Polycarbonate resin composition and molded article obtained by molding the same

Abstract

To provide a polycarbonate resin composition excellent in tensile strength, moisture-heat resistance, chemical resistance, processability, flame retardancy, and fluidity.SOLUTION: A polycarbonate resin composition contains, per 100 pts.wt. of (A) an aromatic polycarbonate resin (component A): (B) 20 to 130 pts.wt. of glass fibers (component B); (C) 1 to 10 pts.wt. of a phenoxy resin and / or an epoxy resin (component C); (D) 0.01 to 3 pts.wt. of a phosphorus-based stabilizer (component D); (E) 5 to 35 pts.wt. of a bromine-based flame retardant (component E); (F) 1 to 10 pts.wt. of a phosphazene compound (component F); and (G) 0.1 to 3 pts.wt. of a drip-preventing agent (component G). Component B contains at least one compound selected from the group consisting of a surface treating agent and a sizing agent. A gas component obtained by heating component B at 400°C for 12 seconds contains a compound represented by the following general formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition containing an aromatic polycarbonate resin, a surface treatment agent and / or a sizing agent, and which, when heated at 400°C for 12 seconds, produces a gas containing a specific compound, the gas comprising glass fiber, a phenoxy resin and / or an epoxy resin, a phosphorus-based stabilizer, a bromine-based flame retardant, a phosphazene compound, and an anti-drip agent, and to a molded article obtained by molding the same. More specifically, the present invention relates to a polycarbonate resin composition that has excellent tensile strength, moist heat resistance, chemical resistance, processability, flame retardancy, and flowability, and is suitable for components that require high strength under various environments. [Background technology]

[0002] Polycarbonate resin is a resin with excellent heat resistance, impact resistance, and dimensional stability, and is widely used in fields such as electrical and electronic components, mechanical components, automotive components, and office equipment components. In recent years, as products have become more highly functional and have longer lifespans, there is a strong demand for resin materials that have high strength, and that can maintain that strength even when used for long periods of time in humid and hot environments or environments where they come into contact with chemicals.

[0003] Conventionally, methods known for improving the mechanical properties such as tensile strength of polycarbonate resins include adding a fibrous filler (Patent Document 1), and adding a fibrous filler and an adhesion promoter to further improve strength (see Patent Documents 2 and 3). However, while these methods improve mechanical properties such as tensile strength, they do not mention moist heat resistance and chemical resistance, and therefore do not fully disclose a method for solving such technical problems. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 2683662 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-292953 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-221072 Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the above, an object of the present invention is to provide a polycarbonate resin composition that is excellent in tensile strength, moist heat resistance, chemical resistance, processability, flame retardancy and flowability, and is suitable for use in members that must maintain high strength even in moist and hot environments or environments in contact with chemicals. [Means for solving the problem]

[0006] As a result of intensive research conducted by the present inventors to solve the above-mentioned problems, they found that a polycarbonate resin composition excellent in tensile strength, moist heat resistance, chemical resistance, processability, flame retardancy and fluidity can be obtained by adding a surface treatment agent and / or a sizing agent to an aromatic polycarbonate resin and heating the resin at 400°C for 12 seconds to produce a gas component containing a specific compound, and then blending the resulting mixture with glass fiber, phenoxy resin and / or epoxy resin, a phosphorus-based stabilizer, a bromine-based flame retardant, a phosphazene compound and an anti-drip agent, thereby completing the present invention.

[0007] That is, the present invention is as follows. 1. A polycarbonate resin composition comprising 100 parts by weight of (A) aromatic polycarbonate resin (component A), 20 to 130 parts by weight of (B) glass fiber (component B), 1 to 10 parts by weight of (C) phenoxy resin and / or epoxy resin (component C), 0.01 to 3 parts by weight of (D) phosphorus-based stabilizer (component D), 5 to 35 parts by weight of (E) bromine-based flame retardant (component E), 1 to 10 parts by weight of (F) phosphazene compound (component F), and 0.1 to 3 parts by weight of (G) anti-drip agent (component G), wherein component B contains at least one compound selected from the group consisting of surface treatment agents and sizing agents, and the gas component obtained by heating component B at 400°C for 12 seconds contains a compound represented by the following general formula (1): [ka] [In the above general formula (1), n ​​is an integer of 1 to 10, each X independently represents an alkylene group having 1 to 5 carbon atoms, and each Y independently represents an alkyl group having 1 to 5 carbon atoms.] 2. The polycarbonate resin composition according to item 1 above, wherein X in the compound represented by general formula (1) is an alkylene group having 3 carbon atoms. 3. The polycarbonate resin composition according to item 1 or 2 above, wherein the compound represented by general formula (1) is 4,8,12,16-tetraoxaeicosan-1-ol. 4. The polycarbonate resin composition according to any one of items 1 to 3 above, wherein component C is a bisphenol A phenoxy resin and / or a bisphenol A epoxy resin. 5. The polycarbonate resin composition according to any one of items 1 to 4 above, which contains 1 to 20 parts by weight of (H) a liquid crystal polyester resin (component H) per 100 parts by weight of component A. 6. The polycarbonate resin composition according to item 5 above, wherein component H is a liquid crystal polyester resin containing repeating units derived from p-hydroxybenzoic acid and repeating units derived from 6-hydroxy-2-naphthoic acid. 7. A molded article obtained by molding the polycarbonate resin composition according to any one of items 1 to 6 above.

[0008] The present invention will be described in detail below.

[0009] (Component A: aromatic polycarbonate resin) The aromatic polycarbonate resin used as component A in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0010] Representative examples of dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylene) Examples of suitable dihydric phenols include 4,4'-(m-phenylenediisopropylidene)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among these, bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0011] In the present invention, in addition to bisphenol A-based polycarbonates, which are general-purpose polycarbonates, it is also possible to use special polycarbonates produced using other dihydric phenols as the A component.

[0012] For example, polycarbonates (homopolymers or copolymers) containing 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 dihydric phenol component are suitable for applications requiring particularly strict resistance to dimensional change due to water absorption and dimensional stability. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, and particularly 10 mol % or more, of the total dihydric phenol components constituting the polycarbonate.

[0013] In particular, when high rigidity and better hydrolysis resistance are required, it is particularly suitable that the component A constituting the resin composition is a copolymer polycarbonate of the following (1) to (3). (1) A copolymer polycarbonate in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and BCF accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate in which, based on 100 mol% of the dihydric phenol components constituting the polycarbonate, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, and even more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, and even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate in which, based on 100 mol% of the dihydric phenol components constituting the polycarbonate, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and Bis-TMC accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%).

[0014] These special polycarbonates may be used alone or in a suitable mixture of two or more kinds, or may be used in a mixture with the commonly used bisphenol A polycarbonate.

[0015] The production methods and properties of these special polycarbonates are described in detail in, for example, Japanese Patent Application Laid-Open Nos. 6-172508, 8-27370, 2001-55435 and 2002-117580.

[0016] Among the various polycarbonates mentioned above, those having water absorption and glass transition temperature (Tg) within the following ranges by adjusting the copolymer composition, etc., have good hydrolysis resistance of the polymer itself and are remarkably excellent in low warpage after molding, and are therefore particularly suitable in fields where dimensional stability is required. (i) a polycarbonate 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) Polycarbonate having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0017] Here, the water absorption rate of polycarbonate is a value measured by using a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm and immersing it in water at 23°C for 24 hours in accordance with ISO 62-1980. Furthermore, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0018] Carbonate precursors that can be used include carbonyl halides, carbonic acid diesters, and haloformates, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0019] When producing an aromatic polycarbonate resin by interfacial polymerization of the dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant to prevent oxidation of the dihydric phenol, etc. may be used as needed. The aromatic polycarbonate resin of the present invention also includes branched polycarbonate resins copolymerized with a trifunctional or higher polyfunctional aromatic compound, polyester carbonate resins copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, copolymerized polycarbonate resins copolymerized with a bifunctional alcohol (including alicyclic), and polyester carbonate resins copolymerized with such bifunctional carboxylic acid and bifunctional alcohol. The resulting aromatic polycarbonate resins may also be a mixture of two or more of the resulting aromatic polycarbonate resins.

[0020] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 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, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0021] The structural units derived from a polyfunctional aromatic compound in the branched polycarbonate preferably account for 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 the structural units derived from a dihydric phenol and the structural units derived from such a polyfunctional aromatic compound.

[0022] In particular, in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, and even more preferably 0.01 to 0.8 mol %, based on the total of 100 mol % including the structural units derived from the dihydric phenol. 1 It can be calculated by H-NMR measurement.

[0023] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The bifunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0024] Reaction modes for producing aromatic polycarbonate resins, such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, are well known in various literatures and patent publications.

[0025] In producing the polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the aromatic polycarbonate resin is not particularly limited, but is preferably 1×10 4 ~5×10 4and more preferably 1.4 × 10 4 ~3×10 4 , and more preferably 1.4 × 10 4 ~2.4×10 4 and particularly preferably 1.7 × 10 4 ~2.1×10 4 The viscosity average molecular weight is 1 × 10 4 Polycarbonate resins with a viscosity average molecular weight of less than 5 × 10 may not be able to achieve good mechanical properties, especially high tensile strength. 4 Resin compositions obtained from aromatic polycarbonate resins exceeding this range may be inferior in versatility due to poor flowability during injection molding.

[0026] The aromatic polycarbonate resin may be obtained by mixing resins having a viscosity average molecular weight outside the above range. 4 ), the entropy elasticity of the resin is improved. As a result, good processability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in processability is even better than that of the branched polycarbonate. In a more preferred embodiment, component A has a viscosity average molecular weight of 7×10 4 ~3×10 5 Polycarbonate resin (A-1-1 component) and viscosity average molecular weight 1 × 10 4 ~3×10 4 The aromatic polycarbonate resin (component A-1-2) has a viscosity average molecular weight of 1.6 × 10 4 ~3.5×10 4 A polycarbonate resin (component A-1) (hereinafter, sometimes referred to as a "polycarbonate resin containing a high molecular weight component") can also be used.

[0027] In the polycarbonate resin containing such a high molecular weight component (component A-1), the molecular weight of component A-1-1 is 7 × 10 4 ~2×10 5 is preferable, and more preferably 8×10 4 ~2×105 , and more preferably 1 × 10 5 ~2×10 5 , particularly preferably 1 × 10 5 ~1.6×10 5 The molecular weight of component A-1-2 is 1 × 10 4 ~2.5×10 4 is preferable, and more preferably 1.1 × 10 4 ~2.4×10 4 , and more preferably 1.2 × 10 4 ~2.4×10 4 , particularly preferably 1.2 × 10 4 ~2.3×10 4 is.

[0028] The high-molecular-weight component-containing polycarbonate resin (component A-1) can be obtained by mixing the components A-1-1 and A-1-2 in various ratios and adjusting the ratio to satisfy a predetermined molecular weight range. Preferably, the component A-1-1 accounts for 2 to 40% by weight, more preferably 3 to 30% by weight, even more preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight, of 100% by weight of component A-1.

[0029] Methods for preparing component A-1 include: (1) a method in which component A-1-1 and component A-1-2 are polymerized independently and then mixed; (2) a method in which an aromatic polycarbonate resin that shows multiple polymer peaks in a molecular weight distribution chart obtained by GPC, as typified by the method disclosed in Japanese Patent Laid-Open No. 5-306336, is produced in the same system, and the aromatic polycarbonate resin is produced so as to satisfy the conditions for component A-1 of the present invention; and (3) a method in which an aromatic polycarbonate resin obtained by such a production method (production method (2)) is mixed with component A-1-1 and / or component A-1-2 that have been produced separately.

[0030] The viscosity average molecular weight in the present invention is determined by first calculating the specific viscosity (η SP) was determined using an Ostwald viscometer from a solution of 0.7 g of polycarbonate dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and calculate the viscosity average molecular weight M using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 M 0.83 c=0.7

[0031] The viscosity average molecular weight of an aromatic polycarbonate resin is calculated as follows: The composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve the soluble components in the composition. The soluble components are collected by filtration through Celite. The solvent in the resulting solution is then removed. The solid obtained after solvent removal is thoroughly dried to obtain a solid of components soluble in methylene chloride. 0.7 g of the solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined in the same manner as above. The viscosity average molecular weight M is then calculated from the specific viscosity in the same manner as above.

[0032] The aromatic polycarbonate resin may be a polycarbonate-polydiorganosiloxane copolymer resin, preferably a copolymer resin prepared by copolymerizing a dihydric phenol represented by the following general formula (2) with a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (4):

[0033] [ka]

[0034] [In the above general formula (2), R 1 and R2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (3):

[0035] [ka]

[0036] [In the above general formula (3), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple groups, they may be the same or different; g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0037] [ka]

[0038] [In the above general formula (4), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0039] Examples of the dihydric phenol (I) represented by the general formula (2) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane 4,4'-dihydroxyphenyl)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. 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 is the most suitable, as it has excellent strength and good durability. These may be used alone or in combination.

[0040] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (4), for example, the compounds shown below are preferably used.

[0041] [ka]

[0042] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, at the end 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, with (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes being particularly preferred. The molecular weight distribution (Mw / Mn) of the hydroxyaryl-terminated polydiorganosiloxanes (II) is preferably 3 or less. To achieve even better low outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

[0043] Furthermore, in order to achieve high impact resistance, the diorganosiloxane degree of polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane degree of polymerization (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, while above the upper limit of this preferred range, poor appearance appears.

[0044] The polydiorganosiloxane content of the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are achieved, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is easily achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are 1 It can be calculated by H-NMR measurement.

[0045] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0046] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the present invention.

[0047] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution.

[0048] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0049] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0050] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0051] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Similarly, the proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0052] The solvent may be any of various inert solvents used in the production of known polycarbonates, either singly or in combination. 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.

[0053] The reaction pressure for oligomer formation is not particularly limited and may be atmospheric, elevated, 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 heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is similar to that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0054] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred and the hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (4), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0055] [ka]

[0056] (In the above general formula (4), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0057] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used 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, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0058] The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0059] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0060] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0061] The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0062] A branching agent can be used in combination with the above-mentioned dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1 Examples include trisphenols such as {1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, and among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being particularly preferred. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, even more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by H-NMR measurement.

[0063] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the inherent pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally determined because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0064] In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of formula [ / c].

[0065] The resulting reaction product (crude product) can be subjected to various post-treatments, such as known separation and purification methods, to recover a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification). The average size of the polydiorganosiloxane domains in a polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. This average size is more preferably 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be fully exhibited, while above the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0066] The average domain size and normalized dispersion of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded articles of the present invention were evaluated using small-angle X-ray scattering (SAXS). Small-angle X-ray scattering measures the diffuse scattering and diffraction that occur in the small-angle region of scattering angles (2θ) less than 10°. In this method, if a substance contains regions with different electron densities of approximately 1 to 100 nm in size, the diffuse scattering of X-rays is measured based on the electron density difference. The particle size of the object being measured is determined based on the scattering angle and scattering intensity. In the case of polycarbonate-polydiorganosiloxane copolymer resins, which form an aggregate structure in which polydiorganosiloxane domains are dispersed within a polycarbonate polymer matrix, the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains causes diffuse scattering of X-rays. The scattering intensity I at each scattering angle (2θ) within a range of scattering angles (2θ) less than 10° is measured to obtain a small-angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical and that there is variation in the particle size distribution, a simulation is performed using commercially available analysis software based on 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. Small-angle X-ray scattering allows for accurate, simple, and reproducible measurement of the average size and particle size distribution of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured using observation with a transmission electron microscope. The average domain size refers to the number average of the individual domain sizes. The 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):

[0067]

number

[0068] The terms "average domain size" and "normalized dispersion" used in connection with the present invention refer to measurements obtained by small-angle X-ray scattering at a 1.0 mm thick section of a three-tiered plate prepared by the method described in the Examples. Analysis was also performed using an isolated particle model that does not take into account interparticle interactions (interparticle interference).

[0069] (Component B: glass fiber) Suitable examples of the glass fibers used as component B in the present invention include glass fibers having a round cross section, flat cross section glass fibers having an average long diameter of 5 to 20 μm and an average ratio of long diameter to short diameter (long diameter / short diameter) of 1.5 to 8, and glass milled fibers. In particular, glass fibers having a round cross section and flat cross section glass fibers having an average long diameter of 5 to 20 μm and an average ratio of long diameter to short diameter (long diameter / short diameter) of 1.5 to 8 are more preferred in terms of tensile strength.

[0070] The glass composition of the above glass fiber is represented by A glass, C glass, E glass, etc. Various glass compositions can be used, and are not particularly limited. Such glass fibers may contain components such as TiO2, SO3, and P2O5 as necessary. Among these, E glass (alkali-free glass) is more preferred.

[0071] The glass fiber contains at least one compound selected from the group consisting of a surface treatment agent and a sizing agent, and the gas component obtained by heating the glass fiber at 400°C for 12 seconds contains a compound represented by the following general formula (1):

[0072] [ka]

[0073] (In the above general formula (1), n ​​is an integer of 1 to 10, each X independently represents an alkylene group having 1 to 5 carbon atoms, and each Y independently represents an alkyl group having 1 to 5 carbon atoms.) In the above general formula (1), X is preferably an alkylene group having 3 carbon atoms.

[0074] Examples of the compound represented by the general formula (1) include 4,8,12,16-tetraoxaeicosan-1-ol, 2,5,8,11-tetraoxatetradecan-13-ol, 4,7,10-trimethyl, 2-propanol, 1-(2-(2-methoxy-1-methylethoxy)-1-methylethoxy), and propane, 1,2-bis(2-methoxy-2-methylethoxy), with 4,8,12,16-tetraoxaeicosan-1-ol being preferred.

[0075] By using glass fibers having such properties, the moist heat resistance and chemical resistance of the polycarbonate resin composition can be significantly improved.

[0076] The gas components are measured in accordance with the methods described in the Examples below. However, if the instruments described in the Examples are difficult to obtain due to discontinuation or other reasons, measurements can be made using other instruments with similar capabilities.

[0077] The content of component B is 20 to 130 parts by weight, preferably 30 to 120 parts by weight, and more preferably 40 to 120 parts by weight, per 100 parts by weight of component A. If the content of component B is less than 20 parts by weight, the improvement in tensile strength will be insufficient. On the other hand, if the content exceeds 130 parts by weight, processability will decrease.

[0078] (Component C: phenoxy resin and / or epoxy resin) Examples of the phenoxy resin used as component C in the present invention include phenoxy resins represented by the following general formula (5).

[0079] [ka] (In the formula, X is at least one group selected from the group consisting of groups represented by the following general formula (6), Y is a residue of a compound that reacts with a hydrogen atom or a hydroxyl group, and n is an integer of 0 or greater.)

[0080] [ka] (In the formula, Ph represents a phenyl group.)

[0081] In the above general formula (5), examples of the compound reactive with a hydroxyl group include esters, carbonates, compounds having an epoxy group, carboxylic acid anhydrides, acid halides, and compounds having an isocyanate group. As the ester, intramolecular esters are particularly preferred, such as caprolactone. Among the phenoxy resins represented by the above general formula (5), compounds in which Y is a hydrogen atom can be easily produced from divalent phenols and epichlorohydrin. Furthermore, compounds in which Y is a residue of a compound reactive with a hydroxyl group can be easily produced by mixing, under heating, a phenoxy resin produced from a divalent phenol and epichlorohydrin with the above compound reactive with a hydroxyl group.

[0082] The epoxy resin used as component C in the present invention includes, for example, an epoxy resin represented by the following general formula (7).

[0083] [ka] (wherein X and n are the same as in formula (5).)

[0084] The epoxy resin represented by the general formula (7) can be easily produced from a dihydric phenol and epichlorohydrin. The dihydric phenol may be a bisphenol A epoxy resin such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, or 4,4'-dihydroxybiphenyl.

[0085] Among these phenoxy resins and epoxy resins, particularly preferred embodiments include bisphenol A type phenoxy resins and / or bisphenol A type epoxy resins.

[0086] Commercially available phenoxy resins and epoxy resins can also be used. Commercially available phenoxy resins (bisphenol A type) include PKHB (manufactured by Gabriel Phenoxies, Mw=32,000), PKHH (manufactured by Gabriel Phenoxies, Mw=52,000), and PKFE (manufactured by Gabriel Phenoxies, Mw=60,000). Commercially available epoxy resins (bisphenol A type) include jER1256 (manufactured by Mitsubishi Chemical Corporation, Mw=50,000).

[0087] The weight-average molecular weight of the phenoxy resin and the epoxy resin is not particularly limited, but is preferably 5,000 to 100,000, more preferably 8,000 to 80,000, and even more preferably 10,000 to 50,000. When the weight-average molecular weight is in the range of 5,000 to 100,000, the mechanical properties may be particularly good.

[0088] The content of Component C is 1 to 10 parts by weight, preferably 1 to 7 parts by weight, and more preferably 2 to 6 parts by weight, per 100 parts by weight of Component A. If the content is too low, exceeding the above range, the tensile strength, moist heat resistance, and chemical resistance will deteriorate. On the other hand, if the content exceeds the above range, the processability will deteriorate.

[0089] (Component D: Phosphorus stabilizer) The polycarbonate resin composition of the present invention must contain a phosphorus-based stabilizer as Component D. The phosphorus-based stabilizer improves thermal stability during production or molding processing, and improves mechanical properties, color, and molding stability. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof, as well as tertiary phosphines. Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, and tris(di-n-butylphenyl)phosphite. bis(2,6-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, etc. Furthermore, as other phosphite compounds, those which react with dihydric phenols to have a cyclic structure can also be used.For example, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and the like can be mentioned. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, triethyl phosphonoacetate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred are triphenyl phosphate, trimethyl phosphate, and triethyl phosphonoacetate.

[0090] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl ... Examples of suitable phosphonite compounds 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. Preferred are tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. These phosphonite compounds can be used in combination with phosphite compounds having an aryl group substituted with two or more alkyl groups, which is preferred. Examples of suitable phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. 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. The phosphorus-based stabilizer can be used alone or in combination of two or more. Among the phosphorus-based stabilizers, it is preferable to use an alkyl phosphate compound, such as triethylphosphonoacetate. It is also a preferred embodiment to use such an alkyl phosphate compound in combination with a phosphite compound and / or a phosphonite compound.

[0091] The content of component D is 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.1 parts by weight, per 100 parts by weight of component A. If the content of component D exceeds 3 parts by weight, moist heat resistance deteriorates. On the other hand, if it is less than 0.01 part by weight, tensile strength does not improve.

[0092] (Component E: Brominated flame retardant) The polycarbonate resin composition of the present invention must contain a brominated flame retardant. The brominated carbonate compound preferably used as the brominated flame retardant is one in which the content of structural units represented by the following general formula (8) is at least 60 mol % of all structural units and the specific viscosity is 0.015 to 0.1.

[0093] [ka]

[0094] [In general formula (8), X is a bromine atom, and R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO2-.] In the formula (8), R preferably represents a methylene group, an ethylene group, an isopropylidene group, or -SO2-, and particularly preferably represents an isopropylidene group.

[0095] The brominated carbonate compound preferably has a small amount of residual chloroformate terminal groups, with a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The terminal chlorine content can be determined by dissolving a sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine to react with the terminal chlorine (terminal chloroformate), and measuring the resultant using an ultraviolet-visible spectrophotometer (Hitachi U-3200). When the terminal chlorine content is 0.3 ppm or less, the thermal stability of the resin composition is improved, enabling molding at higher temperatures, which may result in a resin composition with better processability.

[0096] The brominated carbonate compound preferably has few residual terminal hydroxyl groups. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less, per mol of the constituent unit of the brominated carbonate compound. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring the amount of terminal hydroxyl groups. 1 This can be determined by measuring by H-NMR. When the amount of terminal hydroxyl groups is within this range, the thermal stability of the resin composition may be further improved.

[0097] Such brominated carbonate compounds are commercially available, for example, tetrabromobisphenol A carbonate oligomer (trade names FG-7000, FG-8500) manufactured by Teijin Limited, and these can be used in the present invention.

[0098] The content of component E is 5 to 35 parts by weight, preferably 10 to 35 parts by weight, and more preferably 10 to 30 parts by weight, per 100 parts by weight of component A. If the content of component E is less than 5 parts by weight, the flame retardancy will be poor, and if it exceeds 35 parts by weight, strand breakage and surging will occur during kneading and extrusion, and processability will be poor.

[0099] (Component F: phosphazene compound) The polycarbonate resin composition of the present invention must contain a phosphazene compound, which is preferably a cyclic phenoxyphosphazene represented by the following formula (9).

[0100] [ka] (wherein m represents an integer of 3 to 25, and Ph represents a phenyl group.) A representative commercially available cyclic phenoxyphosphazene is "FP-110" manufactured by Fushimi Pharmaceutical Co., Ltd.

[0101] The content of component F is 1 to 10 parts by weight, preferably 1 to 7 parts by weight, and more preferably 2 to 6 parts by weight, per 100 parts by weight of component A. If the content of component F is less than 1 part by weight, the flowability will be poor, and if it exceeds 10 parts by weight, strand breakage, surging, etc. will occur during kneading and extrusion, and processability will be poor.

[0102] (Component G: Anti-drip agent) The anti-drip agent used as component G in the present invention may be a fluorine-containing polymer having fibril-forming ability, such as polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers), partially fluorinated polymers such as those disclosed in U.S. Patent No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0103] Fibril-forming PTFE has an extremely high molecular weight and tends to bond PTFE molecules together to form fibers under external influences such as shear force. Its molecular weight, calculated from the standard specific gravity, is 1 million to 10 million, more preferably 2 million to 9 million, in number average molecular weight. Such PTFE can be used in solid form or in the form of an aqueous dispersion. Furthermore, such fibril-forming PTFE can be used in a PTFE mixture with other resins to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties.

[0104] Commercially available PTFE products having such fibril-forming ability include, for example, Teflon (registered trademark) 6-J manufactured by Mitsui-Chemours Fluoroproducts, Inc., and Polyflon MPA FA500H and F-201 manufactured by Daikin Industries, Ltd. Representative examples of commercially available aqueous PTFE dispersions include the Fluon D series manufactured by Daikin Industries, Ltd., and Teflon (registered trademark) 31-JR manufactured by Mitsui-Chemours Fluoroproducts, Inc.

[0105] The mixed form of PTFE can be obtained by (1) mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitation to obtain a co-aggregated mixture (methods described in Japanese Patent Application Laid-Open Nos. 60-258263 and 63-154744, etc.), (2) mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Application Laid-Open No. 4-272957), or (3) uniformly mixing an aqueous dispersion of PTFE with an organic polymer particle solution and simultaneously extracting each medium from the mixture. (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous PTFE dispersion (method described in JP-A-06-220210, JP-A-08-188653, etc.), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, and then polymerizing a vinyl monomer in the mixed dispersion to obtain a mixture (method described in JP-A-11-29679, etc.). Commercially available PTFE blends include "Metablen A3800" (trade name) and "Metablen A3750" from Mitsubishi Chemical Corporation.

[0106] The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, based on 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE may be achieved in some cases.

[0107] Examples of styrene-based monomers used as organic polymers in polytetrafluoroethylene blends include, but are not limited to, styrenes that may be substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogens, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethylstyrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, and vinylnaphthalene. The styrene-based monomers can be used alone or in combination of two or more types.

[0108] The acrylic monomer used as the organic polymer in the polytetrafluoroethylene mixture preferably contains a (meth)acrylate derivative which may be substituted. Specifically, the acrylic monomer may be a (meth)acrylate derivative which may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group, such as (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate ... methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhex Examples of the acrylic monomer include, but are not limited to, (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and glycidyl (meth)acrylate; maleimides that may be substituted with an alkyl group or an aryl group having 1 to 6 carbon atoms, such as maleimide, N-methyl-maleimide, and N-phenyl-maleimide; maleic acid, phthalic acid, and itaconic acid. The acrylic monomers can be used alone or in combination. Among these, (meth)acrylonitrile is preferred.

[0109] The amount of the acrylic monomer-derived units contained in the organic polymer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, and even more preferably 8 to 9 parts by weight, per 100 parts by weight of the styrene monomer-derived units. If the amount of the acrylic monomer-derived units is less than 8 parts by weight, the coating strength may decrease, and if it is more than 11 parts by weight, the surface appearance of the molded article may deteriorate.

[0110] The polytetrafluoroethylene mixture of the present invention preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, and even more preferably 0.1 to 0.3% by weight. If the residual moisture content is more than 0.5% by weight, it may have an adverse effect on flame retardancy.

[0111] The process for producing the polytetrafluoroethylene blend of the present invention includes a step of forming a coating layer containing one or more monomers selected from the group consisting of styrene-based monomers and acrylic monomers on the outside of the branched polytetrafluoroethylene in the presence of an initiator. Furthermore, after the coating layer formation step, it is preferable to include a step of drying the mixture so that the residual moisture content is 0.5 wt% or less, preferably 0.2 to 0.4 wt%, and more preferably 0.1 to 0.3 wt%. The drying step can be carried out using a method known in the art, such as hot air drying or vacuum drying.

[0112] The initiator used in the polytetrafluoroethylene-based blend of the present invention may be any initiator used in the polymerization reaction of styrene-based and / or acrylic monomers. Examples of such initiators include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. One or more of the above initiators may be used in the polytetrafluoroethylene-based blend of the present invention depending on the reaction conditions. The amount of the initiator may be freely selected within a range that takes into account the amount of polytetrafluoroethylene and the type and amount of monomer, and is preferably used in an amount of 0.15 to 0.25 parts by weight based on the total amount of the composition.

[0113] The polytetrafluoroethylene mixture of the present invention was produced by the suspension polymerization method according to the following procedure.

[0114] First, water and a branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) were placed in a reactor, and then acrylic monomer, styrene monomer, and cumene hydroperoxide as a water-soluble initiator were added with stirring, and the reaction was carried out at 80 to 90°C for 9 hours. After the reaction was completed, the water was removed by centrifugation for 30 minutes in a centrifuge, yielding a paste-like product. The product paste was then dried in a hot air dryer at 80 to 100°C for 8 hours. The dried product was then pulverized to obtain the polytetrafluoroethylene mixture of the present invention.

[0115] Such suspension polymerization does not require the polymerization step of emulsion dispersion used in emulsion polymerization, as exemplified in Patent Publication No. 3469391, and therefore does not require emulsifiers or electrolyte salts for coagulating and precipitating the latex after polymerization. Furthermore, in polytetrafluoroethylene mixtures produced by emulsion polymerization, the emulsifiers and electrolyte salts in the mixture tend to be mixed together and are difficult to remove, making it difficult to reduce the sodium and potassium metal ions derived from the emulsifiers and electrolyte salts. The polytetrafluoroethylene mixture (component B) used in the present invention is produced by suspension polymerization, and therefore does not use such emulsifiers or electrolyte salts, thereby reducing the sodium and potassium metal ions in the mixture and improving thermal stability and hydrolysis resistance.

[0116] In addition, in the present invention, coated branched PTFE can be used as an anti-drip agent. The coated branched PTFE is a polytetrafluoroethylene-based mixture consisting of branched polytetrafluoroethylene particles and an organic polymer, and has a coating layer made of an organic polymer, preferably a polymer containing units derived from a styrene-based monomer and / or units derived from an acrylic monomer, on the outside of the branched polytetrafluoroethylene. The coating layer is formed on the surface of the branched polytetrafluoroethylene. Furthermore, the coating layer preferably contains a copolymer of a styrene-based monomer and an acrylic monomer.

[0117] The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the polytetrafluoroethylene contained is not branched polytetrafluoroethylene, the drip prevention effect will be insufficient when the amount of polytetrafluoroethylene added is small. The branched polytetrafluoroethylene is in the form of particles, and has a particle diameter of preferably 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more preferably 0.3 to 0.4 μm. If the particle diameter is smaller than 0.1 μm, the surface appearance of the molded article will be excellent, but it is difficult to commercially obtain polytetrafluoroethylene with a particle diameter smaller than 0.1 μm. Furthermore, if the particle diameter is larger than 0.6 μm, the surface appearance of the molded article may deteriorate. The number-average molecular weight of the polytetrafluoroethylene used in the present invention is 1×10 4 ~1×10 7 is preferred, and more preferably 2 × 10 6 ~9×10 6 Generally, polytetrafluoroethylene having a high molecular weight is more preferable in terms of stability. Either powder or dispersion form can be used.

[0118] The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, even more preferably 47 to 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight, relative to 100 parts by weight of the total weight of the coated branched PTFE. When the proportion of branched polytetrafluoroethylene is within this range, good dispersibility of the branched polytetrafluoroethylene may be achieved in some cases.

[0119] The content of G component is 0.1 to 3 parts by weight, preferably 0.15 to 2 parts by weight, and more preferably 0.5 to 1.5 parts by weight, per 100 parts by weight of A component. If the content of G component is greater than this range, costs will increase and processability will deteriorate. On the other hand, if it is less than this range, flame retardancy will be insufficient. Note that the proportion of G component indicates the net amount of anti-drip agent, and in the case of mixed PTFE, it indicates the net amount of PTFE.

[0120] (H component: liquid crystal polyester resin) The liquid crystal polyester resin used as the H component in the present invention is preferably a thermotropic liquid crystal polyester resin, which has the property that polymer molecular chains are aligned in a fixed direction in a molten state. The alignment state may be any of nematic, smectic, cholesteric, and discotic, or may exhibit two or more types. Furthermore, the structure of the liquid crystal polyester resin may be any of main chain, side chain, and rigid main chain / bent side chain structures, but main chain liquid crystal polyester resins are preferred.

[0121] The morphology of the above-mentioned alignment state, i.e., the nature of the anisotropic molten phase, can be confirmed by a conventional polarized light examination method using crossed polarizers. More specifically, the anisotropic molten phase can be confirmed by observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at 40x magnification using a Leitz polarizing microscope. When examined between crossed polarizers, the polymer of the present invention transmits polarized light even in a molten, stationary state, demonstrating optical anisotropy.

[0122] The heat resistance of the liquid crystal polyester resin may be in any range, but it is preferable that it melts and form a liquid crystal phase at a temperature close to the processing temperature of the polycarbonate resin. The liquid crystal polyester preferably has a deflection temperature under load (ISO75-1 / 2, 1.8 MPa load) of 150 to 280°C, preferably 150 to 250°C. Such liquid crystal polyesters belong to the so-called Type II heat resistance category. When such heat resistance is present, they are superior in processability compared to Type I, which has higher heat resistance, and achieve better flame retardancy compared to Type III, which has lower heat resistance.

[0123] The liquid crystal polyester resin used in the present invention preferably contains polyester units and polyesteramide units, and is preferably an aromatic polyester resin or an aromatic polyesteramide resin. A liquid crystal polyester resin partially containing aromatic polyester units and aromatic polyesteramide units in the same molecular chain is also a preferred example.

[0124] Particularly preferred are wholly aromatic polyester resins and wholly aromatic polyesteramide resins having, as unit constituents, one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. More specifically, 1) liquid crystal polyester resins synthesized mainly from one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives, 2) liquid crystal polyester resins synthesized mainly from a) one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives, b) one or more compounds selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives, and c) one or more compounds selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and their derivatives, and 3) liquid crystal polyester resins synthesized mainly from a) one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives. a) a liquid crystalline polyesteramide resin synthesized from two or more compounds selected from the group consisting of aromatic hydroxyamines, aromatic diamines, and derivatives thereof, b) one or more compounds selected from the group consisting of aromatic hydroxyamines, aromatic diamines, and derivatives thereof, and c) one or more compounds selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; 4) a liquid crystalline polyesteramide resin synthesized from mainly a) one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more compounds selected from the group consisting of aromatic hydroxyamines, aromatic diamines, and derivatives thereof, c) one or more compounds selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and d) one or more compounds selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof, but 1) a liquid crystalline polyester resin synthesized from mainly one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof is preferred. Furthermore, a molecular weight modifier may be used in combination with the above-mentioned constituent components, if necessary.

[0125] Preferred examples of specific compounds used in the synthesis of the liquid-crystalline polyester resin used in the polycarbonate resin composition of the present invention include naphthalene compounds such as 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 6-hydroxy-2-naphthoic acid; biphenyl compounds such as 4,4'-diphenyldicarboxylic acid and 4,4'-dihydroxybiphenyl; para-substituted benzene compounds such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol, and p-phenylenediamine, and their nuclear-substituted benzene compounds (substituents selected from chlorine, bromine, methyl, phenyl, and 1-phenylethyl); meta-substituted benzene compounds such as isophthalic acid and resorcinol; and compounds represented by the following general formulas (10), (11), or (12). Among these, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are particularly preferred, and a liquid-crystalline polyester resin obtained by mixing the two is preferred. The ratio of the former is preferably in the range of 90 to 50 mol %, more preferably in the range of 80 to 65 mol %, and the latter is preferably in the range of 10 to 50 mol %, more preferably in the range of 20 to 35 mol %.

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] (wherein X is a group selected from the group consisting of alkylene and alkylidene groups having 1 to 4 carbon atoms, -O-, -SO-, -SO2-, -S-, and -CO-, and Y is a group selected from the group consisting of -(CH2)n- (n = 1 to 4) and -O(CH2)nO- (n = 1 to 4).) In addition to the above-mentioned components, the liquid crystal polyester resin used in the present invention may partially contain polyalkylene terephthalate-derived units that do not exhibit an anisotropic molten phase in the same molecular chain. In this case, the alkyl group has 2 to 4 carbon atoms.

[0130] The liquid crystal polyester resin used in the present invention can be produced by any known method, including polycondensation, without any particular limitations. The liquid crystal polyester resin generally exhibits an inherent viscosity (IV value) of at least about 2.0 dL / g, for example, about 2.0 to 10.0 dL / g, when dissolved in pentafluorophenol at 60°C at a concentration of 0.1% by weight.

[0131] Due to the above characteristics, the liquid crystal polyester resin becomes fine fibril-like during injection molding, and the shape is maintained during the cooling and solidifying process, thereby exhibiting a reinforcing effect on the matrix. Therefore, the liquid crystal polyester resin can impart tensile strength. The liquid crystal polyester resin also has the effect of reducing the viscosity of the resin composition, which can reduce the injection speed and resin pressure.

[0132] The content of component H is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, and even more preferably 2 to 10 parts by weight, per 100 parts by weight of component A. If the content is too low beyond the above range, the tensile strength may be low. On the other hand, if the content exceeds the above range, the tensile strength may also be low.

[0133] (Other additives) Furthermore, the resin composition of the present invention may further contain other thermoplastic resins (e.g., polyarylate resin, fluororesin, polyester resin, polyphenylene sulfide resin, etc.), antioxidants (e.g., hindered phenol compounds, etc.), impact modifiers, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, colorants, inorganic fillers (talc, mica, wollastonite, kaolin, etc.), flame retardants other than component E and component F, and the like, within the scope of the present invention.

[0134] Any method can be used to produce the resin composition of the present invention. For example, the components and optionally other components can be premixed, followed by melt-kneading and pelletizing. Examples of premixing methods include a Nauta mixer, a V-blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. Premixing can also be performed using an extrusion granulator or briquetting machine. After premixing, the components are melt-kneaded in a melt mixer, typically a vented twin-screw extruder, and pelletized using a pelletizer or other device. Other examples of melt mixers include a Banbury mixer, a kneading roll, and a thermostatically stirred vessel. A vented twin-screw extruder is preferred. Alternatively, the components and optionally other components can be fed independently to a melt mixer, typically a twin-screw extruder, without premixing.

[0135] The polycarbonate resin composition of the present invention obtained as described above can be generally injection molded into various products. Furthermore, it is also possible to directly form the resin melt-kneaded in an extruder into sheets, films, profile extrusion molded products, and injection molded products without going through the pelletizing process.

[0136] In such injection molding, molded articles can be obtained using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), 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. Furthermore, either the cold runner method or the hot runner method can be selected for molding. Furthermore, the polycarbonate resin composition of the present invention can also be extrusion molded into various profile extrusion molded articles and sheets.

[0137] Examples of molded articles that can utilize the resin composition of the present invention include electrical and electronic components such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, and computer-related parts; semiconductor manufacturing process-related parts such as IC trays and wafer carriers; home electrical appliance parts and housing materials such as computers, VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture parts such as lamp reflectors and lamp holders; audio product parts such as compact discs, laser discs (registered trademark), and speakers; and communication equipment parts such as ferrules for optical cables, telephone parts, facsimile parts, and modems. copier-related parts such as separation claws and heater holders; mechanical parts such as impellers, fans, gears, bearings, motor parts and cases; automotive parts such as automotive mechanism parts, engine parts, engine room parts, electrical parts and interior parts; cooking utensils such as microwave cooking pots and heat-resistant tableware; heat insulation and soundproofing materials such as flooring and wall materials, support materials such as beams and pillars, building materials or civil engineering and construction materials such as roofing materials; aircraft parts, spacecraft parts, radiation facility components such as nuclear reactors, marine facility components, cleaning jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and medical materials, sensor parts, sanitary fixtures, sporting goods, leisure goods, etc. [Effects of the Invention]

[0138] The polycarbonate resin composition of the present invention is excellent in tensile strength, moist heat resistance, chemical resistance, processability, flame retardancy, and flowability. These properties are not available in conventional techniques, and therefore the industrial effects of the present invention are extremely significant. DETAILED DESCRIPTION OF THE INVENTION

[0139] The present inventors currently consider the best mode of the invention to be a combination of the preferred ranges of each of the above-mentioned requirements, and representative examples thereof are described in the following examples, although the present invention is not limited to these modes. [Example]

[0140] The present invention will be further explained below with reference to examples, which were evaluated by the following methods.

[0141] (Evaluation of Polycarbonate Resin Composition) (i) Tensile strength: Using tensile test pieces obtained by the following method, the tensile strength was measured in accordance with ISO 527 (tensile speed: 5 mm / min, test temperature: 23°C). (ii) Wet heat resistance: Tensile test specimens obtained by the method described below were treated in an atmosphere of 85°C and 85% relative humidity for 1000 hours, then removed and cooled to 23°C. Next, the tensile strength (tensile strength before and after wet heat treatment) was measured according to ISO 527. The obtained values ​​were then applied to the following formula to calculate the tensile strength retention rate. Tensile strength retention rate (%) = (tensile strength after moist heat treatment / tensile strength before moist heat treatment) x 100 (iii) Chemical resistance: Using a tensile test piece obtained by the method described below, a 0.7% strain was applied using a three-point bending test method, and then a cloth impregnated with Magiclean (manufactured by Kao Corporation) was placed over the test piece, and the test piece was left at 23°C for 96 hours, after which the presence or absence of any change in appearance was confirmed. The evaluation was carried out according to the following criteria. ○: No change in appearance was observed. △: Fine cracks are observed. ×: Large cracks that could lead to fracture were observed. (iv) Processability: Stability during extrusion was evaluated according to the following criteria. ◯: The strands are stable during extrusion. △: The strands are slightly unstable during extrusion, but pelletization is possible. ×: The strands are quite unstable during extrusion. Pelletization is difficult or there is a lot of volatile gas. (v)Flame retardant Evaluation was carried out using a vertical flame test with a test piece 0.8 mm thick, according to the method (UL94) specified by the U.S. Underwriters Laboratories, Inc. Note that products that did not fall into the V-0, V-1, or V-2 category were marked as "not V." (vi) Liquidity Fluidity was evaluated using an Archimedes-type spiral flow mold with a channel thickness of 2 mm and a channel width of 8 mm. The spiral flow length was measured by drying the pellets obtained by the method described below at 120°C for 8 hours and then using an injection molding machine (SE130EV-A, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 320°C, a mold temperature of 100°C, and an injection pressure of 147 MPa. The spiral flow length must be 15 cm or more.

[0142] [Examples 1 to 13, Comparative Examples 1 to 15] A mixture consisting of the components excluding component B, with the composition shown in Tables 2 and 3, was fed into the first feed port of an extruder. This mixture was obtained by blending in a V-type blender. Component B was fed into the second feed port using a side feeder. Extrusion was performed using a 30 mm diameter vented twin-screw extruder (TEX30α-38.5BW-3V, Japan Steel Works, Ltd.) at a screw rotation speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa to obtain melt-mixed pellets. The extrusion temperature from the first feed port to the die was 300°C. A portion of the obtained pellets was dried in a hot air circulating dryer at 120°C for 6 hours and then molded into ISO tensile test specimens and UL test specimens (0.8 mm thick) for evaluation using an injection molding machine at a cylinder temperature of 310°C and a mold temperature of 120°C.

[0143] The symbols used for each component in Tables 1 to 3 are as follows: (Component A) A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 19,700, made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite L-1225WX) (B component) B-1: Glass fiber: Chopped glass fiber (product name: ECS 03 T-211H, manufactured by Nippon Electric Glass Co., Ltd., cut length 3 mm) B-2: Glass fiber: Flat cross-section chopped glass fiber (manufactured by Nippon Electric Glass Co., Ltd.: ECS 03 T-211-FGF (product name), major axis 28 μm, minor axis 7 μm, cut length 3 mm) B-3 (Comparative Example): Glass fiber: Chopped glass fiber (manufactured by Nitto Boseki Co., Ltd.: CSG 3PE-455 (product name), cut length 3 mm) B-4 (Comparative Example): Glass fiber: Chopped glass fiber (manufactured by Nitto Boseki Co., Ltd.: CSG 3PE-937 (product name), cut length 3 mm) B-5 (Comparative Example): Glass fiber: Flat cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd.: CSG 3PA-830 (product name), major axis 28 μm, minor axis 7 μm, cut length 3 mm) <Gas analysis> 50 mg of the glass fiber was heated at 400°C for 12 seconds, and the resulting gas was analyzed. The gas was analyzed by GC-MS (gas chromatography mass spectrometry) using a JEOL JMS-Q1500GC. The resulting gas was examined for the presence or absence of the compound represented by general formula (1) above, and evaluated according to the following criteria. The results are shown in Table 1. The detection limit of this analytical method is 0.1 ng. ◯: The compound represented by the above general formula (1) was detected ×: The compound represented by the general formula (1) was not detected.

[0144] [Table 1]

[0145] (C component) C-1: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER-1256 (trade name), weight-average molecular weight 50,000) C-2: Bisphenol A phenoxy resin (manufactured by Gabriel Phenoxies, PKHH (trade name), weight-average molecular weight 52,000) (D component) D-1: Phosphorus stabilizer (Triethylphosphonoacetate JC-224 (trade name) manufactured by Johoku Chemical Industry Co., Ltd.) D-2: Phosphorus stabilizer (trimethyl phosphate (TMP) manufactured by Daihachi Chemical Industry Co., Ltd.) D-3: Phosphorus-based stabilizer (bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, SONGNOX6260PW (trade name), manufactured by Songwon International Japan Co., Ltd.) (E component) E-1: Halogenated carbonate compound (brominated carbonate oligomer having a bisphenol A skeleton, Fire Guard FG-7000 (product name) manufactured by Teijin Limited, bromine content = 52%) (F component) F-1: Cyclic phenoxyphosphazene (Fushimi Pharmaceutical Co., Ltd., Lavitol FP-110T (product name)) (G component) G-1: Anti-drip agent (polytetrafluoroethylene (Daikin Industries, Ltd., Polyflon MPA FA-500H (product name)) (H component) H-1: Liquid crystal polyester resin (liquid crystal polyester resin pellets containing repeating units derived from p-hydroxybenzoic acid and repeating units derived from 6-hydroxy-2-naphthoic acid, manufactured by Polyplastics Co., Ltd., Laperos A-950RX (product name), melting point = 275 to 285°C) (Other ingredients) Release agent: Hiwax HW405MP (Mitsui Chemicals, Inc., low molecular weight polyethylene) Colorant: Carbon black master pellets produced by melt-mixing a total of 100 parts by weight of four components using a twin-screw extruder: 40 parts by weight of carbon black (Carbon Black MA-100 (trade name) manufactured by Mitsubishi Chemical Corporation), 3 parts by weight of white mineral oil (Primol N382 (trade name) manufactured by ExxonMobil), 0.2 parts by weight of Montan acid ester wax (Licowax E powder (trade name) manufactured by Clariant Japan K.K.), and 56.8 parts by weight of bisphenol A polycarbonate resin (CM-1000 (trade name) manufactured by Teijin Limited, viscosity average molecular weight 16,000).

[0146] [Table 2]

[0147] [Table 3]

[0148] It can be seen from Tables 2 and 3 above that the formulation of the present invention provides a polycarbonate resin composition that is excellent in tensile strength, moist heat resistance, chemical resistance, processability, flame retardancy and flowability.

Claims

1. 1. A polycarbonate resin composition comprising 100 parts by weight of (A) aromatic polycarbonate resin (Component A), 20 to 130 parts by weight of (B) glass fiber (Component B), 1 to 10 parts by weight of (C) phenoxy resin and / or epoxy resin (Component C), 0.01 to 3 parts by weight of (D) phosphorus-based stabilizer (Component D), 5 to 35 parts by weight of (E) bromine-based flame retardant (Component E), 1 to 10 parts by weight of (F) phosphazene compound (Component F), and 0.1 to 3 parts by weight of (G) anti-drip agent (Component G), wherein Component B contains at least one compound selected from the group consisting of a surface treatment agent and a sizing agent, and wherein the gas component obtained by heating Component B at 400°C for 12 seconds contains a compound represented by the following general formula (1): 【Chemistry 1】 [In the above general formula (1), n ​​is an integer of 1 to 10, each X independently represents an alkylene group having 1 to 5 carbon atoms, and each Y independently represents an alkyl group having 1 to 5 carbon atoms.]

2. 2. The polycarbonate resin composition according to claim 1, wherein X in the compound represented by the general formula (1) is an alkylene group having 3 carbon atoms.

3. 3. The polycarbonate resin composition according to claim 1, wherein the compound represented by the general formula (1) is 4,8,12,16-tetraoxaeicosan-1-ol.

4. 3. The polycarbonate resin composition according to claim 1, wherein component C is a bisphenol A phenoxy resin and / or a bisphenol A epoxy resin.

5. 3. The polycarbonate resin composition according to claim 1, further comprising 1 to 20 parts by weight of a liquid crystal polyester resin (H) (Component H) per 100 parts by weight of Component A.

6. 6. The polycarbonate resin composition according to claim 5, wherein component H is a liquid crystal polyester resin containing a repeating unit derived from p-hydroxybenzoic acid and a repeating unit derived from 6-hydroxy-2-naphthoic acid.

7. A molded article obtained by molding the polycarbonate resin composition according to claim 1 or 2.

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