Polycarbonate resin composition and molded article comprising same

Abstract

The present invention is a polycarbonate resin composition characterized by containing (A) 100 parts by weight of a resin component (component A) comprising 0-99.9% by weight of an aromatic polycarbonate resin (component A-1) and 0.1-100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component A-2) and (B) 1-50 parts by weight of an additive (component B) for forming a laser-irradiated three-dimensional circuit, with respect to 100 parts by weight of a resin component (component A) comprising 0-99.9% by weight of an aromatic polycarbonate resin (component A-1) and 0.1-100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component A-2). Component A-2 is composed of a polycarbonate block represented by formula (1) and a polydiorganosiloxane block represented by formula (3), and has an aggregate structure in which polydiorganosiloxane domains are dispersed in the matrix of a polycarbonate polymer, and the average size of the polydiorganosiloxane domains is 5 to 5. The polycarbonate-polydiorganosiloxane copolymer resin contains (B) 1-30 parts by weight of an additive (component B) for forming a laser-irradiated three-dimensional circuit per 100 parts by weight of a resin component (component A).

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin composition having excellent plating properties when forming a circuit, and a molded article composed of the same. Background Art

[0002] Due to its excellent transparency, impact resistance, heat resistance, and dimensional stability, polycarbonate resin is used as an engineering plastic in a wide range of fields, including housings for electrical and electronic equipment, automotive interior and exterior components, building materials, furniture, musical instruments, and daily necessities. Various methods for manufacturing antennas and electronic circuits within electronic devices, including mobile phones, including smartphones, have been studied, with a particular focus on methods that enable the three-dimensional design of antennas and electronic circuits within electronic devices. Laser irradiation three-dimensional circuit forming technology has attracted considerable attention as one of the technologies for forming such three-dimensional electronic components. This technology uses, for example, a resin material in which a metal complex is dispersed, reduces the complex using a laser to form catalyst cores, and then selectively plates the metal to form circuits such as antennas without an adhesive layer. As an example of using this laser irradiation three-dimensional circuit forming technology, a resin composition composed of a polycarbonate resin and a specific conductive oxide has been proposed (Patent Document 1). Furthermore, a resin composition capable of appropriately forming a metal thin film under a wide range of laser irradiation conditions has been proposed (Patent Document 2). However, in recent years, demand for laser irradiation three-dimensional circuit forming technology has increased, leading to a demand for polycarbonate resin compositions with even better plating properties and molded articles formed therefrom.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2012-72338

[0006] Patent Document 2: International Publication No. 2014 / 042070 Summary of the Invention

[0007] In view of the above circumstances, an object of the present invention is to provide a polycarbonate resin composition having excellent plating properties when forming a circuit, and a molded article composed of the same.

[0008] The present inventors conducted intensive research to solve the above-mentioned problems and found that by adding an additive for laser irradiation three-dimensional circuit molding to a specific aromatic polycarbonate resin, a polycarbonate resin composition with excellent plating properties when forming circuits that could not be obtained with previous resin compositions can be obtained, thereby completing the present invention.

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

[0010] 1. A polycarbonate resin composition, characterized in that it contains:

[0011] (A) 100 wt% of a resin component (component A) composed of 0 to 99.9 wt% of an aromatic polycarbonate resin (component A-1) and 0.1 to 100 wt% of a polycarbonate-polydiorganosiloxane copolymer resin (component A-2), and

[0012] (B) 1 to 50 parts by weight of an additive for forming a three-dimensional circuit by laser irradiation (component B),

[0013] Component A-2 is a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3), and having a cohesive structure in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer, wherein the average size of the polydiorganosiloxane domains is 5 to 100 nm.

[0014]

[0015] (In the above general formula (1), R 1 and R 2 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 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 the groups, they may be the same or different. a and b 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).

[0016]

[0017] (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 20Each 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 there are multiple alkyl groups, they may be the same or different. c is an integer of 1 to 10, and d is an integer of 4 to 7.

[0018]

[0019] (In the above general formula (3), R 3 、R 4 、R 5 、R 6 、R 7 and R 8 Each is 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; R9 and R10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; e and f are each an integer from 1 to 4; p is a natural number; q is 0 or a natural number; and p+q is a natural number from 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0020] 2. The polycarbonate 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.

[0021] 3. The polycarbonate resin composition according to the above 1 or 2, wherein the content of the polydiorganosiloxane block represented by the above formula (3) in the component A-2 is 0.05 to 50.0% by weight.

[0022] 4. The polycarbonate resin composition according to any one of the above 1 to 3, wherein the component B is an additive for forming a three-dimensional circuit by laser irradiation containing at least two metals.

[0023] 5. The polycarbonate resin composition according to the above item 2, wherein the component C is at least one inorganic filler selected from the group consisting of glass, carbon fiber, and silicate minerals.

[0024] 6. A resin molded article obtained by molding the polycarbonate resin composition according to any one of 1 to 5 above.

[0025] 7. A resin molded article, wherein a plated layer is laminated on the surface of the resin molded article according to the above item 6.

[0026] The polycarbonate resin composition of the present invention exhibits excellent plating properties when formed into circuits and is therefore suitable for use as three-dimensional circuit boards or broadband antennas in various fields, including buildings, construction materials, agricultural materials, marine materials, vehicles, electrical and electronic equipment, machinery, and other applications. Therefore, the present invention has significant industrial benefits. DETAILED DESCRIPTION

[0027] Hereinafter, the present invention will be described in detail.

[0028] The present invention is a polycarbonate resin composition having the following structure.

[0029] A polycarbonate resin composition, characterized in that it contains:

[0030] (A) 100 wt% of a resin component (component A) composed of 0 to 99.9 wt% of an aromatic polycarbonate resin (component A-1) and 0.1 to 100 wt% of a polycarbonate-polydiorganosiloxane copolymer resin (component A-2), and

[0031] (B) 1 to 50 parts by weight of an additive for forming a three-dimensional circuit by laser irradiation (component B),

[0032] Component A-2 is a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3), and having a cohesive structure in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer, wherein the average size of the polydiorganosiloxane domains is 5 to 100 nm.

[0033]

[0034] (In the above general formula (1), R 1 and R 2 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 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 the groups, they may be the same or different. a and b 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).

[0035]

[0036] (In the above general formula (2), R 11 、R12 、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 there are multiple alkyl groups, they may be the same or different. c is an integer of 1 to 10, and d is an integer of 4 to 7.

[0037]

[0038] (In the above general formula (3), R 3 、R 4 、R 5 、R 6 、R 7 and R 8 Each is 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; R9 and R10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; e and f are each an integer from 1 to 4; p is a natural number; q is 0 or a natural number; and p+q is a natural number from 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0039] Each component is described below.

[0040] (Component A: resin component)

[0041] (Component A-1: ​​aromatic polycarbonate resin)

[0042] Aromatic polycarbonate resins are usually prepared by reacting dihydroxy compounds with carbonate precursors using interfacial polycondensation or melt transesterification, or by polymerizing carbonate prepolymers using solid-phase transesterification, or by ring-opening polymerization using cyclic carbonate compounds. The dihydroxy component used herein can be any of the dihydroxy components commonly used as aromatic polycarbonates, or can be either bisphenols or aliphatic diols. The bisphenols preferably represent the following formula (4).

[0043]

[0044] [In the above general formula (4), R 1 and R 2 Each independently represents a hydrogen atom. When there are plural hydrogen atoms, they may be the same or different. a and b are each an integer of 1 to 4. W is at least one group selected from a single bond or a group represented by the following general formula (2).

[0045]

[0046] (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 there are multiple alkyl groups, they may be the same or different. c is an integer of 1 to 10, and d is an integer of 4 to 7.

[0047] Specific examples of bisphenols 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-3,3'-biphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyl diphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxy 4,4'-dihydroxydiphenyl sulfoxide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 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, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(4-hydroxy-3-isobutylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2- Bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(3-ethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-isopropylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-isobutylphenyl)cyclohexane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-cyclohexyl-4 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, bis(4-hydroxy-3-methylphenyl)diphenylmethane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, carbonyl Alkyl-substituted resorcinol with 1 to 3 substituents, 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol, 1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol, 6,6'-dihydroxy-3,3,3',3'-tetramethylspiroindane, 1-methyl-1,3-bis(4-hydroxyphenyl)-3-isopropylcyclohexane, 1-methyl-2-(4-hydroxyphenyl)-3-[1-(4-hydroxyphenyl)isopropyl]cyclohexane, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, etc.

[0048] Examples of the aliphatic diols include 2,2-bis-(4-hydroxycyclohexyl)-propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4'-bis(2-hydroxyethoxy)biphenyl, bis{(2-hydroxyethoxy)phenyl}methane, 1,1-bis{(2-hydroxyethoxy)phenyl}ethane, 1,1-bis{(2-hydroxyethoxy)phenyl}-1-phenylethane, 2,2-bis{(2-hydroxyethoxy)phenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3-methylphenyl}propane, 1,1-bis{(2-hydroxyethoxy)phenyl}-3,3,5-trimethylcyclohexane, 2,2-bis{4-(2-hydroxyethoxy)phenyl}- )-3,3'-biphenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3-isopropylphenyl}propane, 2,2-bis{3-tert-butyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{(2-hydroxyethoxy)phenyl}butane, 2,2-bis{(2-hydroxyethoxy)phenyl}-4-methylpentane, 2,2-bis{(2-hydroxyethoxy)phenyl}octane, 1,1-bis{(2-hydroxyethoxy)phenyl}decane, 2,2-bis{3-bromo-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{3,5-dimethyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{3-cyclohexyl-4-(2-hydroxyethoxy)phenyl} phenyl}propane, 1,1-bis{3-cyclohexyl-4-(2-hydroxyethoxy)phenyl}cyclohexane, bis{(2-hydroxyethoxy)phenyl}diphenylmethane, 9,9-bis{(2-hydroxyethoxy)phenyl}fluorene, 9,9-bis{4-(2-hydroxyethoxy)-3-methylphenyl}fluorene, 1,1-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 1,1-bis{(2-hydroxyethoxy)phenyl}cyclopentane, 4,4'-bis(2-hydroxyethoxy)diphenyl ether, 4,4'-bis(2-hydroxyethoxy)-3,3'-dimethyldiphenyl ether, 1,3-bis[2-{(2-hydroxyethoxy)phenyl}propyl]benzene, 1,4-bis[2-{(2-hydroxyethoxy)phenyl} [1,2-[4-[4-[4-[4-[4-[4-hydroxy-2-oxo-1-yl]-4-thiazolyl]-1-yl]-4-thiazolyl]-1-ol, 1,4-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 1,3-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 4,8-bis{(2-hydroxyethoxy)phenyl}tricyclo[5.2.1.02,6]decane, 1,3-bis{(2-hydroxyethoxy)phenyl}-5,7-dimethyladamantane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 1,4:3,6-dianhydro-D-sorbitol (isosorbide), 1,4:3,6-dianhydro-D-mannitol (isomannitol), 1,4:3,6-dianhydro-L-idiol (isoidiol), etc.

[0049] Among these, aromatic bisphenols are preferred, with 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene being particularly preferred. 2,2-bis(4-hydroxyphenyl)propane and 4,4'-sulfonyldiphenol are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is most preferred due to its excellent strength and durability. These bisphenols can be used alone or in combination of two or more.

[0050] The aromatic polycarbonate resin used as the component A-1 of the present invention can be made into a branched polycarbonate resin by using a branching agent in combination with the above-mentioned dihydroxy compound. Examples of the trifunctional or higher-functional 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-methylbenzyl 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, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof are preferred. Among them, 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.

[0051] These aromatic polycarbonate resins are produced by a conventional reaction method known per se for producing aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or a carbonic acid diester.

[0052] In reactions using, for example, phosgene as a carbonate precursor, the reaction is generally carried out in the presence of an acid-binding agent and a solvent. Examples of acid-binding agents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine. Examples of solvents include halogenated hydrocarbons such as dichloromethane and chlorobenzene. Furthermore, catalysts such as tertiary amines or quaternary ammonium salts may be used to promote the reaction. In this case, the reaction temperature is generally 0 to 40°C, and the reaction time is several minutes to 5 hours. Transesterification reactions using carbonic acid diesters as carbonate precursors are carried out by heating and stirring a predetermined ratio of aromatic dihydroxy components and carbonic acid diesters under an inert gas atmosphere, allowing the generated alcohol or phenol to be distilled off. The reaction temperature varies depending on the boiling point of the generated alcohol or phenol, but is generally in the range of 120 to 300°C. From the initial stage of the reaction, the reaction is completed while reducing the pressure to allow the generated alcohol or phenol to be distilled off. Furthermore, catalysts commonly used in transesterification reactions may be used to promote the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.

[0053] In the present invention, a terminal terminator is used in the polymerization reaction. The terminal terminator is used to adjust the molecular weight. Furthermore, the resulting aromatic polycarbonate resin has excellent thermal stability compared to an uncapped aromatic polycarbonate resin due to the blocked ends. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas (5) to (7).

[0054]

[0055] [In the above general formula (5), A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion has 1 to 9 carbon atoms), and r is an integer of 1 to 5, preferably 1 to 3.]

[0056]

[0057] [In the above general formulas (6) and (7), Y is -R-O-, -R-CO-O-, or -R-O-CO-, where R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50.]

[0058] Specific examples of the monofunctional phenols represented by the general formula (5) include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol, and isooctylphenol. Furthermore, the monofunctional phenols represented by the general formulas (6) and (7) are phenols having long-chain alkyl groups or aliphatic ester groups as substituents. When used to cap the ends of aromatic polycarbonate resins, they not only function as end cappers or molecular weight regulators but also improve the melt flowability of the resin, making molding easier and reducing the water absorption of the resin. Therefore, they are preferably used. As substituted phenols of the general formula (6), those in which n is 10 to 30, particularly 10 to 26, are preferred. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. In addition, as the substituted phenols of the general formula (7), compounds in which Y is -R-CO-O- and R is a single bond are preferred. Preferably, n is 10 to 30, particularly 10 to 26. Specific examples include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, behenyl hydroxybenzoate, and triacontyl hydroxybenzoate. Among these monofunctional phenols, the monofunctional phenols represented by the general formula (5) are preferred, and alkyl-substituted or phenylalkyl-substituted phenols are more preferred, with p-tert-butylphenol, p-cumylphenol, or 2-phenylphenol being particularly preferred. It is preferred that a terminal terminator for these monofunctional phenols be introduced into at least 5 mol%, preferably at least 10 mol%, of the total number of terminals of the resulting aromatic polycarbonate resin. These terminal terminators may be used alone or in combination of two or more.

[0059] The aromatic polycarbonate resin used as the component A-1 of the present invention may be a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or a derivative thereof, without impairing the gist of the present invention.

[0060] The viscosity-average molecular weight of the aromatic polycarbonate resin used as component A-1 of the present invention is preferably in the range of 12,000 to 50,000, more preferably in the range of 12,000 to 30,000, even more preferably in the range of 12,000 to 25,000, and most preferably in the range of 15,000 to 25,000. A molecular weight exceeding 50,000 may result in excessively high melt viscosity, leading to poor moldability, while a molecular weight below 12,000 may lead to problems with mechanical strength. The viscosity-average molecular weight referred to in the present invention is determined as follows: First, using an Ostwald viscometer, the specific viscosity of a solution obtained by dissolving 0.7 g of the aromatic polycarbonate resin in 100 ml of dichloromethane at 20°C is calculated using the following formula. The viscosity-average molecular weight M is determined by substituting the determined specific viscosity into the following formula.

[0061] Specific viscosity (η SP )=(t-t0) / t0

[0062] [t0 is the dripping time of dichloromethane, t is the dripping time of the sample solution]

[0063] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0064] [η] = 1.23 × 10 －4 M 0.83

[0065] c=0.7

[0066] The aromatic polycarbonate resin used as component A-1 of the present invention preferably has a total Cl (chlorine) content of 0 to 200 ppm, more preferably 0 to 150 ppm. If the total Cl content of the aromatic polycarbonate resin exceeds 200 ppm, the color tone and thermal stability may deteriorate, which is not preferred.

[0067] (Component A-2: polycarbonate-polydiorganosiloxane copolymer resin)

[0068] The component A-2 of the present invention is a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3), and having a cohesive structure in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer, wherein the average size of the polydiorganosiloxane domains is 5 to 100 nm.

[0069]

[0070] (In the above general formula (1), R 1 and R 2Each 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 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 the groups, they may be the same or different. a and b are each an integer of 1 to 4. W represents a single bond or at least one group selected from the group represented by the following general formula (2).

[0071]

[0072] (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 there are multiple alkyl groups, they may be the same or different. c is an integer of 1 to 10, and d is an integer of 4 to 7.

[0073]

[0074] (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 9 and R 10Each 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; e and f are each an integer from 1 to 4; p is a natural number; q is 0 or a natural number; and p+q is a natural number from 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0075] Examples of the dihydric phenol (I) from which the carbonate constituent unit represented by the general formula (1) is derived include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane. 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)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'-dimethyl diphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyl diphenol, 4,4'-dihydroxy-3,3'-diphenyl diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyl diphenyl 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, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-isobutylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(3-ethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-isopropylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3- isobutylphenyl)cyclohexane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, bis(4-hydroxy-3-methylphenyl)diphenylmethane, etc.

[0076] 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 durability.

[0077] In the carbonate constituent unit represented by the general formula (3), R 3 、R 4 、R 5 、R 6 、R 7 and R 8 Each independently is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and particularly preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 and R 10Each of the above groups is preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) from which the carbonate constituent unit represented by the general formula (3) is derived, for example, a compound represented by the following general formula [I] is preferably used.

[0078]

[0079] Hydroxyaryl-terminated polydiorganosiloxane (II) can be easily produced by subjecting a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, to a hydrosilylation reaction at the 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 polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane being particularly preferred.

[0080] The degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 4-120, more preferably 30-120, further preferably 30-100, and most preferably 30-95.

[0081] The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably 5.0×10 3 ~5.0×10 4 The viscosity average molecular weight is more preferably 1.0×10 4 ~4.0×10 4 , more preferably 1.5×10 4 ~3.5×10 4 , particularly preferably 1.7×10 4 ~2.5×10 4 If the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is less than 5.0×10 3 , it is difficult to obtain practical mechanical strength in many fields. If it exceeds 5.0×10 4 , the melt viscosity is high, and generally a high molding temperature is required, which sometimes causes problems such as thermal degradation of the resin.

[0082] It should be noted that the polydiorganosiloxane domain in the present invention refers to a domain primarily composed of polydiorganosiloxane dispersed in a polycarbonate matrix, and may contain other components. As described above, the polydiorganosiloxane domain forms a structure through phase separation from the polycarbonate matrix and is therefore not necessarily composed of a single component.

[0083] In the production method of the present invention, only one type of the hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

[0084] Next, the method for producing the preferred polycarbonate-polydiorganosiloxane copolymer resin is described below. A mixed solution of chloroformate compounds containing chloroformate of dihydric phenol (I) and / or carbonate oligomers of dihydric phenol (I) having terminal chloroformate groups is prepared by reacting dihydric phenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of dihydric phenol (I) in a mixture of a water-insoluble organic solvent and an aqueous alkali solution. Phosgene is preferably used as the chloroformate-forming compound.

[0085] When chloroformate compound is generated by dihydric phenol (I), the total amount of dihydric phenol (I) from which the carbonate constituent units represented by the general formula (1) are derived can be made into chloroformate compound at one time, or a part of it can be added as a reaction raw material in the interfacial polycondensation reaction of the latter section in the form of a monomer added later. The monomer added later refers to a substance added in order to quickly carry out the polycondensation reaction of the latter section, and it is not necessary to add it when it is not necessary. The method for the chloroformate compound generation reaction is not particularly limited, and it is usually preferably carried out in a solvent in the presence of an acid binding agent. As needed, a small amount of antioxidants such as sodium sulfite and sodium dithionite can be further added, preferably added. The proportion of chloroformate forming compound used can be appropriately adjusted as long as the stoichiometric ratio (equivalent) of the reaction is considered. In addition, when using phosgene as the preferred chloroformate forming compound, it is preferably possible to adopt a method in which the gasified phosgene is blown into the reaction system.

[0086] As above-mentioned acid binding agent, for example, can use alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate and organic bases such as pyridine or their mixture etc.The usage ratio of acid binding agent also can suitably determine with above-mentioned similarly considering the stoichiometric ratio (equivalent) of reaction.Specifically, with respect to 1 mole of the dihydric phenol (I) that uses in the formation of the chloroformate compound of dihydric phenol (I) (usually 1 mole is equivalent to 2 equivalents), preferably use 2 equivalents or than its slightly excessive acid binding agent.

[0087] As the solvent, any solvent inert to various reactions, such as solvents used in the production of known polycarbonates, may be used alone or in a mixed solvent. 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 preferably used.

[0088] The pressure in the reaction for forming the chloroformate compound is not particularly limited and may be normal pressure, pressurized or reduced pressure, but 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 because heat is generated with the reaction. The reaction time is affected by other conditions and cannot be generalized, but is generally carried out for 0.2 to 10 hours. The pH range in the reaction for forming the chloroformate compound can utilize known interfacial reaction conditions, and the pH is generally adjusted to 10 or above.

[0089] In the production of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, after preparing a mixed solution of a chloroformate compound comprising a chloroformate of a dihydric phenol (I) and a carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group, a dihydroxyaryl-terminated polydiorganosiloxane (II) having carbonate constituent units represented by the general formula (3) is added at a rate of 0.01 mol / min or less relative to 1 mol of the dihydric phenol (I) added when preparing the mixed solution while stirring the mixed solution, so that the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound undergo interfacial polycondensation, thereby obtaining the polycarbonate-polydiorganosiloxane copolymer resin.

[0090] Polycarbonate-polydiorganosiloxane copolymer resins can be prepared into branched polycarbonate-polydiorganosiloxane copolymer resins by using a branching agent in combination with a dihydric phenolic compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in the branched polycarbonate resins 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-methylbenzyl 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, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof are preferred. Among them, 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.

[0091] The method for producing the branched polycarbonate-polydiorganosiloxane copolymer resin may be a method in which a branching agent is added to the mixed solution during the formation reaction of the chloroformate compound, or a method in which a branching agent is added during the interfacial polycondensation reaction after the formation reaction. The proportion of carbonate constituent units derived from the branching agent in the total amount of carbonate constituent units constituting the copolymer resin is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, and particularly preferably 0.05 to 1.0 mol%. It should be noted that the amount of branched structure can be determined by 1 It was calculated by H-NMR measurement.

[0092] The pressure in the system during the polycondensation reaction may be any of reduced pressure, normal pressure or increased pressure, but it is usually preferably carried out at normal pressure or the pressure of the reaction system itself. 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 varies depending on other conditions such as the reaction temperature, so it cannot be generalized, but it is usually carried out for 0.5 to 10 hours. Depending on the situation, the obtained polycarbonate-polydiorganosiloxane copolymer resin may also be subjected to appropriate physical treatment (mixing, classification, etc.) and / or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain the desired reduced viscosity [η SP 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 of desired purity (degree of purification).

[0093] The content of the polydiorganosiloxane block represented by the general formula (3) in the A-2 component is preferably 0.05 to 50% by weight. The content of the polydiorganosiloxane block is more preferably 0.5 to 30% by weight, and further preferably 1 to 20% by weight. When the content is less than 0.05% by weight, the plating property may not be exhibited at a practical level. If it exceeds 50% by weight, the appearance may be poor during injection molding. The degree of polymerization of the diorganosiloxane and the content of the polydiorganosiloxane block can be adjusted by 1 It was calculated by H-NMR measurement.

[0094] The average size of the polydiorganosiloxane domains in the polycarbonate polymer matrix is ​​in the range of 5 to 100 nm. The average size is preferably 5 to 80 nm, and more preferably 7 to 30 nm. Outside of this range, practical plating properties are not achieved.

[0095] The average domain size of the polydiorganosiloxane domain was determined using an 850 nm square (722500 nm) electron microscope (hereinafter sometimes abbreviated as TEM). 2) is measured by observing the cross-section of the resin composition. Specifically, the portion of the depth of 2mm at the intersection of 15mm from the gate and 5mm from the side end of a molded piece with a width of 10mm, a length of 80mm and a thickness of 4.0mm made by injection molding is cut perpendicularly to the flow direction of the resin using a microtome (EM UC6 made by Leica Microsystems) to make an ultrathin section, attached to a grid (EMFINE GRID No.2632F-200-CU 100PC / CA made by JEOL Ltd.), and observed using TEM JEM-2100 made by JEOL Ltd. with an accelerating voltage of 200kV. The observation magnification is 20,000 times. The obtained microscope photograph is subjected to particle analysis using image analysis software Win ROOF Ver.6.6 (Mitani Shoji Co., Ltd.) to obtain the average size of the polydiorganosiloxane domain in the sample slice. Here, the maximum major diameter (the length when the length between any two points on the outer contour line of the particle is maximized) is used as the size of each domain. The same analysis was performed on 5 sample slices, and the average value was used as the value for each sample.

[0096] The content of the polycarbonate-polydiorganosiloxane copolymer resin (A-2) in 100% by weight of component A is 0.1 to 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 100% by weight. If the content is less than 0.1% by weight, practical plating properties are not achieved.

[0097] In the present invention, it is considered that the use of the polycarbonate-polydiorganosiloxane copolymer resin (A-2) improves plating properties during circuit formation because surface roughening is facilitated during laser irradiation, thereby increasing the surface area.

[0098] (Component B: additive for forming a three-dimensional circuit by laser irradiation)

[0099] The additive for forming a three-dimensional circuit by laser irradiation used in the present invention refers to a compound that can be used to form a three-dimensional circuit by laser irradiation. The additive for forming a three-dimensional circuit by laser irradiation may be a synthetic product or a commercial product. In addition, in addition to substances sold as additives for forming a three-dimensional circuit by laser irradiation, commercial products may also be substances sold for other purposes. The additive for forming a three-dimensional circuit by laser irradiation may be a compound containing only one metal, preferably a mixed metal compound containing at least two metals. Examples of the metal include copper, chromium, tin, zinc and antimony. The additive for forming a three-dimensional circuit by laser irradiation may be used alone or in combination of two or more.

[0100] As the additive for forming a three-dimensional circuit by laser irradiation used in the present invention, a compound containing copper is preferred, and a compound containing copper and chromium oxides as main components is more preferred. By using such an additive for forming a three-dimensional circuit by laser irradiation, the plating properties of the resin molded article can be further improved, thereby allowing the surface of the resin molded article to be appropriately plated. Among them, the copper content is preferably 10 to 40% by weight, and the chromium content is preferably 10 to 50% by weight. In addition, as the form in which copper and chromium are contained, a spinel structure is preferred. The spinel structure refers to one of the crystal structures of metal complex oxides of the general formula AB2O4.

[0101] The additive for forming three-dimensional circuits by laser irradiation may contain other metals in addition to copper and chromium. Examples of other metals include antimony, tin, lead, indium, zinc, cadmium, iron, nickel, bismuth, iron, manganese, magnesium, calcium, arsenic, silver, and iron. These metals may exist as oxides.

[0102] Furthermore, the additive for forming three-dimensional circuits by laser irradiation may be a metal compound primarily composed of a metal other than copper and chromium. For example, a compound primarily composed of tin oxide is preferable, and a compound primarily composed of antimony and tin oxide is preferable. The tin content is preferably greater than the antimony content, and the tin content relative to the total amount of tin and antimony is more preferably 80% by weight or greater, and even more preferably 85% by weight or greater. Examples of such compounds include antimony-doped tin oxide and antimony-doped tin oxide, with antimony-doped tin oxide being preferable. Furthermore, in additives for forming three-dimensional circuits by laser irradiation containing antimony and tin oxide, the antimony content relative to the total amount of tin oxide and antimony is preferably 1 to 20% by weight, and more preferably 3 to 15% by weight. Furthermore, in additives for forming three-dimensional circuits by laser irradiation containing antimony and tin oxide, the antimony content relative to the total amount of tin oxide and antimony is preferably 0.5 to 10% by weight, and more preferably 1.0 to 8.0% by weight.

[0103] The average particle size of the additive for forming a three-dimensional circuit by laser irradiation used in the present invention is preferably 0.01 to 50 μm, more preferably 0.05 to 30 μm. With such a configuration, the uniformity of the plated surface state during plating tends to be improved.

[0104] The additive for forming a three-dimensional circuit by laser irradiation used in the present invention is preferably an additive that absorbs light with a wavelength of 1064 nm. By absorbing light with a wavelength of 1064 nm, a plating layer can be easily formed on the surface of the resin molded article.

[0105] The content of component B is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 15 parts by weight, relative to 100 parts by weight of component A. If the content is less than 1 part by weight, the plating properties may be insufficient, while if it exceeds 50 parts by weight, poor appearance may occur during injection molding.

[0106] (Component C: Inorganic filler)

[0107] The polycarbonate resin composition of the present invention may contain various known inorganic fillers as reinforcing fillers. Preferred inorganic fillers include glass (fibrous glass and plate glass), carbon (fibrous carbon and non-fibrous carbon), silicate minerals, calcium carbonate, silicon dioxide, and titanium dioxide. Among these, at least one inorganic filler selected from glass, carbon fiber, and silicate minerals is more preferred.

[0108] (C-1; fibrous glass filling material)

[0109] As fibrous glass fillers, glass fibers, metal-coated glass fibers, and glass milled fibers can be cited. The glass fibers that form the matrix of the above-mentioned fibrous glass fillers are made by rapidly cooling molten glass while stretching it by various methods to form a predetermined fibrous glass fiber. The rapid cooling and stretching in this case are not particularly limited. In addition, the shape of the cross section can be, in addition to a perfect circle, an elliptical, cocoon-shaped, flat, clover-shaped, or other shapes other than a perfect circle. Furthermore, it can also be a shape that is a mixture of a perfect circle and shapes other than a perfect circle. Flatness refers to a shape in which the average value of the major diameter of the fiber cross section is 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and the average value of the ratio of the major diameter to the minor diameter (major diameter / minor diameter) is 1.5 to 8, preferably 2 to 6, and more preferably 2.5 to 5.

[0110] In addition, the average fiber diameter of a fibrous glass filler with a high aspect ratio, such as glass fiber, is preferably 1 to 25 μm, more preferably 3 to 17 μm. When using a fibrous glass filler with an average fiber diameter within this range, it is sometimes possible to exhibit good mechanical strength without damaging the appearance of the molded product. In addition, the fiber length of the fibrous glass filler with a high aspect ratio is preferably 60 to 500 μm, more preferably 100 to 400 μm, and particularly preferably 120 to 350 μm, based on the number average fiber length in the polycarbonate resin composition. It should be noted that the above-mentioned number average fiber length is a value calculated by using an image analyzer to observe the remaining material of the fibrous glass filler collected during treatments such as high-temperature ashing of the molded product, dissolution using a solvent, and decomposition using a chemical reagent, using an optical microscope. In addition, when calculating the above-mentioned value, it is a value obtained by using the fiber diameter as a reference and not counting the material with a length below it. The aspect ratio of the high-aspect-ratio fibrous glass filler is preferably 10 to 200, more preferably 15 to 100, and even more preferably 20 to 50. The aspect ratio refers to a value obtained by dividing the average fiber length by the average fiber diameter.

[0111] Milled glass fibers are typically produced by pulverizing glass fibers using a pulverizer such as a ball mill. The aspect ratio of fibrous glass fillers with a low aspect ratio, such as milled glass fibers, is preferably 2 to 10, more preferably 3 to 8. The fiber length of the low aspect ratio fibrous glass filler, as measured by the number average fiber length in the polycarbonate resin composition, is preferably 5 to 150 μm, more preferably 9 to 80 μm. Furthermore, the average fiber diameter is preferably 1 to 15 μm, more preferably 3 to 13 μm.

[0112] The glass composition of the above-mentioned various fibrous glass filling materials can be applied to various glass compositions represented by A glass, C glass, D glass, E glass, S glass and NE glass, etc., without special limitation. The above-mentioned fibrous glass filling materials may contain components such as TiO2, SO3 and P2O5 as needed. Among these, E glass (alkali-free glass) and NE glass are more preferred. In addition, from the viewpoint of improving mechanical strength, it is preferred to surface-treat the fibrous glass filling materials with a known surface treatment agent, such as a silane coupling agent, a titanate coupling agent or an aluminate coupling agent. In addition, the fibrous glass filling materials (including the metal-coated or metal oxide-coated filling materials described below) are preferably those obtained by bundling treatment using olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins and polyurethane resins. The amount of the bundling agent attached to the fibrous glass filling materials that have been bundled is preferably 0.5 to 8 weight %, more preferably 1 to 4 weight % in 100 weight % of the fibrous glass filling materials.

[0113] Furthermore, the fibrous glass filling material includes a filling material obtained by coating the surface with different kinds of materials. As the above-mentioned different kinds 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 kinds of materials is not particularly limited, and for example, known various plating methods (such as electroplating, chemical plating, hot dip plating, etc.), vacuum evaporation method, ion plating method, CVD method (such as thermal CVD, MOCVD, plasma CVD, etc.), PVD method and sputtering method can be cited.

[0114] (C-2; plate glass filling material)

[0115] Examples of the plate-shaped glass filler include glass flakes, metal-coated glass flakes, and metal oxide-coated glass flakes.

[0116] The glass flakes that form the base of the plate-shaped glass filler are plate-shaped glass fillers manufactured by methods such as cylinder blowing and sol-gel methods. The size of the raw glass flakes can be selected from various sizes depending on 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 the average particle size within this range provides excellent balance between handleability and moldability. Plate-shaped glass fillers typically 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 polycarbonate resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and even more preferably 20 to 80 μm. The number average particle size is calculated using an image analyzer from optical microscopic observation of residual material from the plate-shaped glass filler collected during processes such as high-temperature ashing of the molded article, dissolution with a solvent, and decomposition with a chemical reagent. The above values ​​are calculated by using the flake thickness as a reference, omitting any length shorter than that. 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 can sometimes achieve excellent mechanical strength, appearance, and moldability.

[0117] 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 particular limitation. The above-mentioned glass filling material may contain components such as TiO2, SO3 and P2O5 as needed. Among these, E glass (alkali-free glass) is more preferred. In addition, from the viewpoint of improving mechanical strength, it is preferred to surface-treat the plate glass filling material with a 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 filling material obtained by bundling treatment using olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins and polyurethane resins. 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.

[0118] Furthermore, the plate glass filling material includes a filling material obtained by coating the surface with different types of materials. As the above-mentioned different types 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 well-known plating methods (such as electroplating, chemical plating, hot dip plating, etc.), vacuum evaporation method, ion plating method, CVD method (such as thermal CVD, MOCVD, plasma CVD, etc.), PVD method and sputtering method can be cited.

[0119] (C-3; fibrous carbon filling material)

[0120] As fibrous carbon filler materials, for example, carbon fibers, metal-coated carbon fibers, carbon milled fibers, vapor-deposited carbon fibers, and carbon nanotubes can be cited. The fiber diameter of the carbon nanotube is 0.003 to 0.1 μm, and it can be any of a single layer, a double layer, and a multilayer, preferably a multilayer (so-called MWCNT). Of these, carbon fibers and metal-coated carbon fibers are preferred in terms of excellent mechanical strength and the ability to impart good electrical conductivity. It should be noted that good electrical conductivity has become one of the important properties required of resin materials in recent digital precision devices (e.g., digital cameras).

[0121] As carbon fibers, any of cellulose, polyacrylonitrile, and pitch can be used. In addition, materials obtained by spinning without a non-melting step, such as a method in which a raw material composition formed by spinning or molding a polymer of an aromatic sulfonic acid or its salt through a methylene-type bond and a solvent and then carbonizing the raw material composition can also be used. Furthermore, general-purpose types, medium elastic modulus types, and high elastic modulus types can all be used. Among these, the high elastic modulus type of the polyacrylonitrile system is particularly preferred. In addition, the average fiber diameter of the carbon fibers is not particularly limited, and is usually 3 to 15 μm, preferably 5 to 13 μm. Carbon fibers having 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 preferably 60 to 500 μm, more preferably 80 to 400 μm, and even more preferably 100 to 300 μm, based on the number average fiber length in the polycarbonate resin composition. The above-mentioned number-average fiber length is calculated using an image analyzer by optical microscopic observation of residual carbon fibers collected during processes such as high-temperature ashing of molded articles, dissolution with solvents, and decomposition with chemical reagents. Furthermore, this value is calculated by excluding material with a length less than the fiber diameter. The aspect ratio of carbon fibers 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 is the value obtained by dividing the average fiber length by the average fiber diameter.

[0122] Furthermore, in order to improve the adhesion with the matrix resin and the mechanical strength, it is preferred to perform an oxidation treatment on the surface of the carbon fibers. The oxidation treatment method is not particularly limited, and for example, the following methods can be preferably exemplified: (1) a method of treating the fibrous carbon filler with an acid, an alkali, a salt thereof, or an oxidizing gas; (2) a method of firing the fibers or fibrous carbon filler capable of being converted into a fibrous carbon filler at a temperature of 700°C or higher in the presence of an inert gas containing an oxygen-containing compound; and (3) a method of performing a heat treatment on the fibrous carbon filler after performing an oxidation treatment on the fibrous carbon filler in the presence of an inert gas.

[0123] 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. From the perspective of corrosion resistance of the metal layer, nickel is preferred. As a method of metal coating, various methods previously described for surface coating using different types of materials in plate-shaped glass fillers can be used. Among them, a plating method is preferably used. In addition, in the case of the above-mentioned metal-coated carbon fibers, as the base carbon fibers, the examples cited as the above-mentioned carbon fibers can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. Further preferably, it is 0.2 to 0.35 μm.

[0124] The carbon fibers and metal-coated carbon fibers are preferably bundled with olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins, and polyurethane resins. Fibrous carbon fillers treated with polyurethane resins and epoxy resins are particularly preferred in the present invention due to their excellent mechanical strength.

[0125] (C-4; non-fibrous carbon filling material)

[0126] 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. As carbon black, carbon black having a DBP oil absorption of 100 ml / 100 g to 500 ml / 100 g is preferred in terms of electrical conductivity. The above-mentioned carbon black is generally acetylene black or Ketjen black. Specifically, examples include DENKABLACK manufactured by Denki Kagaku Kogyo Co., Ltd., Vulcan XC-72 and BP-2000 manufactured by CABOT, and Ketjen black EC and Ketjen black EC-600JD manufactured by LION Corporation.

[0127] As graphite, natural graphite or various artificial graphites referred to as graphite in the mineral name can be utilized. As natural graphite, any one of earthy graphite, scaly graphite (also known as vein graphite of blocky graphite) and scaly flake graphite (Flake Graphite) can be utilized. In addition, artificial graphite refers to graphite obtained by heat-treating amorphous carbon and artificially orienting irregularly arranged tiny graphite crystals. In addition to the artificial graphite used in general carbon materials, it also includes aggregated graphite, cracked graphite and pyrolytic graphite. The artificial graphite used in general carbon materials is usually manufactured by graphitization treatment with petroleum coke and coal-based pitch coke as the main raw materials.

[0128] The graphite of the present invention may include expanded graphite that can be thermally expanded by performing a treatment represented by 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. If the average particle size is less than 2 μm, the effect of improving the rigidity is sometimes reduced. If the average particle size exceeds 300 μm, the impact resistance is sometimes significantly reduced, and the so-called graphite floating on the surface of the molded product becomes obvious. It should be noted that the average particle size refers to the particle size of the graphite itself before it becomes a resin composition. In addition, the above-mentioned particle size refers to the value obtained by the laser diffraction and scattering method.

[0129] 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.

[0130] 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 polycarbonate resin, as long as the properties of the composition of the present invention are not impaired.

[0131] (C-5; silicate mineral)

[0132] Preferred silicate minerals include orthosilicates, disilicates, cyclic silicates, and chain silicates. Silicate minerals are in a crystalline state, and the crystals may be in any form that each silicate mineral can take. The crystals may also take various shapes, such as fibers and plates.

[0133] Silicate minerals can be any of a complex oxide, an oxyacid salt (composed of an ionic lattice), or a solid solution. Furthermore, complex oxides can be combinations of two or more single oxides or combinations of two or more single oxides and oxyacid salts. Furthermore, solid solutions can be solid solutions of two or more metal oxides or two or more oxyacid salts. They can also be hydrates. The form of crystal water in hydrates can be any of the following: intercalation as Si-OH in the form of hydrogen silicate ions, ionic intercalation as hydroxide ions (OH-) in metal cations, or intercalation as H2O molecules in the interstices of the structure.

[0134] 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.

[0135] Specific examples of silicate minerals in the metal oxide components include the following: The descriptions in parentheses are names of minerals containing the silicate minerals as main components, and indicate that the compounds in parentheses can be used as examples of metal salts.

[0136] Examples of silicate minerals containing K2O include K2O·SiO2, K2O·4SiO2·H2O, K2O·Al2O3·2SiO2 (hexagonal potassium nephrite), K2O·Al2O3·4SiO2 (leucite) and K2O·Al2O3·6SiO2 (orthoclase).

[0137] Examples of silicate minerals containing Na2O in their components include Na2O·SiO2 and its hydrates, Na2O·2SiO2, 2Na2O·SiO2, Na2O·4SiO2, Na2O·3SiO2·3H2O, Na2O·Al2O3·2SiO2, Na2O·Al2O3·4SiO2 (jadeite), 2Na2O·3CaO·5SiO2, 3Na2O·2CaO·5SiO2 and Na2O·Al2O3·6SiO2 (albite), etc.

[0138] As silicate minerals containing Li2O in their components, there are Li2O·SiO2, 2Li2O·SiO2, Li2O·SiO2·H2O, 3Li2O·2SiO2, Li2O·Al2O3·4SiO2 (petalite), Li2O·Al2O3·2SiO2 (eucryptite) and Li2O·Al2O3·4SiO2 (spodumene), etc.

[0139] Examples of silicate minerals containing BaO include BaO·SiO 2 , 2BaO·SiO 2 , BaO·Al 2 O 3 ·2SiO 2 (barium feldspar), and BaO·TiO 2 ·3SiO 2 (blue cone mineral).

[0140] Examples of silicate minerals containing CaO include 3CaO·SiO2 (alite of cement clinker minerals), 2CaO·SiO2 (belite of cement clinker minerals), 2CaO·MgO·2SiO2 (magnesian feldspar), 2CaO·Al2O3·SiO2 (calcite), a solid solution of magnesian feldspar and calcite (calcite), CaO·SiO2 (wollastonite (both α-type and β-type)), CaO·MgO·2SiO2 (diopside), CaO·MgO·SiO2 (diopside), 3CaO·MgO·2SiO2 (magnesian feldspar), CaO·Al2O3·2SiO2 (anorthite), 5CaO·6SiO2·5H2O (tobermorite, other 5CaO·6SiO2·9H2O, etc.) and other tobermorites. Wollastonite group hydrates, wollastonite group hydrates such as 2CaO·SiO2·H2O (phillipsite), wollastonite group hydrates such as 6CaO·6SiO2·H2O (xonotlite), wollastonite group hydrates such as 2CaO·SiO2·2H2O (leucogeosite), CaO·Al2O3·2SiO2·H2O (hard lawsonite), CaO·FeO·2SiO2 (ferrocalcium pyroxene), 3CaO·2SiO2 (wollastonite), 3CaO·Al2O3·3SiO2 (grossularite), 3CaO·Fe2O3·3SiO2 (andradite), 6CaO·4Al2O3·FeO·SiO2 (pleochroite, pleochroite), as well as clinzoisite, redditorite, allantite, fusiliers, axenite, scawtite and common pyroxene, etc.

[0141] Furthermore, 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 can be used. Furthermore, various blended cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component B. Other examples of silicate minerals containing CaO include blast furnace slag and ferrite.

[0142] 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 (orthopyroxene), 2FeO·SiO2 (fayalite), 3FeO·Al2O3·3SiO2 (almandine), and 2CaO·5FeO·8SiO2·H2O (ferroactinolite).

[0143] Examples of silicate minerals containing CoO include CoO·SiO 2 and 2CoO·SiO 2 .

[0144] 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· 7H2O (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.

[0145] Examples of silicate minerals containing Fe2O3 include Fe2O3·SiO2 and the like.

[0146] Examples of silicate minerals containing ZrO 2 include ZrO 2 ·SiO 2 (zircon) and AZS refractory materials.

[0147] As silicate minerals containing Al2O3 in their components, there are Al2O3·SiO2 (sillimanite, andalusite, kyanite), 2Al2O3·SiO2, Al2O3·3SiO2, 3Al2O3·2SiO2 (mullite), Al2O3·2SiO2·2H2O (kaolin), Al2O3·4SiO2·H2O (pyrophyllite), Al2O3·4SiO2·H2O (bentonite), K2O·3Na2O·4Al2O3·8SiO2 (nepheline), K2O·3Al2O3·6SiO2·2H2O (muscovite, sericite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogopite), as well as various zeolites, fluorphlogopite and biotite.

[0148] Among the above-mentioned silicate minerals, talc, mica, and wollastonite are particularly preferred from the viewpoints of excellent balance between rigidity and impact resistance, excellent resistance to moisture and heat, thermal stability, and appearance, and easy availability.

[0149] (C-5-i; Talc)

[0150] Talc refers to hydrous magnesium silicate, generally represented by the chemical formula 4SiO2·3MgO·2H2O. It typically has a layered, scaly, flaky structure. It is composed of 56-65% by weight of SiO2, 28-35% by weight of MgO, and approximately 5% by weight of H2O. Other minor components include 0.03-1.2% by weight of Fe2O3, 0.05-1.5% by weight of Al2O3, 0.05-1.2% by weight of CaO, 0.2% or less by weight of K2O, and 0.2% or less by weight of Na2O. A more preferred talc composition is 62-63.5% by weight of SiO2, 31-32.5% by weight of MgO, 0.03-0.15% by weight of Fe2O3, 0.05-0.25% by weight of Al2O3, and 0.05-0.25% by weight of CaO. Furthermore, the ignition loss is preferably 2 to 5.5% by weight. With this preferred composition, a resin composition with excellent thermal stability and color tone is obtained, and even at higher molding temperatures, excellent molded articles can be produced. This allows the composition of the present invention to achieve higher fluidity, making it suitable for producing larger or complex-shaped thin-walled molded articles.

[0151] The particle size of talc is preferably in the range of 0.1 to 50 μm (more preferably 0.1 to 10 μm, further preferably 0.2 to 5 μm, and particularly preferably 0.2 to 3.5 μm) as measured by sedimentation method. Therefore, the more preferred talc of the present invention is talc having the above-mentioned preferred composition and an average particle size of 0.2 to 3.5 μm. Furthermore, it is particularly preferred to use talc having a bulk density of 0.5 (g / cm 3) or more as raw materials. As talc meeting the above conditions, "Upn HS-T0.8" manufactured by Hayashi Chemical Industry Co., Ltd. can be exemplified. The average particle size of talc refers to D50 (median particle size of particle size distribution) measured by X-ray transmission method, which is one of the liquid phase sedimentation methods. As a specific example of an apparatus for performing the above measurement, Sedigraph 5100 manufactured by Micromeritics can be cited.

[0152] In addition about the preparation method when talcum is pulverized from raw stone, there is no particular restriction, can utilize axial flow grinding method, ring grinding method, roller mill method, ball mill method, jet mill method and container rotary compression shearing type grinding method etc.And then the talcum after the pulverization preferably utilizes various classifiers to carry out classification treatment, makes the distribution of particle diameter consistent.As classifier, there is no particular restriction, can enumerate impact type inertial force classifier (variable impact machine etc.), utilize Coenda effect type inertial force classifier (elbow jet machine etc.), centrifugal field classifier (multistage cyclone, MicroPlex, dispersion classifier (dispersion separator), Accu-Cut, eddy current classifier, TurboPlex, micro powder classifier (micron separator) and ultrafine classifier (superseparator) etc.) etc.

[0153] Furthermore, talc is preferably in an aggregated state from the viewpoint of its handling properties, and the above-mentioned production methods include a method utilizing degassing and compression, a method utilizing compression using a sizing agent, etc. The method utilizing degassing and compression is particularly preferred because it is simple and prevents unnecessary sizing agent resin components from being mixed into the resin composition of the present invention.

[0154] (C-5-ii; Mica)

[0155] The average particle size of mica is preferably 5 to 250 μm. Mica with an average particle size of 5 to 50 μm is more preferred. When the average particle size of mica is less than 5 μm, it is difficult to obtain the effect of improving rigidity. On the other hand, the resin composition containing mica with an average particle size exceeding 250 μm tends to have saturated mechanical properties, and on the other hand, the appearance and flame retardancy are sometimes deteriorated. It should be noted that the average particle size of mica is measured by laser diffraction and scattering method or vibration screening method. The laser diffraction and scattering method is preferably carried out by vibration screening method on mica with a mesh size of 325 or more of 95% by weight. Vibration screening method is generally used for mica with a particle size above that. The vibration screening method of the present invention is to first use a vibration screening machine to sieve 100 g of the mica powder used through a standard sieve of JIS standard overlapped in the order of mesh size for 10 minutes. The weight of the powder remaining on each sieve is measured to obtain the particle size distribution.

[0156] As the thickness of the mica, mica with a thickness of 0.01 to 1 μm as measured by electron microscope observation can be preferably used. The thickness is more preferably 0.03 to 0.3 μm. As the aspect ratio, an aspect ratio of 5 to 200, more preferably 10 to 100, can be preferably used. The mica used in addition is preferably muscovite mica, which has a Mohs hardness of about 3. Compared with other micas such as phlogopite, muscovite can achieve higher rigidity and higher strength, and solve the problems of the present invention at a higher level. Therefore, the more preferred mica of the present invention is muscovite mica with an average particle size of 5 to 250 μm, more preferably 5 to 50 μm. As the preferred mica, "A-21" manufactured by Yamaguchi Mica Industry Co., Ltd. can be exemplified. In addition, as a mica pulverization method, mica produced by either a dry pulverization method or a wet pulverization method can be used. The dry pulverization method is generally low-cost, but on the other hand, the wet pulverization method can effectively pulverize the mica into a thinner and finer size (the effect of improving the rigidity of the resin composition is higher). In the present invention, mica produced by a wet grinding method is more preferred.

[0157] (C-5-iii; wollastonite)

[0158] The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and further preferably 0.1 to 3 μm. In addition, its aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. As the upper limit of the aspect ratio, 30 or less can be cited. In this fiber diameter, the reinforcing filler is observed with an electron microscope, the diameter of each fiber is obtained, and the number average fiber diameter is calculated from the measured value. The electron microscope is used because it is difficult to accurately measure the size of the grade of the object with an optical microscope. The fiber diameter is obtained by randomly extracting the filler of the object for measuring the fiber diameter from the image obtained by observation with an electron microscope, measuring the fiber diameter near the center, and calculating the number average fiber diameter from the obtained measured value. The observation is carried out with a magnification of about 1000 times and a number of measured roots of 500 or more (preferably 600 or less in operation). On the other hand, the average fiber length is measured by observing the filler with an optical microscope, obtaining the length of each fiber, and calculating the number average fiber length from the measured value. The observation with an optical microscope starts with preparing a sample dispersed in a manner that the fillers do not overlap each other much. Observation is carried out under the condition of 20 times of objective lens, and this observation image is imported into the CCD camera of about 250,000 pixels in the form of image data. The image data obtained is used image analysis device, and the program of the maximum distance between 2 points of image data is utilized to calculate fiber length. Under the above conditions, the size of each pixel is equivalent to the length of 1.25 μm, and it is carried out to measure the number of roots as more than 500 (preferably less than 600 in operation). In order to fully reflect the whiteness originally possessed by wollastonite in the resin composition, it is preferably utilized that a magnetic separator is used to remove the iron component mixed into the raw material ore and the iron component mixed into due to the wear of the equipment when crushing the raw material ore. By the above-mentioned magnetic separator processing, the content of the iron in the wollastonite is converted into Fe2O3 when preferably less than 0.5 weight %. Therefore, the more preferred wollastonite of the present invention is one having a fiber diameter of 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm, an average particle size of 5 to 250 μm, more preferably 5 to 50 μm, and an iron content of 0.5% by weight or less when converted to Fe₂O₃. Examples of such preferred wollastonite include "SH-1250" and "SH-1800" manufactured by Kinsei Matec Co., Ltd., "KGP-H40" manufactured by Kansai Matec Co., Ltd., and "NYGLOS4" manufactured by NYCO Corporation.

[0159] Silicate minerals are preferably not surface-treated, but may be surface-treated with various surface treatment agents, such as silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (such as phosphorous acid, phosphoric acid, carboxylic acids, and carboxylic anhydrides), and waxes. Furthermore, the silicate minerals can be granulated using sizing agents such as various resins, higher fatty acid esters, and waxes to form granules. Among the silicate minerals of the present invention, talc and wollastonite are particularly preferred. These talc and wollastonite offer excellent balance between rigidity and impact resistance, and when incorporated into polycarbonate resins, they exhibit minimal degradation of color tone and appearance (e.g., the formation of silver streaks).

[0160] (C-6; titanium dioxide)

[0161] Titanium dioxide is generally used for various purposes and is well known in itself. There is also titanium dioxide consisting of 100% by weight of TiO2 (it should be noted that in the present invention, the titanium dioxide component of titanium dioxide is recorded as "TiO2", and the entirety including the surface treatment agent is recorded as "titanium dioxide"). However, it is usually surface-treated using oxides of various metals such as aluminum, silicon, titanium, zirconium, antimony, tin, and zinc. In the present invention, preferred titanium dioxide is also titanium dioxide that has been surface-treated with a metal oxide. It should be noted that these metal oxide components used for surface treatment can be a portion present in the TiO2 particle interior.

[0162] Furthermore, titanium dioxide is more preferably surface-treated with an organic compound. As the above-mentioned surface treatment agent, various treatment agents such as polyol-based, amine-based and silicone-based treatment agents can be used. Examples of polyol-based surface treatment agents include pentaerythritol, trimethylolethane and trimethylolpropane, examples of amine-based surface treatment agents include acetate of triethanolamine and acetate of trimethylolamine, and examples of silicone-based surface treatment agents include halogen-substituted silicone compounds and silicone compounds containing alkoxy groups and / or Si-H groups, with the latter silicone compounds being particularly preferred. Examples of halogen-substituted silicone compounds include alkylchlorosilanes, and examples of silicone compounds containing alkoxy groups and / or Si-H groups include alkylalkoxysilanes, alkylalkoxysiloxanes and alkylhydrogensiloxanes.

[0163] The silane and siloxane compounds may have a portion of their alkyl groups substituted with phenyl groups, but more preferably, none of the alkyl groups are substituted with phenyl groups. The alkyl groups preferably have 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. The alkoxy groups preferably have 1 to 4 carbon atoms, and methoxy groups are particularly preferred.

[0164] The crystal form of titanium dioxide in the present invention may be any of anatase and rutile types, and they may also be mixed as needed. In terms of initial mechanical properties and long-term durability, rutile type is more preferred. It should be noted that rutile type crystals may also contain anatase type crystals. Furthermore, substances produced by the sulfuric acid method, chlorine method, and other various methods of TiO2 can be used, but the chlorine method is more preferred. In addition, the shape of titanium dioxide is not particularly limited, but particulate titanium dioxide is more preferred. The average particle size of titanium dioxide is preferably 0.01 to 0.4 μm, more preferably 0.1 to 0.3 μm, and further preferably 0.15 to 0.25 μm. The above average particle size is calculated by measuring each single particle size based on electron microscope observation and calculating its number average.

[0165] Coating the TiO2 surface with various metal oxides can be carried out using various commonly used methods. For example, it can be produced by the following steps 1) to 8). Specifically, the following methods can be mentioned: 1) preparing an aqueous slurry of dry-pulverized untreated TiO2, 2) wet-pulverizing the slurry and micronizing it, 3) collecting the microparticle slurry, 4) adding a water-soluble compound of a metal salt to the microparticle slurry, 5) neutralizing and coating the TiO2 surface with a hydrated metal oxide, 6) removing byproducts, adjusting the pH of the slurry, filtering, and washing with pure water, 7) drying the washed filter cake, and 8) pulverizing the dried product using a jet mill or the like. In addition to the above methods, methods can be mentioned in which TiO2 particles react with an active metal compound in the gas phase. Furthermore, in coating the TiO2 surface with a metal oxide surface treatment agent, the surface treatment can be followed by sintering, re-surfacing, or sintering and re-surfacing. In addition, the surface treatment with metal oxides can be either high-density or low-density (porous). As is clear from the above conditions, the titanium dioxide of the present invention is surface-treated with aluminum oxide and silicon oxide. These can be surface-treated in any order or as a mixture, but it is preferred that the aluminum oxide treatment be followed by the silicon oxide treatment. More preferably, the titanium dioxide is surface-treated with an organosilicon compound containing an alkoxy group and / or Si-H group after the metal oxide treatment as described above.

[0166] The content of component C is preferably 1 to 150 parts by weight, more preferably 3 to 100 parts by weight, and even more preferably 5 to 50 parts by weight relative to 100 parts by weight of component A. If the content is less than 1 part by weight, plating adhesion may be insufficient, while if it exceeds 150 parts by weight, poor appearance may occur during injection molding.

[0167] (Regarding other additives)

[0168] The polycarbonate resin composition of the present invention may contain various stabilizers, mold release agents, toners, impact modifiers, fillers, flame retardants, and the like for reducing the molecular weight during molding and stabilizing the color tone.

[0169] (i) Flame retardants

[0170] The polycarbonate resin composition of the present invention may be blended with various compounds known as flame retardants. The blending of flame retardant compounds not only improves flame retardancy but also, depending on the properties of the compounds, can enhance antistatic properties, fluidity, rigidity, and thermal stability.

[0171] Examples of the flame retardants include (1) organic metal salt flame retardants (e.g., organic sulfonic acid alkali (earth) metal salts, borate metal salt flame retardants, and stannate metal salt flame retardants), (2) organic phosphorus flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphazene oligomer compounds, and phosphonamide compounds), (3) organic silicon flame retardants composed of organic silicon compounds, and (4) halogen flame retardants (e.g., brominated epoxy resins, brominated polystyrene, brominated polycarbonates (including oligomers), brominated polyacrylates, and chlorinated polyethylene).

[0172] (1) Organic metal salt flame retardants

[0173] Organic metal salt flame retardants are advantageous in that they can substantially maintain heat resistance and impart antistatic properties to a considerable extent. The most advantageous organic metal salt flame retardant used in the present invention is a fluorine-containing organic metal salt compound. The fluorine-containing organic metal salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a hydrocarbon group substituted by fluorine and a cationic component composed of a metal ion. As more preferred specific examples, metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates can be exemplified. The fluorine-containing organic metal salt compound can be used alone or in combination of two or more. Among them, metal salts of fluorine-substituted organic sulfonic acids are preferred, and metal salts of sulfonic acids having perfluoroalkyl groups are particularly preferred. The number of carbon atoms of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8.

[0174] The metal ions that constitute the metal salt-based flame retardant are alkali metals or alkaline earth metals. Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium, and examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Alkali metals are more preferred. Therefore, the preferred organometallic salt-based flame retardant is an alkali metal perfluoroalkyl sulfonate. Among the above-mentioned alkali metals, rubidium and cesium are preferred when higher transparency is required. On the other hand, since they are not universal and difficult to purify, they are sometimes disadvantageous in terms of cost. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they are sometimes disadvantageous in terms of transparency. Taking these actual conditions into consideration, the alkali metals used in the alkali metal perfluoroalkyl sulfonate can be differentiated, with potassium perfluoroalkyl sulfonate being the most preferred, as it offers an excellent balance of properties in various aspects. The above-mentioned potassium salt can also be used in combination with an alkali metal perfluoroalkyl sulfonate composed of another alkali metal.

[0175] Examples of the perfluoroalkylsulfonic acid alkali metal salt include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctanesulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate. These can be used alone or in combination of two or more. Among these, potassium perfluorobutanesulfonate is particularly preferred.

[0176] The fluorine ion content of the above-mentioned fluorine-containing organic metal salt measured by ion chromatography is preferably 50 ppm or less, more preferably 20 ppm or less, and further preferably 10 ppm or less. The lower the fluorine ion content, the better the flame retardancy and light resistance. The lower limit of the fluorine ion content can actually be 0, but considering the purification time and effect, it is preferably about 0.2 ppm in practice. The perfluoroalkylsulfonic acid alkali metal salt with the above-mentioned fluorine ion content can be purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in ion exchange water 2 to 10 times the weight of the metal salt at a temperature in the range of 40 to 90°C (more preferably 60 to 85°C). The perfluoroalkylsulfonic acid alkali metal salt is generated by a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or a method of neutralizing perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide (more preferably the latter method). In addition, the ion exchange water is particularly preferably water with a resistance value of 18 MΩ·cm or more. The liquid containing the dissolved metal salt is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. The liquid is then cooled to a temperature between 0 and 40°C, more preferably between 10 and 35°C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitably purified perfluoroalkylsulfonic acid alkali metal salt.

[0177] The content of the fluorinated organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, and even more preferably 0.008 to 0.13 parts by weight, relative to 100 parts by weight of component A. The greater the content within this preferred range, the more effectively the desired effects of the fluorinated organometallic salt (e.g., flame retardancy, antistatic properties, etc.) can be achieved, while also minimizing the adverse effects on the light resistance of the polycarbonate resin composition.

[0178] As other organometallic salt flame retardants other than the above-mentioned fluorine-containing organometallic salt compounds, metal salts of organic sulfonic acids that do not contain fluorine atoms are preferred. Examples of such metal salts include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids (all of which do not contain fluorine atoms).

[0179] Preferred examples of the aliphatic sulfonic acid metal salt include alkali (earth) metal salts of alkylsulfonic acids, and these can be used alone or in combination of two or more kinds (herein, the term "alkali (earth) metal salt" is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkylsulfonic acid used in the alkali (earth) metal salt of alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, and the like, and these can be used alone or in combination of two or more kinds.

[0180] Examples of the aromatic sulfonic acid used in the aromatic sulfonic acid alkali (earth) metal salt 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 via methylene bonds. These may be used alone or in combination of two or more.

[0181] Specific examples of aromatic sulfonic acid alkali (earth) metal salts include, for example, disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfonate isophthalate, sodium 5-sulfonate isophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butylphenylene oxide) polysulfonate, and potassium sulfonate of benzenesulfonate. , sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium terephthalate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenyl sulfone-3-sulfonate, potassium diphenyl sulfone-3-sulfonate, dipotassium diphenyl sulfone-3,3'-disulfonate, dipotassium diphenyl sulfone-3,4'-disulfonate, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenyl sulfoxide-4-sulfonate, formaldehyde condensate of sodium naphthalenesulfonate and formaldehyde condensate of sodium anthracenesulfonate, etc.

[0182] On the other hand, as the alkali (earth) metal salts of sulfate esters, in particular, alkali (earth) metal salts of sulfate esters of monohydric and / or polyhydric alcohols can be mentioned. Examples of the sulfate esters of the monohydric and / or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, sulfate esters of polyoxyethylene alkylphenyl ether, mono- / di- / tri- / tetrasulfate of pentaerythritol, sulfate ester of monolauric acid monoglyceride, sulfate ester of monopalmitic acid monoglyceride, and sulfate ester of monostearic acid monoglyceride. As the alkali (earth) metal salts of these sulfate esters, preferably, alkali (earth) metal salts of lauryl sulfate can be mentioned.

[0183] In addition, other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfone amides, such as alkali (earth) metal salts of saccharin, N-(p-tolylsulfonyl)-p-toluenesulfonimide, N-(N'-benzylaminocarbonyl)-p-aminobenzenesulfonimide and N-(phenylcarboxyl)-p-aminobenzenesulfonimide.

[0184] Among the above-mentioned metal salts of organic sulfonic acids not containing fluorine atoms, preferred are alkali (or earth) metal salts of aromatic sulfonic acids, with potassium salts being particularly preferred. When such alkali (or earth) metal salts of aromatic sulfonic acids are incorporated, the content thereof is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and even more preferably 0.01 to 0.1 part by weight, relative to 100 parts by weight of component A.

[0185] (2) Organic phosphorus flame retardants

[0186] As the organophosphorus flame retardant of the present invention, condensed phosphate compounds and phosphazene compounds are preferred.

[0187] 1) Condensed phosphate compounds

[0188] As the condensed phosphate ester compound, an aryl phosphate compound is preferably used. Condensed phosphate ester compounds have a plasticizing effect and are therefore advantageous in improving molding processability. As the aryl phosphate ester compound, various phosphate compounds conventionally known as flame retardants can be used, and in particular, one or more phosphate compounds represented by the following general formula (8) are more preferably used.

[0189]

[0190] (In the above general formula (8), M represents a divalent organic group derived from a dihydric phenol, Ar 1 、Ar 2 、Ar 3 and Ar 4 Each represents a monovalent organic group derived from a monohydric phenol. a, b, c, and d are each independently 0 or 1, and m is an integer from 0 to 5. In the case of a mixture of condensed phosphates having different degrees of polymerization m, m represents the average value thereof and is a value from 0 to 5.

[0191] The phosphate compound of the above formula may be a mixture of compounds having different m numbers. In the case of such a mixture, the average m 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 1 to 1.14.

[0192] Preferred specific examples of the dihydric phenol from which M is derived include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide. Among them, resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.

[0193] As a derivative of the above Ar 1 、Ar 2 、Ar 3 and Ar 4 Preferred specific examples of the monohydric phenol include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Among them, phenol and 2,6-dimethylphenol are preferred.

[0194] The monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris(2,4,6-tribromophenyl)phosphate, tris(2,4-dibromophenyl)phosphate, and tris(4-bromophenyl)phosphate.

[0195] On the other hand, specific examples of phosphate compounds not substituted with halogen atoms include monophosphate compounds such as tris(2,6-xylyl)phosphate, phosphate oligomers based on resorcinol bis(di(2,6-xylyl)phosphate), phosphate oligomers based on 4,4-dihydroxydiphenylbis(diphenylphosphate), and phosphate oligomers based on bisphenol A bis(diphenylphosphate). (Here, the term "based" means that it may contain a small amount of other components with different degrees of polymerization, and more preferably, it means that the component in the above formula (14) where m=1 is contained in an amount of 80% by weight or more, more preferably 85% by weight or more, and even more preferably 90% by weight or more.)

[0196] 2) Phosphazene compounds

[0197] Phosphazene compounds have a plasticizing effect and are therefore advantageous in improving molding processability. As the phosphazene compound, various phosphazene compounds known as flame retardants can be used, and phosphazene compounds represented by the following general formulas (9) and (10) are preferred.

[0198]

[0199] (In the above general formulas (9) and (10), X 1 、X 2 、X 3 、X 4 represents hydrogen, hydroxyl, amino, or an organic group containing no halogen atoms. In addition, r represents an integer from 3 to 10.

[0200] In the above formulas (9) and (10), X 1 、X 2 、X 3 、X 4 Examples of the organic group not containing a halogen atom represented by , include alkoxy, phenyl, amino, and allyl groups. Among them, the cyclic phosphazene compound represented by the above formula (9) is preferred, and X in the above formula (9) is particularly preferred. 1 、X 2 It is a cyclic phenoxyphosphazene containing a phenoxy group.

[0201] The content of the organophosphorus flame retardant is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and even more preferably 2 to 12 parts by weight, relative to 100 parts by weight of component A.

[0202] (3) Silicone flame retardants

[0203] The organosilicon compound used as the organosilicon flame retardant of the present invention improves flame retardancy through a chemical reaction during combustion. Various compounds previously proposed as flame retardants for aromatic polycarbonate resins can be used as such. It is believed that during combustion, the organosilicon compound forms a structure by bonding with itself or with components derived from the resin, or by a reduction reaction during the formation of this structure, imparting a flame retardant effect to the polycarbonate resin. Therefore, it is preferred to contain a group that is highly reactive in the aforementioned reaction. More specifically, it is preferred to contain a specified amount of at least one group selected from alkoxy groups and hydrogen (i.e., Si-H groups). The content ratio of these groups (alkoxy groups, Si-H groups) is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and even more preferably in the range of 0.15 to 0.6 mol / 100 g. This ratio is determined by measuring the amount of hydrogen or alcohol generated per unit weight of the organosilicon compound using an alkaline decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, with a methoxy group being particularly preferred.

[0204] Generally speaking, the structure of an organosilicon compound is formed by arbitrarily combining the following four types of siloxane units.

[0205] M unit: (CH3)3SiO 1 / 2 、H(CH3)2SiO 1 / 2 、H2(CH3)SiO 1 / 2 、(CH3)2(CH2=CH)SiO 1 / 2 、(CH3)2(C6H5)SiO 1 / 2 、(CH3)(C6H5)(CH2=CH)SiO 1 / 2 Monofunctional siloxane units such as D units: (CH3)2SiO, H(CH3)SiO, H2SiO, H(C6H5)SiO, (CH3)(CH2=CH)SiO, (C6H5)2SiO and other difunctional siloxane units, T units: (CH3)SiO 3 / 2 、(C3H7)SiO 3 / 2 、HSiO 3 / 2 、(CH2=CH)SiO 3 / 2 、(C6H5)SiO 3 / 2 Q unit: a tetrafunctional siloxane unit represented by SiO2.

[0206] Specific representative 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 even more preferred.

[0207] Here, the coefficients m, n, p, and q in the above formula are integers greater than 1 representing the degree of polymerization of each siloxane unit. 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 flame retardancy improves as the degree falls within the above preferred range. Furthermore, as described below, organosilicon compounds containing a predetermined amount of aromatic groups also exhibit excellent transparency and color tone.

[0208] When any one of m, n, p, and q is a value of 2 or more, the siloxane unit having this coefficient may be two or more siloxane units having different bonded hydrogen atoms or organic residues.

[0209] 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. Specific 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. More preferred are alkyl groups, alkenyl groups, or aryl groups having 1 to 8 carbon atoms. Alkyl groups such as methyl, ethyl, and propyl groups are particularly preferred.

[0210] Furthermore, the organosilicon compound used as the organosilicon flame retardant preferably contains an aromatic group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (11) is 10 to 70% by weight (more preferably 15 to 60% by weight).

[0211]

[0212] (In the above general formula (11), X each independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. n represents an integer from 0 to 5. Furthermore, when n in formula (11) is 2 or greater, different types of X may be used.)

[0213] The organosilicon compound used as the organosilicon flame retardant may contain a reactive group in addition to the above-mentioned Si—H group and alkoxy group. Examples of the reactive group include amino group, carboxyl group, epoxy group, vinyl group, mercapto group, and methacryloxy group.

[0214] Preferred examples of the organosilicon compound having a Si—H group include organosilicon compounds containing at least one structural unit represented by the following general formulae (12) and (13).

[0215]

[0216] (In the above general formula (12) and formula (13), Z 1 ~Z 3 Each independently represents a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (14). α1 to α3 each independently represent 0 or 1. m1 represents an integer of 0 or 1 or greater. Furthermore, in formula (12), the repeating unit when m1 is 2 or greater may be a plurality of different repeating units.

[0217]

[0218] (In the above general formula (14), Z 4 ~Z 8 Each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. α4 to α8 each independently represent 0 or 1. m2 represents an integer of 0 or 1 or greater. Furthermore, in formula (14), the repeating unit when m2 is 2 or greater may be a plurality of different repeating units.

[0219] Among the organosilicon compounds used in the organosilicon-based flame retardant, examples of the organosilicon compound having an alkoxy group include at least one compound selected from the group consisting of compounds represented by the general formula (15) and the general formula (16).

[0220]

[0221] (In the above general formula (15), β 1 represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. 1 , γ 2 , γ 3 , γ 4 , γ 5 and γ 6 represents an alkyl group and a cycloalkyl group having 1 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, at least one of which is an aryl group or an aralkyl group. 1 , δ 2 and δ3 represents an alkoxy group having 1 to 4 carbon atoms.)

[0222]

[0223] (In the above general formula (16), β 2 and β 3 represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. 7 , γ 8 , γ 9 , γ 10 , γ 11 , γ 12 , γ 13 and γ 14 represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or an aralkyl group having 6 to 12 carbon atoms, at least one of which is an aryl group or an aralkyl group. 4 , δ 5 , δ 6 and δ 7 represents an alkoxy group having 1 to 4 carbon atoms.)

[0224] The content of the above components is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of component A.

[0225] (4) Halogen flame retardants

[0226] As the halogen-based flame retardant of the present invention, brominated polycarbonates (including oligomers) are particularly preferred. Brominated polycarbonates have excellent heat resistance and can significantly improve flame retardancy. The brominated polycarbonate used in the present invention is a brominated polycarbonate compound in which the constituent units represented by the following general formula (17) account for at least 60 mol%, preferably at least 80 mol%, of all constituent units, and particularly preferably consists essentially of constituent units represented by the following general formula (17).

[0227]

[0228] (In the above general formula (17), X is a bromine atom, and R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO2-.)

[0229] In the above formula (17), R preferably represents a methylene group, an ethylene group, an isopropylidene group, or -SO2-, and isopropylidene group is particularly preferred.

[0230] Brominated polycarbonate has a low number of residual chloroformate terminal groups, and the terminal chlorine content is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. This 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 content using a UV-visible spectrophotometer (Hitachi U-3200). A terminal chlorine content of 0.3 ppm or less improves the thermal stability of the polycarbonate resin composition, enabling higher temperature molding. Consequently, a polycarbonate resin composition with improved moldability can be provided.

[0231] In addition, the brominated polycarbonate preferably has a small amount of 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 brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving the sample in deuterated chloroform and using 1 The terminal hydroxyl group content is preferably the above-mentioned amount because the thermal stability of the polycarbonate resin composition is further improved.

[0232] The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-mentioned specific viscosity calculation formula used to calculate the viscosity average molecular weight of the polycarbonate resin as component A of the present invention.

[0233] The content of the above components is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, and even more preferably 0.05 to 7 parts by weight, relative to 100 parts by weight of component A.

[0234] (ii) Fluorinated anti-drip agents

[0235] The polycarbonate resin composition of the present invention may contain a fluorinated anti-drip agent. By using the fluorinated anti-drip agent in combination with the flame retardant, better flame retardancy can be obtained. Examples of the fluorinated anti-drip agent include fluorinated polymers having fibril-forming ability. Examples of the polymer include polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers), partially fluorinated polymers disclosed in U.S. Patent No. 4,379,910, and polycarbonate resins manufactured from fluorinated diphenols. Polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0236] Polytetrafluoroethylene (fibrillated PTFE) with fibril-forming ability has an extremely high molecular weight and shows a tendency to combine PTFE with each other and become fibrous by external forces such as shear force. Its number average molecular weight is in the range of 1.5 million to tens of millions. The above lower limit is more preferably 3 million. The above number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380°C, as disclosed in Japanese Patent Publication No. 6-145520. That is, the melt viscosity of fibrillated PTFE at 380°C measured by the method described in the above publication is 10 7 ~10 13 Poise range, preferably 10 8 ~10 12 The range of poise.

[0237] Above-mentioned PTFE, except solid shape, can also use the PTFE of aqueous dispersion form.In addition, in order to improve the dispersibility in resin, obtain better flame retardancy and mechanical properties, the above-mentioned PTFE with fibril forming ability can also use the PTFE mixture of mixed form with other resins.In addition, as disclosed in Japanese Patent Laid-Open No. 6-145520 communique, also preferably utilize the PTFE that has the structure of shell as core, as low-molecular-weight polytetrafluoroethylene with above-mentioned fibrillated PTFE.

[0238] Examples of commercially available fibrillated PTFE include TEFLON (registered trademark) 6J from DuPont-Mitsui Fluorochemicals Co., Ltd. and POLYFLON MPAFA500 and F-201L from Daikin Chemical Industries, Ltd. Representative commercially available aqueous dispersions of fibrillated PTFE include Fluon AD-1 and AD-936 from Asahi-ICIF Fluoropolymers Co., Ltd., Fluon D-1 and D-2 from Daikin Chemical Industries, Ltd., and TEFLON (registered trademark) 30J from DuPont-Mitsui Fluorochemicals Co., Ltd.

[0239] As a mixed form of fibrillated PTFE, PTFE obtained by the following methods can be used: (1) a method of mixing an aqueous dispersion of fibrillated PTFE with an aqueous dispersion or solution of an organic polymer to perform coprecipitation to obtain a co-coagulated mixture (methods described in Japanese Patent Application Laid-Open No. 60-258263, Japanese Patent Application Laid-Open No. 63-154744, etc.); (2) a method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (method described in Japanese Patent Application Laid-Open No. 4-272957); (3) mixing an aqueous dispersion of fibrillated PTFE with organic polymer particles. (4) a method of uniformly mixing the aqueous dispersion of PTFE and the organic polymer dispersion and simultaneously removing the respective media from the mixture (methods described in Japanese Patent Application Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 08-188653, etc.); (5) a method of uniformly mixing the aqueous dispersion of PTFE and the organic polymer dispersion and then polymerizing the vinyl monomer in the mixed dispersion to obtain a mixture (methods described in Japanese Patent Application Laid-Open No. 11-29679, etc.). Examples of commercially available fibrillated PTFE in these mixed forms include "METABLEN A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals Co., Ltd., and "POLY TS AD001" (trade name) manufactured by Pacific Interchem Corporation.

[0240] In order not to reduce the mechanical strength of the above-mentioned fibrillated PTFE, it is preferably micro-dispersed as much as possible. As a way to achieve the above-mentioned micro-dispersion, the fibrillated PTFE of the above-mentioned mixed form is advantageous. In addition, the method of directly supplying the PTFE in the form of an aqueous dispersion to a melt-kneading machine is also conducive to micro-dispersion. But it should be noted that the PTFE in the form of an aqueous dispersion can slightly deteriorate the color tone. As the ratio of the fibrillated PTFE of the mixed form, in 100 wt % of the above-mentioned mixture, the fibrillated PTFE is preferably 10 to 80 wt %, more preferably 15 to 75 wt %. When the ratio of the fibrillated PTFE is within the above-mentioned range, the good dispersibility of the fibrillated PTFE can be achieved.

[0241] The content of the above components is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and even more preferably 0.05 to 1.5 parts by weight, relative to 100 parts by weight of component A.

[0242] (iii) Stabilizer

[0243] The polycarbonate resin composition of the present invention may contain various known stabilizers, such as phosphorus stabilizers, hindered phenol antioxidants, ultraviolet absorbers, and light stabilizers.

[0244] (iii-1) Phosphorus stabilizer

[0245] Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, as well as tertiary phosphines. Among these, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, triorganophosphate compounds, and acidic phosphate compounds are particularly preferred. It should be noted that the organic groups in acidic phosphate compounds include monosubstituted, disubstituted, and mixtures thereof. These compounds are also included in the following exemplary compounds corresponding to these compounds.

[0246] Examples of triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenylcresyl phosphate, diphenylmono-obiphenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphates are preferred. The number of carbon atoms in these trialkyl phosphates is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

[0247] Examples of the acid phosphate compounds include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, and bisphenol A acid phosphate. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective in improving thermal stability and are preferred because of their high stability.

[0248] Examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris(diethylphenyl) phosphite, tris(diisopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris( Pentaerythritol diphosphite, bis(2,6-di-tert-butylphenyl) ester, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite and dicyclohexyl pentaerythritol diphosphite, etc.

[0249] Furthermore, as other phosphite compounds, compounds having a cyclic structure formed by reacting with dihydric phenols may also be used. Examples include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

[0250] Examples of the phosphite compound include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphite, and bis(2,4-di-tert-butylphenyl)-4-phenyl The phosphite compounds are preferably tetrakis(di-tert-butylphenyl)-biphenylene diphosphite, bis(di-tert-butylphenyl)-phenyl-phenyl phosphite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenyl phosphite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenyl phosphite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenyl phosphite. Preferably, tetrakis(di-tert-butylphenyl)-biphenylene diphosphite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphite are used. More preferably, tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphite and bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphite are used in combination with the phosphite compounds having an aryl group substituted with two or more alkyl groups.

[0251] Examples of the phosphonate compound include dimethyl phenylphosphonate, diethyl phenylphosphonate, and dipropyl phenylphosphonate.

[0252] Examples of the tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0253] Preferred phosphorus stabilizers include triorganophosphate compounds, acidic phosphate compounds, and phosphite compounds represented by the following general formula (18). In particular, triorganophosphate compounds are preferably added.

[0254]

[0255] (In the above general formula (18), R and R' represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different.)

[0256] As described above, the phosphite compound is preferably tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphite. Stabilizers containing this phosphite as a main component are commercially available as Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by CIBASPECIALTY CHEMICALS), and both can be used.

[0257] In addition, more preferred phosphite compounds in the above formula (18) are distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite.

[0258] (iii-2) Hindered phenol antioxidants

[0259] As the hindered phenol compound, various compounds commonly blended in resins can be used. Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methylaminomethyl)phenol, 6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl] terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxyphenyl)propionate] 1,1,2-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di- tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxycinnamic acid), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxyphenyl)propionyloxy] ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) acetate [hydroxy-5-methylphenyl)acetoxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate, etc.

[0260] Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane is particularly preferred. These hindered phenol-based antioxidants may be used alone or in combination of two or more.

[0261] It is preferred to add either a phosphorus-based stabilizer or a hindered phenol-based antioxidant. A phosphorus-based stabilizer is particularly preferred, and a triorganophosphate compound is more preferred. The content of each of the phosphorus-based stabilizer and hindered phenol-based antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 part by weight, per 100 parts by weight of component A.

[0262] (iii-3) Ultraviolet absorber

[0263] The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Since the polycarbonate resin composition of the present invention has a good color tone, the addition of an ultraviolet absorber can maintain the color tone for a long time even when used outdoors.

[0264] Examples of the benzophenone-based compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone trihydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0265] Among the benzotriazole series, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzotriazole) Polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as copolymers of 2-(2'-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, are also included.

[0266] Examples of hydroxyphenyltriazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol. Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol.

[0267] Among the cyclic imidoesters, for example, 2,2'-p-phenylenebis(3,1-benzo Oxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzo Oxazine-4-one) and 2,2'-(2,6-naphthalene)bis(3,1-benzo Oxazine-4-one) etc.

[0268] Examples of the ultraviolet absorber include, specifically, cyanoacrylate-based agents such as 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0269] Furthermore, the UV absorber may be a polymeric UV absorber obtained by copolymerizing the UV absorbing monomer and / or the light stabilizing monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate, using a structure of a monomer compound capable of free radical polymerization. Preferred examples of the UV absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylate.

[0270] Among the above, benzotriazole and hydroxyphenyltriazine are preferred from the perspective of ultraviolet absorption ability, and cyclic imine and cyanoacrylate are preferred from the perspective of heat resistance and color tone. The above ultraviolet absorbers can be used alone or in combination of two or more.

[0271] The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, further preferably 0.03 to 1 part by weight, and most preferably 0.05 to 0.5 parts by weight, relative to 100 parts by weight of component A.

[0272] (iii-4) Other heat stabilizers

[0273] The polycarbonate resin composition of the present invention may also contain other heat stabilizers in addition to the above-mentioned phosphorus stabilizers and hindered phenol antioxidants. The above-mentioned other heat stabilizers are preferably used in combination with any one of these stabilizers and antioxidants, and particularly preferably used in combination with both. As the above-mentioned other heat stabilizers, for example, lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene can be preferably exemplified (the details of the above-mentioned stabilizers are described in Japanese Patent Application Laid-Open No. 7-233160). The above-mentioned compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBASPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers obtained by mixing this compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above-mentioned company can be preferably exemplified. The above-mentioned pre-mixed stabilizers can also be used in the present invention. The content of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, relative to 100 parts by weight of the component A.

[0274] Other examples of other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. These stabilizers are particularly effective when the polycarbonate resin composition is used for rotational molding. The amount of these sulfur-containing stabilizers added is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A.

[0275] (iv) Release agent

[0276] The polycarbonate resin composition of the present invention may also be formulated with known release agents such as fatty acid esters, polyolefin waxes, organosilicon compounds, fluorine compounds (such as fluorinated oils represented by polyfluoroalkyl ethers), paraffin wax, and beeswax to improve productivity during molding and the dimensional accuracy of molded products. The polycarbonate resin composition of the present invention exhibits excellent fluidity, resulting in excellent pressure transmission and uniform deformation of molded products. On the other hand, complex molded products with increased demolding resistance may result in deformation of the molded product during demolding. The combination of these specific ingredients can address these issues without compromising the properties of the polycarbonate resin composition.

[0277] The above-mentioned fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid. The above-mentioned aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having a valence of 0 or more. In addition, the number of carbon atoms of the alcohol is preferably 3 to 32, more preferably 5 to 30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Among the fatty acid esters of the present invention, full esters are preferred from the perspective of excellent thermal stability at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less (substantially 0 can be used). In addition, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Furthermore, the iodine value of the fatty acid ester is preferably 10 or less (substantially 0 can be used). These properties can be obtained by the method specified in JIS K 0070.

[0278] Examples of polyolefin waxes include ethylene homopolymers with a molecular weight of 1,000 to 10,000, homopolymers or copolymers of α-olefins having 3 to 60 carbon atoms, or copolymers of ethylene and α-olefins having 3 to 60 carbon atoms. The molecular weight is the number average molecular weight measured by GPC (gel permeation chromatography) in terms of standard polystyrene. The upper limit of the number average molecular weight is more preferably 6,000, and even more preferably 3,000. The number of carbon atoms of the α-olefin component in the polyolefin wax is preferably 60 or less, and more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Preferred polyolefin waxes are ethylene homopolymers or copolymers of ethylene and α-olefins having 3 to 60 carbon atoms. The proportion of α-olefins having 3 to 60 carbon atoms is preferably 20 mol% or less, and more preferably 10 mol% or less. Commercially available products known as so-called polyethylene waxes can be preferably used.

[0279] The content of the release agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and even more preferably 0.02 to 3 parts by weight, relative to 100 parts by weight of the component A.

[0280] (v) Dyes and pigments

[0281] The polycarbonate resin composition of the present invention may further contain various dyes and pigments to provide molded articles exhibiting diverse designs. Examples of the dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dimethicone dyes, and the like. Oxazine-based dyes, isoindolinone-based dyes, and phthalocyanine-based dyes. Furthermore, the polycarbonate resin composition of the present invention may be blended with a metallic pigment to achieve a more pronounced metallic color. Aluminum powder is preferred as the metallic pigment. Furthermore, blending with a fluorescent brightener or a fluorescent dye that emits light other than fluorescent brighteners can provide a more pronounced design effect by producing a luminescent color.

[0282] Examples of the fluorescent dye (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthene-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and show little degradation during the molding of polycarbonate resins.

[0283] The content of the dye and pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, relative to 100 parts by weight of the component A.

[0284] (vi) Compounds having thermal radiation absorbing ability

[0285] The polycarbonate resin composition of the present invention may contain a compound having the ability to absorb thermal radiation. Preferred examples of the above-mentioned compounds include phthalocyanine-based near-infrared absorbers, ATO, ITO, metal oxide-based near-infrared absorbers such as iridium oxide, ruthenium oxide, and iminium oxide, metal boride-based near-infrared absorbers such as lanthanum boride, cerium boride, and tungsten boride, and tungsten oxide-based near-infrared absorbers, as well as various metal compounds with excellent near-infrared absorption capabilities, and carbon fillers. As the above-mentioned phthalocyanine-based near-infrared absorbers, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of carbon fillers include carbon black, graphite (including natural and artificial), and fullerene, with carbon black and graphite being preferred. These may be used singly or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and even more preferably 0.001 to 0.07 parts by weight relative to 100 parts by weight of component A. In the resin composition of the present invention, the content of the metal oxide near-infrared absorber, the metal boride near-infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably in the range of 0.5 to 100 ppm.

[0286] (vii) Light Diffuser

[0287] The polycarbonate resin composition of the present invention may be blended with a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymer microparticles, low-refractive-index inorganic microparticles such as calcium carbonate, and composites thereof. These polymer microparticles are already known as light diffusing agents for polycarbonate resins. More preferred examples include acrylic crosslinked particles with a particle size of several μm and organosilicon crosslinked particles such as polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include spheres, discs, columns, and amorphous shapes. The spheres need not be perfect spheres and include deformed spheres, while the columns include cubes. Preferred light diffusing agents are spherical, and the more uniform their particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 3 parts by weight, relative to 100 parts by weight of component A. It should be noted that two or more light diffusing agents may be used in combination.

[0288] (viii) White pigment for high light reflection

[0289] The polycarbonate resin composition of the present invention may be formulated with a highly reflective white pigment to impart a light-reflecting effect. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as this white pigment. The content of this highly reflective white pigment is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, per 100 parts by weight of component A. It should be noted that two or more highly reflective white pigments may be used in combination.

[0290] (ix) Antistatic agent

[0291] The polycarbonate resin composition of the present invention may need antistatic properties, and in this case, it is preferable to contain an antistatic agent. Examples of the antistatic agent include (1) dodecylbenzenesulfonic acid Arylsulfonic acid represented by salt Salts and alkylsulfonic acids Salts and other organic sulfonic acids salt, and tetrafluoroboric acid salts such as boric acid Salt. Relative to 100 parts by weight of component A, the The content of the salt is preferably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably 1.5 to 3 parts by weight.

[0292] As antistatic agents, for example, (2) organic sulfonic acid alkali (earth) metal salts such as organic lithium sulfonate, organic sodium sulfonate, organic potassium sulfonate, organic cesium sulfonate, organic rubidium sulfonate, organic calcium sulfonate, organic magnesium sulfonate and organic barium sulfonate can be cited. As described above, the above metal salts can also be used as flame retardants. More specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, etc. can be exemplified. The content of the organic sulfonic acid alkali (earth) metal salt is preferably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight relative to 100 parts by weight of component A. Alkali metal salts such as potassium, cesium and rubidium are particularly preferred.

[0293] Examples of antistatic agents include (3) organic sulfonic acid ammonium salts such as alkylsulfonic acid ammonium salts and arylsulfonic acid ammonium salts. The amount of the ammonium salt is preferably 0.05 parts by weight or less based on 100 parts by weight of the total of component A, component B, and component C. Examples of antistatic agents include (4) polymers containing a poly(oxyalkylene) glycol component such as polyetheresteramide. The amount of the polymer is preferably 5 parts by weight or less based on 100 parts by weight of component A.

[0294] (x) Organic fibrous filling materials

[0295] In addition to the inorganic filler, the polycarbonate resin composition of the present invention may also contain a known organic fibrous filler as a reinforcing filler. Here, the organic fibrous filler refers to an organic filler having a fibrous shape (including a rod-like, needle-like, flat shape, or a shape in which the axis extends in multiple directions).

[0296] The fiber diameter of the organic fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 13 μm, and even more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is more preferably 1 μm. The fiber diameter mentioned herein refers to the number-average fiber diameter. It should be noted that the above number-average fiber diameter is a value calculated from scanning electron microscopic images of the residue collected after dissolving the molded article in a solvent or decomposing the resin with an alkaline compound, and the ash residue collected after ash treatment in a crucible.

[0297] Examples of the organic fibrous filler include heat-resistant fibrous organic fillers represented by heat-resistant organic fibers such as aramid fibers, polyimide fibers, and polybenzothiazole fibers, and plant-derived fibrous fillers such as hemp and bamboo.

[0298] The aspect ratio of the organic fibrous filler is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of the above-mentioned filler is the value in the resin composition. The organic fibrous filler can be surface-treated with various coupling agents in the same manner as the above-mentioned inorganic fibrous filler, can also be bundled with various resins, and can also be granulated by compression.

[0299] The content of the organic fibrous filler is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, further preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less, relative to 100 parts by weight of component A.

[0300] (xi) Other additives

[0301] The polycarbonate resin composition of the present invention may contain, in addition to components A and B, thermoplastic resins, elastomers, other flow modifiers, antimicrobial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents, ionic liquids, and the like.

[0302] Examples of the other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, polypropylene and other polyolefin resins, polystyrene resins, acrylonitrile / styrene copolymers (AS resins), acrylonitrile / butadiene / styrene copolymers (ABS resins), polymethacrylate resins, phenolic resins, epoxy resins, cyclic polyolefin resins, polylactic acid resins, polycaprolactone resins, and thermoplastic fluororesins (e.g., represented by polyvinylidene fluoride resins).

[0303] In addition, examples of elastomers include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, MBS (methyl methacrylate / styrene / butadiene) rubber as core-shell elastomers, MAS (methyl methacrylate / acrylonitrile / styrene) rubber, etc.

[0304] The content of other thermoplastic resins is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the component A.

[0305] (Method for producing polycarbonate resin composition)

[0306] The method for producing the polycarbonate resin composition of the present invention is not particularly limited, and known methods may be used. For example, the following method may be used: after thoroughly mixing component A, component B, and any other additives using a premixing device such as a V-type mixer, a Henschel mixer, a mechanochemical device, or an extrusion mixer, the premix is ​​granulated using an extrusion granulator, a briquetting machine, or the like as needed, followed by melt-kneading using a melt-kneading machine such as a vented twin-screw extruder, and then pelletized using a pelletizer.

[0307] Other examples include: methods in which each component is independently supplied to a melt kneader such as a vented twin-screw extruder; methods in which each component is supplied to a melt kneader using a supercritical fluid; methods in which a portion of each component is premixed and then supplied to the melt kneader independently of the remaining components. Examples of methods for premixing a portion of each component include methods in which components other than component A are premixed and then mixed into component A or supplied directly to the extruder. Examples of premixing methods include methods in which, when a powdered substance is contained as component A, a masterbatch of the additive diluted with the powder is prepared by blending a portion of the powder with a compounded additive and utilizing the masterbatch. Furthermore, methods in which a single component is independently supplied midway through the melt extruder are also possible. It should be noted that when a liquid substance is present among the compounded components, a so-called liquid injection device or liquid addition device may be used for supplying the mixture to the melt extruder.

[0308] As forcing machine, can preferably use the forcing machine with the vent that can degas the moisture in the raw material, the volatile gas produced by melt mixing resin.Preferably be provided with the vacuum pump that produces moisture, volatile gas and discharges efficiently to the outside of forcing machine from vent.Also can be provided with the screen cloth that is used for removing the foreign matter etc. that is mixed in the extrusion raw material in the zone before the extruder die head in addition, remove foreign matter from resin combination.As above-mentioned screen cloth, can enumerate metal mesh, screen changer (Screen Changer), sintered metal plate (disc filter etc.) etc.As melt mixing machine, except twin-shaft extruder, can also enumerate Banbury mixer, mixing roller, single-shaft extruder, the multi-shaft extruder more than three shafts etc.

[0309] The extruded resin as described above is directly cut to granulate it, or after forming a strand, the strand is cut with a granulator to granulate it. When granulating, it is necessary to reduce the influence of external dust, etc., and it is preferred to purify the atmosphere around the extruder. Furthermore, in the manufacture of the above-mentioned particles, various methods that have been proposed in the polycarbonate resin for optical discs can be used to appropriately narrow the shape distribution of the particles, reduce the amount of erroneously cut objects, reduce the amount of fine powder generated during transportation or conveying, and reduce the amount of bubbles (vacuum bubbles) generated inside the strands and particles. These methods can achieve high molding cycles and reduce the rate of occurrence of adverse conditions such as silver streaks. In addition, the shape of the particles can be general shapes such as cylinders, prisms and spheres, and more preferably cylinders. 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.

[0310] The polycarbonate resin composition of the present invention can be produced by injection molding pellets prepared as described above to produce molded articles, thereby manufacturing various products. Injection molding can employ conventional molding methods, including injection compression molding, injection pressure molding, gas-assisted injection molding, foam molding (including methods involving supercritical fluid injection), insert molding, in-mold coating molding, thermal insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding. Molding can also be performed using either a cold runner or hot runner method.

[0311] The polycarbonate resin composition of the present invention can also be used in the form of various special-shaped extruded articles, sheets, films, and the like through extrusion molding. Sheets and films can also be molded using methods such as inflation, calendaring, and casting. Furthermore, the polycarbonate resin composition of the present invention can be molded into heat-shrinkable tubes by applying specific stretching operations. The polycarbonate resin composition of the present invention can also be formed into molded articles through methods such as rotational molding and blow molding.

[0312] The present inventors believe that the best embodiment of the invention at present is an embodiment that combines the preferred ranges of the above-mentioned requirements, and representative examples thereof are described in the following embodiments. Of course, the present invention is not limited to these embodiments.

[0313] Example

[0314] Each measurement item in the examples was measured by the following method.

[0315] 1. Evaluation of aromatic polycarbonate resins

[0316] (i) Viscosity average molecular weight (Mv)

[0317] The specific viscosity (η) was calculated from the following formula using an Ostwald viscometer from a solution obtained by dissolving an aromatic polycarbonate resin in 100 ml of dichloromethane at 20°C. SP ),

[0318] Specific viscosity (η SP )=(t-t0) / t0

[0319] [t0 is the dripping time of dichloromethane, t is the dripping time of the sample solution]

[0320] The specific viscosity (η SP ) The viscosity average molecular weight Mv is calculated by the following mathematical formula.

[0321] η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity)

[0322] [η] = 1.23 × 10 －4 Mv 0.83

[0323] c=0.7

[0324] 2. Evaluation of polycarbonate resin composition

[0325] (i) Surface appearance

[0326] The surface appearance of 50 mm × 100 mm × 1 mm thick plate-shaped test pieces obtained by the following method was visually observed and evaluated as follows. The evaluation results are shown in Tables 1 and 2. Appearance defects caused by injection molding include silver streaks, flow marks, and surface roughness.

[0327] ○: No appearance defect was observed.

[0328] △: Appearance defects due to injection molding were partially observed.

[0329] ×: Appearance defects due to injection molding were observed on the entire surface of the molded article.

[0330] (ii) Plateability

[0331] (ii-i) Plating precipitation

[0332] Plating was performed under the following conditions using 50 mm × 100 mm × 1 mm thick plate-shaped test pieces obtained by the following method. Plating precipitation was evaluated by visually inspecting the thickness of the metal film deposited within the specified time period. The evaluation results are shown in Tables 1 and 2. Comparative Examples 1-3 and 2-3 could not be evaluated due to poor surface appearance.

[0333] ◎: The metal thin film is uniform and thick as a whole.

[0334] ○: The metal thin film is relatively thick but slightly uneven.

[0335] △: There is a metal thin film, but it is uneven. (Practical level)

[0336] ×: A small amount of metal film is present. (Not yet practically applicable)

[0337] XX: There is almost no metal film.

[0338] (ii-ii) Plating adhesion

[0339] Using a 50 mm × 100 mm × 1 mm thick plate-shaped test piece obtained by the following method, plating was performed under the following conditions. Regarding the plating adhesion, in order to evaluate the adhesion between the plated metal film and the resin within a specified time, a checkerboard peeling test was performed and evaluated as follows. It should be noted that the checkerboard peeling test was implemented based on 4-6 in "JIS K5600 General Test Methods for Paints". The evaluation results are shown in Tables 1 and 2. It should be noted that Comparative Examples 3 and 4 could not be evaluated due to poor surface appearance. In addition, Comparative Examples 2-1, 2-2, 2-6 and 2-7 could not be evaluated due to insufficient plating precipitation.

[0340] ○: No peeling occurred.

[0341] ×: Peeling occurred.

[0342] [Examples 1-1 to 1-14, Comparative Examples 1-1 to 1-5, Examples 2-1 to 2-23, Comparative Examples 2-1 to 2-5]

[0343] (Preparation of Plate-Shaped Test Specimens)

[0344] Aromatic polycarbonate resin, polycarbonate-polydiorganosiloxane copolymer resin, an additive for laser-irradiated three-dimensional circuit formation, an inorganic filler, and various other additives were mixed in a mixer according to the amounts listed in Tables 1 to 4, and then melt-kneaded using a vented twin-screw extruder to produce pellets. Each additive was pre-mixed with the aromatic polycarbonate resin at a concentration of 10 to 100 times the amount used, and the entire mixture was mixed in a mixer. Extrusion was performed using a 30 mm diameter vented twin-screw extruder (TEX30α-38.5BW-3V, produced by The Japan Steel Works, Ltd.) at a screw speed of 230 rpm, a discharge rate of 25 kg / h, a vacuum of 3 kPa at the vent port, and an extrusion temperature of 270°C from the first supply port to the second supply port and 280°C from the second supply port to the die head. A mixture of aromatic polycarbonate resin, polycarbonate-polydiorganosiloxane copolymer resin, an additive for laser-irradiated three-dimensional circuit formation, an inorganic filler, and various other additives was fed into the extruder from the first feed port. The first feed port referred to here is the port farthest from the die. The resulting pellets were dried in a hot air circulation dryer at 120°C for 5 hours and then molded into test pieces for evaluation using an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a barrel temperature of 280°C and a mold temperature of 80°C.

[0345] (Plating treatment)

[0346] After plating under the following conditions, the molded article was evaluated for plating properties. The resulting test pieces were printed with a 1064 nm YAG laser using a KEYENCE MDX-2000 at a pulse frequency of 80 kHz, a scanning speed of 2 m / s, an output of 1.45 W, a laser spot diameter of 60 μm, and an overlap of 30 μm over a width of 5 mm. The following procedures were then performed.

[0347] (a) Degreasing (at 45°C for 5 minutes) OPC CLEANER MIC*150ml / L

[0348] (b) Ultrasonic water washing (2 minutes at room temperature)

[0349] (c) Chemical copper plating (55°C, 10 minutes) OPC COPPER MIC-ST*

[0350] (d) Water washing (1 minute)

[0351] (e) Activation (30°C, 1 minute): ICP ACCERA 200 ml / L, 35% hydrochloric acid 85 ml / L

[0352] (f) Water washing (1 minute)

[0353] (g) Chemical nickel plating (80°C, 10 minutes) ICP NICORON GM-M 120ml / L, ICP NICORON GM-150ml / L

[0354] (h) Drying

[0355] (The treatment liquids marked with * are trade names of Okuno Pharmaceutical Co., Ltd.)

[0356] The components represented by the symbols in Tables 1 to 4 are as follows.

[0357] (A ingredient)

[0358] A-1-1: Aromatic polycarbonate resin [Polycarbonate resin powder with a viscosity-average molecular weight of 22,400, manufactured by Teijin Limited, Panlite L-1225WP (product name)]

[0359] A-2-1: Polycarbonate-polydiorganosiloxane copolymer resin [polydiorganosiloxane block content: 8 wt%, average siloxane polymerization degree (p+q): 37, average polydiorganosiloxane domain size: 10 nm]

[0360] A-2-2: Polycarbonate-polydiorganosiloxane copolymer resin [polydiorganosiloxane block content: 4 wt%, average siloxane polymerization degree (p+q): 50, average polydiorganosiloxane domain size: 30 nm]

[0361] A-2-3: Polycarbonate-polydiorganosiloxane copolymer resin [polydiorganosiloxane block content: 12 wt%, average siloxane polymerization degree (p+q): 70, average polydiorganosiloxane domain size: 60 nm]

[0362] A-2-4: Polycarbonate-polydiorganosiloxane copolymer resin [polydiorganosiloxane block content: 0.1 wt%, average siloxane polymerization degree (p+q): 20, average polydiorganosiloxane domain size: 2 nm]

[0363] A-2-5: Polycarbonate-polydiorganosiloxane copolymer resin [polydiorganosiloxane block content: 10 wt%, average siloxane polymerization degree (p+q): 200, average polydiorganosiloxane domain size: 120 nm]

[0364] (Component B)

[0365] B-1: Copper / chromium oxide [manufactured by Shepherd Color Japan, Inc., Black 1G (trade name)]

[0366] B-2: Antimony tin oxide [Keeling & Walker, Stanostat CP5C (trade name)]

[0367] B-3: Antimony trioxide [manufactured by Nippon Seiko Co., Ltd., STOX-M (trade name)]

[0368] B-4: Titanium oxide / tin-antimony oxide [Mitsubishi Materials Co., Ltd., W-1 (trade name)]

[0369] B-5: Aluminum-doped zinc oxide [manufactured by Hakusui Tech Co., Ltd., 23K (trade name)]

[0370] (Component C)

[0371] C-1: Glass fiber [manufactured by Nitto Bosho Co., Ltd., CS-3PE-455 (trade name)]

[0372] C-2: Glass flake [Nippon Sheet Glass Co., Ltd., MEG160FYX (trade name)]

[0373] C-3: Talc [Victory light TK-RC (product name) manufactured by Katsumitsuyama Industry Co., Ltd.]

[0374] C-4: Mica [manufactured by Yamaguchi Mica Industry Co., Ltd., A-41 (product name)]

[0375] C-5: Wollastonite [manufactured by KinseiMatec Co., Ltd., SH-1250 (trade name)]

[0376] C-6: Carbon fiber [manufactured by Teijin Limited, HTC493 (product name)]

[0377] C-7: Carbon black [Koshigaya Chemicals Co., Ltd., RB-90003S (trade name)]

[0378] C-8: Titanium oxide [manufactured by Resino Color Industry Co., Ltd., DCF-T-17007 (trade name)]

[0379] (Other ingredients)

[0380] STB-1: Hindered phenol antioxidant [Irganox 1076 (trade name), manufactured by BASF Corporation]

[0381] STB-2: Phosphite stabilizer [manufactured by BASF Corporation, Irgafos 168 (trade name)]

[0382] L: Pentaerythritol fatty acid ester-based release agent [Rikester EW-400 (trade name) manufactured by Riken Vitamin Co., Ltd.]

[0383] [Table 1]

[0384]

[0385] [Table 2]

[0386] Table 2

[0387]

[0388] [Table 3]

[0389]

[0390] [Table 4]

[0391] Table 4

[0392]

Claims

1. A polycarbonate resin composition, characterized in that contain: (A) 100 weight percent of a resin component (Component A) composed of 0 to 99.9 weight percent of an aromatic polycarbonate resin (Component A-1) and 0.1 to 100 weight percent of a polycarbonate-polydiorganosiloxane copolymer resin (Component A-2), and (B) 1 to 50 parts by weight of component B, an additive for forming a three-dimensional circuit by laser irradiation, Component A-2 is a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3), and having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, wherein the average size of the polydiorganosiloxane domains is 5 to 100 nm. In the general formula (1), R 1 and R 2 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 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 the groups, they may be the same or different; a and b 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); In the 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 there are plural groups, they may be the same or different; c is an integer of 1 to 10, and d is an integer of 4 to 7; In the general formula (3), R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted 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, e and f are each an integer from 1 to 4, p is a natural number, q is 0 or a natural number, p+q is a natural number from 4 to 150, and X is a divalent aliphatic group having 2 to 8 carbon atoms.

2. The polycarbonate 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 polycarbonate resin composition according to claim 1 or 2, characterized in that The content of the polydiorganosiloxane block represented by the formula (3) in the component A-2 is 0.05 to 50.0% by weight.

4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein Component B is an additive for forming three-dimensional circuits by laser irradiation, containing at least two metals.

5. The polycarbonate resin composition according to claim 2, wherein Component C is at least one inorganic filler selected from the group consisting of glass, carbon fiber, and silicate minerals. 6 . A resin molded article obtained by molding the polycarbonate resin composition according to claim 1 .

7. A resin molded article, comprising the resin molded article according to claim 6 and a plated layer laminated on its surface.

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