Polycarbonate resin composition and circuit molded article for communication equipment

Abstract

The present invention provides: a polycarbonate resin composition having excellent appearance, flame retardancy, and plating properties during circuit formation; and a circuit molded article for communication equipment, the circuit molded article comprising said polycarbonate resin composition. This polycarbonate resin composition contains (A) 100 parts by weight of a polycarbonate resin (component A), (B) 1 to 15 parts by weight of a polyphosphonate compound (component B), and (C) 3 to 15 parts by weight of an additive (component C) for laser irradiation three-dimensional circuit molding.

Description

Polycarbonate resin composition and circuit molded articles for communication equipment

[0001] This invention relates to a polycarbonate resin composition comprising a polycarbonate resin, a polyphosphonate compound, and an additive for laser irradiation three-dimensional circuit molding. More specifically, it relates to a polycarbonate resin composition that exhibits excellent appearance, flame retardancy, and plating properties during circuit formation.

[0002] Polycarbonate resin is used as an engineering plastic in a wide range of fields, including electrical and electronic equipment housings, automotive interior and exterior parts, building materials, furniture, musical instruments, and general merchandise, due to its excellent transparency, impact resistance, heat resistance, and dimensional stability. In this context, various methods for manufacturing antennas and electronic circuits inside electronic devices such as mobile phones, including smartphones, are being investigated, and there is a particular need for a method that allows for three-dimensional design of antennas and electronic circuits inside electronic devices. One such technology for forming three-dimensional electronic components is laser irradiation 3D circuit molding technology, which is attracting attention. This technology uses, for example, a resin material in which a metal complex is dispersed, and the complex is reduced by laser light to act as a catalytic nucleus, allowing for the direct formation of circuits such as antennas by selective plating without the need for an adhesive layer. As an example of using such laser irradiation 3D circuit molding technology, a resin composition consisting of polycarbonate resin and a specific conductive oxide has been proposed (Patent Document 1). Furthermore, a resin composition capable of appropriately forming a thin metal film under a wide range of laser irradiation conditions has also been proposed (Patent Document 2). However, in recent years, the demand for laser irradiation 3D circuit molding technology has been increasing, and there is a growing need for polycarbonate resin compositions and molded products made therefrom that offer superior plating performance.

[0003] Japanese Patent Publication No. 2012-72338, International Publication No. 2014 / 042070

[0004] In view of the above, the object of the present invention is to provide a polycarbonate resin composition that is excellent in appearance, flame retardancy, and plateability during circuit formation, and a circuit molded product for communication equipment made therefrom.

[0005] As a result of diligent research to solve the above problems, the present inventors have discovered that by adding a polyphosphonate compound and an additive for laser irradiation three-dimensional circuit molding to a polycarbonate resin, it is possible to obtain a polycarbonate resin composition that is superior in appearance, flame retardancy, and good plating properties during circuit formation, which could not be obtained with conventional resin compositions, and thus arrived at the present invention.

[0006] In other words, the present invention is as follows: 1. A polycarbonate resin composition containing (A) 100 parts by weight of polycarbonate resin (component A), (B) 1 to 15 parts by weight of polyphosphonate compound (component B), and (C) 3 to 15 parts by weight of laser irradiation additive for three-dimensional circuit molding (component C). 2. The polycarbonate resin composition according to item 1, wherein component A is a polycarbonate resin containing 1 to 100% by weight of polycarbonate-polydiorganosiloxane copolymer resin (component A-1). 3. The polycarbonate resin composition according to item 2, wherein the polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as component A-1 is 0.1 to 50% by weight. 4. A polycarbonate resin composition according to any one of paragraphs 1 to 3 above, wherein component B is a polyphosphonate homopolymer consisting of repeating units represented by the following formula (4) or a poly(phosphonate-carbonate) copolymer consisting of repeating units represented by the following formulas (4) and (5). (In the formula, Y is an alkylidene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, -O-, -S-, -SO-, -SO) ２ (This indicates - or -CO-, where R represents an alkyl group having 1 to 10 carbon atoms.) 5. A polycarbonate resin composition according to item 4, wherein component B has a phosphorus content of 5% by weight or more and 20% by weight or less. 6. A polycarbonate resin composition according to any one of items 1 to 5, wherein component C is a laser-irradiated three-dimensional circuit molding additive containing at least two metals. 7. A polycarbonate resin composition according to item 6, wherein component C is a compound containing at least two selected from the group consisting of copper, chromium, tin, and antimony. 8. A polycarbonate resin composition according to any one of items 1 to 7, for circuit molding. 9. A circuit molded article for communication equipment made from the circuit-molding polycarbonate resin composition according to item 8. 10. A method for manufacturing a circuit molded article for communication equipment with a circuit, comprising: irradiating a part of the surface of the circuit molded article for communication equipment according to item 9 with laser light to reduce component C to form a catalyst nucleus; and performing selective plating on the circuit molded article for communication equipment having the catalyst nucleus to form a circuit on the circuit molded article for communication equipment.

[0007] The polycarbonate resin composition of the present invention, comprising an aromatic polycarbonate resin, a polyphosphonate compound, and an additive for laser irradiation three-dimensional circuit molding, exhibits excellent appearance, flame retardancy, and plating properties during circuit formation. Therefore, it can be suitably used as a broadband antenna in various fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electrical and electronic equipment, machinery, and other applications, and as a three-dimensional design tool for electronic devices. Consequently, the industrial benefits of the present invention are extremely significant.

[0008] The present invention will be described in detail below. <Component A: Polycarbonate Resin> The polycarbonate resin used as component A of the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of reaction methods include interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0009] Typical examples of divalent phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, and 4,4'-(p-phenyl Examples include bis(4-hydroxyphenyl)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred divalent phenols are bis(4-hydroxyphenyl)alkanes, among which bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0010] In this invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins manufactured using other divalent phenols as component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as part or all of the divalent phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly demanding. It is preferable that these divalent phenols other than BPA be used in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is especially preferable that component A constituting the polycarbonate resin composition be one of the copolymer polycarbonate resins (1) to (3) below.

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

[0012] These special polycarbonate resins may be used individually or mixed in appropriate combinations of two or more types. They can also be mixed with commonly used bisphenol A type polycarbonate resins. The manufacturing methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Publication No. 6-172508, Japanese Patent Publication No. 8-27370, Japanese Patent Publication No. 2001-55435, and Japanese Patent Publication No. 2002-117580.

[0013] Furthermore, among the various polycarbonate resins mentioned above, those whose copolymer composition and other properties have been adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges are particularly suitable for fields requiring morphological stability because they exhibit excellent hydrolysis resistance of the polymer itself and outstandingly low warpage after molding. (i) A polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0014] Here, the water absorption rate of the polycarbonate resin was measured using a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm, after immersion in water at 23°C for 24 hours in accordance with ISO 62-1980. The glass transition temperature (Tg) was determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0015] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

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

[0017] Branched polycarbonate resins can impart properties such as drip prevention to the polycarbonate resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 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 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0018] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be produced as a side reaction, but the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols. １ It can be calculated by H-NMR measurement.

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

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

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

[0022] The viscosity-average molecular weight referred to in the present invention is first determined by the specific viscosity (η ＳＰ ) obtained from the following formula using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η ＳＰ ) = (t - t ０ ) / t ０ [t ０ is the dropping seconds of methylene chloride, and t is the dropping seconds of the sample solution] The viscosity-average molecular weight M is calculated from the obtained specific viscosity (η ＳＰ ) by the following formula. η ＳＰ / c = [η] + 0.45 × [η] <( ２c (where [η] is the intrinsic viscosity) [η] = 1.23×10 －４ M ０．８３ c = 0.7 Also, the viscosity-average molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble components in the composition. The soluble components are collected by filtration through Celite. Thereafter, the solvent in the resulting solution is removed. The solid after solvent removal is dried sufficiently to obtain a solid of the component dissolved in methylene chloride. From a solution obtained by dissolving 0.7 g of such a solid in 100 ml of methylene chloride, the specific viscosity at 20°C is determined in the same manner as above, and the viscosity-average molecular weight M is calculated from the specific viscosity in the same manner as above.

[0023] The polycarbonate resin of the present invention is preferably a polycarbonate resin containing 1 to 100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component A-1). The content of component A-1 is more preferably 30 to 100% by weight, and even more preferably 70 to 100% by weight. When the content of component A-1 is less than 1% by weight, sufficient plating properties [plating uniformity, plating uniformity (laser condition dependence), and plating adhesion (laser condition dependence)] may not be obtained.

[0024] Further, the polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as component A-1 is preferably 0.1 to 50% by weight. Such a polydiorganosiloxane component content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. Above the lower limit of such a suitable range, the plating properties [plating uniformity, plating uniformity (laser condition dependence), and plating adhesion (laser condition dependence)] and flame retardancy may be excellent, and below the upper limit of such a suitable range, a stable appearance that is not easily affected by molding conditions may be obtained. Such a polydiorganosiloxane degree of polymerization and polydiorganosiloxane content can be calculated by １ H-NMR measurement.

[0025] Polycarbonate-polydiorganosiloxane copolymer resins can be obtained by copolymerizing a divalent phenol represented by the following general formula (1) with a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0026]

[0027] [In the above general formula (1), R １ and R ２ Each of these independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups of each, they may be the same or different. e and f are integers 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 general formula (2) below.

[0028]

[0029] [In the above general formula (2), R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ Each of these 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 ２０Each of these 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. If there are multiple groups, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0030]

[0031] [In the above general formula (3), R ３ , R ４ , R ５ , R ６ , R ７ and R ８ Each is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R ９ and R １０ Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 4 and 350. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0032] Examples of divalent phenols (I) represented by 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, and 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-H 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,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0033] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is the most suitable. These may be used individually or in combination of two or more.

[0034] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), the following compounds are preferably used, for example.

[0035]

[0036] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosiliculation reaction of olefinic unsaturated carbon-carbon bonded phenols, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol, to the ends of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, and (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxanes (II) preferably have a molecular weight distribution (Mw / Mn) of 3 or less. Furthermore, in order to exhibit excellent low outgassing and low-temperature impact resistance during high-temperature molding, such molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this suitable range is exceeded, the amount of outgassing during high-temperature molding increases, and the low-temperature impact resistance may be poor.

[0037] Furthermore, in order to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is preferably 10 to 300. More preferably, the degree of diorganosiloxane polymerization (p+q) is 10 to 200, even more preferably 12 to 150, and particularly preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, and above the upper limit of this preferred range, appearance defects appear.

[0038] In the present invention, only one hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more may be used. Furthermore, other comonomers other than the above-mentioned divalent phenol (1) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in a range of 10% by weight or less relative to the total weight of the copolymer, as long as it does not interfere with the present invention.

[0039] In the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by the reaction of a divalent phenol (1) with a carbonate ester-forming compound in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution.

[0040] In generating the oligomer of divalent phenol (1), the entire amount of divalent phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a portion of it may be added as a reaction material to the subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to expedite the subsequent polycondensation reaction, and it is not necessary to add it if it is not needed. The method of this oligomer generation reaction is not particularly limited, but it is generally preferred to carry it out in a solvent in the presence of an acid binder.

[0041] The proportion of ester-forming compounds used can be adjusted as appropriate, taking into account the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using gaseous ester-forming compounds such as phosgene, a suitable method is to bubble them into the reaction system.

[0042] Examples of acid binders 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 proportion of acid binder used should be determined appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder relative to the number of moles of divalent phenol (1) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0043] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0044] There are no particular restrictions on the reaction pressure for oligomer formation; it can be atmospheric pressure, pressurized pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization is often exothermic, it is desirable to cool the reaction with water or ice. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out in 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0045] In this invention, a mixed solution containing an oligomer of divalent phenol (1) having terminal chloroformate groups is obtained, and while stirring the mixed solution, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, is added to the divalent phenol (1), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0046] When carrying out an interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into consideration the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders 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. Specifically, when adding a portion of the hydroxyaryl-terminated polydiorganosiloxane (II) or the divalent phenol (1) as a post-added monomer to this reaction step, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the post-added divalent phenol (1) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0047] The polycondensation reaction between the oligomer of divalent phenol (1) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0048] In such polymerization reactions, end-terminating agents or molecular weight modifiers are commonly used. Examples of end-terminating agents include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenols, p-tert-butylphenol, p-cumylphenol, and tribromophenol, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenylalkylates, and alkyl etherphenols. The amount used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all divalent phenolic compounds used, and it is naturally possible to use two or more compounds in combination.

[0049] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added. The reaction time for such polymerization is preferably 30 minutes or more, more preferably 50 minutes or more. Optionally, a small amount of antioxidant such as sodium sulfite or hydrosulfide may be added.

[0050] Branching agents can be used in combination with the above-mentioned divalent phenolic compounds to form branched polycarbonate-polydiorganosiloxanes. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucid, or 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 4-{4-[1 Examples include trisphenols such as 1-bis(4-hydroxyphenyl)ethyl]benzene-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The proportion of polyfunctional compounds in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, even more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%, of the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. １ It can be calculated by 1H NMR measurement.

[0051] The reaction pressure can be reduced, atmospheric, or pressurized, but it is usually preferable to use atmospheric pressure or the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization often generates heat, water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be specified in general terms, but it is usually carried out in 0.5 to 10 hours.

[0052] Depending on the circumstances, the obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking, partial decomposition, etc.) to obtain the desired reduced viscosity [η ＳＰ It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of [c].

[0053] The resulting reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification) by various post-treatment methods, such as known separation and purification methods.

[0054] The average size of polydiorganosiloxane domains in polycarbonate-polydiorganosiloxane copolymer resin molded articles is preferably in the range of 1 to 40 nm. More preferably, this average size is 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, and above the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0055] The average domain size and normalized dispersion of polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product of the present invention were evaluated by small-angle X-ray scattering (SAXS). Small-angle X-ray scattering is a method for measuring diffuse scattering and diffraction occurring in the small-angle region with a scattering angle (2θ) < 10° or less. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in size in the material, diffuse scattering of X-rays is measured due to the difference in electron density. The particle size of the object to be measured is determined based on this scattering angle and scattering intensity. In the case of polycarbonate-polydiorganosiloxane copolymer resins, which form an aggregated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. By measuring the scattering intensity I at each scattering angle (2θ) in the range of less than 10°, a small-angle X-ray scattering profile is measured. Assuming that the polydiorganosiloxane domains are spherical domains and that there is variability in the particle size distribution, a simulation is performed using commercially available analysis software from a hypothetical particle size and a hypothetical particle size distribution model to determine the average size and particle size distribution (normalized variance) of the polydiorganosiloxane domains. The small-angle X-ray scattering method allows for accurate, simple, and reproducible measurement of the average size and particle size distribution of polydiorganosiloxane domains dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope. The average domain size refers to the average of the number of individual domain sizes. Normalized variance refers to a parameter that normalizes the spread of the particle size distribution by the average size. Specifically, it is the value obtained by normalizing the variance of polydiorganosiloxane domain sizes by the average domain size, and is expressed by the following formula (1).

[0056] In equation (1) above, δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the mean domain size.

[0057] The terms "average domain size" and "normalized variance" used in relation to this invention refer to measurements obtained by measuring a 1.0 mm thick portion of a three-tiered plate prepared by the method described in the examples using the small-angle X-ray scattering method. Furthermore, the analysis was performed using an isolated particle model that does not consider interparticle interactions (interparticle interference).

[0058] <Component B: Polyphosphonate Compound> The polycarbonate resin composition of the present invention contains 1 to 15 parts by weight of a polyphosphonate compound per 100 parts by weight of polycarbonate resin. The content is preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight, and even more preferably 5 to 7 parts by weight. If the content of component B is less than 1 part by weight, the plating properties [plating uniformity, plating uniformity (laser condition dependent), and plating adhesion (laser condition dependent)] and flame retardancy deteriorate. If the content of component B exceeds 15 parts by weight, the surface appearance deteriorates. Furthermore, if a phosphorus-based flame retardant other than a polyphosphonate compound is used, the plating uniformity (laser condition dependent) and / or plating adhesion (laser condition dependent) deteriorate.

[0059] There are no particular limitations on the polyphosphonate compounds used in the present invention, and various types can be used, but preferred are polyphosphonate homopolymers consisting of repeating units represented by the following formula (4) or poly(phosphonate-carbonate) copolymers consisting of repeating units represented by the following formulas (4) and (5).

[0060]

[0061] (In the formula, Y is an alkylidene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, -O-, -S-, -SO-, -SO) ２ (This indicates - or -CO-, where R represents an alkyl group having 1 to 10 carbon atoms.)

[0062] The alkylidene group having 1 to 10 carbon atoms may be linear or branched, and preferred examples include ethylidene, isopropylidene, butylidene, and hexylidene groups, with those having 1 to 6 carbon atoms being particularly preferred. The alkylene group having 1 to 10 carbon atoms may be methylene, ethylene, propylene, butylene, pentylene, and hexylene groups, with those having 1 to 6 carbon atoms being particularly preferred. The cycloalkylene group having 5 to 12 carbon atoms may be cyclopentylene, cyclohexylene, and 2-isopropyl-1,4-cyclohexylene groups, with those having 6 to 10 carbon atoms being particularly preferred. The cycloalkylidene group having 5 to 12 carbon atoms may be cyclopentylidene and cyclohexylidene groups, with those having 6 to 10 carbon atoms being particularly preferred. In particular, Y is more preferably a cyclohexylidene group, more preferably an isopropylidene group, and especially preferably an isopropylidene group.

[0063] As described above, R in the phosphonic acid residue of formula (4) is an alkyl group having 1 to 10 carbon atoms, and the number of carbon atoms of the alkyl group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. These groups may be branched. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc., with methyl group, ethyl group, and propyl group being preferred, methyl group and ethyl group being more preferred, and methyl group being particularly preferred.

[0064] As a polyphosphonate homopolymer consisting of repeating units represented by the above formula (4), a polymer composed of 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) residues and phosphonic acid residues is particularly preferred.

[0065] The polycarbonate unit in formula (5) above is composed of a 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) residue and a carbonate residue.

[0066] In the poly(phosphonate-carbonate) copolymer, the molar ratio of the polyphosphonate repeating unit represented by formula (4) to the polycarbonate repeating unit represented by formula (5) (polyphosphonate repeating unit represented by formula (4): polycarbonate repeating unit represented by formula (5)) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30.

[0067] Polyphosphonate compounds are preferably 5% by weight or more in phosphorus content from the viewpoint of flame retardancy, and high flame retardancy can be easily ensured even with a low phosphorus content. The lower limit of the phosphorus content is more preferably 5.5% by weight, even more preferably 6% by weight, and particularly preferably 6.5% by weight. The upper limit of the content is preferably 20% by weight, more preferably 15% by weight, and even more preferably 10% by weight. Polyphosphonate homopolymers and poly(phosphonate-carbonate) copolymers may be included together, and each may be used individually or two or more may be used in any combination and ratio.

[0068] Polyphosphonate compounds can be produced by known methods, such as those described in Japanese Patent Publication No. 56-5823 and Japanese Patent Publication No. 56-104934. For example, they can be obtained by melt transesterification of alkylphosphonate diphenyl and bisphenol in the presence of a known transesterification catalyst. They are also commercially available from FRX Polymers, Inc. in the United States under trade names such as "Nofia HM1100".

[0069] <Component C: Additive for Laser Irradiation 3D Circuit Forming> The laser irradiation 3D circuit forming additive used in the present invention is a compound that, when incorporated, enables 3D circuit forming by laser irradiation. Preferably, the additive is such that 5 parts by weight are added to 100 parts by weight of Teijin PC (Panlite(R) L-1225WP, etc.) resin, and a YVO4 laser with a wavelength of 1064 nm is used, with an output of 1.45 W, a frequency of 80 kHz, and a speed of 2 m / s, and a plating can be formed on the laser-irradiated surface using a standard electroless copper plating process. The laser irradiation 3D circuit forming additive may be a synthetic product or a commercially available product. In addition to commercially available products for laser irradiation 3D circuit forming, the commercially available product may be a substance sold for other purposes. Preferably, the laser irradiation 3D circuit forming additive is a compound containing at least two metals. Examples of such metals include copper, chromium, tin, and antimony. The additive used for laser-irradiated three-dimensional circuit molding may be one type only, or two or more types may be used in combination.

[0070] The average particle size of the laser-irradiated three-dimensional circuit molding additive used in this invention is preferably 0.01 to 50 μm, and more preferably 0.05 to 30 μm. This configuration tends to result in good uniformity of the plated surface when plating is applied. For particle sizes up to about 10 μm, the value is determined by the median diameter (D50) of the particle size distribution measured by X-ray transmission, one of the liquid-phase sedimentation methods, and for particle sizes of 10 μm or more, the value is determined by the median diameter (D50) of the particle size distribution measured by laser diffraction / scattering.

[0071] The content of component C is 3 to 15 parts by weight, preferably 3 to 10 parts by weight, and more preferably 4 to 7 parts by weight, per 100 parts by weight of component A. If the content is less than 3 parts by weight, the plating properties [plating uniformity, plating uniformity (laser condition dependent), and plating adhesion (laser condition dependent)] are insufficient, and if it exceeds 15 parts by weight, the surface appearance deteriorates.

[0072] <Other Components> The polycarbonate resin composition of the present invention utilizes additives used for improvements in thermal stability and aesthetic appeal. These additives are described in detail below.

[0073] (I) Heat stabilizers The polycarbonate resin composition of the present invention may be blended with various known stabilizers. Examples of stabilizers include phosphorus-based stabilizers, hindered phenol-based antioxidants, ultraviolet absorbers, and light stabilizers.

[0074] (I-1) Phosphorus-based stabilizers Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and their esters, as well as tertiary phosphines. Among these, phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferred. The organic group in the acid phosphate compounds may be monosubstituted, disubstituted, or a mixture thereof. The following example compounds corresponding to these compounds may also include any of these.

[0075] Examples of triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphates are preferred. The number of carbon atoms in such trialkyl phosphates is preferably 1 to 22, more preferably 1 to 4. Trimethyl phosphate is a particularly preferred trialkyl phosphate.

[0076] Examples of acid phosphate compounds include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, and bisphenol A acid phosphate. Among these, long-chain dialkyl acid phosphates with 10 or more carbon atoms are preferred because they are effective in improving thermal stability and the acid phosphate itself has high stability.

[0077] Examples of phosphite compounds 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) Examples include bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl 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, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

[0078] Furthermore, other phosphite compounds that react with divalent phenols to form cyclic structures can also be used. Examples include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

[0079] 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 Examples include (2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, with tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite being preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. Such phosphonite compounds can be used in combination with phosphite compounds having aryl groups substituted with two or more alkyl groups, and this is preferable.

[0080] Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0081] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0082] (I-2) Hindered phenol antioxidants Various compounds commonly used in resins can be used as hindered phenol compounds. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl- 4-Hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methylbenzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-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-methyl6-(3-tert-butyl-5 -methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(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-hydroxyphenyl) (4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methyl 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-2,4Examples include 6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

[0083] Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. In particular, 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 antioxidants can be used alone or in combination of two or more.

[0084] It is preferable that either a phosphorus-based stabilizer or a hindered phenol-based antioxidant be included. In particular, it is preferable that a phosphorus-based stabilizer be included, and more preferably that a triorganophosphate compound be included. The content of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 parts by weight, per 100 parts by weight of component A.

[0085] (I-3) UV absorber The polycarbonate resin composition of the present invention may contain a UV absorber. Since the polycarbonate resin composition of the present invention also has a good hue, the inclusion of a UV absorber allows this hue to be maintained for a long period of time even when used outdoors.

[0086] Examples of benzophenone compounds 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-sulfoxytrihydridebenzophenone, 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.

[0087] Examples of benzotriazole derivatives include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-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, and 2-(2-hydroxy-5-tert-octylphenyl)benzotri Examples of polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton include azole, 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-benzoxazine-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer.

[0088] Examples of hydroxyphenyltriazine compounds include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butyloxyphenol. Furthermore, examples include compounds in which the phenyl group of the above example compounds has been replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol.

[0089] Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one).

[0090] Examples of UV absorbers include, specifically, cyanoacrylate-based 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.

[0091] Furthermore, the above-mentioned ultraviolet absorber may also be a polymer-type ultraviolet absorber obtained by copolymerizing such ultraviolet-absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate, by adopting the structure of a monomer compound that can undergo radical polymerization. Examples of the above-mentioned ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.

[0092] Among the above, benzotriazole and hydroxyphenyltriazine types are preferred in terms of ultraviolet absorption capacity, while cyclic iminoester and cyanoacrylate types are preferred in terms of heat resistance and hue. The above ultraviolet absorbers may be used individually or as a mixture of two or more.

[0093] The amount of ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, even more preferably 0.03 to 1 part by weight, and most preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of component A.

[0094] (I-4) Other Heat Stabilizers The polycarbonate resin composition of the present invention may also contain other heat stabilizers besides the phosphorus-based stabilizers and hindered phenol-based antioxidants described above. Such other heat stabilizers are preferably used in combination with either of these stabilizers and antioxidants, and are particularly preferably used in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as those represented 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 Japanese Patent Application Publication No. 7-233160). Such compounds are commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and these compounds can be used. Furthermore, stabilizers obtained by mixing these compounds with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. In the present invention, such pre-mixed stabilizers can also be used. The content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of component A.

[0095] Other examples of 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 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, per 100 parts by weight of component A.

[0096] (II) Release Agents The polycarbonate resin composition of the present invention may further contain known release agents such as fatty acid esters, polyolefin waxes, silicone compounds, fluorine compounds (such as fluorine oils represented by polyfluoroalkyl ethers), paraffin wax, and beeswax, for the purpose of improving productivity during molding and improving the dimensional accuracy of molded products. The polycarbonate resin composition of the present invention has good fluidity, resulting in good pressure propagation and the production of molded products with uniform strain. On the other hand, in the case of molded products with complex shapes that result in high release resistance, there is a risk of deformation of the molded product during release. The incorporation of the above-mentioned specific components solves this problem without impairing the properties of the polycarbonate resin composition.

[0097] Such fatty acid esters are esters of an aliphatic alcohol and an aliphatic carboxylic acid. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol with two or more carbon atoms. The number of carbon atoms in the alcohol is preferably 3 to 32, more preferably 5 to 30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Among these, saturated aliphatic carboxylic acids are preferred. The fatty acid esters of the present invention are preferred in that the total ester (full ester) exhibits excellent thermal stability at high temperatures. The acid value of the fatty acid ester of the present invention is preferably 20 or less (may take substantially 0). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Furthermore, the iodine value of the fatty acid ester is preferably 10 or less (may take substantially 0). These properties can be determined by the method specified in JIS K 0070.

[0098] Examples of polyolefin waxes include ethylene homopolymers, 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, all having a molecular weight of 1,000 to 10,000. The molecular weight is the number-average molecular weight measured in terms of standard polystyrene by GPC (gel permeation chromatography). The upper limit of this number-average molecular weight is more preferably 6,000, and even more preferably 3,000. The number of carbon atoms in the α-olefin component of the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. A preferred polyolefin wax is an ethylene homopolymer or a copolymer 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, more preferably 10 mol% or less. A commercially available product known as polyethylene wax is preferably used.

[0099] The release agent content 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, per 100 parts by weight of component A.

[0100] (III) Anti-dripping agent As an anti-dripping agent, a fibril-forming fluorine-containing polymer is preferably used, and polytetrafluoroethylene (fibrillated PTFE) is particularly preferred. The fibrillated PTFE may be fibrillated PTFE alone, or a mixed form of fibrillated PTFE, i.e., a polytetrafluoroethylene mixture consisting of fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has an extremely high molecular weight and tends to bond with other PTFE particles to form fibers under external forces 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. This number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380°C, as disclosed, for example, in Japanese Patent Application Publication No. 6-145520. That is, the fibrillated PTFE has a melt viscosity at 380°C measured by the method described in the publication, which is in the range of 107 to 1013 poise, preferably in the range of 108 to 1012 poise. Such fibrillated PTFE can be used in solid form as well as in aqueous dispersion form. Furthermore, it is also possible to use a PTFE mixture in the form of a mixture with other resins to improve dispersibility in the resin and to obtain even better flame retardancy and mechanical properties.

[0101] Furthermore, as disclosed in Japanese Patent Publication No. 6-145520, a structure having such fibrillated PTFE as a core and low molecular weight polytetrafluoroethylene as a shell is also preferably used.

[0102] Examples of commercially available fibrillated PTFE include Teflon® 6J from Mitsui DuPont Fluorochemicals Ltd., and Polyflon MPa FA500 and F-201L from Daikin Chemical Industries, Ltd.

[0103] As for the mixed form of fibrillated PTFE, (1) a method of mixing an aqueous dispersion of fibrillated PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-aggregated mixture (methods described in Japanese Patent Publication No. 60-258263, Japanese Patent Publication No. 63-154744, etc.), (2) a method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (method described in Japanese Patent Publication No. 4-272957), (3) a method of uniformly mixing an aqueous dispersion of fibrillated PTFE with an organic polymer particle solution and obtaining a co-aggregated mixture from such mixture (4) A method of removing each medium simultaneously (as described in Japanese Patent Publication No. 06-220210, Japanese Patent Publication No. 08-188653, etc.), (5) A method of polymerizing monomers that form an organic polymer in an aqueous dispersion of fibrillated PTFE (as described in Japanese Patent Publication No. 9-95583), and (6) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, further polymerizing vinyl monomers in the mixed dispersion, and then obtaining a mixture (as described in Japanese Patent Publication No. 11-29679, etc.) can be used.

[0104] Examples of commercially available fibrillated PTFE in these mixed forms include the Metabren A series, represented by Mitsubishi Rayon Co., Ltd.'s "Metablen A3000" (product name), "Metablen A3700" (product name), and "Metablen A3800" (product name), Shine Polymer's SN3300B7 (product name), and GE Specialty Chemicals' "BLENDEX B449" (product name).

[0105] The proportion of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and most preferably 20% to 80% by weight, of 100% by weight of the mixture.

[0106] When the proportion of fibrillated PTFE in the mixed form is within this range, good dispersibility of the fibrillated PTFE can be achieved. The content of fibrillated PTFE is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 0.5 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of component A. If the content is less than 0.005 parts by weight, the flame retardant effect is difficult to obtain, and if it exceeds 20 parts by weight, the thermal shock resistance (electromagnetic shielding properties) may decrease.

[0107] (IV) Dyes and Pigments The polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles that exhibit diverse design properties. Examples of dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can also be blended with metallic pigments to obtain better metallic colors. Aluminum powder is suitable as a metallic pigment. In addition, by blending with fluorescent whitening agents or other fluorescent dyes that emit light, it is possible to provide even better design effects that take advantage of the luminescent color.

[0108] (V) Fluorescent Whitening Agent In the polycarbonate resin composition of the present invention, the fluorescent whitening agent is not particularly limited as long as it is used to improve the color tone of the resin, etc. to white or bluish-white, and examples include stilbene-based, benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specifically, examples include CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Company, and "Hakkoll PSR" manufactured by Showa Chemical Co., Ltd. Here, the fluorescent whitening agent has the effect of absorbing the ultraviolet energy of light rays and radiating this energy to the visible region. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, and more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of component A. Even if the amount exceeds 0.1 parts by weight, the effect of improving the color tone of the composition may be small.

[0109] (VI) Compounds having heat-absorbing properties The polycarbonate resin composition of the present invention may contain compounds having heat-absorbing properties. Suitable examples of such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide, and titanium oxide, various metal compounds with excellent near-infrared absorption properties such as metal boride-based and tungsten oxide-based near-infrared absorbers such as lanthanum boride, cerium boride, and tungsten boride, and carbon fillers. As an example of such a phthalocyanine-based near-infrared absorber, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily obtainable. Examples of carbon fillers include carbon black, graphite (including both natural and artificial), and fullerene, with carbon black and graphite being preferred. These can be used individually or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and even more preferably 0.001 to 0.07 parts by weight, per 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 in the polycarbonate resin composition of the present invention is preferably in the range of 0.1 to 200 ppm (by weight), and more preferably in the range of 0.5 to 100 ppm.

[0110] (VII) Light Diffuser The polycarbonate resin composition of the present invention can be given a light diffusing effect by incorporating a light diffusing agent. Examples of such light diffusing agents include polymer microparticles, inorganic microparticles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer microparticles are already known as light diffusing agents for thermoplastic resins. More preferably, examples include acrylic crosslinked particles with a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane. Examples of light diffusing agent shapes include spherical, disc-shaped, columnar, and amorphous. Such spherical shapes do not need to be perfect spheres and include deformed ones, and such columnar shapes include cubes. Preferred light diffusing agents are spherical, and the more uniform the particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 3 parts by weight, per 100 parts by weight of component A. Two or more types of light diffusing agents can be used in combination.

[0111] (VIII) White pigment for high light reflectivity The polycarbonate resin composition of the present invention can be given a light reflectivity effect by incorporating a white pigment for high light reflectivity. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment. The content of such a white pigment for high light reflectivity is preferably 3 to 30 parts by weight, and more preferably 8 to 25 parts by weight, per 100 parts by weight of component A. Two or more types of white pigments for high light reflectivity can be used in combination.

[0112] (IX) Antistatic agent The polycarbonate resin composition of the present invention may require antistatic performance, and in such cases, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) phosphonium aryl sulfonates represented by phosphonium dodecylbenzenesulfonate salt, phosphonium alkyl sulfonates and other phosphonium borate salts, and phosphonium borate salts such as phosphonium tetrafluoroborate salt. The content of the phosphonium salt is appropriately 5 parts by weight or less per 100 parts by weight of component A, preferably in the range of 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably 1.5 to 3 parts by weight. Examples of antistatic agents include (2) alkali (earth) metal salts of organic sulfonates such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. As mentioned above, such metal salts are also used as flame retardants. More specifically, examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of alkali (earth) metal salt of organic sulfonic acid is appropriately 0.5 parts by weight or less per 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight. Alkali metal salts such as potassium, cesium, and rubidium are particularly preferred.

[0113] Examples of antistatic agents include (3) ammonium alkyl sulfonates and ammonium aryl sulfonates, which are organic ammonium sulfonates. The amount of the ammonium salt is appropriate to be 0.05 parts by weight or less per 100 parts by weight of the components consisting of components A and B. Examples of antistatic agents include (4) polymers containing a poly(oxyalkylene) glycol component, such as polyether ester amide, as a constituent component. The amount of the polymer is appropriate to be 5 parts by weight or less per 100 parts by weight of component A.

[0114] (X) Fillers The polycarbonate resin composition of the present invention may be compounded with various fillers known as reinforcing fillers. Various fibrous fillers, plate-shaped fillers and granular fillers can be used as such fillers. Here, plate-shaped fillers are fillers whose shape is plate-like (including those with uneven surfaces or those with curved plates). Granular fillers are fillers of shapes other than these, including irregular shapes.

[0115] Examples of fibrous fillers include glass fibers, metal-coated glass fibers, and glass-milled fibers. The glass fibers that form the base of such fibrous glass fillers are obtained by rapidly cooling molten glass while stretching it in various ways to form a predetermined fibrous shape. The rapid cooling and stretching in this case are not particularly limited. In addition to a circular cross-section, the shape of the cross-section may be other than a perfect circle, such as an ellipse, cocoon shape, flattened shape, and trefoil shape. Furthermore, a mixture of circular and non-circular shapes is also acceptable. A flattened shape is defined as a shape in which the average 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 ratio of major axis to minor axis (major axis / minor axis) is 1.5 to 8, preferably 2 to 6, and even more preferably 2.5 to 5.

[0116] Furthermore, the average fiber diameter of fibrous glass fillers having a high aspect ratio, such as glass fibers, is preferably 1 to 25 μm, and more preferably 3 to 17 μm. When a filler with an average fiber diameter in this range is used, it may be possible to achieve good mechanical strength without impairing the appearance of the molded product. In addition, the fiber length of the high aspect ratio fibrous glass filler is preferably 60 to 500 μm, more preferably 100 to 400 μm, and particularly preferably 120 to 350 μm, as the number average fiber length in the polycarbonate resin composition. The number average fiber length is calculated by an image analysis device from images obtained by observing the residue of the filler collected by processing such as high-temperature ashing of the molded product, dissolution with a solvent, and decomposition with chemicals using an optical microscope. Furthermore, in calculating this value, the fiber diameter is used as a guideline, and fibers with a length less than that are not counted. The aspect ratio of the high aspect ratio fibrous glass filler is preferably 10 to 200, more preferably 15 to 100, and even more preferably 20 to 50. The aspect ratio of the filler is the value obtained by dividing the average fiber length by the average fiber diameter.

[0117] Glass milled fibers are typically manufactured by shortening glass fibers using a pulverizer such as a ball mill. The aspect ratio of fibrous glass fillers having a low aspect ratio, such as glass milled fibers, is preferably 2 to 10, more preferably 3 to 8. The fiber length of the low aspect ratio fibrous glass filler is preferably 5 to 150 μm, more preferably 9 to 80 μm, as the number average fiber length in the polycarbonate resin composition. The average fiber diameter is preferably 1 to 15 μm, more preferably 3 to 13 μm.

[0118] Preferred examples of plate-shaped fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-shaped fillers in which dissimilar materials such as metals or metal oxides are surface-coated to these fillers. The particle size is preferably in the range of 0.1 to 300 μm. In the region up to about 10 μm, this particle size is the value obtained by 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 from 10 to 50 μm, this is the value obtained by the median diameter (D50) of the particle size distribution measured by the laser diffraction / scattering method; and in the region from 50 to 300 μm, this is the value obtained by the vibrating sieving method. This particle size is the particle size in the polycarbonate resin composition. The plate-shaped filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based materials, or it may be a granulated product that has been bundled or compressed 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.

[0119] (XI) Elastomer The polycarbonate resin composition of the present invention may also contain an elastomer in small amounts, within a range that does not impair the effects of the present invention and that allows the effects of the present invention to be exhibited. The amount of elastomer added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and most preferably 3 parts by weight or less, per 100 parts by weight of component A. Examples of elastomers include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and core-shell type elastomers such as MBS (methyl methacrylate / styrene / butadiene) rubber, MB (methyl methacrylate / butadiene) rubber, and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

[0120] (XII) Laser Marking Additive The polycarbonate resin composition of the present invention may contain a laser marking additive. By blending the laser marking additive with the laser irradiation three-dimensional circuit molding additive in the polycarbonate resin composition of the present invention, the composition absorbs lasers more readily than a polycarbonate resin composition that does not contain a laser marking additive. As a result, when a resin molded product is formed, the resin on the surface portion of the resin molded product that has been irradiated with a laser is removed, and the laser irradiation three-dimensional circuit molding additive is more easily exposed. The exposed laser irradiation three-dimensional circuit molding additive is more easily irradiated with a laser, and as a result, the polycarbonate resin composition of the present invention can appropriately form a plating layer on the surface of a resin molded product even under a wider range of laser irradiation conditions than conventional methods. In particular, since plating can be formed even with a small amount of laser irradiation, productivity can be improved.

[0121] The laser marking additive used in this invention is not particularly limited. For example, one example is a laser marking additive that can be added in 2 parts by weight to a polycarbonate resin, a film with a thickness of 200 μm formed by press, a plate with carbon black added to it placed under the resulting film, and when a laser under predetermined conditions is applied, it is possible to print on the surface of the film, but not on the plate with carbon black added.

[0122] Examples of such laser marking additives include compounds comprising oxides containing copper and molybdenum, oxides containing bismuth and gallium and / or neodymium, pigments in which a flaky mica substrate is coated with tin oxide doped with antimony, arsenic, bismuth, copper, gallium, germanium, or their oxides, polymeric substances to which copper monophosphate or molybdenum oxide is added, and lower-order titanium oxide and / or carbon black. Furthermore, only one type of laser marking additive may be used, or two or more types may be used in combination.

[0123] The average particle size of the laser marking additive used in the present invention is preferably 0.01 to 50 μm, and more preferably 0.1 to 10 μm. For particle sizes up to about 10 μm, this refers to the value of the median diameter (D50) of the particle size distribution measured by X-ray transmission, one of the liquid phase sedimentation methods, and for particles larger than 10 μm, it refers to the value of the median diameter (D50) of the particle size distribution measured by laser diffraction / scattering.

[0124] The content of the laser marking additive is preferably 30 to 200 parts by weight, more preferably 40 to 150 parts by weight, and even more preferably 50 to 100 parts by weight, per 100 parts by weight of component A. If the content is less than 30 parts by weight, the adhesion of the metal thin film may not be sufficient, and if it exceeds 200 parts by weight, the strength may decrease and the dielectric properties may increase.

[0125] (XIII) Flame retardants The resin composition of the present invention may use various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins, in combination with polyphosphonate compounds. Preferably, (i) halogen-based flame retardants (e.g., brominated polycarbonate compounds), (ii) metal salt-based flame retardants (e.g., alkali (earth) metal salts of organic sulfonates, metal borate salt-based flame retardants, and metal stainate salt-based flame retardants), and (iii) silicone-based flame retardants consisting of silicone compounds. The compound blend used as a flame retardant not only improves flame retardancy but also brings about improvements in properties such as antistatic properties, fluidity, rigidity, and thermal stability, depending on the properties of each compound.

[0126] The flame retardant content is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and even more preferably 0.08 to 25 parts by weight, per 100 parts by weight of component A. If the flame retardant content is less than 0.01 parts by weight, sufficient flame retardancy may not be obtained, and if it exceeds 30 parts by weight, the mechanical properties may deteriorate significantly.

[0127] (XIV) Other Additives The polycarbonate resin composition of the present invention may contain other fluid modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and photochromic agents.

[0128] <Regarding the production of the polycarbonate resin composition> The polycarbonate resin composition of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. In producing such pellets, the above-mentioned various reinforcing fillers and additives can also be incorporated.

[0129] <Regarding the manufacture of molded products> The polycarbonate resin composition of the present invention can be used to manufacture various molded products by injection molding pellets manufactured as described above. Furthermore, it is also possible to directly manufacture sheets, films, irregularly shaped extruded products, direct blow molded products, and injection molded products from the polycarbonate resin composition melted and kneaded in an extruder without going through pellets. In such injection molding, molded products can be obtained using injection molding methods such as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by injection of supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding. Furthermore, the polycarbonate resin composition of the present invention can also be used in the form of various irregularly shaped extruded products, sheets, and films by extrusion molding. Inflation molding, calendering, and casting methods can also be used for molding sheets and films. Furthermore, by applying specific stretching operations, it is possible to mold it as a heat-shrinkable tube. The polycarbonate resin composition of the present invention can also be molded into a product by rotational molding or blow molding. This molded product is useful as a circuit molded product for communication equipment.

[0130] <Method for Manufacturing Circuit Molded Products for Communication Devices with Circuits> Circuit molded products for communication devices of the present invention can have circuits such as antennas directly formed on them using laser irradiation three-dimensional circuit molding technology. Specifically, a part of the surface of the circuit molded product for communication devices of the present invention is irradiated with laser light, thereby reducing the C component to form a catalyst nucleus, and then selective plating is performed on the circuit molded product for communication devices having the catalyst nucleus, thereby directly forming a circuit on the circuit molded product for communication devices without an adhesive layer.

[0131] The embodiments for carrying out the present invention will be a combination of preferred ranges of the above requirements, but representative examples are described in the following embodiments. Of course, the present invention is not limited to these embodiments.

[0132] Examples and comparative examples of the present invention will be described in detail below, but the present invention is not limited thereto. The measurement items in the examples were measured using the methods described below.

[0133] 1. Evaluation of aromatic polycarbonate resins (i) Viscosity-average molecular weight (Mv) Specific viscosity (η) calculated by the following formula ＳＰ The specific viscosity (η) was determined using an Ostwald viscometer from a solution prepared by dissolving aromatic polycarbonate resin in 100 ml of methylene chloride at 20°C. ＳＰ ) = (t - t ０ ) / t ０ [t ０ [where θ is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall] The specific viscosity (η) was determined. ＳＰ The viscosity-average molecular weight Mv was calculated from 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

[0134] 2. Evaluation of the resin composition (i) Surface appearance The surface appearance of a 50 mm × 50 mm × 2 mm thick plate-shaped test piece obtained by the method described below was visually observed and evaluated as follows. The evaluation results are shown in Table 2. Note that appearance defects due to injection molding include silver, flow marks, and roughness of the surface appearance. A: No appearance defects were observed. B: Appearance defects caused by injection molding were partially observed. C: Appearance defects caused by injection molding were observed.

[0135] (ii) Plating Uniformity A 50 mm x 50 mm x 2 mm thick plate-shaped test piece obtained by the method described below was plated under the following conditions. Plating performance was evaluated by visually determining the thickness of the metal thin film plated within a predetermined time, as follows. The evaluation results are shown in Table 2. A: The metal thin film is uniformly thick throughout. (Practical level) B: The metal thin film is thick, but somewhat uneven. (Practical level) C: The metal thin film is present, but uneven. (Not meeting practical level)

[0136] (iii) Plating uniformity (laser condition dependent) Plate-shaped test pieces measuring 50 mm x 50 mm x 2 mm thick obtained by the method described below were plated under the 30 conditions listed in Table 1. Plating performance was evaluated by visually determining the thickness of the metal thin film plated within a predetermined time, as follows. The evaluation results are shown in Table 2. A: All test pieces plated under the 30 conditions had a uniformly thick metal thin film applied throughout. B: Among the test pieces plated under the 30 conditions, there were 1 to 5 samples where the metal thin film was applied but uneven. C: Among the test pieces plated under the 30 conditions, there were 6 or more samples where the metal thin film was applied but uneven.

[0137]

[0138] (iv) Plating adhesion (laser condition dependent) Using plate-shaped test pieces measuring 50 mm x 50 mm x 2 mm thick obtained by the method described below, plating was performed under the 30 conditions listed in Table 1, and the adhesion between the metal thin film and the resin was evaluated as follows. The evaluation results are shown in Table 2. The cross-section peel test was performed in accordance with JIS K5600 General Test Methods for Paints, 4-6. A: No peeling occurred in the cross-section peel test for all test pieces plated under the 30 conditions. B: Among the test pieces plated under the 30 conditions, 1 to 5 samples showed peeling in the cross-section peel test. C: Among the test pieces plated under the 30 conditions, 6 or more samples showed peeling in the cross-section peel test.

[0139] (v) Flame retardancy Tests were conducted using test specimens with thicknesses of 0.6 mm, 1.0 mm, and 1.5 mm, prepared according to the UL94 standard using the method described below. Based on the test results, the flame retardancy was evaluated to one of the following grades: UL-94 V-0, V-1, V-2, or Not-V (out of specification). The flame retardancy of the polycarbonate resin composition of the present invention must be V-0 for test specimens with thicknesses of 0.5 mm, 1.0 mm, or 1.5 mm.

[0140] [Examples 1-10, Comparative Examples 1-6] (i) Preparation of evaluation test specimens Polycarbonate resin, polyphosphonate compound, laser irradiation 3D circuit molding additive, and various other additives were mixed in a blender in the amounts shown in Table 2, and then melt-kneaded using a vented twin-screw extruder to obtain pellets. For each of the additives used, a premix was prepared with the polycarbonate resin at a concentration of 10 to 100 times the amount of each additive, and then the entire mixture was mixed using a blender. Extrusion was performed using a 30 mmφ vented twin-screw extruder (TEX30α-38.5BW-3V manufactured by Japan Steel Works Ltd.), with a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa. The extrusion temperature was 300°C from the first supply port to the second supply port, and 310°C from the second supply port to the die section, and melt-kneaded to obtain pellets. Polycarbonate resin and additives were supplied to the extruder from the first supply port. The first feed port referred to here is the feed port furthest from the die. The obtained pellets were dried at 120°C for 5 hours in a hot air circulation dryer, and then 50 mm x 50 mm x 2 mm thick plate-shaped test pieces and UL94 test pieces were molded using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) under molding conditions of cylinder temperature 300°C and mold temperature 80°C.

[0141] (ii) Plating conditions for "(ii) Evaluation of plating uniformity" As a plating process, a plate-shaped test piece measuring 50 mm x 50 mm x 2 mm thick was printed with a width of 5 mm using a 1064 nm YVO4 laser with a Keyence MDX-2000 under the conditions of frequency 100 kHz, speed 2 m / s, output 5 W, laser spot diameter 60 μm, and overlap 30 μm, and then the following operations (a) to (h) were performed. (a) Degreasing (5 minutes at 45°C) OPC Cleaner MIC* 150 ml / L (b) Ultrasonic water washing (2 minutes at room temperature) (c) Electroless copper (55°C, 10 minutes) OPC Copper MIC-ST* (d) Water washing (1 minute) (e) Activation (30°C, 1 minute) ICP Accelerator 200 ml / L, 35% hydrochloric acid 85 ml / L (f) Water washing (1 minute) (g) Electroless nickel (80°C, 10 minutes) ICP Nicolon GM-M 120 ml / L, ICP Nicolon GM-1 50 ml / L (h) Drying (The treatment solutions marked with * are product names of Okuno Pharmaceutical Co., Ltd.)

[0142] (iii) Plating conditions for evaluation of "(iii) Plating uniformity (laser condition dependent)" and "(iv) Plating adhesion (laser condition dependent)": As a plating process, a plate-shaped test piece measuring 50 mm x 50 mm x 2 mm thick was printed with a width of 5 mm using a 1064 nm YVO4 laser with a laser spot diameter of 60 μm and overlap of 30 μm under the 30 conditions (frequency, speed, and output) listed in Table 1, using a Keyence MDX-2000. Then, operations (a) to (h) above were performed.

[0143] The components indicated by symbols in Table 2 are as follows: (Component A) A-1: ​​Aromatic polycarbonate resin (Aromatic polycarbonate resin powder with a viscosity-average molecular weight of 22,400, produced by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, Panlite L-1225WP (product name)) A-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity-average molecular weight of 23,500, PDMS content of 8.4%, PDMS degree of polymerization of 37) A-3: In a reactor equipped with a polycarbonate resin thermometer, stirrer, and reflux condenser obtained by the manufacturing method described below, 4,555 parts of 48% sodium hydroxide aqueous solution and 22,730 parts of deionized water were charged. 298 parts of 9,9-bis(4-hydroxyphenyl)fluorene, 820 parts of 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,799 parts of 2,2-bis(4-hydroxyphenyl)propane, 71.0 parts of p-tert-butylphenol, and 7.94 parts of hydrosulfite were dissolved in these mixtures. Then, 13,415 parts of methylene chloride were added, and under stirring, 2,000 parts of phosgene were blown in over approximately 70 minutes at 15-25°C. After the phosgene was blown in, 650 parts of 48% sodium hydroxide aqueous solution and 87.6 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.94 parts of triethylamine were added, and the reaction was completed by stirring at 28-35°C for 1 hour. After the reaction was complete, the product was diluted with methylene chloride and washed with water, then hydrochloric acid was added to make it acidic and washed with water, and the washing with water was repeated until the conductivity of the aqueous phase was approximately the same as that of deionized water to obtain a methylene chloride solution of polycarbonate resin. Next, this solution was passed through a filter with a mesh size of 0.3 μm and then dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing part, and the polycarbonate resin was flakebed while the methylene chloride was distilled off, and the liquid-containing flakes were subsequently crushed and dried to obtain a powdered polycarbonate resin.

[0144] (Component B) B-1: Polyphosphonate homopolymer consisting of repeating units represented by formula (4) above (Nofia HM1100, manufactured by FRX Polymer Co., Ltd.) B-2: Poly(phosphonate-carbonate) copolymer consisting of repeating units represented by formula (4) and formula (5) above (Nofia C6000, manufactured by FRX Polymer Co., Ltd.) B-3 (Comparative Example): Aromatic condensed phosphate ester (PX200, manufactured by Daihachi Kogyo Co., Ltd.) B-4 (Comparative Example): Phenyl phosphonitrile ester (FP-110T, manufactured by Fushimi Pharmaceutical Co., Ltd.)

[0145] (Component C) C-1: Composite oxide of copper and chromium (Black 1G, manufactured by Shepherd Color Japan Inc.) C-2: Titanium oxide coated with antimony tin oxide (W-1, manufactured by Mitsubishi Materials Corporation)

[0146] (Other ingredients) E: Talc (manufactured by Katsumitsuyama Mining Co., Ltd., TK-RC) F: Polytetrafluoroethylene resin (manufactured by Daikin Industries, Ltd., FA500H) S-1: Hindered phenol antioxidant (manufactured by ADEKA Corporation, ADEKA Stab AO-50) S-2: Phosphate antioxidant (manufactured by ADEKA Corporation, ADEKA Stab 2112) CB: Carbon black (manufactured by Koshigaya Chemical Industries Co., Ltd., RB-90003S)

[0147]

[0148] Table 2 shows that the formulation of the present invention yields a polycarbonate resin composition with excellent appearance, flame retardancy, and plateability during circuit formation.

Claims

1. A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A), (B) 1 to 15 parts by weight of polyphosphonate compound (component B), and (C) 3 to 15 parts by weight of laser irradiation additive for three-dimensional circuit molding (component C).

2. The polycarbonate resin composition according to claim 1, wherein component A is a polycarbonate resin containing 1 to 100% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component A-1).

3. The polycarbonate resin composition according to claim 2, wherein the polydiorganosiloxane content in the polycarbonate-polydiorganosiloxane copolymer resin used as component A-1 is 0.1 to 50% by weight.

4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the component B is a polyphosphonate homopolymer composed of repeating units represented by the following formula (4) or a poly(phosphonate-carbonate) copolymer composed of repeating units represented by the following formula (4) and the following formula (5). (In the formula, Y represents an alkylidene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, -O-, -S-, -SO-, -SO ２ -, or -CO-, and R represents an alkyl group having 1 to 10 carbon atoms.) 5. The polycarbonate resin composition according to claim 4, wherein component B has a phosphorus content of 5% by weight or more and 20% by weight or less.

6. The polycarbonate resin composition according to any one of claims 1 to 5, wherein component C is a laser-irradiated three-dimensional circuit molding additive containing at least two metals.

7. The polycarbonate resin composition according to claim 6, wherein component C is a compound comprising at least two selected from the group consisting of copper, chromium, tin, and antimony.

8. A polycarbonate resin composition according to any one of claims 1 to 7, for use in circuit molding.

9. A circuit molded article for communication equipment, comprising the polycarbonate resin composition for circuit molding described in claim 8.

10. A method for manufacturing a circuit molded product for communication equipment with a circuit, comprising: irradiating a part of the surface of the circuit molded product for communication equipment described in claim 9 with laser light to reduce the C component and form a catalyst nucleus; and performing selective plating on the circuit molded product for communication equipment having the catalyst nucleus, thereby forming a circuit on the circuit molded product for communication equipment.

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