Polycarbonate resin composition and circuit molded article for communication equipment

Abstract

To provide a polycarbonate resin composition that is excellent in good adhesion to a metal thin film during circuit formation, and long-term durability, in addition to the strength and the low dielectric property.SOLUTION: A polycarbonate resin composition is characterized by containing (B) a circuit formation stabilizer (B component) by 10 to 5000 pts.wt. to (A) 100 pts.wt. of an aromatic polycarbonate resin (A component) excluding the B component.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition comprising an aromatic polycarbonate resin and a circuit formation stabilizer. More specifically, the present invention relates to a polycarbonate resin composition having strength, low dielectric properties, good adhesion to a metal thin film during circuit formation, and long-term durability.

Background Art

[0002] Polycarbonate resins are excellent in transparency, impact resistance, heat resistance, and dimensional stability, and are used as engineering plastics in a wide range of fields such as the casings of electrical and electronic devices, automotive interior and exterior parts, building materials, furniture, musical instruments, and sundries. Among these, various methods for manufacturing antennas inside electronic devices such as mobile phones including smartphones have been studied. In particular, there is a demand for a broadband antenna that can be used in relatively high-frequency bands such as the Sub6 band, microwave band, and millimeter-wave band, and a method for three-dimensionally designing the antenna in an electronic device. As one of the techniques for forming such a three-dimensional antenna, laser irradiation three-dimensional circuit forming technology has attracted attention. This technology uses, for example, a resin material in which a metal complex is dispersed, and reduces the complex with laser light to form a catalytic nucleus, and can directly form a circuit such as an antenna without an adhesive layer by selective plating. As an example using such laser irradiation three-dimensional circuit forming technology, for example, a resin composition comprising a polycarbonate resin and a specific conductive oxide (Patent Document 1), and a resin composition capable of appropriately forming a metal thin film under a wide range of laser irradiation conditions have been proposed (Patent Document 2). However, in both cases, the dielectric properties are increased by the metal complex incorporated in the resin composition, and the radio wave loss required for an antenna that can be used in a high-frequency band becomes large and is insufficient. In addition, a technique has been proposed in which laser irradiation three-dimensional circuit forming is possible without using a metal complex in the resin composition (Patent Document 3). However, the polycarbonate resin used in the examples has insufficient long-term durability and low dielectric properties. As described above, a polycarbonate resin composition having strength, low dielectric properties, good adhesion to a metal thin film during circuit formation, and long-term durability has not been obtained.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a polycarbonate resin composition having strength, low dielectric properties, good adhesion to a metal thin film during circuit formation, and long-term durability.

Means for Solving the Problems

[0005] As a result of intensive studies to solve such problems, the present inventors have found that by adding a circuit formation stabilizer to a specific aromatic polycarbonate resin, in addition to strength and low dielectric properties that could not be obtained with conventional resin compositions, a polycarbonate resin composition having good adhesion to a metal thin film during circuit formation and long-term durability can be obtained, and thus the present invention has been achieved.

[0006] That is, according to the present invention, there is provided a polycarbonate resin composition characterized by containing (1) 10 to 5000 parts by weight of a circuit formation stabilizer (component B) with respect to 100 parts by weight of an aromatic polycarbonate resin (component A) excluding component B.

[0007] One of the more preferred embodiments of the present invention is that the component (A) is an aromatic polycarbonate resin containing 1 to 100% by weight of a polycarbonate-polyorganosiloxane copolymer resin (component (A-1)) composed of a polycarbonate block represented by the following formula (1) and a polyorganosiloxane block represented by the following formula (3), and the polyorganosiloxane content in 100% by weight of the component (A-1) is 0.05 to 20.0% by weight. The polycarbonate resin composition according to the above configuration 1 is characterized by this.

[0008]

Chemical formula

[0009] (In the above general formula (1), R 1 and R 2 each independently represent a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of each, they may be the same or different. a and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond and a group represented by the following general formula (2).)

[0010]

Chemical formula

[0011] (In the above general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. c is an integer from 1 to 10, and d is an integer from 4 to 7.)

[0012] [Chemical formula]

[0013] (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 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. 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.)

[0014] One of the more preferred embodiments of the present invention is that the component (B) in (3) is a circuit formation stabilizer containing at least one selected from the group consisting of (B-1) a compound (B-1 component) containing 10 mol% or more of a carbonate structural unit represented by the following formula (4) and (B-2) a compound (B-2 component) containing 10 mol% or more of a carbonate structural unit represented by the following formula (5) excluding the B-1 component, and the polycarbonate resin composition according to the above configuration 1 or 2 is characterized in this.

[0015]

Chemical formula

[0016] (In the above general formula (4), R 1 and R 2 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom, R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, R 5 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and n represents an integer of 0 to 10.)

[0017]

Chemical formula

[0018] (In the above general formula (5), R 1 and R 2 each independently represent a group selected from an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted aralkyl group having 7 to 15 carbon atoms, R 3 and R 4Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, an optionally substituted aralkyl group having 7 to 15 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted cycloalkoxy group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 15 carbon atoms, an optionally substituted aralkyloxy group having 7 to 15 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. a and b are natural numbers from 1 to 3, and W is a single bond or at least one group selected from the group consisting of the groups represented by the above general formula (2).)

[0019] One of the more preferred embodiments of the present invention is that (4) the B-2 component is (B-2-1) represented by the following formula (6) a compound (B-2-1 component) composed of a structural unit (A) represented by the following formula (7), a structural unit (B) represented by the following formula (8), and a structural unit (C) represented by the following formula (8), wherein the proportion of the structural unit (A) in all the structural units is 5 to 15 mol%, the proportion of the structural unit (B) is 20 to 60 mol%, and the proportion of the structural unit (C) is 25 to 75 mol%, and (B-2-2) a repeating structural unit (B) represented by the following formula (7) and a repeating structural unit (C) represented by the following formula (8), and the proportion of the structural unit (B) in all the structural units is 20 to 100 mol%, and the proportion of the structural unit (C) is 0 to 80 mol%. The polycarbonate resin composition according to the above configuration 3, which is characterized in that it is a circuit formation stabilizer containing at least one selected from the group consisting of the compounds (B-2-2 components).

[0020]

Chemical formula

[0021] (In the above general formula (6), R 1 and R 2Each is independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.

[0022]

Chemical formula

[0023] (In the above general formula (7), R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom. X is a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom, or an oxygen atom.)

[0024]

Chemical formula

[0025] (In the above general formula (8), W is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms.)

[0026] One of the more preferred embodiments of the present invention is the polycarbonate resin composition according to the above configuration 4, wherein the structural unit (A) is a structural unit derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, the structural unit (B) is a structural unit derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane, and the structural unit (C) is a structural unit derived from 2,2-bis(4-hydroxyphenyl)propane.

[0027] One of the more preferred embodiments of the present invention is that the component (6) B-1 contains 20 mol% or more of a structural unit derived from 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, or 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane. The polycarbonate resin composition according to any one of the above configurations 3 to 5, which is characterized in that it is a compound containing the above components.

[0028] One of the more preferred embodiments of the present invention is that the polycarbonate resin composition according to any one of the above configurations 1 to 6 is for circuit molding.

[0029] One of the more preferred embodiments of the present invention is that the circuit molding product for communication equipment is made of the polycarbonate resin composition for circuit formation according to the above configuration 7.

[0030] Hereinafter, the present invention will be specifically described.

[0031] (Component A: Aromatic polycarbonate resin) The aromatic polycarbonate resin used in the present invention is an aromatic polycarbonate resin excluding component B. The aromatic polycarbonate resin is usually obtained by reacting a dihydroxy compound with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. In addition, it can also be obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method or by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. The dihydroxy component used here may be any one that is usually used as the dihydroxy component of an aromatic polycarbonate, and may be bisphenols or aliphatic diols. As the bisphenols, bisphenols represented by the following formula (9) are preferably used.

[0032]

Chemical formula

[0033] [In the above general formula (9), R 1 and R 2 each independently represent a hydrogen atom, and when there are a plurality of them, they may be the same or different. a and b are each an integer from 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2).

[0034] [Chemical formula]

[0035] (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 represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. R 19 and R 20 each independently represent a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. c is an integer from 1 to 10, and d is an integer from 4 to 7.)]

[0036] Specific examples of bisphenols include, for example, 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'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, and the like.

[0037] 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)-3,3'-biphenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3-isopropylphenyl}propane, 2,2-bis{3-t-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}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}propyl]benzene, 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 (isomannide), 1,4:3,6-dianhydro-L-iditol (isoidide) and the like can be mentioned.,

[0038] Among these, aromatic bisphenols are preferable, and among them, 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 are preferable, and particularly 2,2-bis(4-hydroxyphenyl)propane and 4,4'-sulfonyldiphenol are preferable. Among them, 2,2-bis(4-hydroxyphenyl)propane having excellent strength and good durability is most suitable. Further, these may be used alone or in combination of two or more kinds.,

[0039] The polycarbonate resin used as Component A of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other tris-phenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, etc. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and particularly 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

[0040] These polycarbonate resins are produced by reaction means known per se for producing ordinary 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. The basic means of the production method will be briefly described.

[0041] In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine, is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. In addition, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction. In this case, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out using an inactive The reaction is carried out by a method in which a predetermined ratio of aromatic dihydroxy components is heated and stirred with a carbonic acid diester under an atmosphere of an oxidizing gas, and the alcohol or phenols produced are distilled off. The reaction temperature varies depending on the boiling point of the alcohol or phenols produced, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning of the reaction to distill off the alcohol or phenols produced. In addition, a catalyst usually used in transesterification reactions can be used to promote the reaction. Examples of carbonic acid diesters 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.

[0042] In the present invention, a terminal terminator is used in the polymerization reaction. The terminal terminator is used to adjust the molecular weight, and the obtained polycarbonate resin has excellent thermal stability compared to those not having the terminals blocked, since the terminals are blocked. As such terminal terminators, monofunctional phenols represented by the following general formulas (10) to (12) can be mentioned.

[0043] [ka]

[0044] [In the above general formula (10), A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl part has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl part has 1 to 9 carbon atoms), and r is an integer of 1 to 5, preferably 1 to 3.]

[0045] [Chemical formula]

[0046] [Chemical formula]

[0047] [In the above general formulas (11) and (12), 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, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50.]

[0048] Specific examples of the monofunctional phenols represented by the above general formula (10) include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol, and isooctylphenol. Further, the monofunctional phenols represented by the above general formulas (11) and (12) are phenols having a long-chain alkyl group or aliphatic ester group as a substituent. When the terminals of the polycarbonate resin are blocked using these, they not only function as terminal stoppers or molecular weight regulators, but also improve the melt fluidity of the resin, making the molding process easier, and have the effect of lowering the water absorption rate of the resin, and are preferably used. Among the substituted phenols of the above general formula (11), those with n being 10 to 30, particularly 10 to 26, are preferred. Specific examples thereof include, for example, decylphenol, dodecylpheno Examples include lauryl, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like. Further, as the substituted phenols of the general formula (12), compounds in which Y is -R-CO-O- and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26 are preferred. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, the monofunctional phenols represented by the general formula (10) are preferred, more preferably alkyl-substituted or phenylalkyl-substituted phenols, and particularly preferably p-tert-butylphenol, p-cumylphenol or 2-phenylphenol. It is desirable that these monofunctional phenol end-capping agents be introduced at least 5 mol%, preferably at least 10 mol% at the ends with respect to all the ends of the obtained polycarbonate resin. The end-capping agents may be used alone or in admixture of two or more.

[0049] The polycarbonate resin used as component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired.

[0050] The viscosity-average molecular weight of the polycarbonate resin used as Component A of the present invention preferably ranges from 12,000 to 50,000, more preferably from 12,000 to 30,000, still more preferably from 12,000 to 25,000, and most preferably from 15,000 to 25,000. When the molecular weight exceeds 50,000, the melt viscosity may become too high and the moldability may be poor. When the molecular weight is less than 12,000, problems may occur in mechanical strength. Further, the viscosity-average molecular weight of the aromatic polycarbonate resin other than Component A-1 preferably ranges from 10,000 to 16,000, more preferably from 10,500 to 16,000, and still more preferably from 11,000 to 15,800. When the molecular weight exceeds 16,000, the surface appearance may deteriorate, and when the molecular weight is less than 10,000, the strength may decrease. The viscosity-average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from the specific viscosity calculated by the following formula from a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride at 20°C. The obtained specific viscosity is inserted into the following formula to obtain the viscosity-average molecular weight M.

[0051] Specific viscosity (η SP )=(t - t0) / t0 [t0 is the dropping time in seconds of methylene chloride, t is the dropping time in seconds of the sample solution] η SP / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 M 0.83 c = 0.7

[0052] The total Cl (chlorine) content in the resin of the polycarbonate resin used as Component A of the present invention is preferably 0 to 200 ppm, more preferably 0 to 150 ppm. When the total Cl content in the polycarbonate resin exceeds 200 ppm, the hue and thermal stability may deteriorate, which is not preferable.

[0053] Component A of the present invention is preferably an aromatic polycarbonate resin containing 1 to 100% by weight of a polycarbonate - polydiorganosiloxane copolymer resin (Component A - 1) composed of a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3). The content of Component A - 1 is more preferably 1 to 70% by weight, and even more preferably 5 to 50% by weight. When the content of Component A - 1 is less than 1% by weight, sufficient strength may not be obtained.

[0054]

Chemical formula

[0055] In the above general formula (1), R 1 and R 2 each independently represent a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group. When there are a plurality of each, they may be the same or different. a and b are each an integer from 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2).

[0056]

Chemical formula

[0057] (In the above general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. c is an integer from 1 to 10, and d is an integer from 4 to 7.)]

[0058] [Chemical formula]

[0059] [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 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. 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 of 4 or more and 150 or less. natural number. X is a divalent aliphatic group having 2 to 8 carbon atoms.)]

[0060] Examples of the divalent phenol (I) that induces the carbonate structural unit represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the like can be mentioned.,

[0061] Among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferable, and particularly 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferable. Among them, 2,2-bis(4-hydroxyphenyl)propane having excellent strength and good durability is most preferable. Further, these may be used alone or in combination of two or more kinds.,

[0062] In the carbonate structural unit represented by the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group is particularly preferable. R 9and R 10 are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) that induces the carbonate structural unit represented by the general formula (3) above, for example, a compound represented by the following general formula (I) is preferably used.

[0063] [Chemical formula]

[0064] p + q is preferably 4 to 120, more preferably 30 to 120, still more preferably 30 to 100, and most preferably 30 to 60.

[0065] Next, the method for producing the above-preferred polycarbonate-polydiorganosiloxane copolymer resin will be described below. In a mixed solution of an organic solvent insoluble in water and an aqueous alkali solution in advance, by reacting a dihydric phenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of the dihydric phenol (I), a mixed solution of a chloroformate compound containing a chloroformate of the dihydric phenol (I) and / or a carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group is prepared. Phosgene is preferably used as the chloroformate-forming compound.

[0066] In producing the chloroformate compound from the dihydric phenol (I), the total amount of the dihydric phenol (I) that induces the carbonate structural unit represented by the above general formula (1) may be used as the chloroformate compound at once, or a part thereof may be added as a post-added monomer as a reaction raw material to the subsequent interfacial polycondensation reaction. The post-added monomer is added to promptly advance the subsequent polycondensation reaction, and it is not necessarily added if not necessary. The method for this chloroformate compound production reaction is not particularly limited, but usually, a method of performing the reaction in a solvent in the presence of an acid binder is suitable. Further, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them. The usage ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When using phosgene, which is a suitable chloroformate-forming compound, a method of blowing gasified phosgene into the reaction system can be preferably adopted.

[0067] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. The usage ratio of the acid binder may also be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, it is preferable to use 2 equivalents or a slightly excessive amount of the acid binder per mole of the dihydric phenol (I) used for forming the chloroformate compound of the dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents).

[0068] As the solvent, various solvents inert to the reaction, such as those used in the production of known polycarbonates, may be used alone or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

[0069] The pressure in the production reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, increased pressure, or reduced pressure. However, it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 °C. In many cases, heat is generated during the reaction, so it is desirable to cool with water or ice. The reaction time depends on other conditions and cannot be generally specified, but it is usually carried out in 0.2 to 10 hours. In the production reaction of the chloroformate compound, the pH range can utilize known interfacial reaction conditions, and the pH is usually adjusted to 10 or more.

[0070] In the production of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, after preparing a mixed solution of a chloroformate compound containing a chloroformate of a dihydric phenol (I) and a carbonate oligomer of a dihydric phenol (I) having a terminal chloroformate group in this way, while stirring the mixed solution, a dihydroxyaryl-terminated polydiorganosiloxane (II) that induces a carbonate structural unit represented by the general formula (3) is added at a rate of 0.01 mol / min or less per 1 mol of the dihydric phenol (I) charged in the preparation of the mixed solution, and the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer resin.

[0071] The polycarbonate-polydiorganosiloxane copolymer resin can be made into a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent in combination with a divalent phenol-based compound. Examples of the trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other tris-phenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, etc. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and particularly 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

[0072] The method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin may be a method in which a branching agent is contained in the mixed solution during the production reaction of the chloroformate compound, or a method in which a branching agent is added during the interfacial polycondensation reaction after the production reaction. The proportion of the carbonate structural unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, and particularly preferably 0.05 to 1.0 mol% in the total amount of the carbonate structural units constituting the copolymer resin. Regarding the amount of such a branched structure 1 it can be calculated by 1H-NMR measurement.

[0073] The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but usually, it can be preferably carried out at normal pressure or about the autogenous pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 °C. Since heat is usually generated during polymerization, it is desirable to carry out water cooling or ice cooling. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally specified, but it is usually carried out for 0.5 to 10 hours. Optionally, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (such as mixing, fractionation, etc.) and / or chemical treatment (such as polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate-polydiorganosiloxane copolymer resin with a desired reduced viscosity SP / c]. The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (degree of purification) by performing various post-treatments such as known separation and purification methods.

[0074] The content of the polydiorganosiloxane block represented by the following general formula (13) contained in the above general formula (3) is preferably 1.0 to 20.0% by weight, more preferably 1.0 to 15.0% by weight, still more preferably 1.0 to 10.0% by weight, and most preferably 1.0 to 8.0% by weight based on the total weight of the polycarbonate resin composition.

[0075]

Chemical formula

[0076] (In the above general formula (13), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less.)

[0077] The content of the polydiorganosiloxane in 100% by weight of Component A-1 is preferably 0.05 to 20.0% by weight, more preferably 0.5 to 15.0% by weight, and even more preferably 1.0 to 10.0% by weight. When the content is less than 0.05% by weight, the strength may be insufficient, and when it exceeds 20.0% by weight, the appearance may deteriorate due to the polydiorganosiloxane.

[0078] (Component B: Circuit formation stabilizer) The circuit formation stabilizer used as Component B in the present invention is a compound that can improve the adhesion and long-term durability of the circuit formed by laser irradiation. The circuit formation stabilizer is preferably a compound containing at least one selected from the group consisting of (B-1) a compound (Component B-1) containing 10 mol% or more of a carbonate structural unit represented by the following formula (4) and (B-2) a compound (Component B-2) containing 10 mol% or more of a carbonate structural unit represented by the following formula (5) excluding Component B-1. Only one type of circuit formation stabilizer may be used, or two or more types may be used in combination.

[0079] [Chemical formula]

[0080] (In the above general formula (4), R 1 and R 2 are each independently an alkyl group or a halogen atom having 1 to 6 carbon atoms, R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, R 5 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and n represents an integer of 0 to 10.)

[0081] [Chemical formula]

[0082] (In the above general formula (5), R1 , R 2 each independently represents a group selected from an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted aralkyl group having 7 to 15 carbon atoms. R 3 , R 4 each independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, an optionally substituted aralkyl group having 7 to 15 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted cycloalkoxy group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 15 carbon atoms, an optionally substituted aralkyloxy group having 7 to 15 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. a and b are natural numbers from 1 to 3, and W is a single bond or at least one group selected from the group consisting of the groups represented by the above general formula (2).)

[0083] In the B-1 component, the proportion of the carbonate structural unit represented by the above formula (4) with respect to 100 mol% of all the structural units is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, particularly preferably 30 mol% or more, and most preferably 50 mol% or more. When the proportion of the structural unit is less than 10 mol%, the effect of reducing radio wave loss, the adhesion of the metal thin film, and the long-term durability may be inferior. The upper limit of the content is preferably 100 mol%.

[0084] Examples of the diphenol that induces the carbonate structural unit (A) represented by the above formula (4) include 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-isopropylphenyl)cyclohexane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-isopropylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and the like. Preferred diphenols are structural units derived from 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)cyclohexane or 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane. Particularly preferred diphenols are 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane and / or 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane.

[0085] In addition, carbonate bond repeating units derived from other dihydric phenols may be contained as long as the objects and characteristics of the present invention are not impaired.Typical examples of such other dihydric phenols include 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5-dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1'-bis-(4-hydroxyphenyl)-ortho-diisopropylbenzene, 1,1'-bis-(4-hydroxyphenyl)-meta-diisopropylbenzene, 1,1'-bis-(4-hydroxyphenyl)-para-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxydiphenyl ester, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, etc. These can be used alone or in combination of two or more. The most preferred dihydric phenol is bisphenol C.

[0086] The B-2 component is a compound containing 10 mol% or more of the carbonate structural unit represented by the above formula (5) excluding the B-1 component. The content is preferably 15 to 100 mol%, more preferably 20 to 100 mol%, and still more preferably 30 to 100 mol%. When the content is less than 10 mol%, the circuit formation stability and transmission characteristics may be inferior.

[0087] The carbonate structural unit represented by the above general formula (5) is usually derived from a dihydroxy compound and a carbonate precursor.

[0088] Examples of the dihydroxy compound that induces the carbonate structural unit represented by the above general formula (5) include 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-t-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-t-butyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-cyclohexyl-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, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, etc. are mentioned.

[0089] Among them, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are more preferred, and 2,2-bis(4-hydroxy-3-methylphenyl)propane is most preferred.

[0090] Component B-2 is preferably a circuit formation stabilizer containing at least one selected from the group consisting of (B-2-1) a compound (component B-2-1) composed of a structural unit (A) represented by the following formula (6), a structural unit (B) represented by the following formula (7), and a structural unit (C) represented by the following formula (8), wherein the proportion of the structural unit (A) in all the structural units is 5 to 15 mol%, the proportion of the structural unit (B) is 20 to 60 mol%, and the proportion of the structural unit (C) is 25 to 75 mol%, and (B-2-2) a compound (component B-2-2) composed of a repeating structural unit (B) represented by the following formula (7) and a repeating structural unit (C) represented by the following formula (8), wherein the proportion of the structural unit (B) in all the structural units is 20 to 100 mol%, and the proportion of the structural unit (C) is 0 to 80 mol%.

[0091]

Chemical formula

[0092] (In the above general formula (6), R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)

[0093]

Chemical formula

[0094] (In the above general formula (7), R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom. X is a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylidene group, a sulfur atom, or an oxygen atom.)

[0095]

Chemical formula

[0096] (In the above general formula (8), W is a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms.)

[0097] In the structural unit (A) represented by the above formula (6), R 1 and R 2 are each preferably independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

[0098] Examples of the diphenol that induces the structural unit (A) include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. The most preferred diphenol is 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.)

[0099] In the B-2-1 component, the proportion of the structural unit (A) with respect to all the structural units is 5 to 15 mol%, preferably 5 to 12 mol%, more preferably 8 to 10 mol%. When the proportion of the structural unit (A) exceeds 15 mol%, the heat resistance is improved, but the strength and the long-term durability of the circuit may be inferior. When the proportion of the structural unit (A) is less than 5 mol%, the strength may be inferior.)

[0100] In the structural unit (B) represented by the above formula (7), R 3and R 4 is preferably an alkyl group having 1 to 6 carbon atoms independently, and X is preferably a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms.

[0101] Examples of the diphenol that induces the structural unit (B) include 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as bisphenol C), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, etc. The most preferred diphenol is bisphenol C.

[0102] In the B-2-1 component, the proportion of the structural unit (B) to all the structural units is 20 to 60 mol%, preferably 30 to 50 mol%. When the proportion of the structural unit (B) exceeds 60 mol%, the strength may be inferior. When the proportion of the structural unit (B) is less than 20 mol%, the circuit formation stability may be inferior.

[0103] Examples of the diphenol that induces the structural unit (C) include 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A), 4,4'-dihydroxy-1,1-biphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl thioether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, etc. The most preferred diphenol is bisphenol A.

[0104] In the B-2-1 component, the proportion of the structural unit (C) to all the structural units is 25 to 75 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol%, and even more preferably 40 to 60 mol%. When the proportion of the structural unit (C) exceeds 75 mol%, the circuit formation stability may be poor. When the proportion of the structural unit (C) is less than 25 mol%, the strength may be poor.

[0105] The B-1 component may contain a carbonate bond repeating unit derived from other divalent phenols other than the structural units (A), (B), and (C) as long as the object and characteristics of the present invention are not impaired.

[0106] As the divalent phenol that induces the structural units other than the structural units (A), (B), and (C), preferably 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, resorcinol substituted with an alkyl group having 1 to 3 carbon atoms, 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. are exemplified. For other details of such polycarbonates, they are described in, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580.

[0107] In the B-2-2 component, the constitutional units (B) and (C) are the same as those in the B-2-1 component. In the B-2-2 component, the proportion of the constitutional unit (B) relative to all constitutional units is 20 to 100 mol%, preferably 25 to 100 mol%, more preferably 40 to 100 mol%. When the proportion of the constitutional unit (B) is less than 20 mol%, the dielectric properties increase, and the adhesion and long-term durability of the metal thin film may decrease.

[0108] The circuit formation stabilizer used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include the interfacial polycondensation method, the melt transesterification method, the solid-phase transesterification method of a carbonate prepolymer, and the ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a monohydric phenol terminal stopper is usually used. Further, it may be a branched polycarbonate obtained by polymerizing a trifunctional component, or may be a circuit formation stabilizer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and a vinyl monomer.

[0109] In a reaction using, for example, phosgene as the carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. Also, for promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. At that time, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. At that time, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.

[0110] The transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by heating and stirring a predetermined proportion of an aromatic dihydroxy component and a carbonic acid diester in an inert gas atmosphere to distill off the generated alcohol or phenols. The reaction temperature varies depending on the boiling points of the generated alcohol or phenols, etc., but is usually in the range of 120 to 300°C. The reaction is carried out under reduced pressure from the beginning to complete the reaction while distilling off the generated alcohol or phenols. Also, a catalyst usually used in the transesterification reaction can 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, dibutyl carbonate, etc. Among these, diphenyl carbonate is particularly preferred.

[0111] Monofunctional phenols usually used as terminal terminators can be used. Especially in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as terminal terminators for molecular weight adjustment, and the obtained circuit-forming stabilizer has a terminal blocked by a group based on monofunctional phenols, so it is superior in thermal stability compared to those without it. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, p-long-chain alkylphenol, etc.

[0112] The circuit formation stabilizer used in the present invention can copolymerize an aliphatic diol as required. For example, isosorbide: 1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutane diol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, cyclohex-1,4-ylenedimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol) may be mentioned.

[0113] The circuit formation stabilizer used in the present invention can copolymerize a fatty acid as required. For example, 1,10-dodecanedioic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 3-hydroxybenzoic acid (mHBA), and 4-hydroxybenzoic acid (pHBA) may be mentioned.

[0114] The circuit formation stabilizer used in the present invention includes a compound obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. As the aliphatic difunctional carboxylic acid, α,ω-dicarboxylic acid is preferred. Examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized within a range that does not inhibit the purpose. They may be copolymerized.

[0115] The circuit formation stabilizer used in the present invention may also be a branched circuit formation stabilizer by copolymerizing a structural unit containing a polyfunctional aromatic compound having three or more functional groups as necessary. Preferred examples of the polyfunctional aromatic compound having three or more functional groups used in the branched circuit formation stabilizer include 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and tris-phenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The structural unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1 to 1.2 mol%, and particularly preferably 0.2 to 1.0 mol% in total 100 mol% with the structural unit from other divalent components.

[0116] Also, the branched structural unit may be derived not only from a polyfunctional aromatic compound but also from a side reaction that occurs during the polymerization reaction by the melt transesterification method without using a polyfunctional aromatic compound. Regarding the ratio of such a branched structure 1It can be calculated by 1H-NMR measurement.

[0117] The content of component B is 10 to 5000 parts by weight, preferably 50 to 3500 parts by weight, and more preferably 100 to 2000 parts by weight with respect to 100 parts by weight of component A. If the content is less than 10 parts by weight, the dielectric properties become high, and the adhesion and long-term durability of the metal thin film are not sufficient. If it exceeds 5000 parts by weight, the strength is not sufficient.

[0118] (Regarding other additives) For the polycarbonate resin composition of the present invention, various stabilizers, release agents, colorants, impact modifiers, fillers, flame retardants, etc. for stabilizing the molecular weight reduction and hue during molding processing can be used. In the resin composition of the present invention, additives for laser irradiation three-dimensional circuit molding and laser marking additives cannot be used because the radio wave loss required for antennas used in high-frequency bands increases.

[0119] (i) Flame retardant Various compounds known as flame retardants can be blended in the polycarbonate resin composition of the present invention. The blending of the compounds used as flame retardants not only improves the flame retardancy but also brings about, for example, improvements in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

[0120] Such flame retardants include (1) organometallic salt-based flame retardants (such as alkali (earth) metal salts of organic sulfonic acids, metal salt-based borate flame retardants, and metal salt-based stannate flame retardants), (2) organic phosphorus-based flame retardants (such as monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (3) silicone-based flame retardants composed of silicone compounds, and (4) halogen-based flame retardants (such as brominated epoxy resins, brominated polystyrenes, brominated polycarbonates (including oligomers), brominated polyacrylates, and chlorinated polyethylene).

[0121] (1) Organometallic salt-based flame retardant Organometallic salt-based flame retardants are advantageous in that they can maintain substantially the heat resistance and can impart a certain degree of antistatic property. The organometallic salt-based flame retardant most preferably used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound composed of an anion component consisting of an organic acid having a fluorine-substituted hydrocarbon group and a cation component consisting of metal ions. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfuric acid esters, and metal salts of fluorine-substituted organic phosphoric acid esters. The fluorine-containing organometallic salt compounds can be used alone or in admixture of two or more. Among them, the metal salt of a fluorine-substituted organic sulfonic acid is preferred, and particularly preferred is the metal salt of a sulfonic acid having a perfluoroalkyl group. Here, 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 still more preferably in the range of 1 to 8.

[0122] The metal constituting the metal ions of the organometallic salt-based flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium. More preferably, it is an alkali metal. Therefore, a preferred organometallic salt-based flame retardant is an alkali metal perfluoroalkylsulfonate. Among such alkali metals, rubidium and cesium are suitable when a higher requirement for transparency is needed. However, since they are not widely used and difficult to purify, they may be disadvantageous in terms of cost as a result. On the other hand, lithium and sodium are advantageous in terms of cost and flame retardancy, but may be disadvantageous in terms of transparency. Considering these factors, the alkali metals in the alkali metal perfluoroalkylsulfonate can be used appropriately, but the potassium salt of perfluoroalkylsulfonic acid, which has an excellent balance of properties in all aspects, is most preferred. Such a potassium salt can also be used in combination with an alkali metal perfluoroalkylsulfonate composed of other alkali metals.

[0123] Examples of such alkali metal perfluoroalkyl sulfonates 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.

[0124] The content of fluoride ions in the above-mentioned fluorine-containing organic metal salt, as measured by ion chromatography, is preferably 50 ppm or less, more preferably 20 ppm or less, and still more preferably 10 ppm or less. The lower the content of fluoride ions, the better the flame retardancy and light resistance. Although the lower limit of the content of fluoride ions can be substantially 0, from the balance between the purification man-hours and the effect, about 0.2 ppm is preferably practical. The perfluoroalkylsulfonic acid alkali metal salt with such a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in ion-exchanged water that is 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 produced by a method of neutralizing perfluoroalkylsulfonic acid with a carbonate or hydroxide of an alkali metal, or by a method of neutralizing perfluoroalkylsulfonyl fluoride with a carbonate or hydroxide of an alkali metal (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ·cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Then, the solution is cooled to a range of 0 to 40 °C, more preferably 10 to 35 °C. Crystals precipitate upon cooling. The precipitated crystals are taken out by filtration. Thereby, a preferably purified perfluoroalkylsulfonic acid alkali metal salt is produced.

[0125] The content of the fluorine-containing organic metal salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, and still more preferably 0.008 to 0.13 parts by weight with respect to 100 parts by weight of Component A. Within such a preferable range, the effects expected from the blending of the fluorine-containing organic metal salt (such as flame retardancy and antistatic properties) are exerted, and the adverse effect on the light resistance of the polycarbonate resin composition is also reduced.

[0126] As other organometallic salt-based 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 (none of which contain fluorine atoms).

[0127] Preferred examples of aliphatic sulfonic acid metal salts include alkali (earth) metal salts of alkylsulfonic acids, and these can be used alone or in combination of two or more (here, the notation of alkali (earth) metal salts is used to mean both alkali metal salts and alkaline earth metal salts). Preferred examples of alkanesulfonic acids used for such alkali (earth) metal salts of alkylsulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, etc., and these can be used alone or in combination of two or more.

[0128] Examples of aromatic sulfonic acids used for alkali (earth) metal salts of aromatic sulfonic acids include at least one acid selected from the group consisting of sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonates, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfonesulfonic acids, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates formed by methylene-type bonds of aromatic sulfonic acids, and these can be used alone or in combination of two or more.

[0129] Specific examples of the alkali (earth) metal salts of aromatic sulfonic acids include, for example, disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, poly potassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butylphenylene oxide) polysulfonate, potassium benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, 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 benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracenesulfonate, etc.

[0130] On the one hand, examples of the alkali (alkaline earth) metal salts of sulfuric acid esters include, in particular, the alkali (alkaline earth) metal salts of sulfuric acid esters of monohydric and / or polyhydric alcohols. Examples of such sulfuric acid esters of monohydric and / or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, sulfuric acid ester of polyoxyethylene alkyl phenyl ether, mono-, di-, tri-, and tetra-sulfuric acid esters of pentaerythritol, sulfuric acid ester of monolaurin, sulfuric acid ester of monopalmitin, and sulfuric acid ester of monostearin. Preferred examples of the alkali (alkaline earth) metal salts of these sulfuric acid esters include the alkali (alkaline earth) metal salts of lauryl sulfate.

[0131] Examples of other alkali (alkaline earth) metal salts include the alkali (alkaline earth) metal salts of aromatic sulfonamides, such as the alkali (alkaline earth) metal salts of saccharin, N-(p-toluenesulfonyl)-p-toluenesulfonimide, N-(N'-benzylaminocarbonyl)sulfanylimide, and N-(phenylcarboxyl)sulfanylimide.

[0132] Among the above, the preferred metal salts of organic sulfonic acids that do not contain fluorine atoms are the alkali (alkaline earth) metal salts of aromatic sulfonic acids, and potassium salts are particularly preferred. When formulating such alkali (alkaline earth) metal salts of aromatic sulfonic acids, their content is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and still more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of Component A.

[0133] (2) Organic phosphorus-based flame retardants As the organic phosphorus-based flame retardants of the present invention, condensed phosphate ester compounds and phosphazene compounds are suitable.

[0134] 1) Condensed phosphate ester compounds As the condensed phosphate ester compound, an aryl phosphate compound is preferably used. Since the condensed phosphate ester compound has a plasticizing effect, it is advantageous in that it can improve the moldability. As the aryl phosphate compound, various phosphate compounds known as flame retardants can be used, but more preferably, one or more phosphate compounds represented by the following general formula (14) can be mentioned.

[0135] [Chemical formula]

[0136] (In the above general formula (14), M represents a divalent organic group derived from a diphenol, and Ar 1 , Ar 2 , Ar 3 , and Ar 4 each represent a monovalent organic group derived from a monophenol. a, b, c, and d are each independently 0 or 1, m is an integer from 0 to 5, and in the case of a mixture of condensed phosphate esters with different degrees of polymerization m, m represents the average value and is a value from 0 to 5.)

[0137] The phosphate compound of the above formula may be a mixture of compounds having different m values. In the case of such a mixture, the average m value is preferably in the range of 0.5 to 1.5, more preferably 0.8 to 1.2, still more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

[0138] Suitable specific examples of the diphenol 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.

[0139] The above Ar 1 , Ar2 、Ar 3 、and Ar 4 Preferable specific examples of the monohydric phenols that induce

[0140]

[0141] Ar

[0142] 2) Phosphazene compound Phosphazene compounds are advantageous in terms of enhancing the moldability because they have a plasticizing effect. As the phosphazene compound, various phosphazene compounds known as conventional flame retardants can be used, but the phosphazene compounds represented by the following general formulas (15) and (16) are preferable.

[0143]

Chemical formula

[0144]

Chem.

[0145] (In the above general formulas (15) and (16), X 1 , X 2 , X 3 , X 4 represents an organic group that does not contain a hydrogen atom, a hydroxyl group, an amino group, or a halogen atom. Also, r represents an integer from 3 to 10.)

[0146] In the above formulas (15) and (16), examples of the organic group that does not contain a halogen atom represented by X 1 , X 2 , X 3 , X 4 include, for example, an alkoxy group, a phenyl group, an amino group, an allyl group, etc. Among them, the cyclic phosphazene compound represented by the above formula (15) is preferable, and further, the cyclic phenoxyphosphazene in which X 1 , X 2 in the above formula (15) is a phenoxy group is particularly preferable.) The content of the organic phosphorus flame retardant is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and still more preferably 2 to 12 parts by weight with respect to 100 parts by weight of the A component.)

[0147] (3) Silicone flame retardant The silicone compound used as the silicone-based flame retardant of the present invention improves the flame retardancy by chemical reactions during combustion. As such a compound, various compounds previously proposed as flame retardants for aromatic polycarbonate resins can be used. It is considered that the silicone compound imparts a flame retardant effect to the polycarbonate resin by forming a structure by itself bonding or bonding with components derived from the resin during combustion, or by a reduction reaction during the formation of the structure. Therefore, it is preferably included a group with high activity in such a reaction, and more specifically, it is preferably included a predetermined amount of at least one group selected from an alkoxy group and hydrogen (i.e., Si-H group). As the content ratio of such a group (alkoxy group, Si-H group), the range of 0.1 to 1.2 mol / 100 g is preferable, the range of 0.12 to 1 mol / 100 g is more preferable, and the range of 0.15 to 0.6 mol / 100 g is still more preferable. Such a ratio is determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by an alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

[0148] Generally, the structure of the silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is, 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 and other monofunctional siloxane units, 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 trifunctional siloxane units such as 3 / 2 , and Q units: tetrafunctional siloxane units represented by SiO2.

[0149] Specifically, the structures of silicone compounds used as silicone flame retardants include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, DnTpQq as indicative formulas. Among these, preferred structures of silicone compounds are MmDn, MmTp, MmDnTp, MmDnQq, and more preferred structures are MmDn or MmDnTp.

[0150] Here, the coefficients m, n, p, q in the above indicative formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each indicative formula is the average degree of polymerization of the silicone compound. This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more suitable this range is, the more excellent the flame retardancy becomes. As will be described later, in silicone compounds containing a predetermined amount of aromatic groups, transparency and hue are also excellent.

[0151] Also, when any of m, n, p, q is a numerical value of 2 or more, the siloxane unit with that coefficient can be two or more types of siloxane units with different bonding hydrogen atoms or organic residues.

[0152] The silicone compound may be linear or have a branched structure. Further, 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 such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and decyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as tolyl group. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, in particular, alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, and propyl group are preferable.

[0153] Furthermore, the silicone compound used as the silicone-based flame retardant preferably contains an aryl group. More preferably, the proportion (amount of aromatic group) of the aromatic group represented by the following general formula (17) is 10 to 70% by weight (more preferably 15 to 60% by weight).

[0154] [Chemical formula]

[0155] (In the above general formula (17), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. n represents an integer of 0 to 5. Further, when n is 2 or more in formula (17), different types of X can be taken respectively.)

[0156] The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the above Si-H group and alkoxy group. Examples of such reactive groups include amino group, carboxyl group, epoxy group, vinyl group, mercapto group, and methacryloxy group.

[0157] As the silicone compound having an Si-H group, a silicone compound containing at least one or more of the structural units represented by the following general formulas (18) and (19) is preferably exemplified.

[0158] [Chemical]

[0159] [Chemical]

[0160] (In the above general formula (18) and formula (19), 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 (20). α1 to α3 each independently represent 0 or 1. m1 represents an integer of 0 or 1 or more. Further, when m1 is 2 or more in formula (18), the repeating units can take a plurality of repeating units different from each other.)

[0161] [Chemical]

[0162] (In the above general formula (20), 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 more. Further, when m2 is 2 or more in formula (20), the repeating units can take a plurality of repeating units different from each other.)

[0163] In silicone compounds used as silicone-based flame retardants, examples of the silicone compound having an alkoxy group include at least one compound selected from the compounds represented by general formula (21) and general formula (22).

[0164] [Chemical]

[0165] (In the above general formula (21), β1 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 and an aralkyl group having 6 to 12 carbon atoms. γ1, γ2, γ3, γ4, γ5, and γ6 represent 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, and at least one group is an aryl group or an aralkyl group. δ1, δ2, and δ3 represent an alkoxy group having 1 to 4 carbon atoms.)

[0166] [Chemical formula]

[0167] (In the above general formula (22), β2 and β3 represent 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 and an aralkyl group having 6 to 12 carbon atoms. γ7, γ8, γ9, γ10, γ11, γ12, γ13 and γ14 represent 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, and at least one group is an aryl group or an aralkyl group. δ4, δ5, δ6, and δ7 represent an alkoxy group having 1 to 4 carbon atoms.)

[0168] The content of the above component is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of component A.

[0169] (4) Halogen-based flame retardant As the halogen-based flame retardant of the present invention, brominated polycarbonate (including oligomers) is particularly suitable. Brominated polycarbonate is excellent in heat resistance and can significantly improve flame retardancy. The brominated polycarbonate used in the present invention has a structural unit represented by the following general formula (23) accounting for at least 60 mol%, preferably at least 80 mol% of all the structural units, and particularly preferably a brominated polycarbonate compound substantially composed of the structural unit represented by the following general formula (23).

[0170]

Chem.

[0171] (In the above general formula (23), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO2-.)

[0172] Also, in such formula (23), preferably, R represents a methylene group, an ethylene group, an isopropylidene group, -SO2-, and particularly preferably an isopropylidene group.)

[0173] The brominated polycarbonate preferably has few remaining chloroformate group terminals and the terminal chlorine content is 0.3 ppm or less, more preferably 0.2 ppm or less. Such terminal chlorine content can be determined by dissolving the sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine to react with terminal chlorine (terminal chloroformate), and measuring this with an ultraviolet-visible spectrophotometer (U-3200 manufactured by Hitachi, Ltd.). When the terminal chlorine content is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible. As a result, a polycarbonate resin composition with more excellent molding processability is provided.)

[0174] Also, the brominated polycarbonate preferably has few remaining hydroxyl group terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less, per mole of the structural unit of the brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving the sample in deuterochloroform and 1 measuring it by the 1H-NMR method. With such an amount of terminal hydroxyl groups, the thermal stability of the polycarbonate resin composition is further improved, which is preferable.)

[0175] 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-described calculation formula for the specific viscosity used when calculating the viscosity average molecular weight of the polycarbonate resin which is Component A of the present invention.

[0176] The content of the above component is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, still more preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of Component A.

[0177] (ii) Fluorine-containing anti-dripping agent The polycarbonate resin composition of the present invention can contain a fluorine-containing anti-dripping agent. By using such a fluorine-containing anti-dripping agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of such a fluorine-containing anti-dripping agent include fluorine-containing polymers having fibril-forming ability, and examples of such polymers include polytetrafluoroethylene, tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in U.S. Patent No. 4379910, polycarbonate resins produced from fluorinated diphenols, etc., but polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0178] Polytetrafluoroethylene having fibril-forming ability (fibrillated PTFE) has an extremely high molecular weight and tends to form fibers by bonding PTFE molecules to each other by an external action such as shear force. Its number average molecular weight is in the range of 1.5 million to tens of millions. The lower limit is more preferably 3 million. Such a number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380°C as disclosed in JP-A-6-145520. That is, fibrillated PTFE has a melt viscosity at 380°C measured by the method described in this publication of 10 7 ~10 13in the range of poise, preferably 10 8 ~10 12 in the range of poise.

[0179] Such PTFE can be used not only in solid form but also in the form of an aqueous dispersion. Further, PTFE having such fibril-forming ability can improve its dispersibility in a resin, and it is also possible to use a PTFE mixture in a mixed form with other resins to obtain better flame retardancy and mechanical properties. Also, as disclosed in Japanese Patent Laid-Open No. 6-145520, those having a structure with such fibrillated PTFE as the core and low molecular weight polytetrafluoroethylene as the shell are preferably used.

[0180] Examples of commercially available fibrillated PTFE include, for example, Teflon (registered trademark) 6J of Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L of Daikin Chemical Industries, Ltd., and the like. Examples of commercially available aqueous dispersions of fibrillated PTFE include Fluon AD-1, AD-936 manufactured by Asahi Kasei Fluoropolymers Co., Ltd., Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., and Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., etc.

[0181] Examples of the mixed-form fibrillated PTFE include: (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (methods described in JP-A-60-258263, JP-A-63-154744, etc.); (2) a method in which an aqueous dispersion of fibrillated PTFE and dried organic polymer particles are mixed (method described in JP-A-4-272957); (3) a method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from such a mixture (methods described in JP-A-06-220210, JP-A-08-188653, etc.); (4) a method in which a monomer for forming an organic polymer is polymerized in an aqueous dispersion of fibrillated PTFE (method described in JP-A-9-95583); and (5) a method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, then a vinyl monomer is polymerized in the mixed dispersion, and thereafter a mixture is obtained (method described in JP-A-11-29679, etc.). Commercially available products of these mixed-form fibrillated PTFEs include "Metablen A3800" (trade name) of Mitsubishi Rayon Co., Ltd., "Blendex B449" (trade name) manufactured by GE Specialty Chemicals, and "Poly TS AD001" (trade name) manufactured by Pacific Interchem Corporation, etc.

[0182] Since the above fibrillated PTFE does not reduce mechanical strength, it is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the above mixed-form fibrillated PTFE is advantageous. Also, a method of directly supplying the aqueous dispersion form to a melt kneader is also advantageous for fine dispersion. However, it is necessary to consider that the aqueous dispersion form slightly deteriorates in hue. As the ratio of fibrillated PTFE in the mixed form, 10 to 80% by weight, more preferably 15 to 75% by weight, of fibrillated PTFE is preferable in 100% by weight of such a mixture. When the ratio of fibrillated PTFE is within such a range, good dispersibility of fibrillated PTFE can be achieved.

[0183] The content of the above component is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and still more preferably 0.05 to 1.5 parts by weight with respect to 100 parts by weight of Component A.

[0184] (iii) Stabilizer Various known stabilizers can be incorporated into the polycarbonate resin composition of the present invention. Examples of the stabilizer include phosphorus-based stabilizers, hindered phenol-based antioxidants, ultraviolet absorbers, and light stabilizers.

[0185] (iii-1) Phosphorus-based stabilizer Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphinic acid, and their esters, and tertiary phosphines. Among these, phosphorous acid, phosphoric acid, phosphonic acid, phosphinic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferred. Note that the organic groups in the acid phosphate compound include any of mono-substituted, di-substituted, and mixtures thereof. The same shall apply to the following exemplified compounds corresponding to the compound.

[0186] Examples of the triorganophosphate compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl cresyl phosphate, diphenyl mono-ortho-xenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphates are preferred. The carbon number of such trialkyl phosphates is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

[0187] Examples of the acid phosphate compound 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 the thermal stability, and are preferred because the acid phosphate itself has high stability.

[0188] 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(di-iso-propylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, 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.

[0189] As other phosphite compounds, those having a cyclic structure by reacting with divalent phenols can also be used. For example, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, etc. are exemplified.

[0190] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, etc. Among them, tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such phosphonite compounds can be preferably used in combination with phosphite compounds having an aryl group substituted with two or more of the above alkyl groups.

[0191] Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, etc.

[0192] Examples of the tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. Particularly preferred tertiary phosphine is triphenylphosphine.

[0193] Suitable phosphorus stabilizers are triorganophosphate compounds, acid phosphate compounds, and phosphite compounds represented by the following general formula (24). In particular, it is preferable to blend triorganophosphate compounds.

[0194] [Chemical formula]

[0195] (In the above general formula (24), R and R' each 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 as or different from each other.) As described above, tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite is preferable as the phosphonite compound, and stabilizers mainly composed of the phosphonite are commercially available as Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and either can be used.

[0196] Among the above formula (24), more preferable phosphite compounds 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.

[0197] (iii-2) hindered phenol antioxidant As the hindered phenol compound, various compounds usually blended in resins can be used. Examples of such hindered phenol compounds 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-hydroxybenzyl phosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethyl ethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-trithio-bis(2,6-di-tert-butylphenol), 2,2'-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanurate, 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-hydroxy-5-methylphenyl)acetyloxy}-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. are exemplified.,

[0198] Among the above compounds, in the present invention, 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-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used. Particularly, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane is preferred. The above hindered phenol-based antioxidants can be used alone or in combination of two or more.

[0199] It is preferable that either a phosphorus-based stabilizer or a hindered phenol-based antioxidant is blended. Particularly, it is preferable that a phosphorus-based stabilizer is blended, and it is more preferable that a triorganophosphate compound is blended. The contents of the phosphorus-based stabilizer and the hindered phenol-based antioxidant are preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 part by weight, respectively, based on 100 parts by weight of Component A.

[0200] (iii-3) Ultraviolet absorber The polycarbonate resin composition of the present invention can contain an ultraviolet absorber. Since the polycarbonate resin composition of the present invention also has a good hue, the addition of an ultraviolet absorber can maintain such a hue for a long period even in outdoor use.

[0201] In the case of benzophenones, examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0202] In the case of benzotriazoles, examples include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzot Liazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer are exemplified.

[0203] In the case of hydroxyphenyltriazines, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol are exemplified. Further, compounds in which the phenyl group of the above-exemplified compounds is a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, are exemplified.

[0204] In the case of cyclic imino esters, for example, 2,2’-p-phenylenebis(3,1-benzoxazin-4-one), 2,2’-(4,4’-diphenylene)bis(3,1-benzoxazin-4-one), and 2,2’-(2,6-naphthalene)bis(3,1-benzoxazin-4-one) are exemplified.

[0205] Also, as ultraviolet absorbers, specifically in the case of cyanoacrylates, for example, 1,3-bis-[(2’-cyano-3’,3’-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene are exemplified.

[0206] Furthermore, the above ultraviolet absorber may be a polymer-type ultraviolet absorber obtained by copolymerizing a monomer having a structure of a radically polymerizable monomer compound, such an ultraviolet-absorbing monomer and / or a light-stable monomer having a hindered amine structure, with a monomer such as alkyl (meth)acrylate. Examples of the above ultraviolet-absorbing monomer preferably 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 (meth)acrylate ester.

[0207] Among these, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability, and cyclic iminoester-based and cyanoacrylate-based are preferable in terms of heat resistance and hue. The above ultraviolet absorber may be used alone or as a mixture of two or more. The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 part by weight, and most preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of Component A.

[0208]

[0209] (iii-4) Other heat stabilizers In the polycarbonate resin composition of the present invention, other heat stabilizers other than the above phosphorus-based stabilizer and hindered phenol-based antioxidant can also be blended. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone-based stabilizers typified by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY 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 company is preferably exemplified. Such pre-mixed stabilizers can also be used in the present invention. The content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of Component A.

[0210] Examples of other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the polycarbonate resin composition is applied to rotational molding. The blending amount of such sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of Component A.

[0211] (iv) Release agent The polycarbonate resin composition of the present invention can further be blended with known mold release agents such as fatty acid esters, polyolefin waxes, silicone compounds, fluorine compounds (such as fluorine oils represented by polyfluoroalkyl ethers), paraffin waxes, and beeswax for the purpose of improving productivity during molding and dimensional accuracy of molded articles. Since the polycarbonate resin composition of the present invention has good fluidity, pressure transmission is good, and a molded article with uniform strain can be obtained. On the other hand, in the case of a molded article with a complex shape where the mold release resistance becomes large, there is a risk of deformation of the molded article during mold release. The blending of the above specific components solves such problems without impairing the properties of the polycarbonate resin composition.

[0212] Such a fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid. Such an aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol with two or more valences. The carbon number 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 with 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. The fatty acid ester of the present invention is preferred in that the total ester (full ester) has excellent thermal stability at high temperatures. The acid value of the fatty acid ester in the present invention is preferably 20 or less (substantially zero can be taken). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value of the fatty acid ester is preferably 10 or less (substantially zero can be taken). These properties can be determined by the methods specified in JIS K 0070.

[0213] Examples of the polyolefin wax include homopolymers of ethylene, 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, with a molecular weight of 1,000 to 10,000. Such molecular weight is the number average molecular weight measured in terms of standard polystyrene by the GPC (gel permeation chromatography) method. The upper limit of such 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 homopolymers of ethylene 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. Those commercially available as so-called polyethylene waxes are preferably used. 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 with respect to 100 parts by weight of Component A.

[0214] (v) Dyes and pigments The polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles exhibiting various design properties. 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 ultramarine, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can be blended with metallic pigments to obtain better metallic colors. Aluminum powder is suitable as the metallic pigment. In addition, by blending a fluorescent whitening agent or other fluorescent dyes that emit light, a better design effect utilizing the emitted light color can be imparted.

[0215] Examples of the fluorescent dyes (including fluorescent brighteners) 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, thiazine-based fluorescent dyes, and diamino stilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and little deterioration during the molding process of polycarbonate resins, are preferred.

[0216] The content of the dye or pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of Component A.

[0217] (vi) Compounds having a heat ray absorption ability The polycarbonate resin composition of the present invention can contain a compound having a heat ray absorption ability. Examples of such compounds include phthalocyanine-based near-infrared absorbers, ATO, ITO, metal oxide-based near-infrared absorbers such as iridium oxide and ruthenium oxide, and indium oxide, metal boride-based and tungsten oxide-based near-infrared absorbers such as lanthanum boride, cerium boride, and tungsten boride, and various metal compounds having excellent near-infrared absorption ability, as well as carbon fillers. Examples of such phthalocyanine-based near-infrared absorbers include MIR-362 manufactured by Mitsui Chemicals, Inc., which is commercially available and easily obtainable. Examples of carbon fillers include carbon black, graphite (including both natural and artificial), and fullerene, and carbon black and graphite are preferred. These can be used alone or in combination of two or more. Phthalocyanine-based near-infrared absorbers The content is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and still more preferably 0.001 to 0.07 parts by weight with respect to 100 parts by weight of Component A. The content of the metal oxide-based near-infrared absorber, metal boride-based near-infrared absorber, and 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 in the resin composition of the present invention.

[0218] (vii) Light diffusing agent A light diffusing agent can be blended into the polycarbonate resin composition of the present invention to impart a light diffusing effect. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for polycarbonate resins. More preferably, examples include acrylic cross-linked particles with a particle size of several μm and silicone cross-linked particles typified by polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include spherical, disk-shaped, columnar, and irregular shapes. Such spherical shapes do not necessarily have to be perfect spheres and include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform its particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of Component A. Incidentally, two or more light diffusing agents can be used in combination.

[0219] (viii) White pigment for high light reflection A white pigment for high light reflection can be blended into the polycarbonate resin composition of the present invention to impart a light reflection effect. As such a white pigment, titanium dioxide (especially titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferred. The content of such a white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight with respect to 100 parts by weight of Component A. Incidentally, two or more white pigments for high light reflection can be used in combination.

[0220] (ix) Antistatic agent In the polycarbonate resin composition of the present invention, antistatic performance may be required, and in such a case, it is preferably included an antistatic agent. Examples of such antistatic agents include (1) phosphonium arylsulfonates typified by phosphonium dodecylbenzenesulfonate, and organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and phosphonium borates such as phosphonium tetrafluoroborate. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably in the range of 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and still more preferably 1.5 to 3 parts by weight, based on 100 parts by weight of Component A.

[0221] Examples of antistatic agents include (2) organic sulfonic acid alkali (earth) metal salts such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Such metal salts are also used as flame retardants as described above. More specifically, examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is suitably 0.5 part by weight or less, preferably in the range of 0.001 to 0.3 part by weight, and more preferably 0.005 to 0.2 part by weight, based on 100 parts by weight of Component A. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferred.

[0222] Examples of antistatic agents include (3) organic sulfonic acid ammonium salts such as alkylsulfonic acid ammonium salts and arylsulfonic acid ammonium salts. The ammonium salt is suitably 0.05 part by weight or less based on a total of 100 parts by weight of Component A, Component B, and Component C. Examples of antistatic agents include (4) polymers containing a poly(oxyalkylene) glycol component such as polyether ester amide as a constituent component thereof. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of Component A.

[0223] (x) Filler In the polycarbonate resin composition of the present invention, various known fillers can be blended as reinforcing fillers. As such fillers, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including any of a rod shape, a needle shape, a flat shape, or a shape in which its axis extends in a plurality of directions), and the plate-like filler has a plate-like shape (including those having irregularities on the surface or those having a curved plate). The granular filler is a filler having a shape other than these including an irregular shape.

[0224] The above fibrous or plate-like shapes are often obvious from the shape observation of the filler. However, for example, as a difference from so-called irregular shapes, those having an aspect ratio of 3 or more can be said to be fibrous or plate-like.

[0225] Preferred examples of the plate-like filler include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and plate-like fillers obtained by surface coating these fillers with different materials such as metals and metal oxides. The particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to a value based on the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods, in the region up to about 10 μm, and a value based on the median diameter (D50) of the particle size distribution measured by the laser diffraction / scattering method in the region of 10 to 50 μm, and a value obtained by the vibratory sieving method in the region of 50 to 300 μm. Such a particle size is the particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based coupling agents, and may be agglomerated or compression-treated with various resins such as olefin-based resins, styrene-based resins, acrylic-based resins, polyester-based resins, epoxy-based resins, and urethane-based resins, or higher fatty acid esters.

[0226] The fibrous filler preferably has a fiber diameter in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is preferably 13 μm, more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm. The fiber diameter referred to here means the number average fiber diameter. The number average fiber diameter is a value calculated from an image obtained by observing the residue collected after dissolving the molded product in a solvent or decomposing the resin with a basic compound, and the ash residue collected after ashing in a crucible using a scanning electron microscope.

[0227] Examples of such fibrous fillers include fibrous inorganic fillers such as glass fiber, flat-section glass fiber, glass milled fiber, glass flake, carbon fiber, flat-section carbon fiber, carbon milled fiber, metal fiber, basalt fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker, aluminum borate whisker, calcium carbonate whisker, titanium oxide whisker, wollastonite, zonoite, palygorskite (attapulgite), and sepiolite; fibrous heat-resistant organic fillers typified by heat-resistant organic fibers such as aramid fiber, polyimide fiber, and polybenzothiazole fiber; vegetable fibers such as hemp and bamboo; and fibrous fillers obtained by surface coating these fillers with different materials such as metals and metal oxides. Examples of the fillers surface-coated with different materials include metal-coated glass fiber, metal-coated glass flake, titanium oxide-coated glass flake, and metal-coated carbon fiber. The method for surface coating with different materials is not particularly limited, and examples thereof include various known plating methods (e.g., electroplating, electroless plating, hot dipping, etc.), vacuum evaporation method, ion plating method, CVD method (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD method, and sputtering method.

[0228] Here, the fibrous filler refers to a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is the value in the resin composition. Further, the flat cross-section glass fiber means that the average value of the major axis 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 axis to the minor axis (major axis / minor axis) is 1.5 to 8, preferably 2 to 6, still more preferably 2.5 to 5. The fibrous filler may also be surface-treated with various coupling agents in the same manner as the above-mentioned plate-like filler, may be subjected to a bundling treatment with various resins, etc., and may be granulated by a compression treatment.

[0229] The content of the filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less with respect to 100 parts by weight of the component A.

[0230] (xi) Other additives In the polycarbonate resin composition of the present invention, a thermoplastic resin other than the component A and the component B, an elastomer, other flow modifiers, an antibacterial agent, a dispersant such as liquid paraffin, a photocatalyst-based antifouling agent and a photochromic agent, an ionic liquid, etc. can be blended.

[0231] Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polystyrene resins, acrylonitrile / styrene copolymers (AS resins), acrylonitrile / butadiene / styrene copolymers (ABS resins), polymethacrylate resins, phenol resins, epoxy resins, cyclic polyolefin resins, polylactic acid resins, polycaprolactone resins, and thermoplastic fluorine resins (represented by, for example, polyvinylidene fluoride resin), etc.

[0232] Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and core-shell type elastomers such as MBS (methyl methacrylate / styrene / butadiene) rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber. 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 Component A.

[0233] (Method for producing polycarbonate resin composition) There is no particular limitation on the method for producing the polycarbonate resin composition of the present invention, and well-known methods can be used. For example, Component A, Component B, and optionally other additives are sufficiently mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and then, if necessary, granulation of such a premixed mixture is performed using an extrusion granulator, briquetting machine, etc., and then melt-kneaded using a melt-kneader typified by a vented twin-screw extruder, and then pelletized using a pelletizer.

[0234] In addition, methods such as a method of independently supplying each component to a melt-kneader typified by a vented twin-screw extruder, a method of supplying to a melt-kneader using a supercritical fluid, and a method of supplying a part of each component to a melt-kneader independently after premixing a part of each component are also included. Examples of the method of premixing a part of each component include a method of premixing components other than Component A in advance and then mixing them with Component A or directly supplying them to an extruder. Examples of the premixing method include, when Component A includes those having a powder form, producing a masterbatch of an additive diluted with a powder by blending the additive with a part of such powder, and using such a masterbatch. Further, a method of independently supplying one component from the middle of a melt extruder is also included. When there is a liquid component among the components to be blended, a so-called liquid injection device or liquid addition device can be used for supplying to the melt extruder.

[0235] As the extruder, those having a vent capable of degassing moisture in the raw material and volatile gases generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed at the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. Further, a screen for removing foreign matters mixed in the extrusion raw material or the like is installed in the zone in front of the die part of the extruder, and it is also possible to remove the foreign matters from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

[0236] Examples of the melt-kneader include a Banbury mixer, a kneading roll, a single-screw extruder, a multi-screw extruder having three or more shafts, in addition to a twin-screw extruder.

[0237] The resin extruded as described above is directly cut and pelletized, or after forming a strand, the strand is cut by a pelletizer and pelletized. When it is necessary to reduce the influence of external dust or the like during pelletization, it is preferable to clean the atmosphere around the extruder. Further, in the production of such pellets, various methods already proposed for polycarbonate resins for optical disks can be used to appropriately narrow the shape distribution of the pellets, reduce miscuts, reduce fine powder generated during transportation or shipping, and reduce bubbles (vacuum bubbles) generated inside the strand or pellet. By these formulations, high cycle molding and reduction of the defective occurrence rate such as silver can be achieved. The shape of the pellet can take a general shape such as a cylinder, a prism, and a sphere, but more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still 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 still more preferably 2.5 to 3.5 mm.

[0238] The polycarbonate resin composition of the present invention can be used to manufacture various products by injection molding the pellets usually produced as described above to obtain molded articles. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding can be mentioned. Also, either a cold runner system or a hot runner system can be selected for molding.

[0239] Further, the polycarbonate resin composition of the present invention can also be used in the form of various shaped extruded articles, sheets, films, etc. by extrusion molding. Also, for the molding of sheets and films, an inflation method, a calender method, a casting method, etc. can also be used. Furthermore, it is also possible to mold it into a heat-shrinkable tube by applying a specific stretching operation. Also, it is possible to obtain molded articles from the polycarbonate resin composition of the present invention by rotational molding, blow molding, etc.

Advantages of the Invention

[0240] The resin composition comprising the aromatic polycarbonate resin and the circuit formation stabilizer of the present invention has, in addition to strength and low dielectric properties, good adhesion and long-term durability with a metal thin film during circuit formation. Therefore, it can be suitably used as a three-dimensional design material for broadband antennas in various fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electric and electronic devices, machinery, and other fields, and for the antennas in these fields in electronic devices. Therefore, the industrial effect of the present invention is extremely great.

Modes for Carrying Out the Invention

Embodiments

[0241] The mode for carrying out the present invention is an aggregation of the preferred ranges of the above-mentioned respective requirements. For example, representative examples thereof are described in the following examples. Of course, the present invention is not limited to these forms.

Examples

[0242] Next, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited thereto. Each measurement item in the examples was measured by the following method.

[0243] 1. Evaluation of aromatic polycarbonate resin (i) Viscosity average molecular weight (Mv) The specific viscosity (η SP ) calculated by the following formula was determined using an Ostwald viscometer from a solution prepared by dissolving an aromatic polycarbonate resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t - t0) / t0 [t0 is the falling time of methylene chloride, t is the falling time of the sample solution] The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η SP ) by the following formula. η SP / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23×10 -4 Mv 0.83 c = 0.7

[0244] 2. Evaluation of resin composition (i) Impact property (Charpy impact value) (with notch) Measurement was carried out in accordance with ISO179 (measurement condition: 23°C) using a test piece with a length of 80 mm × width of 10 mm × thickness of 4 mm obtained by the following method. (ii) Dielectric property Using a test piece with a length of 300 mm × width of 300 mm × thickness of 1 mm obtained by the following method, a 20 cm microstrip line was created by etching, and the radio wave transmissivity at 10 GHz was measured using a vector network analyzer. The higher this value, the lower the dielectric property. (iii) Adhesion After plating under the following conditions using a 50 mm × 100 mm × 1 mm plate-shaped test piece obtained by the following method, the adhesion between the metal thin film and the resin was evaluated. The cross-cut tape test was carried out in accordance with 4-6 of "JIS K5600 General Test Methods for Paints". ○: There is no unplated part. And no peeling occurred in the cross-cut tape test using cellophane tape. △: There is no unplated part, but peeling occurred in the cross-cut tape test using cellophane tape. ×: Unplated parts occur. And peeling occurred in the cross-cut tape test using cellophane tape. (iv) Long-term durability After plating under the following conditions using a 50 mm × 100 mm × 1 mm plate-shaped test piece obtained by the following method, it was treated for 1,000 hours in an environment of 80°C and 85% RH, and then the same adhesion evaluation as in (iii) was carried out. ○: There is no unplated part. And no peeling occurred in the cross-cut tape test using cellophane tape. △: There is no unplated part, but peeling occurred in the cross-cut tape test using cellophane tape 。 ×: Unplated parts occur. And peeling occurred in the cross-cut tape test using cellophane tape.

[0245] [Examples 1 to 16, Comparative Examples 1 to 6] (Preparation of evaluation test pieces) An aromatic polycarbonate resin, a circuit formation stabilizer, and various additives were mixed in a blender at the compounding amounts shown in Tables 1 and 2, and then melt-kneaded using a vented twin-screw extruder to obtain pellets. For each of the various additives to be used, a preliminary mixture with the aromatic polycarbonate resin was prepared in advance with a concentration 10 to 100 times the compounding amount as a guide, and then the overall mixing was carried out using a blender. Extrusion was carried out using a vented twin-screw extruder with a diameter of 30 mm φ (TEX30α-38.5BW-3V manufactured by Nippon Steel Works, Ltd.), at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum degree of 3 kPa. The extrusion temperature was 300 °C from the first feed port to the second feed port and 310 °C from the second feed port to the die part for melt-kneading to obtain pellets. The polycarbonate resin and the additives were supplied to the extruder from the first feed port. Here, the first feed port refers to the feed port farthest from the die. The obtained pellets were dried in a hot air circulation dryer at 120 °C for 5 hours, and then test pieces for evaluation were molded using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) under molding conditions of a cylinder temperature of 300 °C and a mold temperature of 80 °C.

[0246] Among such molded products, the evaluation of adhesion and long-term durability was carried out after plating according to the conditions shown below. As the plating process, the obtained test piece was printed with a width of 5 mm using a 1064 nm YVO4 laser of Keyence's MDX-2000 at a frequency of 80 kHz, a speed of 2 m / s, an output of 1.45 W, a laser spot diameter of 60 μm, and an overlap of 30 μm, and then the following operations were carried out.

[0247] (a) Degreasing (OPC Cleaner MIC at 45 °C for 5 minutes * 150 ml / L) (b) Ultrasonic water washing (at 60 °C for 1 minute, 95 parts by weight of deionized water / 5 parts by weight of triethanolamine) (c) Catalyst application (at 35 °C for 4 minutes, 1 L of deionized water / 380 mg of palladium chloride / 200 ml of anhydrous hydrochloric acid) (d) Catalyst activation (at 60 °C for 2 minutes, 1 L of deionized water / 120 g of ammonium fluoride) (e) Electroless copper plating (at 48 °C, 220 minutes, 1 L of deionized water / (copper plating bath + replenisher)*1 100 mL / Alkali replenisher *2 80 mL / Complexing agent *3 50 mL / Stabilizer *4 1 mL / Formaldehyde 6 g) *1: 8 parts by weight of copper sulfate, 1 part by weight of polyethylene glycol, 0.02 part by weight of stabilizer, 90.98 parts by weight of deionized water *2: 40 parts by weight of sodium hydroxide, stabilizer *4 0.02 part by weight, 59.98 parts by weight of deionized water *3: 50 parts by weight of sodium hydroxide, stabilizer *4 0.02 part by weight, 49.98 parts by weight of deionized water *4: 0.2 part by weight of potassium selenocyanate, 6 parts by weight of potassium cyanide, 93.8 parts by weight of deionized water (f) Water washing (1 minute) (h) Drying (The treatment liquids marked with * are product names of Okuno Pharmaceutical Co., Ltd.) The results of each evaluation are shown in Tables 1 and 2. The components with symbol notations in Tables 1 and 2 are as follows.

[0248] (Component A) A-1: Aromatic polycarbonate resin (a polycarbonate resin powder with a viscosity average molecular weight of 15,500 produced by a conventional method from bisphenol A and phosgene, Panlite CM-1000 (product name) manufactured by Teijin Limited) A-2: Aromatic polycarbonate resin (a polycarbonate resin powder with a viscosity average molecular weight of 19,700 produced by a conventional method from bisphenol A and phosgene, Panlite L-1225WX (product name) manufactured by Teijin Limited) A-3: Aromatic polycarbonate resin (a polycarbonate resin powder with a viscosity average molecular weight of 23,900 produced by a conventional method from bisphenol A and phosgene, Panlite L-1250WP (product name) manufactured by Teijin Limited) A-4: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 23,500, PDMS content 8.4% by weight, PDMS degree of polymerization 37)

[0249] (Component B) B-1-1: After purging the reactor equipped with a thermometer, a stirrer, and a reflux condenser with nitrogen to create a nitrogen atmosphere, 93.3 parts of a 25% aqueous sodium hydroxide solution and 182 parts of ion-exchanged water were charged. To this, 11.8 parts of 1,1-bis(4-hydroxy Phenyl )-3,3,5-trimethylcyclohexane (hereinafter referred to as BP-TMC), 2,2 -bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as BP-C) 39.9 parts, and 0.1 part of sodium hydrosulfite were dissolved, and then 231 parts of methylene chloride were added. Subsequently, after purging the reaction vessel with nitrogen for 10 minutes, 25 parts of phosgene were blown in at 18 - 21 °C over about 60 minutes with stirring. After the blowing-in of phosgene was completed, 15.6 parts of a 25% aqueous sodium hydroxide solution and 1.05 parts of p-tert-butylphenol were added, stirring was restarted, 0.05 part of triethylamine was added after emulsification, and the mixture was further stirred at 20 - 27 °C for 1 hour to complete the reaction. After the reaction was completed, the product was diluted with methylene chloride at room temperature and washed with water, and then acidified with hydrochloric acid and washed with water. Washing with pure water was repeated until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water to obtain a methylene chloride solution of polycarbonate. Next, it was dropped into warm water in a kneader with a partition chamber having a foreign matter outlet in the bearing part, and the polycarbonate was flaked while distilling off methylene chloride. Subsequently, the liquid-containing flakes were pulverized and dried to obtain a powdery polycarbonate resin. B-1-2: The same operations as in Example 1 were carried out except that 29.6 parts of BP-TMC and 24.9 parts of BP-C were used to obtain a powdery polycarbonate resin. B-1-3: Charge a reactor equipped with a thermometer, a stirrer, and a reflux condenser with 4,760 parts of a 48% aqueous sodium hydroxide solution and 20,779 parts of ion-exchanged water. Dissolve 4,271 parts of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane and 8.54 parts of hydrosulfite therein, then add 15,945 parts of methylene chloride. While stirring, blow 2,000 parts of phosgene into the solution at 15 - 25°C over about 60 minutes. After the blowing of phosgene is completed, add 595 parts of a 48% aqueous sodium hydroxide solution and 86.6 parts of p-tert-butylphenol, resume stirring, add 5.01 parts of triethylamine after emulsification, and further stir at 26 - 33°C for 1 hour to complete the reaction. After the reaction is completed, dilute the product with methylene chloride, wash it with water, acidify it with hydrochloric acid and wash it with water again, and repeat the water washing until the conductivity of the aqueous phase is almost the same as that of ion-exchanged water to obtain a methylene chloride solution of polycarbonate. Then, pass this solution through a filter with a pore size of 0.3 μm, and further drop it into warm water in a kneader with a separation chamber having a foreign matter removal port at the bearing part. While distilling off methylene chloride, flake the polycarbonate, and subsequently grind and dry the liquid-containing flakes to obtain a powdery polycarbonate resin. B-1-4: After purging the reactor equipped with a thermometer, stirrer, and reflux condenser with nitrogen to create a nitrogen atmosphere, 592 parts of a 48% aqueous sodium hydroxide solution and 2,909 parts of ion-exchanged water were charged. 135 parts of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 255 parts of BP-C, and 1.1 parts of hydrosulfite were dissolved therein, and then 1,984 parts of methylene chloride were added. Subsequently, the reaction vessel was purged with nitrogen for 10 minutes, and then 240 parts of phosgene were blown in at 18 - 21 °C over about 60 minutes with stirring. After the blowing-in of phosgene was completed, 74 parts of a 48% aqueous sodium hydroxide solution and 81 parts of p-tert-butylphenol were added, stirring was restarted, 0.5 part of triethylamine was added after emulsification, and the mixture was stirred at 20 - 27 °C for 1 hour to complete the reaction. After the reaction was completed, the product was diluted with methylene chloride and washed with water at room temperature, and then acidified with hydrochloric acid and washed with water. Washing with pure water was repeated until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, and a methylene chloride solution of polycarbonate was obtained. Next, it was dropped into warm water in a kneader with a separation chamber having a foreign matter outlet in the bearing part, and the polycarbonate was flaked while distilling off methylene chloride. Subsequently, the liquid-containing flakes were pulverized and dried to obtain a powdery polycarbonate resin.

[0250] B-2-1: Charge 4,555 parts of a 48% aqueous sodium hydroxide solution and 22,730 parts of ion-exchanged water into a reactor equipped with a thermometer, a stirrer, and a reflux condenser. Dissolve 298 parts of 9,9-bis(4-hydroxyphenyl)fluorene, 1,820 parts of BP-C, 1,799 parts of 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as BP-A), 71.0 parts of p-tert-butylphenol, and 7.94 parts of hydrosulfite into the solution. Then add 13,415 parts of methylene chloride, and blow 2,000 parts of phosgene into the mixture at 15 to 25 °C over about 70 minutes with stirring. After the blowing of phosgene is completed, add 650 parts of a 48% aqueous sodium hydroxide solution and 87.6 parts of p-tert-butylphenol, restart stirring, add 3.94 parts of triethylamine after emulsification, and stir at 28 to 35 °C for 1 hour to complete the reaction. After the reaction is completed, dilute the product with methylene chloride, wash with water, add hydrochloric acid to make it acidic, wash with water, and repeat the water washing until the conductivity of the aqueous phase is almost the same as that of ion-exchanged water to obtain a methylene chloride solution of a polycarbonate resin. Next, pass this solution through a filter with a pore size of 0.3 μm, and then drop it into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing part. While distilling off methylene chloride, flake the polycarbonate, and then continue to grind and dry the liquid-containing flakes to obtain a powdery polycarbonate resin. B-2-2: Charge 3,844 parts of 48% aqueous sodium hydroxide solution and 22,380 parts of ion-exchanged water into a reactor equipped with a thermometer, a stirrer, and a reflux condenser. After dissolving 1,992 parts (7.8 mol) of BP-C and 1,773 parts (7.8 mol) of BP-A therein, add 13,210 parts of methylene chloride, and blow 2,000 parts of phosgene into it at 15 - 25 °C over about 60 minutes with stirring. After the blowing of phosgene is completed, add 640 parts of 48% aqueous sodium hydroxide solution and 93.2 parts of p-tert-butylphenol, resume stirring, add 3.24 parts of triethylamine after emulsification, and further stir at 28 - 33 °C for 1 hour to complete the reaction. After the reaction is completed, dilute the product with methylene chloride, wash it with water, acidify it with hydrochloric acid, wash it with water, and repeat the water washing until the conductivity of the aqueous phase is almost the same as that of ion-exchanged water to obtain a methylene chloride solution of polycarbonate. Next, pass this solution through a filter with a pore size of 0.3 μm, and further drop it into warm water in a kneader with an isolation chamber having a foreign matter removal port at the bearing part, and flake the polycarbonate while distilling off methylene chloride. Subsequently, grind and dry the liquid-containing flakes to obtain a powdery polycarbonate resin.

[0251] (Other components) S-1: Tris(2,4-di-tert-butylphenyl) phosphite (ADEKA 2112) S-2: 3,9-Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane (ADEKA AO-80) UV: Benzotriazole-based ultraviolet absorber (manufactured by Ciba Specialty Chemicals: Tinuvin 234) L: Low molecular weight polyethylene (Mitsui Chemicals, Inc. Hiwax HW405MP (trade name)) CB: Carbon black (Koshigaya Kasei Kogyo Co., Ltd. RB-90003S)

[0252]

Table 1

[0253]

Table 2

[0254] It can be seen from Table 1 and Table 2 that the polycarbonate resin composition according to the formulation of the present invention is excellent in strength, low dielectric properties, good adhesion to the metal thin film during circuit formation, and long-term durability.

Claims

1. (A) A circuit forming stabilizer (Component B) selected from the group consisting of at least one selected from the group consisting of a polycarbonate resin (Component B-1) containing at least one structural unit selected from the group consisting of structural units derived from 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, structural units derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane, and structural units derived from 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and (B-2) a polycarbonate resin (Component B-2) containing at least one structural unit selected from the group consisting of structural units derived from 9,9-bis(4-hydroxyphenyl)fluorene, structural units derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane, and structural units derived from 2,2-bis(4-hydroxyphenyl)propane, excluding Component B-1, is contained in an amount of 10 to 5000 parts by weight based on 100 parts by weight of an aromatic polycarbonate resin (Component A) excluding Component B. A polycarbonate resin composition for circuit molding, characterized in that it is used for circuit molding.

2. Component A is an aromatic polycarbonate resin containing 1 to 100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (Component A-1) composed of a polycarbonate block represented by the following formula (1) and a polydiorganosiloxane block represented by the following formula (3), and the polydiorganosiloxane content in 100% by weight of Component A-1 is 0.05 to 20.0% by weight. The polycarbonate resin composition according to Claim 1. 【Chemical 1】 (In the above general formula (1), R １ and R ２ each independently represent a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of each, they may be the same or different. a and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond and a group represented by the following general formula (2).) [Chemical 2] (In the general formula (2) above, R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and R １９ and R ２０ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different, c is an integer of 1 to 10, and d is an integer of 4 to 7.) 【Chemical Formula 3】 (In the general formula (3) above, R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ９ and R １０ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, e and f are each an integer of 1 to 4, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

3. A circuit molded article for a communication device, comprising the polycarbonate resin composition for circuit formation according to Claim 1 or 2.

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