O, 3Li2O·2SiO2, Li2O·Al2O3·4SiO2 (petalite), Li2O·Al2O3·2SiO2 (eucryptite) and Li2O·Al2O3·4SiO2 (spodumene).

[0147] Examples of silicate minerals containing BaO as a component include BaO.SiO 2 , 2BaO.SiO 2 , BaO.Al 2 O 3 .2SiO 2 (barium feldspar), and BaO.TiO 2 .3SiO 2 (bentonite).

[0148] Examples of silicate minerals containing CaO include 3CaO·SiO2 (tricalcium silicate of cement clinker mineral), 2CaO·SiO2 (dicalcium silicate of cement clinker mineral), 2CaO·MgO·2SiO2 (magnesium chalcedony), 2CaO·Al2O3·SiO2 (calcium aluminum chalcedony), a solid solution of magnesium chalcedony and chalcedony (chalcedony), CaO·SiO2 (wollastonite (including both α-type and β-type)), CaO·MgO·2SiO2 (diopside), CaO·MgO·SiO2 (diopside), 3CaO·MgO·2SiO2 (magnesium chalcedony), CaO·Al2O3·2SiO2 (calcium feldspar), 5CaO·6SiO2·5H2O (tobermorite, and 5CaO·6SiO2·9H2O, etc.), and hydrated tobermorite groups. Wollastonite hydrates such as 2CaO·SiO2·H2O (phillipsite), wollastonite hydrates such as 6CaO·6SiO2·H2O (xonotlite), wollastonite hydrates such as 2CaO·SiO2·2H2O (leucote), CaO·Al2O3·2SiO2·H2O (lawnite), CaO·FeO·2SiO2 (ferrocalcium pyroxene), 3CaO·2SiO (brown zircon), 3CaO·Al2O3·3SiO2 (grossular garnet), 3CaO·Fe2O3·3SiO2 (andradite), 6CaO·4Al2O3·FeO·SiO2 (pleochroite), as well as clinzoisite, carnelian, chrysotile, fulvite, axestone, skewite and common pyroxene, etc.

[0149] Examples of silicate minerals containing CaO include Portland cement. The type of Portland cement is not particularly limited, and any of ordinary, early-strength, ultra-early-strength, moderate-heat, sulfate-resistant, and white types may be used. Various blended cements, such as blast furnace cement, silica cement, and fly ash cement, may also be used as component C. Other examples of silicate minerals containing CaO include blast furnace slag and ferrite.

[0150] Examples of silicate minerals containing ZnO include ZnO·SiO2, 2ZnO·SiO2 (serratite), and 4ZnO·2SiO2·H2O (hemimorphite). Examples of silicate minerals containing MnO include MnO·SiO2, 2MnO·SiO2, CaO·4MnO·5SiO2 (rhodonite), and nautilus. Examples of silicate minerals containing FeO include FeO·SiO2 (orthoferropyroxene), 2FeO·SiO2 (fayalite), 3FeO·Al2O3·3SiO2 (almandine), and 2CaO·5FeO·8SiO2·H2O (ferroactinolite).

[0151] Examples of silicate minerals containing CoO as a component include CoO·SiO 2 and 2CoO·SiO 2 .

[0152] Examples of silicate minerals containing MgO include MgO·SiO2 (talc, enstatite), 2MgO·SiO2 (forsterite), 3MgO·Al2O3·3SiO2 (pyrope), 2MgO·2Al2O3·5SiO2 (cordierite), 2MgO·3SiO2·5H2O, 3MgO·4SiO2·H2O (talc), 5MgO·8SiO2·9H2O (attapulgite), 4MgO·6SiO2·7 H2O (sepiolite), 3MgO·2SiO2·2H2O (chrysolite), 5MgO·2CaO·8SiO2·H2O (tremolite), 5MgO·Al2O3·3SiO2·4H2O (chlorite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogopite), Na2O·3MgO·3Al2O3·8SiO2·H2O (glaucophane), as well as magnesia tourmaline, anthophyllite, ferromagnesian amphibole, vermiculite, montmorillonite, etc.

[0153] Examples of silicate minerals containing Fe2O3 as a component include Fe2O3·SiO2 and the like.

[0154] Examples of silicate minerals containing ZrO 2 as a component include ZrO 2 ·SiO 2 (zircon) and AZS refractory materials.

[0155] As silicate minerals whose components contain Al2O3, there are 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 (dolomite, sericite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogopite), as well as various zeolites, fluorphlogopite and biotite.

[0156] Among the above-mentioned silicate minerals, talc, mica, and wollastonite are particularly preferred because they have an excellent balance between rigidity and impact resistance, excellent resistance to moisture and heat, thermal stability, and appearance, and are easily available.

[0157] <Component D: Flame retardant>

[0158] The flame retardant of component D can be mixed with various compounds known as flame retardants for polycarbonate resins. Among them, at least one flame retardant selected from the group consisting of (D-1) halogenated carbonate compounds (component D-1), (D-2) phosphate compounds (component D-2), (D-3) phosphazene compounds (component D-3), (D-4) metal sulfonates (component D-4), and (D-5) organosilicon compounds (component D-5) is preferred.

[0159] The content of component D is preferably 0.01 to 25 parts by weight, more preferably 0.015 to 22 parts by weight, and even more preferably 0.02 to 20 parts by weight relative to 100 parts by weight of component A. When the content of component D is 0.01 to 25 parts by weight, it is sometimes possible to achieve both a sufficient effect of improving flame retardancy and an effect of preventing a decrease in strength during molding.

[0160] <Component D-1: Halogenated carbonate compound>

[0161] As the halogenated carbonate compound used in the present invention, it is preferred to use a halogenated carbonate compound in which the structural unit represented by the following general formula (4) accounts for at least 60 mol % of all structural units and has a specific viscosity of 0.015 to 0.1.

[0162]

[0163] [In the general formula (4), X is a halogen atom, and R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO2-.]

[0164] In the above formula (4), R preferably represents a methylene group, an ethylene group, an isopropylidene group, or -SO2-, and particularly preferably represents an isopropylidene group. In addition, X is preferably a bromine atom.

[0165] The halogenated carbonate compound preferably has a small amount of residual chloroformate groups at the terminal and a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The terminal chlorine content can be determined by dissolving a sample in dichloromethane, adding 4-(p-nitrobenzyl)pyridine to react with the terminal chlorine (terminal chloroformate), and measuring the reaction using a UV-visible spectrophotometer (Hitachi U-3200). If the terminal chlorine content is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and high-temperature molding can be performed. As a result, a resin composition with better molding processability can sometimes be provided.

[0166] In addition, the halogenated carbonate compound preferably has fewer residual hydroxyl terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less, relative to 1 mol of the constituent units of the halogenated carbonate compound. The amount of terminal hydroxyl groups can be determined by dissolving the sample in deuterated chloroform and using 1 The amount of terminal hydroxyl groups can be determined by measuring with the H-NMR method. If the amount of terminal hydroxyl groups is within the above range, the thermal stability of the polycarbonate resin composition may be further improved.

[0167] The specific viscosity of the halogenated carbonate compound is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the halogenated carbonate compound is calculated according to the calculation formula used to calculate the viscosity average molecular weight of the polycarbonate resin as the component A-1 of the present invention.

[0168] The halogenated carbonate compounds are commercially available, for example, tetrabromobisphenol A carbonate oligomers (trade names FG-7000 and FG-8500) manufactured by Teijin Limited, and these can be used in the present invention.

[0169] <Component D-2: Phosphate ester compound>

[0170] The phosphate compound used in the present invention refers to a phosphate compound other than the component B, and is preferably a phosphate compound, particularly an aryl phosphate compound.

[0171] The phosphate compound preferably has a molecular weight of 300 or more. If the molecular weight is less than 300, the difference between the boiling point of the phosphate compound and the combustion temperature of the resin composition becomes large, and the phosphate compound may volatilize more during combustion, thereby reducing the effect as a flame retardant.

[0172] As the phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (5) can be used.

[0173]

[0174] (In the general formula (5), X is a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide; n is an integer from 0 to 5, or, in the case of a mixture of phosphates having different n numbers, is the average value thereof; R 1 、R 2 、R 3 and R 4 Each is independently a monophenol residue derived from an aromatic group selected from phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol.

[0175] The phosphate compound of the above general formula may be a mixture of compounds having different n numbers. In the case of the above mixture, the average n number is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, further preferably 0.95 to 1.15, and particularly preferably in the range of 1 to 1.14.

[0176] Preferred specific examples of the dihydric phenol from which X in the general formula (5) is derived include resorcinol, bisphenol A, and dihydroxydiphenyl. Among them, resorcinol and bisphenol A are preferred.

[0177] As the derivative of R in the above general formula (5) 1 、R 2 、R 3 and R 4 Preferred specific examples of the monohydric phenol include phenol, cresol, xylenol, and 2,6-dimethylphenol. Among them, phenol and 2,6-dimethylphenol are preferred.

[0178] Specific examples of the phosphate compound represented by the general formula (5) are preferably monophosphate compounds such as triphenyl phosphate and tris(2,6-xylyl)phosphate, as well as phosphate oligomers mainly composed of resorcinol bis[di(2,6-xylyl)phosphate], phosphate oligomers mainly composed of 4,4-dihydroxydiphenylbis(diphenylphosphate), and phosphate oligomers mainly composed of bisphenol A bis(diphenylphosphate). Among them, phosphate oligomers mainly composed of resorcinol bis[di(2,6-xylyl)phosphate], phosphate oligomers mainly composed of 4,4-dihydroxydiphenylbis(diphenylphosphate), and phosphate oligomers mainly composed of bisphenol A bis(diphenylphosphate) are preferred.

[0179] <Component D-3: Phosphazene compound>

[0180] The phosphazene compound used in the present invention is not particularly limited as long as it is a compound that does not contain halogen atoms and has a phosphazene structure in its molecule. The phosphazene structure referred to herein is a structure represented by the formula: -P(R2)=N- [wherein R2 is an organic group]. Phosphazenes are represented by the general formulas (6) and (7).

[0181]

[0182] (In general formulae (6) and (7), X1, X2, X3, and X4 represent hydrogen, a hydroxyl group, an amino group, or an organic group containing no halogen atoms. In addition, n represents an integer of 3 to 10.)

[0183] In the above general formulae (6) and (7), examples of the organic group not containing a halogen atom represented by X1, X2, X3, and X4 include alkoxy, phenyl, amino, and allyl groups. Among them, the cyclic phenoxyphosphazene represented by the following general formula (8) is preferred.

[0184]

[0185] [In the general formula (8), m represents an integer of 3 to 25. Ph represents a phenyl group.]

[0186] Examples of commercially available phosphazene compounds include SPS-100, SPR-100, SA-100, SPB-100, and SPB-100L (all manufactured by Otsuka Chemical Co., Ltd.), and FP-100 and FP-110 (all manufactured by Fushimi Pharmaceutical Co., Ltd.).

[0187] <Component D-4: Metal Sulfonate>

[0188] The metal used in the metal sulfonate used in the present invention is preferably an alkali metal or an alkaline earth metal, more preferably an alkali metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium. Lithium, sodium, and potassium are particularly preferred.

[0189] The sulfonic acid used in the metal sulfonate used in the present invention is preferably an organic sulfonic acid, more preferably an aliphatic sulfonic acid or an aromatic sulfonic acid.

[0190] The aliphatic sulfonic acid is preferably an alkylsulfonic acid, more preferably a fluoroalkylsulfonic acid in which a portion or all of the alkyl groups are substituted with fluorine atoms, and most preferably a perfluoroalkylsulfonic acid in which all of the alkyl groups are substituted with fluorine atoms. Preferred examples of perfluoroalkylsulfonic acids include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid. Those having 1 to 8 carbon atoms are particularly preferred. These can be used alone or in combination of two or more.

[0191] Examples of the aromatic sulfonic acid include at least one acid selected from the group consisting of monomeric or polymeric sulfonic acids of aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonic esters, monomeric or polymeric aromatic sulfonic acids, sulfonic acids of monomeric or polymeric aromatic sulfones, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids based on methylene bonds. These may be used alone or in combination of two or more.

[0192] <Component D-5: Silicone compound>

[0193] The organosilicon compound used in the present invention preferably contains highly reactive groups. Preferred examples include alkoxy groups and Si—H groups. The content of these groups is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably 0.12 to 1 mol / 100 g, and even more preferably 0.15 to 0.6 mol / 100 g. This content can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the organosilicon compound by alkaline decomposition.

[0194] The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

[0195] Generally speaking, the structure of an organosilicon compound is formed by arbitrarily combining the following four types of siloxane units. 1 / 2 、H(CH3)2SiO 1 / 2 、H2(CH3)SiO 1 / 2 、(CH3)2(CH2=CH)SiO 1 / 2 、(CH3)2(C6H5)SiO 1 / 2 、(CH3)(C6H5)(CH2=CH)SiO 1 / 2 Monofunctional siloxane units such as D units: (CH3)2SiO, H(CH3)SiO, H2SiO, H(C6H5)SiO, (CH3)(CH2=CH)SiO, (C6H5)2SiO, difunctional siloxane units such as T units: (CH3)SiO 3 / 2、(C3H7)SiO 3 / 2 、HSiO 3 / 2 、(CH2=CH)SiO 3 / 2 、(C6H5)SiO 3 / 2 trifunctional siloxane unit, Q unit: tetrafunctional siloxane unit represented by SiO2.

[0196] Specific exemplary structures of the organosilicon compounds used in silicone flame retardants include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Preferred organosilicon compound structures include MmDn, MmTp, MmDnTp, and MmDnQq, with MmDn or MmDnTp being more preferred.

[0197] Here, the coefficients m, n, p, and q in the above formula represent the degree of polymerization of each siloxane unit and are integers greater than 1. The sum of the coefficients in each formula is the average degree of polymerization of the organosilicon compound. This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, even more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more preferred the range, the better the flame retardancy. Furthermore, as described later, organosilicon compounds containing a predetermined amount of aromatic groups also exhibit excellent transparency and hue. As a result, good reflected light is obtained.

[0198] When any one of m, n, p, and q is a numerical value of 2 or greater, the siloxane unit representing the coefficient may be a siloxane unit having two or more different types of bonded hydrogen atoms or organic residues.

[0199] The organosilicon compound may be linear or branched. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specifically, examples of the organic residue include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and decyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, and aralkyl groups such as tolyl. Alkyl groups, alkenyl groups, or aryl groups having 1 to 8 carbon atoms are further preferred. Alkyl groups such as methyl, ethyl, and propyl groups are particularly preferred, having 1 to 4 carbon atoms.

[0200] Furthermore, organosilicon compounds used as organosilicon flame retardants preferably contain aromatic groups. On the other hand, silane compounds and siloxane compounds used as organic surface treatment agents for titanium dioxide pigments achieve desirable effects without containing aromatic groups, significantly different from organosilicon flame retardants in their preferred formulations. More preferred organosilicon flame retardants are those containing aromatic groups (aromatic group content) in an amount of 10 to 70% by weight (more preferably 15 to 60% by weight).

[0201] <Component E: Anti-drip agent>

[0202] Examples of the anti-dripping agent used as component E in the present invention include fluorine-containing polymers having fibril-forming ability, such as polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers), partially fluorinated polymers disclosed in U.S. Patent No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0203] The molecular weight of PTFE with fibril-forming ability is extremely high, and under external forces such as shearing force, it shows a tendency for the PTFE to adhere to each other into a fibrous state. Its molecular weight is calculated as a number-average molecular weight determined by standard specific gravity, ranging from 1,000,000 to 10,000,000, and more preferably from 2,000,000 to 9,000,000. In addition to solid form, the above-mentioned PTFE can also be used in the form of an aqueous dispersion. In addition, the above-mentioned PTFE with fibril-forming ability can also be used in a PTFE mixture in a mixed form with other resins to improve the dispersibility in the resin and thus obtain good flame retardancy and mechanical properties.

[0204] Examples of commercially available fibril-forming PTFE include Teflon (registered trademark) 6-J from Chemours-Mitsui Fluoroproducts Co., Ltd. and Polyflon MPAFA500H and F-201 from Daikin Industries, Ltd. Representative commercially available aqueous dispersions of PTFE include Fluon D series from Daikin Industries, Ltd. and Teflon (registered trademark) 31-JR from Chemours-Mitsui Fluoroproducts Co., Ltd.

[0205] As mixed PTFE, those obtained by the following methods can be used, namely, (1) a method of mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer to obtain a co-coagulated mixture by coprecipitation (methods described in Japanese Patent Application Laid-Open Nos. 60-258263 and 63-154744), (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Application Laid-Open No. 4-272957), (3) a method of uniformly mixing an aqueous dispersion of PTFE with a solution of organic polymer particles and There are methods for simultaneously removing each medium from the above-mentioned mixture (methods described in Japanese Patent Application Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 08-188653, etc.), (4) a method for polymerizing monomers that form an organic polymer in an aqueous dispersion of PTFE (method described in Japanese Patent Application Laid-Open No. 9-95583), and (5) a method for uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion and then polymerizing a vinyl monomer in the mixed dispersion to obtain a mixture (method described in Japanese Patent Application Laid-Open No. 11-29679, etc.). Commercially available products of these mixed forms of PTFE include "Metablen A3800" (trade name) and "Metablen A3750" of Mitsubishi Chemical Corporation.

[0206] The proportion of PTFE in the mixed form is preferably 1 to 60 wt%, more preferably 5 to 55 wt%, based on 100 wt% of the PTFE mixture. When the proportion of PTFE is within the above range, good dispersibility of PTFE may be achieved.

[0207] Examples of styrene monomers used as organic polymers for use in polytetrafluoroethylene-based mixtures include, but are not limited to, styrenes which may be substituted with one or more groups selected from alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogens, such as o-methylstyrene, m-methylstyrene, p-methylstyrene, dimethylstyrene, ethylstyrene, p-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, vinylxylene, and vinylnaphthalene. These styrene monomers may be used alone or as a mixture of two or more.

[0208] The acrylic monomer used as the organic polymer for the polytetrafluoroethylene-based mixture includes a (meth)acrylate derivative which may be substituted. Specifically, examples of the acrylic monomers include, but are not limited to, (meth)acrylate derivatives that may be substituted with one or more groups selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group, such as (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and glycidyl (meth)acrylate; maleimides that may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group, such as maleimide, N-methyl-maleimide, and N-phenyl-maleimide; maleic acid, phthalic acid, and itaconic acid. These acrylic monomers may be used alone or in combination of two or more. Among them, (meth)acrylonitrile is preferred.

[0209] In addition, as the anti-dripping agent in the present invention, coated branched PTFE can be used. The coated branched PTFE is a polytetrafluoroethylene-based mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and the outside of the branched polytetrafluoroethylene has a coating composed of an organic polymer, preferably a polymer comprising units from styrene monomers and / or units from acrylic acid monomers. The coating is formed on the surface of the branched polytetrafluoroethylene. In addition, the coating preferably comprises a copolymer of styrene monomers and acrylic acid monomers.

[0210] The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the polytetrafluoroethylene contained is not branched polytetrafluoroethylene, the anti-drip effect when a small amount of polytetrafluoroethylene is added becomes insufficient. The branched polytetrafluoroethylene is in granular form and has a particle size of preferably 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and further preferably 0.3 to 0.4 μm. Although the surface appearance of the molded article is excellent when the particle size is less than 0.1 μm, polytetrafluoroethylene with a particle size of less than 0.1 μm is difficult to obtain commercially. In addition, when the particle size is greater than 0.6 μm, the surface appearance of the molded article sometimes deteriorates. The number average molecular weight of the polytetrafluoroethylene used in the present invention is preferably 1×10 4 ~1×10 7 , more preferably 2×10 6 ~9×10 6 Generally, high molecular weight polytetrafluoroethylene is more preferred in terms of stability. It can be used in the form of powder or dispersion.

[0211] The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, further preferably 47 to 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight, relative to 100 parts by weight of the total weight of the coated branched PTFE. When the proportion of the branched polytetrafluoroethylene is within the above range, good dispersibility of the branched polytetrafluoroethylene may be achieved.

[0212] The content of component E is preferably 0.05 to 3 parts by weight relative to 100 parts by weight of component A, more preferably 0.1 to 2 parts by weight, and even more preferably 0.2 to 1.5 parts by weight. If it is greater than this range, not only will the cost increase, but also the extrusion processability may become insufficient. On the other hand, if it is less than this range, the flame retardancy may become insufficient and the tensile strength may also decrease. It should be noted that the ratio of the above-mentioned component E represents the net content of the anti-dripping agent. In the case of PTFE in a mixed form, it represents the net content of PTFE.

[0213] <Production of Thermoplastic Resin Composition>

[0214] Any method may be employed to produce the thermoplastic resin composition of the present invention. For example, the following method may be employed: Component A, Component B, and any other components are thoroughly mixed using a premixing mechanism such as a V-type mixer, a Henschel mixer, a mechanochemical device, or an extrusion mixer; the premix is then pelletized using an extrusion pelletizer, a briquetting machine, or the like, as needed; the premix is then melt-kneaded using a melt-kneading machine such as a vented twin-screw extruder; and the mixture is pelletized using a pelletizer.

[0215] In addition, there are also methods of independently supplying each component to a melt kneader such as a vented twin-screw extruder, and methods of pre-mixing a portion of each component and then supplying the components to a melt kneader independently of the remaining components. Examples of methods of pre-mixing a portion of each component include a method in which components other than component A are pre-mixed and then mixed with the thermoplastic resin of component A or directly supplied to an extruder.

[0216] For example, when a powdered component is included as component A, a method for premixing can be used: a portion of the powder is blended with the additive to be formulated to create a powder-diluted additive masterbatch, and the masterbatch can be used. Alternatively, a method can be used in which one component is independently fed midway into a melt extruder. If a liquid component is included in the formulated components, a so-called liquid injection device or liquid addition device can be used to feed the melt extruder.

[0217] As an extruder, it is possible to preferably use a device having an exhaust port that can degas the moisture in the raw material, the volatile gas produced by the melt-mixed resin. It is preferred to be provided with a vacuum pump for efficiently discharging moisture and volatile gas to the outside of the extruder from the exhaust port. In addition, a wire mesh for removing foreign matter mixed into the extruded raw material, etc., can also be provided in the region before the extruder die portion, to remove foreign matter from the resin combination. As the above-mentioned wire mesh, metal mesh, screen changer, sintered metal plate (disc filter etc.) etc. can be enumerated.

[0218] Examples of the melt kneading machine include a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more screws, in addition to a twin-screw extruder.

[0219] The extruded resin as described above is directly cut and pelletized, or the strands are formed and then cut and pelletized using a pelletizer. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferred to clean the atmosphere around the extruder. Furthermore, in the manufacture of the above-mentioned pellets, various methods that have been proposed in the polycarbonate resin for optical discs can be used to appropriately narrow the shape distribution of the pellets, reduce the amount of erroneously cut products, reduce the amount of fine powder generated during transportation or conveying, and reduce the amount of bubbles (vacuum bubbles) generated inside the strands and pellets. Through these treatment methods, it is possible to achieve high molding cycles and reduce the proportion of defects such as silver streaks. In addition, the shape of the pellets can be a general shape such as a cylinder, a prism, and a sphere, and is more preferably a cylinder. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 3.5 mm.

[0220] <Molded products>

[0221] The thermoplastic resin composition of the present invention can be manufactured into various products by injection molding the pellets usually obtained by the above method. In the above injection molding, not only the usual molding method can be used, but also injection molding methods such as injection compression molding, injection stamping molding, gas-assisted injection molding, foam molding (including molding based on injection of supercritical fluid), insert molding, in-mold coating molding, heat-insulating metal mold molding, rapid heating and cooling metal mold molding, two-color molding, sandwich molding and ultra-high-speed injection molding can be used to obtain molded products according to the purpose. The advantages of these various molding methods are well known. In addition, molding can select any one of the cold runner method and the hot runner method.

[0222] The present inventors believe that the best embodiment of the present invention currently includes the preferred ranges of the above-mentioned requirements, and representative examples thereof are described in the following examples. However, the present invention is not limited to these embodiments.

[0223] Example

[0224] The present invention will be further described below with reference to Examples, but the present invention is not limited thereto. Evaluations were conducted on the following items.

[0225] (i) Discoloration during retention

[0226] The pellets obtained from each composition in the examples were dried in a hot air dryer at 100°C for 5 hours and then injected 100 times into 150 mm × 150 mm × 2 mm square plaques using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U·S-MIV) at the temperatures shown in the table. The molding machine was then interrupted to allow the resin to remain in the barrel. After 15 minutes, the square plaques were molded again. The hue of the plaques before and after the retention period was measured using a Tokyo Denshoku color analyzer TC-1800MKII, and the color difference (ΔE) before and after the retention period was calculated.

[0227] (ii) Strength retention during retention

[0228] A high-speed surface impact test was conducted using the square plate used in "(i) Discoloration during Retention." The fracture energy of the square plate was measured before and after retention, and the strength retention before and after retention was calculated using the following formula. The measurement was conducted using a Hydroshot HTM-1 manufactured by Shimadzu Corporation at 23°C and a test speed of 7 m / s.

[0229] Strength retention (%) = [fracture energy after retention / fracture energy before retention] × 100

[0230] (iii) Recyclability

[0231] The square plates used in "(i) Discoloration during Retention" were left horizontally outdoors in Midori-ku, Chiba City, for one year before being crushed and remolded into square plates. The hue and breaking energy of the unused and remolded square plates were measured using the same methods as for "(i) Discoloration during Retention" and "(ii) Strength Retention during Retention," and the color difference (ΔE) and strength retention were calculated.

[0232] (iv) Flame retardancy

[0233] Pellets obtained from the compositions of the examples were dried in a hot air dryer at 100°C for 5 hours. UL test pieces, 1.5 mm thick, were then continuously molded using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U·S-MIV) at the temperatures shown in the table. Based on the UL94 method, these were classified as V-0, V-1, V-2, and HB. In cases where flammability was so poor that it did not fit any of the classifications, "Not-V" was indicated. Note that flame retardancy must be classified as V-0, V-1, V-2, or HB.

[0234] (v) Flexural modulus

[0235] The flexural modulus value was measured using the test piece before retention used in "(i) Strength retention during retention".

[0236] [Examples 1-1 to 1-12, Examples 2-1 to 2-15, Examples 3-1 to 3-13, Comparative Examples 1-1 to 1-5, Comparative Examples 2-1 to 2-3, Comparative Examples 3-1 to 3-3, Reference Examples 1 to 3]

[0237] Resin compositions composed of the mixing ratios shown in Tables 1, 2, and 3 were prepared in the following manner. It should be noted that the symbols in the following tables are used for explanation. The components in the proportions shown in the table were weighed, mixed evenly using a roller, and the mixture was fed into an extruder to prepare the resin composition. The extruder used was a vented twin-screw extruder manufactured by Nippon Steel Works: TEX-30XSST (fully meshed, co-rotating, double-threaded screw). It should be noted that the glass fiber, plate-shaped glass filler, and fibrous carbon filler in the inorganic filler were supplied from the second supply port, and the other components were supplied from the first supply port. The extrusion conditions were a discharge rate of 20 kg / h, a screw speed of 150 rpm, an exhaust vacuum of 3 kPa, and an extrusion temperature of the temperature shown in the table. The obtained pellets were used to form test pieces for evaluation using an injection molding machine using the above method. The evaluation results are shown in Tables 1 to 3. It should be noted that the components listed in Tables 1 to 3 are as follows.

[0238] (Component A: thermoplastic resin)

[0239] A-1-1: Aromatic polycarbonate resin (a polycarbonate resin powder having a viscosity-average molecular weight of 20,700 produced from bisphenol A and phosgene by a conventional method, Panlite L-1225WS (product name) manufactured by Teijin Limited)

[0240] A-1-2: Modified polycarbonate resin powder with a viscosity average molecular weight of 22,300 obtained by the following method

[0241] A reactor equipped with a thermometer, a stirrer, and a reflux cooler was charged with 4229 parts of a 48% aqueous sodium hydroxide solution and 20,000 parts of ion-exchanged water. 2191 parts of 1,1-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as Bis-1), 1951 parts of bisphenol A, and 8.3 parts of sodium dithionite were dissolved therein. 11,620 parts of dichloromethane were then added, and 2200 parts of phosgene were blown into the mixture at 15-25°C over approximately 60 minutes while stirring. After the phosgene blowing was completed, 704 parts of a 48% aqueous sodium hydroxide solution and 102 parts of p-tert-butylphenol were added, and the mixture was stirred again. After emulsification, 4.32 parts of triethylamine was added, and the mixture was further stirred at 28-33°C for 1 hour to terminate the reaction. After the reaction is complete, the product is diluted with dichloromethane and washed with water. The solution is then acidified with hydrochloric acid and washed with water. This water washing is repeated until the conductivity of the aqueous phase is approximately equal to that of ion-exchanged water, yielding a dichloromethane solution of polycarbonate resin. This solution is then passed through a 0.3 μm filter and added dropwise to warm water in a kneader equipped with an isolation chamber and a foreign matter removal port in the bearing. The dichloromethane is then distilled off, resulting in the formation of polycarbonate resin flakes. The liquid-containing flakes are then pulverized and dried to yield a powder.

[0242] A-1-3: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19800, PDMS content 4.2%, PDMS degree of polymerization 37)

[0243] A-2: ABS resin (SUNTAC AT-07 (trade name), manufactured by Japan A&L Co., Ltd., butadiene rubber component approximately 17.5% by weight, weight-average rubber particle size 1.2 μm, produced by bulk polymerization)

[0244] A-3: Polyethylene terephthalate (TRN-8550FF (trade name) manufactured by Teijin Co., Ltd.)

[0245] A-4: AS resin (LITAC ABS-207 (trade name) manufactured by Japan A&L Co., Ltd.)

[0246] A-5: PS resin (GP-110 (trade name) manufactured by IRPC Public Company Limited)

[0247] A-6: AAS resin (777K (trade name) manufactured by INEOS)

[0248] (Component B: Phosphate metal salt)

[0249] B-1: stearyl acid phosphate zinc salt (LBP-1830 purified (trade name), manufactured by Sakai Chemical Co., Ltd., acid value 49.9 mgKOH / g)

[0250] B-2: stearyl acid phosphate zinc salt (JP-518Zn (trade name), manufactured by Johoku Chemical Industry Co., Ltd., acid value 54.5 mgKOH / g)

[0251] B-3: (Comparative Example) stearyl acid phosphate zinc salt (LBP-1830 (trade name), manufactured by Sakai Chemical Co., Ltd., acid value 56.6 mgKOH / g)

[0252] (Component C: Inorganic filler)

[0253] C-1: Glass fiber (3PE937 (product name) manufactured by Nitto Bosho Co., Ltd.)

[0254] C-2: Glass flake (MEG160FYX (product name) manufactured by Nippon Sheet Glass Co., Ltd.)

[0255] C-3: Carbon fiber (HT C493 (product name) manufactured by Teijin Limited)

[0256] C-4: Non-fibrous carbon filler (EN-250HT (product name) manufactured by Nishimura Graphite Co., Ltd.)

[0257] C-5: Talc (Victory Light TK-RC (product name) manufactured by Katsumitsuyama Mining Co., Ltd.)

[0258] (Component D: flame retardant)

[0259] D-1: Tetrabromobisphenol A carbonate oligomer (FG-7000 (product name) manufactured by Teijin Limited)

[0260] D-2: Phosphate ester containing resorcinol bis(2,6-dimethylphenyl)phosphate as the main component (PX-200 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)

[0261] D-3: Cyclic phenoxyphosphazene (FP-110 (trade name) manufactured by Fushimi Pharmaceutical Co., Ltd.)

[0262] D-4: Potassium perfluorobutanesulfonate (F-TOP KSBF (product name) manufactured by Mitsubishi Materials Corporation)

[0263] D-5: Organosiloxane flame retardant containing Si—H groups, methyl groups, and phenyl groups (X-40-2600J (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.)

[0264] (Component E: anti-dripping agent)

[0265] E-1: Polytetrafluoroethylene (Polyflon MPFA500B (trade name) manufactured by Daikin Industries, Ltd.)

[0266]

[0267]

[0268]

Claims

1. A thermoplastic resin composition comprising 0.001 to 1 part by weight of (B) a phosphoric acid ester metal salt having an acid value of 10 to 55 mgKOH / g, as component B, based on 100 parts by weight of (A) a thermoplastic resin, as component A.

2. The thermoplastic resin composition according to claim 1, wherein The inorganic filler (C), ie, the component C, is contained in an amount of 1 to 150 parts by weight relative to 100 parts by weight of the component A.

3. The thermoplastic resin composition according to claim 1 or 2, wherein The flame retardant (D), ie, component D, is contained in an amount of 0.01 to 25 parts by weight relative to 100 parts by weight of component A.

4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein The (E) anti-dripping agent, ie, component E, is contained in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of component A.

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

6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein Component A is at least one thermoplastic resin selected from the group consisting of (A-1) polycarbonate resin (component A-1), (A-2) ABS resin (component A-2), and (A-3) polyester resin (component A-3).

7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein The content of the component A-1 is 40 to 100 parts by weight based on 100 parts by weight of the component A.

8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein Component B is stearyl acid phosphate zinc salt.

9. The thermoplastic resin composition according to claim 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-shaped 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).

10. The thermoplastic resin composition according to claim 3, wherein Component D is at least one flame retardant selected from the group consisting of (D-1) a halogenated carbonate compound (component D-1), (D-2) a phosphate ester compound (component D-2), (D-3) a phosphazene compound (component D-3), (D-4) a metal sulfonate (component D-4), and (D-5) an organosilicon compound (component D-5).

11. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 10.

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