Polycarbonate resin composition

Abstract

A polycarbonate resin composition characterized by containing 55-90% by mass of a polycarbonate resin (A) having a viscosity average molecular weight of 17,500-30,000 and 10-45% by mass of a graft copolymer (B) containing an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2), and a diene rubber polymer component (b3), with respect to 100 parts by mass of the total of (A) and (B), the amount of the graft copolymer (B) being less than or equal to 100 parts by mass. The present invention relates to a composition containing 0.001-0.3 parts by mass of a specific triaryl phosphate (C) represented by general formula (1) and 0.001-0.3 parts by mass of a compound (D) having a phenol structure, and the compound (D) having a phenol structure contains at least one of 4-tert-butylphenol, 2, 4-di-tert-butylphenol, 4-alpha-cumylphenol, and bisphenol A.

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having excellent weather resistance and a molded article of the polycarbonate resin composition. Background Art

[0002] Polycarbonate resins have excellent mechanical properties such as impact resistance, etc., and also have excellent heat resistance, excellent transparency, etc., and therefore are widely used in various applications such as various optical parts, parts in electrical and electronic equipment, automotive interior and exterior decoration parts, OA equipment parts, sheets, machine parts, building materials, etc.

[0003] However, due to the poor weather resistance of polycarbonate resin, its use is subject to certain restrictions. For example, its outdoor use or indoor use under fluorescent light may cause product discoloration or reduced strength.

[0004] To solve this problem, various light stabilizers have been conventionally used alone or in combination. A known example of such a light stabilizer is a benzotriazole-based ultraviolet absorber. However, blending such an ultraviolet absorber with a polycarbonate resin causes another problem, namely, a decrease in the color tone of the polycarbonate resin composition, which is induced by thermal degradation during melt-kneading and molding operations.

[0005] In addition, various additives have been tried to be blended with polycarbonate resins to impart high functionality. For example, Patent Document 1 describes that a fiber-reinforced polycarbonate resin composition having excellent dimensional stability, mechanical strength, and fluidity can be obtained by mixing 5 to 15% by mass of triphenyl phosphate with 85 to 95% by mass of polycarbonate resin.

[0006] With the rapid development of greater functionality and higher performance of various devices and equipment in recent years, improvement in weather resistance, in particular, of polycarbonate resins has been strongly desired.

[0007] [Citation list]

[0008] [Patent Document]

[0009] [Patent Document 1] Japanese Patent No. 3308657 Summary of the invention

[0010] Problem that the invention aims to solve

[0011] An object (problem) of the present invention is to provide a polycarbonate resin composition that exhibits excellent weather resistance, good impact resistance and heat resistance, and good fluidity (moldability).

[0012] Solutions for solving problems

[0013] As a result of extensive and intensive studies to solve this problem, the present inventors have found that a polycarbonate resin composition containing a small amount of a specific triaryl phosphate compound exhibits excellent weather resistance as well as good impact resistance and heat resistance relative to polycarbonate and a polymer alloy of a graft polymer such as ABS resin, thereby completing the present invention.

[0014] The present invention relates to a polycarbonate resin composition and a molded article described below.

[0015] 1. A polycarbonate resin composition, comprising: 55 to 90% by mass of a polycarbonate resin (A) having a viscosity average molecular weight of 17,500 to 30,000; 10 to 45% by mass of a graft copolymer (B) containing an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2) and a diene rubber polymer component (b3); and, relative to 100 parts by mass of the total mass of (A) and (B),

[0016] 0.001 to 0.3 parts by mass of a triaryl phosphate (C) represented by the general formula (1); and 0.001 to 0.3 parts by mass of a compound (D) having a phenol structure,

[0017] The compound (D) having a phenol structure includes at least one of 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol and bisphenol A.

[0018]

[0019] (In formula (1), R 1 ~R 5 are independently hydrogen atoms or C 1-12 alkyl.)

[0020] 2. The polycarbonate resin composition according to 1 above, wherein R on each aromatic ring in formula (1) 1 ~R 5 At least one of them is C 1-12 alkyl.

[0021] 3. The polycarbonate resin composition according to 1 above, wherein R on each aromatic ring in formula (1) 1 and R 3 C 1-12 Alkyl, R on each aromatic ring 2 , R 4 and R 5 A hydrogen atom.

[0022] 4. The polycarbonate resin composition according to 3 above, wherein R on each aromatic ring in formula (1) 1 and R 3 is tert-butyl, and R2 , R 4 and R 5 A hydrogen atom.

[0023] 5. The polycarbonate resin composition according to item 1 above, wherein the triaryl phosphate (C) comprises at least one of triphenyl phosphate, tri(2,4-di-tert-butylphenyl) phosphate and tri(4-tert-butylphenyl) phosphate.

[0024] 6. The polycarbonate resin composition according to item 1 above, further comprising: 0.001 to 0.3 parts by mass of triaryl phosphite (E) based on 100 parts by mass of the total mass of (A) and (B).

[0025] 7. Pellets comprising the polycarbonate resin composition according to any one of 1 to 6 above.

[0026] 8. A molded article comprising the polycarbonate resin composition according to any one of 1 to 6 above.

[0027] 9. A molded article comprising pellets of the polycarbonate resin composition according to 7 above.

[0028] Effects of the Invention

[0029] The polycarbonate resin composition according to the present invention exhibits high weather resistance, and is excellent in impact resistance, heat resistance, and fluidity (formability). DETAILED DESCRIPTION

[0030] Hereinafter, in order to describe the present invention in detail, embodiments, examples, etc. are provided.

[0031] Unless otherwise specifically stated, in the present specification, "to" in the description of a numerical range is used in the sense of including the numerical values ​​provided before and after "to" as the lower limit and the upper limit.

[0032] The polycarbonate resin composition according to the present invention characteristically comprises: 55-90% by mass of a polycarbonate resin (A) having a viscosity average molecular weight of 17500-30000; 10-45% by mass of a graft copolymer (B) containing an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2) and a diene rubber polymer component (b3); 0.001-0.3 parts by mass of a triaryl phosphate (C) given by the above general formula (1) relative to 100 parts by mass of the total mass of (A) and (B); and 0.001-0.3 parts by mass of a compound (E) having a phenol structure,

[0033] The compound (D) having a phenol structure includes at least one of 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol and bisphenol A.

[0034] [Polycarbonate resin (A)]

[0035] The polycarbonate resin (A) used in the present invention is not particularly limited, and various polycarbonate resins can be used. Polycarbonate resins can be classified into aromatic polycarbonate resins in which each carbon directly bonded to a carbonate bond is an aromatic carbon and aliphatic polycarbonate resins in which they are aliphatic carbons, and any of them can be used. Among them, for polycarbonate resin (A), aromatic polycarbonate resins are preferred in consideration of, for example, heat resistance, mechanical properties, and electrical properties.

[0036] Among the monomers used as raw materials for the aromatic polycarbonate resin, the aromatic dihydroxy compounds include the following:

[0037] Dihydroxybenzenes, such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene;

[0038] Dihydroxybiphenyls, such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl and 4,4′-dihydroxybiphenyl;

[0039] dihydroxynaphthalenes, for example 2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene;

[0040] dihydroxydiaryl ethers, for example 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene and 1,3-bis(4-hydroxyphenoxy)benzene;

[0041] Bis(hydroxyaryl)alkanes, for example,

[0042] 2,2-bis(4-hydroxyphenyl)propane (i.e. bisphenol A),

[0043] 1,1-Bis(4-hydroxyphenyl)propane,

[0044] 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e. bisphenol C),

[0045] 2,2-Bis(3-methoxy-4-hydroxyphenyl)propane,

[0046] 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane,

[0047] 1,1-Bis(3-tert-butyl-4-hydroxyphenyl)propane,

[0048] 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propane,

[0049] 2,2-Bis(3-cyclohexyl-4-hydroxyphenyl)propane,

[0050] 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane,

[0051] α,α′-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene,

[0052] 1,3-Bis[2-(4-hydroxyphenyl)-2-propyl]benzene,

[0053] Bis(4-hydroxyphenyl)methane,

[0054] Bis(4-hydroxyphenyl)cyclohexylmethane, Bis(4-hydroxyphenyl)phenylmethane,

[0055] Bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2 -bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, and 1,1-bis(4-hydroxyphenyl)dodecane;

[0056] Bis(hydroxyaryl)cycloalkanes, for example, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,

[0057] 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane,

[0058] 1,1-Bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane,

[0059] 1,1-bis(4-hydroxyphenyl)-3-tert-butylcyclohexane,

[0060] 1,1-Bis(4-hydroxyphenyl)-4-tert-butylcyclohexane,

[0061] 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, and

[0062] 1,1-Bis(4-hydroxyphenyl)-4-phenylcyclohexane;

[0063] Bisphenols containing a fluorene ring (Cardo) structure, such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0064] Dihydroxydiaryl sulfides, for example 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

[0065] Dihydroxydiaryl sulfoxides, such as 4,4′-dihydroxydiphenyl sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; and

[0066] Dihydroxydiaryl sulfones, for example 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone.

[0067] Among the aforementioned, bis(hydroxyaryl)alkanes are preferred, among which bis(4-hydroxyphenyl)alkanes are preferred, and from the viewpoint of impact resistance and heat resistance, 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) are particularly preferred.

[0068] One kind of the aromatic dihydroxy compound may be used, or any combination of two or more kinds in any ratio may be used.

[0069] Among monomers serving as raw materials of the polycarbonate resin, carbonate precursors may be exemplified by carbonyl halides and carbonate esters, etc. One carbonate precursor may be used, or any combination of two or more in any ratio may be used.

[0070] The carbonyl halide can be specifically exemplified by phosgene and halogenated formates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds.

[0071] The carbonate esters can be specifically exemplified by diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and carbonates of dihydroxy compounds such as dicarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds and cyclic carbonates.

[0072] The method for producing the polycarbonate resin (A) is not particularly limited, and any method can be used. Examples thereof are interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-state transesterification of prepolymers. Among them, the polycarbonate resin (A) produced by interfacial polymerization or melt transesterification is preferred because this provides greater improvement in moisture and heat resistance, wherein interfacial polymerization is particularly preferred.

[0073] The molecular weight of the polycarbonate resin (A) is expressed as a viscosity average molecular weight (Mv) converted from the solution viscosity measured at a temperature of 25° C. using dichloromethane as a solvent, and is preferably 10,000 to 50,000, more preferably 10,000 to 40,000, still more preferably 10,000 to 30,000, and even more preferably 10,000 to 26,000, preferably 10,500 or more, more preferably 11,000 or more, particularly preferably 11,500 or more, most preferably 12,000 or more, and preferably 24,000 or less, particularly preferably 20,000 or less. The mechanical strength of the polycarbonate resin composition according to the present invention can be further improved by making the viscosity average molecular weight equal to or greater than the lower limit of the range shown. By making the viscosity average molecular weight equal to or less than the upper limit of the range shown, the decrease in the fluidity of the polycarbonate resin composition according to the present invention can be suppressed, thereby improving the molding processability and facilitating the molding operation.

[0074] A mixture of two or more polycarbonate resins having different viscosity average molecular weights may be used. In this case, a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed.

[0075] The viscosity average molecular weight [Mv] is the value calculated using the Schnell viscosity equation, i.e., η = 1.23 × 10 -4 Mv 0.83 , where the intrinsic viscosity [η] (unit: dl / g) at 25°C is measured using dichloromethane as a solvent and an Ubbelohde viscometer. The intrinsic viscosity [η] is the specific viscosity [η] measured at each solution concentration [C] (g / dl) using the following formula: sp ] calculated value.

[0076] [Mathematical formula 1]

[0077]

[0078] In addition, the polycarbonate resin (A) may contain a polycarbonate oligomer to improve the appearance of the molded product and improve fluidity. The viscosity average molecular weight [Mv] of the polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. When contained, the content of the polycarbonate oligomer is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[0079] The polycarbonate resin (A) may be not only a virgin raw material but also a polycarbonate resin that has been recycled from post-consumer products (also known as a material recycled polycarbonate resin), and preferably contains both virgin raw materials and recycled resins, and may consist of recycled polycarbonate resins. The proportion of recycled polycarbonate resin in the polycarbonate resin (A) is preferably 40% or more, or 50% or more, or 60% or more, or 80% or more, and particularly preferably 100%.

[0080] [Graft copolymer (B)]

[0081] The graft copolymer (B) contained in the polycarbonate resin composition according to the present invention is a graft copolymer containing an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2) and a diene rubber polymer component (b3). The graft copolymer (B) preferably contains 40 to 80% by mass of the aromatic vinyl monomer component (b1), 10 to 30% by mass of the vinyl cyanide monomer component (b2) and 10 to 50% by mass of the diene rubber polymer component (b3), and may further contain 0 to 30% by mass of an additional monomer component (b4).

[0082] Examples of the aromatic vinyl monomer component (b1) in the graft copolymer (B) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, etc.; styrene is particularly preferred.

[0083] The proportion of the aromatic vinyl monomer component (b1) in 100% by mass of the graft copolymer (B) is preferably in the range of 40 to 80% by mass, more preferably 45% by mass or more, even more preferably 50% by mass or more, particularly preferably 55% by mass or more, and more preferably 75% by mass or less, even more preferably 70% by mass or less, particularly preferably 65% ​​by mass or less.

[0084] Examples of the vinyl cyanide monomer component (b2) in the graft copolymer (B) include acrylonitrile, methacrylonitrile, and the like; particularly preferred is acrylonitrile.

[0085] The proportion of the vinyl cyanide monomer component (b2) in 100% by mass of the graft copolymer (B) is preferably in the range of 10 to 30% by mass, more preferably 12% by mass or more, even more preferably 14% by mass or more, particularly preferably 15% by mass or more, and more preferably 28% by mass or less, even more preferably 26% by mass or less, particularly preferably 25% by mass or less.

[0086] Examples of the diene rubber polymer component (b3) in the graft copolymer (B) include rubber components such as polybutadiene, polyisoprene and styrene-butadiene copolymers. The proportion of the diene rubber polymer component (b3) in 100% by mass of the graft copolymer (B) is preferably in the range of 10 to 50% by mass, more preferably 13% by mass or more, still more preferably 14% by mass or more, particularly preferably 15% by mass or more, and more preferably 45% by mass or less.

[0087] An additional monomer component (b4) copolymerizable with these components may be copolymerized. In this case, examples of the additional copolymerizable vinyl monomer include maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide; acrylamide monomers such as acrylamide, N-methylacrylamide; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride; unsaturated acids such as acrylic acid, methacrylic acid; glycidyl acrylate; glycidyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; methoxypolyethylene glycol methacrylate, and the like.

[0088] The proportion of the additional monomer component (b4) in 100% by mass of the graft copolymer (B) is preferably in the range of 0 to 30% by mass, more preferably 20% by mass or less, still more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 3% by mass or less, and particularly preferably 2% by mass or less.

[0089] Specific preferred examples of the graft copolymer (B) include acrylonitrile-butadiene-styrene graft copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene graft copolymer, acrylonitrile·ethylene-propylene-diene·styrene copolymer, etc. Among them, acrylonitrile-butadiene-styrene graft copolymer (ABS resin) is particularly preferred.

[0090] The graft copolymer (B) is generally produced by a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and any of these methods may be used.

[0091] The content of the graft copolymer (B) is 10 to 45% by mass, preferably 12% by mass or more, more preferably 15% by mass or more, preferably 42% by mass or less, more preferably 40% by mass or less, relative to the total mass of the polycarbonate resin (A) and the graft copolymer (B), 100% by mass. The graft copolymer (B) contained within this range helps to impart excellent heat resistance and fluidity to the resulting resin composition. If the content of the graft copolymer (B) exceeds 45% by mass, the heat resistance of the resin composition is reduced. If the content is less than 10% by mass, the fluidity is reduced.

[0092] [Triaryl phosphate (C)]

[0093] The polycarbonate resin composition according to the present invention contains triaryl phosphate (C) represented by the general formula (1). As used herein, aryl refers to a group containing an aromatic group, and particularly preferably refers to phenyl.

[0094] [C2]

[0095]

[0096] R in formula (1) 1 ~R 5 are independently a hydrogen atom or a C 1-12 Alkyl. C 1-12 The alkyl group is preferably C 1-8 Alkyl, preferred examples of which are methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl. Among them, C 1-6 Alkyl, particularly preferably C 1-4 alkyl.

[0097] When R on the three aromatic rings in formula (1) 1 ~R 5 When two or more of the groups are alkyl groups, these alkyl groups may be the same or different.

[0098] The triaryl phosphate (C) is preferably such that in formula (1), R on each aromatic ring 1 ~R 5 At least one of them is C 1-12 alkyl.

[0099] In addition, it is more preferred that R on each aromatic ring 1 and R 3 C 1-12 Alkyl, R on each aromatic ring 2 , R 4 , R 5 A hydrogen atom.

[0100] Specific examples of the triaryl phosphate (C) are triphenyl phosphate, tricresyl phosphate, tri-xylyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-di-xylyl phosphate, xylyl phenyl phosphate, ethyl phenyl diphenyl phosphate, diethyl phenyl phenyl phosphate, propyl phenyl diphenyl phosphate, dipropyl phenyl phenyl phosphate, tripropyl phenyl phosphate, butyl phenyl diphenyl phosphate, dibutyl phenyl phenyl phosphate, tributyl phenyl phosphate, and the like.

[0101] The triaryl phosphate (C) is preferably triphenyl phosphate or tri(4-tert-butylphenyl) phosphate. 1 and R 3 is tert-butyl, and R 2 , R 4 , R 5 The triaryl phosphate (C) is particularly preferably tri(2,4-di-tert-butylphenyl) phosphate.

[0102] The triaryl phosphate (C) may be used alone or in combination of two or more.

[0103] The content of triaryl phosphate (C) is 0.001 to 0.3 parts by mass relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B). The resin composition containing this amount of triaryl phosphate (C) combined with a specified amount of a compound having a phenolic structure (D) exhibits excellent weather resistance and also has a good color tone. The content of triaryl phosphate (C) is preferably 0.002 parts by mass or more, more preferably 0.003 parts by mass or more, or 0.004 parts by mass or more, particularly preferably 0.005 parts by mass or more, and preferably 0.25 parts by mass or less, more preferably 0.2 parts by mass or less, or 0.15 parts by mass or less, or 0.13 parts by mass or less, particularly preferably 0.1 parts by mass or less.

[0104] [Compound having a phenol structure (D)]

[0105] The polycarbonate resin composition according to the present invention contains the above-mentioned compound (D) having a phenol structure.

[0106] The compound (D) having a phenol structure in which a hydroxyl group is directly bonded to a benzene ring is 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol or bisphenol A. Among them, 4-tert-butylphenol, 4-α-cumylphenol and 2,4-di-tert-butylphenol are more preferred.

[0107] The compound (D) having a phenol structure may be contained alone or in combination of two or more compounds (D).

[0108] The content of the compound (D) having a phenol structure is 0.001 to 0.03 parts by mass relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B). When two or more compounds (D) having a phenol structure are contained, the total content is the content of the compound (D) having a phenol structure. The resin composition containing the compound (D) having a phenol structure in this amount combined with the triaryl phosphate (C) relative to the polycarbonate resin (A) and the graft copolymer (B) exhibits high weather resistance and excellent impact resistance, heat resistance and fluidity (formability).

[0109] The content of the compound (D) having a phenol structure is preferably 0.0015 parts by mass or more, more preferably 0.002 parts by mass or more, or 0.003 parts by mass or more, particularly preferably 0.004 parts by mass or more, relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B), and is preferably 0.025 parts by mass or less, more preferably 0.02 parts by mass or less, or 0.015 parts by mass or less, particularly preferably 0.013 parts by mass or less.

[0110] When 4-tert-butylphenol is contained as the compound (D) having a phenol structure, the content thereof is preferably 0.0012 to 0.01 parts by mass, more preferably 0.002 to 0.003 parts by mass, based on 100 parts by mass of the total mass of (A) and (B).

[0111] When 2,4-di-tert-butylphenol is contained as the compound (D) having a phenol structure, the content thereof is preferably 0.0012 to 0.01 parts by mass, more preferably 0.002 to 0.003 parts by mass, based on 100 parts by mass of the total mass of (A) and (B).

[0112] When 4-α-cumylphenol is contained, the content thereof is preferably 0.0012 to 0.01 parts by mass, more preferably 0.002 to 0.003 parts by mass, based on 100 parts by mass of the total mass of (A) and (B).

[0113] When bisphenol A is contained as the compound (D) having a phenol structure, the content thereof is preferably 0.002 to 0.03 parts by mass, more preferably 0.004 to 0.01 parts by mass, based on 100 parts by mass of the total mass of (A) and (B).

[0114] 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol or bisphenol A may be present in a free state as those used in the production of the polycarbonate resin (A) or produced as a by-product, or those derived from a recycled polycarbonate resin, and the amounts of these are also included in the amount of the compound (D) having a phenol structure.

[0115] [Triaryl phosphite (E)]

[0116] The polycarbonate resin composition according to the present invention preferably further contains triaryl phosphite (E). As used herein, the aryl group refers to a group containing a monocyclic or polycyclic aromatic group, and particularly preferably refers to a phenyl group.

[0117] Preferred examples of the triaryl phosphite (E) include triphenyl phosphite, tri(p-tolyl) phosphite, tri(p-nonylphenyl) phosphite, tri(mononyl / dinonylphenyl) phosphite, tri(2,4-di-tert-butylphenyl) phosphite, tri(naphthyl) phosphite, tri(p-chlorophenyl) phosphite, tri(p-fluorophenyl) phosphite, diphenylbenzylphosphine, diphenyl(p-hydroxyphenyl) phosphite, diphenyl-1,4-dihydroxyphenyl-2-phosphite, phenylnaphthylbenzylphosphine, etc. Particularly preferred are triphenyl phosphite and tri(2,4-di-tert-butylphenyl) phosphite.

[0118] When contained, the content of triaryl phosphite (E) is preferably 0.001 to 0.3 parts by mass relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B). The resin composition containing this amount of triaryl phosphite (E) combined with triaryl phosphate (C) exhibits a better color tone. The content of aryl phosphine is more preferably 0.005 parts by mass or more, even more preferably 0.008 parts by mass or more, particularly preferably 0.01 parts by mass or more, and more preferably 0.25 parts by mass or less, even more preferably 0.2 parts by mass or less, or 0.15 parts by mass or less, 0.1 parts by mass or less, or 0.05 parts by mass or less, particularly preferably 0.04 parts by mass or less.

[0119] [Phenolic antioxidants]

[0120] The polycarbonate resin composition according to the present invention preferably further contains a phenolic antioxidant.

[0121] For example, the phenolic antioxidant may be preferably a hindered phenolic antioxidant. Specific examples include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2 ,4,6-triyl) tri-p-cresol, 4,6-bis(octylthiomethyl)o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, etc.

[0122] Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are particularly preferred. One phenolic antioxidant may be used, or any combination of two or more in any ratio may be used.

[0123] When contained, the content of the phenolic antioxidant is preferably 0.001 mass part or more, more preferably 0.01 mass part or more, and preferably 1 mass part or less, more preferably 0.5 mass part or less, relative to 100 mass parts of the total mass of the polycarbonate resin (A) and the graft copolymer (B). When the phenolic antioxidant is contained in an amount above the lower limit of the range shown, its effect can be fully exerted. In addition, when the phenolic antioxidant is contained in an amount below the upper limit of the range shown, economic efficiency is allowed, and a plateau of the effect is not observed.

[0124] [Release agent]

[0125] The resin composition according to the present invention preferably further contains a mold release agent.

[0126] Examples of the release agent include aliphatic carboxylic acids, aliphatic carboxylic acid / alcohol esters, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.

[0127] Aliphatic carboxylic acids include saturated or unsaturated monobasic, dibasic or tribasic aliphatic carboxylic acids. Aliphatic carboxylic acids include alicyclic carboxylic acids. Among them, preferred aliphatic carboxylic acids are monobasic or dibasic carboxylic acids having 6 to 36 carbon atoms, and more preferably saturated monobasic aliphatic carboxylic acids having 6 to 36 carbon atoms. Specific examples of these aliphatic carboxylic acids are palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetratriacontanoic acid, montanic acid, adipic acid and azelaic acid.

[0128] For example, the same aliphatic carboxylic acids as described above can be used for the aliphatic carboxylic acids in the aliphatic carboxylic acid / alcohol esters. On the other hand, alcohols can be exemplified by saturated or unsaturated monohydric alcohols or polyhydric alcohols. These alcohols may have substituents, such as fluorine atoms, aromatic groups, etc. Among the aforementioned, monohydric or polyhydric saturated alcohols having a carbon number of 30 or less are preferred, and aliphatic saturated monohydric alcohols and aliphatic saturated polyhydric alcohols having a carbon number of 30 or less (in each case) are more preferred. Here, aliphatic is used as a term that also includes alicyclic compounds.

[0129] The alcohols under consideration may be specifically exemplified by the following: octanol, decyl alcohol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentyl glycol, di-trimethylolpropane and dipentaerythritol.

[0130] The ester may contain an aliphatic carboxylic acid and / or an alcohol as an impurity. In addition, the ester may be a single compound, or may be a mixture of multiple compounds. One aliphatic carboxylic acid or any combination of two or more in any ratio may be used for the aliphatic carboxylic acid constituting one ester by bonding therein, and one alcohol or any combination of two or more in any ratio may be used for the alcohol constituting one ester by bonding therein.

[0131] Specific examples of the aliphatic carboxylic acid / alcohol esters are beeswax (a mixture in which myristyl palmitate is a main component), stearyl stearate, behenyl behenate, stearyl behenate, glyceryl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0132] Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, C 3-12 Oligomers of α-olefins. Aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbons may be partially oxidized.

[0133] Among the foregoing, paraffin wax, polyethylene wax and partially oxidized polyethylene wax are preferred, and paraffin wax and polyethylene wax are more preferred.

[0134] The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.

[0135] The aliphatic hydrocarbon may be a single substance; however, a mixture of aliphatic hydrocarbons having various composition components and / or molecular weights may be used as long as the main component is within the above range.

[0136] Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil and fluoroalkyl silicone oil.

[0137] A single mold release agent as described above may be contained, or any combination of two or more in any ratio may be contained.

[0138] The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B). When the content of the release agent is less than the lower limit of the range shown, the demolding effect may not be satisfactory. On the other hand, when the content of the release agent exceeds the upper limit of the range shown, hydrolysis resistance may be reduced, and mold contamination may occur during injection molding, etc.

[0139] [Ultraviolet light absorber]

[0140] The polycarbonate resin composition according to the present invention preferably further contains an ultraviolet absorber.

[0141] The ultraviolet absorber can be exemplified by inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxalylanilide compounds, malonate compounds, hindered amine compounds, etc. Among the aforementioned, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By containing an organic ultraviolet absorber, the resin composition according to the present invention can have good transparency and good mechanical properties.

[0142] Specific examples of the benzotriazole compound include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[2′-hydroxy-3′,5′-bis(α,α-dimethylbenzyl)phenyl]benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol, among which 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol are preferred, and 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole is particularly preferred.

[0143] Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2′-dihydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone.

[0144] Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate.

[0145] Specific examples of the cyanoacrylate compound include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.

[0146] A specific example of the oxalic acid anilide compound is 2-ethoxy-2'-ethyl oxalic acid dianilide.

[0147] The malonate compound is preferably an ester of 2-(alkylene)malonic acid, and more preferably an ester of 2-(1-arylalkylene)malonic acid.

[0148] When contained, the content of the ultraviolet absorber is usually 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B). If the content of the ultraviolet absorber is less than the lower limit of the indicated range, the improvement of weather resistance and light resistance may be insufficient, while if the content of the ultraviolet absorber exceeds the upper limit of the indicated range, for example, mold deposition or the like may be generated, and mold contamination may be caused.

[0149] The ultraviolet absorber may be contained alone or in any combination of two or more in any ratio.

[0150] [Additives, etc.]

[0151] The polycarbonate resin composition according to the present invention may contain additives other than those mentioned above, such as fluorescent brighteners, pigments (including titanium oxide, etc.), dyes, flame retardants, impact resistance enhancers, plasticizers, compatibilizers, etc. These additives may be contained alone or in combination of two or more.

[0152] In addition, resins other than the polycarbonate resin (A) and the graft copolymer (B) may be contained. Such additional resins may be exemplified by thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate; styrene resins such as polystyrene resin (GPPS), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; and polymethacrylate resin.

[0153] When contained, the content of resins other than the polycarbonate resin (A) and the graft copolymer (B) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B).

[0154] [Example]

[0155] In order to confirm the effects of the polycarbonate resin composition according to the present invention, a polycarbonate resin composition was manufactured as described below; however, the present invention should not be construed as being limited to or by the following examples.

[0156] Table 1 below provides the components used.

[0157] [Table 1]

[0158]

[0159] (Examples 1 to 17 and Comparative Examples 1 to 8)

[0160] The above components were blended in the ratios (parts by mass) shown in Table 2 and thereafter, and fed to a twin-screw extruder ("TEM26SX", from Toshiba Machine Co., Ltd.), kneaded at a screw speed of 150 rpm, a discharge rate of 25 kg / hr, and a barrel temperature of 260° C., and extruded from the front end of the extrusion nozzle in the form of strands. The strands thus obtained were quenched in a water tank, and then cut and granulated with a pelletizer to obtain pellets of a polycarbonate resin composition.

[0161] <mvr>

[0162] The pellets obtained in the above manner were dried at 100° C. for 5 hours, and then MVR or melt volume rate (unit: g / 10 min) was measured according to ISO 1133 at a measuring temperature of 250° C. and a load of 2.16 kgf.

[0163] <Notched Charpy Strength>

[0164] The pellets obtained in the above manner were dried at 100°C for 5 hours and then injection molded using an injection molding machine ("NEX80III", from NISSEIPLASTIC INDUSTRIAL CO., LTD.) at a barrel temperature of 260°C and a mold temperature of 60°C to obtain ISO multi-purpose test pieces (4 mmt).

[0165] The ISO multi-purpose test pieces (4 mm t) thus obtained were used to measure the notched Charpy strength (unit: kJ / m 2 ).

[0166] <Heat resistance DTUL (deflection temperature under load)>

[0167] In accordance with ISO 75-1 and ISO 75-2, a constant bending load (1.80 MPa) is applied to a 4 mm x 10 mm ISO multi-purpose test piece (4mmt) at midspan in the flat direction, and the temperature (in °C) at which the deformation of the test piece at the midspan reaches 0.34 mm is measured as the temperature increases at a constant rate.

[0168] <Weather resistance (ΔE)>

[0169] The obtained pellets were injection molded using an injection molding machine "EC50SXII" from Toshiba Machine Co., Ltd. at a barrel temperature of 260°C and a mold temperature of 60°C to obtain a plate-shaped molded product having a width of 60 mm, a depth of 90 mm, and a thickness of 2 mm.

[0170] A xenon weathering tester ("Ci4400", from Atlas Electric Devices Company) was used at a temperature of 89°C with a wavelength of 300 to 400 nm and an irradiation intensity of about 55 W / m 2 The plate-shaped molded products thus obtained were subjected to a light fastness treatment for 100 hours (those containing titanium oxide were subjected to 300 hours). The color tone of the plate-shaped molded products before and after the light fastness treatment was measured using "SE6000" of NIPPOIN DENSHOKUINDUSTRIES CO., LTD. under the reflection conditions of D65 light source and 10° viewing angle, and the color difference ΔE was obtained for the evaluation of light fastness.

[0171] The color difference ΔE is preferably 7.5 or less, or when titanium oxide is contained, preferably 1.4 or less.

[0172] The evaluation results are shown in Table 2 and below.

[0173] [Table 2]

[0174]

[0175] [Table 3]

[0176]

[0177] [Table 4]

[0178]

[0179] [Table 5]

[0180]

[0181] [Table 6]

[0182]

[0183] Industrial Applicability

[0184] The polycarbonate resin composition according to the present invention exhibits high weather resistance and excellent impact resistance, heat resistance and fluidity (formability), and thus can be advantageously used for various molded articles.< / mvr>

Claims

1. A polycarbonate resin composition, comprising: 55 to 90% by mass of a polycarbonate resin (A) having a viscosity average molecular weight of 17,500 to 30,000; 10 to 45% by mass of a graft copolymer (B) containing an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2) and a diene rubber polymer component (b3); and, relative to 100 parts by mass of the total mass of (A) and (B), 0.001 to 0.3 parts by mass of a triaryl phosphate (C) represented by the general formula (1); and 0.001 to 0.3 parts by mass of a compound (D) having a phenol structure, in, The compound (D) having a phenol structure comprises at least one of 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol and bisphenol A, In formula (1), R 1 ~R 5 are independently hydrogen atoms or C 1-12 alkyl.

2. The polycarbonate resin composition according to claim 1, wherein R on each aromatic ring in formula (1) 1 ~R 5 At least one of them is C 1-12 alkyl.

3. The polycarbonate resin composition according to claim 1, wherein R on each aromatic ring in formula (1) 1 and R 3 C 1-12 alkyl, and each aromatic ring R 2 , R 4 and R 5 A hydrogen atom.

4. The polycarbonate resin composition according to claim 3, wherein R on each aromatic ring in formula (1) 1 and R 3 is tert-butyl, and R 2 , R 4 and R 5 A hydrogen atom. 5 . The polycarbonate resin composition according to claim 1 , wherein the triaryl phosphate (C) comprises at least one of triphenyl phosphate, tri-2,4-di-tert-butylphenyl phosphate, and tri-4-tert-butylphenyl phosphate. 6 . The polycarbonate resin composition according to claim 1 , further comprising: 0.001 to 0.3 parts by mass of triaryl phosphite (E) based on 100 parts by mass of the total mass of (A) and (B). 7 . Pellets comprising the polycarbonate resin composition according to claim 1 . 8 . A molded article comprising the polycarbonate resin composition according to claim 1 . 9 . A molded article comprising pellets of the polycarbonate resin composition according to claim 7 .

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