Polycarbonate resin composition

Abstract

The present invention relates to a polycarbonate resin composition comprising 55-90 mass% of a polycarbonate resin (A) having a viscosity average molecular weight of 17,500-30,000 and 10-45 mass% of a graft copolymer (B) comprising an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2), and a diene-based rubber polymer component (b3). The polycarbonate resin composition contains 0.001-0.3 parts by mass of an aryl phosphine oxide (C) and 0.001-0.3 parts by mass of a compound (D) having a phenol structure, based on 100 parts by mass of the total of (A) and (B). The polycarbonate resin composition is characterized in that 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. The polycarbonate resin composition is also characterized in that: the compound (D) has a phenol structure;

Description

TECHNICAL FIELD

[0001] The present application relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having excellent weather resistance and a molded body of the polycarbonate resin composition. BACKGROUND

[0002] Polycarbonate resins have excellent mechanical properties such as impact resistance and the like, and also have excellent heat resistance and excellent transparency and the like, and thus are widely used for many uses such as various optical parts, parts in electrical and electronic equipment, automotive interior and exterior decorative parts, OA equipment parts, sheets, mechanical parts, and building materials, and the like.

[0003] However, polycarbonate resins have somewhat limited uses due to their poor weather resistance. For example, their outdoor use or indoor use under fluorescent lamp irradiation leads to discoloration or strength reduction of the products.

[0004] In order to solve this problem, various light stabilizers have been used conventionally, either alone or in combination. A known example of such light stabilizers is a benzotriazole-based ultraviolet absorber. However, compounding such an ultraviolet absorber with a polycarbonate resin leads to another problem, i.e., hue deterioration of the polycarbonate resin composition, which is caused by thermal deterioration during melt kneading and molding processing.

[0005] Further, attempts have been made to compound various additives with polycarbonate resins to impart high functionality. For example, Patent Literature 1 describes that a fiber-reinforced polycarbonate resin composition excellent in dimensional stability, mechanical strength, and flowability can be obtained by mixing 5 to 15 mass% of triphenyl phosphate in 85 to 95 mass% of a polycarbonate resin.

[0006] With the rapid development of high functionality and high performance of various devices and equipment in recent years, there is a strong need for improvement of polycarbonate resins, particularly in weather resistance.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT LITERATURE

[0009] Patent Literature 1: Japanese Patent No. 3308657 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

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

[0012] SOLUTION TO THE PROBLEM

[0013] As a result of extensive and intensive studies made in order to solve the problem, the present inventors have made the present application after finding that a polycarbonate resin composition of a polymer alloy containing a small amount of aryl phosphine oxide and a small amount of a prescribed compound having a phenol structure with respect to a polycarbonate and a graft polymer (e.g., an ABS resin) exhibits excellent weather resistance as well as favorable impact resistance and heat resistance.

[0014] The present application relates to the following polycarbonate resin composition and molded body.

[0015] 1. A polycarbonate resin composition comprising: 55 to 90 mass% of a polycarbonate resin (A) having a viscosity average molecular weight of 17500 to 30000; 10 to 45 mass% of a graft copolymer (B) containing an aromatic vinyl monomer component (bl), a vinyl cyan monomer component (b2), and a diene rubber polymer component (b3); and 0.001 to 0.3 parts by mass and 0.001 to 0.3 parts by mass, respectively, with respect to 100 parts by mass of the total of (A) and (B), of an aryl phosphine oxide (C) and a compound (D) having a phenol structure,

[0016] wherein the compound (D) having a phenol structure contains at least one of 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol, and bisphenol A.

[0017] 2. The polycarbonate resin composition of the above 1, wherein the aryl phosphine oxide (C) is triphenyl phosphine oxide.

[0018] 3. The polycarbonate resin composition of the above 1 or 2, further comprising 0.001 to 0.3 parts by mass of an aryl phosphine (E) with respect to 100 parts by mass of the total of (A) and (B).

[0019] 4. The polycarbonate resin composition of the above 3, wherein the aryl phosphine (E) is triphenyl phosphine.

[0020] 5. A pellet of the polycarbonate resin composition of any one of the above 1 to 4.

[0021] 6. A molded body comprising the polycarbonate resin composition of any one of the above 1 to 4.

[0022] 7. A molded body comprising the pellet of the polycarbonate resin composition of the above 5.

[0023] Effects of the Invention

[0024] The polycarbonate resin composition according to the present application exhibits high weather resistance, and is excellent in impact resistance, heat resistance, and flowability (moldability). DETAILED DESCRIPTION

[0025] Hereinafter, embodiments and examples, etc. are provided to describe the present application in detail.

[0026] In the present specification, unless specifically stated otherwise, the use of "~ (to)" means to include the numerical value recited before and after it as a lower limit value and an upper limit value.

[0027] The polycarbonate resin composition according to the present application is characterized by: 55 to 90 mass% of a polycarbonate resin (A) having a viscosity average molecular weight of 17500 to 30000; 10 to 45 mass% of a graft copolymer (B) containing an aromatic vinyl monomer component (bl), a vinyl cyan monomer component (b2), and a diene rubber polymer component (b3); and 0.001 to 0.3 parts by mass and 0.001 to 0.3 parts by mass, respectively, relative to 100 parts by mass of the total of (A) and (B), of an aryl phosphine oxide (C) and a compound (D) having a phenol structure,

[0028] The compound (D) having a phenol structure contains at least one of 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-a-cumylphenol, and bisphenol A.

[0029] [Polycarbonate Resin (A)]

[0030] The polycarbonate resin (A) used in the present application can be of any kind. Only one polycarbonate resin can be used, or any combination of two or more polycarbonate resins in any ratio can be used.

[0031] Polycarbonate resins can be classified into aromatic polycarbonate resins (in which each of the carbons directly bonded to the carbonates bond is an aromatic carbon) and aliphatic polycarbonate resins (in which each of the carbons directly bonded to the carbonates bond is an aliphatic carbon), and any of these can be used. In view of, for example, heat resistance, mechanical properties, and electrical properties, for the polycarbonate resin (A), aromatic polycarbonate resins are preferred among them.

[0032] Among the monomers that are raw materials for aromatic polycarbonate resins, aromatic dihydroxy compounds can be exemplified as follows:

[0033] Dihydroxybenzenes, such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene;

[0034] Dihydroxydiphenyls, such as 2,5-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, and 4,4'-dihydroxydiphenyl;

[0035] Dihydroxy naphthalenes, such as 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;

[0036] Dihydroxydiaryl ethers, such as 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;

[0037] Bis(hydroxyaryl)alkanes, such as

[0038] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A),

[0039] 1,1 -bis(4-hydroxyphenyl)propane,

[0040] 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C),

[0041] 2,2-bis(3-methoxy-4-hydroxyphenyl)propane,

[0042] 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane,

[0043] 1,1 -bis(3-tert-butyl-4-hydroxyphenyl)propane,

[0044] 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,

[0045] 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,

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

[0047] α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene,

[0048] 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,

[0049] Bis(4-hydroxyphenyl)methane,

[0050] Bis(4-hydroxyphenyl)cyclohexylmethane,

[0051] Bis(4-hydroxyphenyl)phenylmethane,

[0052] Bis(4-hydroxyphenyl)(4-propylphenyl)methane,

[0053] Bis(4-hydroxyphenyl) naphthylmethane,

[0054] Bis(4-hydroxyphenyl) naphthylmethane,

[0055] 1,1 -Bis(4-hydroxyphenyl)ethane,

[0056] 1,1 -Bis(4-hydroxyphenyl)-1 -phenylethane,

[0057] 1,1 -Bis(4-hydroxyphenyl)-1 -naphthylethane,

[0058] 1,1 -Bis(4-hydroxyphenyl)butane,

[0059] 2,2-Bis(4-hydroxyphenyl)butane,

[0060] 2,2-Bis(4-hydroxyphenyl)pentane,

[0061] 1,1 -Bis(4-hydroxyphenyl)hexane,

[0062] 2,2-Bis(4-hydroxyphenyl)hexane,

[0063] 1,1 -Bis(4-hydroxyphenyl)octane,

[0064] 2,2-Bis(4-hydroxyphenyl)octane,

[0065] 4,4-Bis(4-hydroxyphenyl)heptane,

[0066] 2,2-Bis(4-hydroxyphenyl)nonane,

[0067] 1,1 -Bis(4-hydroxyphenyl)decane, and

[0068] 1,1 -Bis(4-hydroxyphenyl)dodecane;

[0069] Bis(hydroxyaryl)cycloalkanes, for example,

[0070] 1,1 -Bis(4-hydroxyphenyl)cyclopentane,

[0071] 1,1 -Bis(4-hydroxyphenyl)cyclohexane,

[0072] 1,1 -Bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane,

[0073] 1,1 -Bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane,

[0074] 1,1 -Bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane,

[0075] 1,1 -Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,

[0076] 1, 1 -bis(4-hydroxy-3, 5 -dimethylphenyl)-3, 3, 5 -trimethylcyclohexane,

[0077] 1, 1 -bis(4-hydroxyphenyl)-3 -propyl-5 -methylcyclohexane,

[0078] 1, 1 -bis(4-hydroxyphenyl)-3 -tert-butylcyclohexane,

[0079] 1, 1 -bis(4-hydroxyphenyl)-4-tert-butylcyclohexane,

[0080] 1, 1 -bis(4-hydroxyphenyl)-3 -phenylcyclohexane, and

[0081] 1, 1 -bis(4-hydroxyphenyl)-4-phenylcyclohexane;

[0082] Bisphenols containing a cardo structure, for example, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0083] Dihydroxydiaryl sulfides, for example, 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide;

[0084] Dihydroxydiaryl sulfoxides, for example, 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; and

[0085] Dihydroxydiaryl sulfones, for example, 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone.

[0086] Among these, bis(hydroxyaryl)alkanes are preferred, and among these, bis(4-hydroxyphenyl)alkanes are preferred, with 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) being particularly preferred from the standpoints of impact resistance and heat resistance.

[0087] An aromatic dihydroxy compound can be used, or any combination of two or more aromatic dihydroxy compounds in any ratio can be used.

[0088] Among monomers that are raw materials for polycarbonate resins, carbonate precursors can be exemplified by carbonyl halides and carbonic acid esters. One carbonate precursor can be used, or any combination of two or more carbonate precursors in any ratio can be used.

[0089] Carbonyl halides can be specifically exemplified by phosgene and haloformic acid esters such as bischloroformate esters of dihydroxy compounds and monochloroformate esters of dihydroxy compounds.

[0090] The carbonate ester can specifically exemplified as diaryl carbonate esters such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonate esters 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.

[0091] The production method of the polycarbonate resin (A) is not particularly limited, and any method can be used. Examples thereof are interfacial polymerization method, melt transesterification method, pyridine method, ring-opening polymerization method of cyclic carbonate compound, and solid phase transesterification method of prepolymer. Among them, the polycarbonate resin (A) produced by the interfacial polymerization method or the melt transesterification method is preferred because it provides greater improvement in the moisture heat resistance, with the interfacial polymerization method being particularly preferred.

[0092] The viscosity average molecular weight (Mv) of the polycarbonate resin (A) used in the present application is in the range of 17500 to 30000. The polycarbonate resin composition comprising the polycarbonate resin (A) having a viscosity average molecular weight in this range together with the aryl phosphine oxide (C) and the compound (D) having a phenolic structure can exhibit advantageous impact resistance and heat resistance, good flowability (moldability) and excellent weather resistance. The polycarbonate resin having an Mv lower than 17500 tends to result in insufficient impact resistance, poor weather resistance and reduced heat resistance. The polycarbonate resin having an Mv higher than 30000 tends to result in reduced flowability, so that high temperature molding at a temperature of 300°C or higher is required, in which case the graft copolymer (B) is likely to deteriorate due to heat, resulting in a reduction in impact resistance.

[0093] The viscosity average molecular weight (Mv) is preferably at least 18000, more preferably at least 18500, at least 19000 or at least 19500, particularly preferably at least 20000, and preferably not more than 29000, more preferably not more than 26000.

[0094] A mixture of two or more polycarbonate resins having different viscosity average molecular weights can be used, in which case a polycarbonate resin having a viscosity average molecular weight outside the above range can be mixed so that the viscosity average molecular weight of the mixture is within the range.

[0095] The viscosity average molecular weight Mv of the polycarbonate resin (A) refers to the value calculated using Schnell's viscosity formula, i.e., η = 1.23 x 10 - 4 Mv 0.83 The value calculated using dichloromethane as the solvent and using an Ubbelohde viscometer to determine the intrinsic viscosity [η] at a temperature of 25°C (unit: dl / g). The intrinsic viscosity [η] is the value calculated using the following formula and the specific viscosity [η sp ] measured at each solution concentration [C] (g / dl).

[0096] [Math. 1]

[0097] Further, the polycarbonate resin (A) can contain a polycarbonate oligomer, thereby bringing about an improved appearance and an improvement in flowability to the molded body. The viscosity average molecular weight [Mv] of the polycarbonate oligomer is generally at least 1500, preferably at least 2000, and generally not more than 9500, preferably not more than 9000. When the polycarbonate oligomer is contained, the content of the polycarbonate oligomer is preferably not more than 30% by mass of the polycarbonate resin (including the polycarbonate oligomer).

[0098] The polycarbonate resin (A) can not only be a virgin raw material, but also a polycarbonate resin regenerated from a used article (also referred to as a material-recycled polycarbonate resin), and further preferably contains both a virgin raw material and a recycled resin, and can be composed of a recycled polycarbonate resin. The proportion of the recycled polycarbonate resin in the polycarbonate resin (A) is preferably at least 40%, or at least 50%, or at least 60%, or at least 80%, and can be particularly preferably 100%.

[0099] [graft copolymer (B)]

[0100] The graft copolymer (B) contained in the polycarbonate resin composition according to the present application is a graft copolymer containing an aromatic vinyl monomer component (bl), a vinyl cyan 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 (bl), 10 to 30% by mass of the vinyl cyan monomer component (b2), and 10 to 50% by mass of the diene rubber polymer component (b3), and can further contain 0 to 30% by mass of another monomer component (b4).

[0101] Examples of the aromatic vinyl monomer component (bl) in the graft copolymer (B) include styrene, a-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinyl naphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, etc.; styrene is particularly preferred.

[0102] The proportion of the aromatic vinyl monomer component (bl) in 100% by mass of the graft copolymer (B) is preferably in the range of 40 to 80% by mass, more preferably at least 45% by mass, still more preferably at least 50% by mass, particularly preferably at least 55% by mass, and more preferably not more than 75% by mass, still more preferably not more than 70% by mass, particularly preferably not more than 65% by mass.

[0103] Examples of the vinyl cyan monomer component (b2) in the graft copolymer (B) include acrylonitrile and methacrylonitrile, and the like; acrylonitrile is particularly preferred.

[0104] The proportion of the vinyl cyan monomer component (b2) in 100 mass% of the graft copolymer (B) is preferably in the range of 10 to 30 mass%, more preferably at least 12 mass%, still more preferably at least 14 mass%, particularly preferably at least 15 mass%, and more preferably not more than 28 mass%, still more preferably not more than 26 mass%, particularly preferably not more than 25 mass%.

[0105] Examples of the diene rubber polymer component (b3) in the graft copolymer (B) include rubber components such as polybutadiene, polyisoprene, and styrene-butadiene copolymer. The proportion of the diene rubber polymer component (b3) in 100 mass% of the graft copolymer (B) is preferably in the range of 10 to 50 mass%, more preferably at least 13 mass%, still more preferably at least 14 mass%, particularly preferably at least 15 mass%, and more preferably not more than 45 mass%.

[0106] Other monomer components (b4) copolymerizable with these components can be copolymerized. In such cases, examples of the other copolymerizable vinyl monomers include maleimide-based monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; acrylamide-based monomers such as acrylamide and N-methylacrylamide; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; glycidyl acrylate; glycidyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; methoxy polyethylene glycol methacrylate; and the like.

[0107] The proportion of the other monomer components (b4) in 100 mass% of the graft copolymer (B) is preferably in the range of 0 to 30 mass%, more preferably not more than 20 mass%, still more preferably not more than 10 mass%, even more preferably not more than 5 mass%, particularly preferably not more than 3 mass%, and particularly preferably not more than 2 mass%.

[0108] Specific preferred examples of the graft copolymer (B) include acrylonitrile-butadiene-styrene graft copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene graft copolymer, and acrylonitrile·ethylene-propylene-diene·styrene copolymer, and the like. Among these, acrylonitrile-butadiene-styrene graft copolymer (ABS resin) is particularly preferred.

[0109] The graft copolymer (B) is generally produced by a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and the like, and any of these methods can be used.

[0110] The content of the graft copolymer (B) is 10 to 45 mass%, preferably at least 12 mass%, more preferably at least 15 mass%, and preferably not more than 42 mass%, more preferably not more than 40 mass%, relative to 100 mass% of the total mass of the polycarbonate resin (A) and the graft copolymer (B). The graft copolymer (B) in the content in this range contributes to imparting excellent heat resistance and flowability to the resulting resin composition. If the content of the graft copolymer (B) exceeds 45 mass%, the heat resistance of the resin composition can decrease. If the content is less than 10 mass%, the flowability can decrease.

[0111] [aryl phosphine oxide (C)]

[0112] The polycarbonate resin composition according to the present application contains an aryl phosphine oxide (C). As used herein, aryl represents a group which can have a substituent and which contains a monocyclic or polycyclic aromatic group, and particularly preferably represents a phenyl group which can have a substituent.

[0113] Preferred examples of the aryl phosphine oxide (C) include triphenyl phosphine oxide, diphenyl butyl phosphine oxide, diphenyl octadecyl phosphine oxide, tri(p-tolyl) phosphine oxide, tri(p-nonylphenyl) phosphine oxide, tri(naphthyl) phosphine oxide, diphenyl(hydroxymethyl) phosphine oxide, diphenyl(acetyloxymethyl) phosphine oxide, diphenyl(β-ethylcarboxyethyl) phosphine oxide, tri(p-chlorophenyl) phosphine oxide, tri(p-fluorophenyl) phosphine oxide, diphenylbenzyl phosphine oxide, diphenyl-β-cyanoethyl phosphine oxide, diphenyl(p-hydroxyphenyl) phosphine oxide, diphenyl-1,4-dihydroxyphenyl-2-phosphine oxide, and phenyl naphthyl benzyl phosphine oxide. Triaryl phosphine oxides are preferred, and triphenyl phosphine oxide is particularly preferred.

[0114] The content of the aryl phosphine oxide (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). A resin composition containing the aryl phosphine oxide (C) in this amount can exhibit excellent weather resistance in combination with the compound (D) having a phenolic structure. The content of the aryl phosphine oxide (C) is preferably at least 0.002 parts by mass, more preferably at least 0.003 parts by mass, particularly preferably at least 0.004 parts by mass, and preferably not more than 0.25 parts by mass, more preferably not more than 0.2 parts by mass, or not more than 0.15 parts by mass, or not more than 0.13 parts by mass, particularly preferably not more than 0.1 parts by mass.

[0115] [compound (D) having a phenolic structure]

[0116] The polycarbonate resin composition according to the present application contains a compound (D) having a phenolic structure.

[0117] In the present application, the compound (D) having a phenol structure, which is a compound in which a hydroxyl group is directly bonded to a benzene ring, does not include the phenol-based antioxidant described later. The compound (D) having a phenol structure in the present application includes at least one of 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol, and bisphenol A. Among them, 4-tert-butylphenol, 4-α-cumylphenol, and 2,4-di-tert-butylphenol are more preferable.

[0118] The compound (D) having a phenol structure can be contained alone, or two or more compounds (D) can be contained in combination.

[0119] The content of the compound (D) having a phenol structure is 0.001 to 0.3 parts by mass with respect 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 thereof is the content of the compound (D) having a phenol structure. The resin composition in which the compound (D) having a phenol structure is contained in this amount with respect to the polycarbonate resin (A) and the graft copolymer (B) and the aryl phosphine oxide (C) is excellent in weather resistance and in impact resistance, heat resistance, and flowability (moldability).

[0120] The content of the compound (D) having a phenol structure is preferably at least 0.0015 parts by mass, more preferably at least 0.002 parts by mass, particularly preferably at least 0.003 parts by mass, and preferably not more than 0.25 parts by mass, more preferably not more than 0.2 parts by mass, or not more than 0.1 parts by mass, not more than 0.05 parts by mass, or not more than 0.01 parts by mass, particularly preferably not more than 0.005 parts by mass, with respect to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B).

[0121] In the case where 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 0.0015 to 0.005 parts by mass, still more preferably 0.002 to 0.0048 parts by mass, particularly preferably 0.003 to 0.0045 parts by mass, with respect to 100 parts by mass of the total mass of (A) and (B).

[0122] In the case where 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 0.0015 to 0.005 parts by mass, still more preferably 0.002 to 0.0048 parts by mass, particularly preferably 0.003 to 0.0045 parts by mass, with respect to 100 parts by mass of the total mass of (A) and (B).

[0123] In the case of containing 4-α-cumylphenol, the content thereof is preferably 0.0012 to 0.01 parts by mass, more preferably 0.0015 to 0.005 parts by mass, still more preferably 0.002 to 0.0048 parts by mass, and particularly preferably 0.003 to 0.0045 parts by mass, relative to 100 parts by mass of the total of (A) and (B).

[0124] In the case of containing bisphenol A as the compound (D) having a phenolic structure, the content thereof is preferably 0.002 to 0.03 parts by mass, more preferably 0.004 to 0.01 parts by mass, relative to 100 parts by mass of the total of (A) and (B).

[0125] 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-α-cumylphenol, or bisphenol A can exist in a free state (such as those used or generated as by-products in the production of the polycarbonate resin (A), or those derived from recycled polycarbonate resin), and the amount thereof is also included in the amount of the compound (D) having a phenolic structure.

[0126] [aryl phosphine (E)]

[0127] The polycarbonate resin composition according to the present application preferably further contains an aryl phosphine (E). As used herein, aryl represents a group which can have a substituent and which contains a monocyclic or polycyclic aromatic group, and particularly preferably represents a phenyl group which can have a substituent.

[0128] Preferred examples of the aryl phosphine (E) include triphenyl phosphine, diphenyl butyl phosphine, diphenyl octadecyl phosphine, tri(p-tolyl) phosphine, tri(p-nonylphenyl) phosphine, tri(naphthyl) phosphine, diphenyl(hydroxymethyl) phosphine, diphenyl(acetyloxymethyl) phosphine, diphenyl(β-ethylcarboxyethyl) phosphine, tri(p-chlorophenyl) phosphine, tri(p-fluorophenyl) phosphine, diphenylbenzyl phosphine, diphenyl-β-cyanoethyl phosphine, diphenyl(p-hydroxyphenyl) phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine, and phenylnaphthylbenzyl phosphine. Triaryl phosphines, triphenyl phosphine, and tri-mesityl phosphine, and the like are preferred, and triphenyl phosphine is particularly preferred.

[0129] When the aryl phosphine (E) is contained, the content of the aryl phosphine (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 the aryl phosphine (E) in this amount and containing the aryl phosphine oxide (C) and the compound (D) having a phenol structure can exhibit further improved weather resistance. The content of the aryl phosphine (E) is more preferably at least 0.005 parts by mass, still more preferably at least 0.008 parts by mass, particularly preferably at least 0.01 parts by mass, and more preferably not more than 0.25 parts by mass, still more preferably not more than 0.2 parts by mass, or not more than 0.15 parts by mass, not more than 0.1 parts by mass, or not more than 0.05 parts by mass, and particularly preferably not more than 0.04 parts by mass.

[0130] [aryl phosphine]

[0131] The polycarbonate resin composition according to the present application preferably further contains a triaryl phosphite. As used herein, aryl represents a group which can have a substituent and which contains a monocyclic or polycyclic aromatic group, and particularly preferably represents a phenyl group which can have a substituent.

[0132] Preferred examples of the triaryl phosphite include triphenyl phosphite, tris(p-tolyl) phosphite, tris(p-nonylphenyl) phosphite, tris(mono- / di-nonyl-phenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(naphthyl) phosphite, tris(p-chlorophenyl) phosphite, tris(p-fluorophenyl) phosphite, diphenylbenzyl phosphite, diphenyl(p-hydroxyphenyl) phosphite, diphenyl-1,4-dihydroxyphenyl-2-phosphite, and phenylnaphthylbenzyl phosphite, and the like. Triphenyl phosphite and tris(2,4-di-t-butylphenyl) phosphite are particularly preferred.

[0133] When the triaryl phosphite is contained, the content of the triaryl phosphite 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 triaryl phosphite contained in this amount in combination with the aryl phosphine oxide (C) and the compound (D) having a phenol structure can contribute to further improvement of the retention heat stability. The content of the triaryl phosphite is more preferably at least 0.005 parts by mass, still more preferably at least 0.008 parts by mass, particularly preferably at least 0.01 parts by mass, and more preferably not more than 0.25 parts by mass, still more preferably not more than 0.2 parts by mass, or not more than 0.15 parts by mass, not more than 0.1 parts by mass, or not more than 0.05 parts by mass, and particularly preferably not more than 0.04 parts by mass.

[0134] [phenol-based antioxidant]

[0135] The polycarbonate resin composition according to the present application preferably further contains a phenol-based antioxidant.

[0136] For example, the phenol-based antioxidant can preferably be a hindered phenol-based 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, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] diethyl phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(m-terphenyl-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl) o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[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-triazin-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0137] 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 preferable. One phenol-based antioxidant can be used, or two or more of any combination in any ratio can be used.

[0138] When the phenol-based antioxidant is contained, the content of the phenol-based antioxidant is preferably at least 0.001 parts by mass, more preferably at least 0.01 parts by mass, and preferably not more than 1 parts by mass, more preferably not more than 0.5 parts by mass, relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B). When the phenol-based antioxidant is contained in an amount equal to or greater than the lower limit of the range, the phenol-based antioxidant can sufficiently exert its function. Furthermore, when the phenol-based antioxidant is contained in an amount not greater than the upper limit of the range, the phenol-based antioxidant allows economic efficiency without observing a plateau of the effect.

[0139] [Release agent]

[0140] The resin composition according to the present application preferably further contains a release agent.

[0141] The releasing agent can exemplify aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and silicone-based silicone oils.

[0142] The aliphatic carboxylic acid can exemplify saturated or unsaturated, monovalent, divalent, or trivalent aliphatic carboxylic acids. Here, the aliphatic carboxylic acid also includes alicyclic carboxylic acids. Among them, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbons, and a saturated monovalent aliphatic carboxylic acid having 6 to 36 carbons is more preferred. Specific examples of these aliphatic carboxylic acids are palmitic acid, stearic acid, hexanoic acid, decanoic acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myricyl alcohol, melissic acid, montanic acid, adipic acid, and azelaic acid.

[0143] For the aliphatic carboxylic acid in the ester of aliphatic carboxylic acids and alcohols, for example, the same aliphatic carboxylic acid as described above can be used. On the other hand, the alcohol can exemplify saturated or unsaturated, monohydric or polyhydric alcohols. These alcohols can have substituents such as fluorine atoms and aryl groups, etc. Among them, monovalent or polyhydric saturated alcohols having not more than 30 carbons are preferred, and aliphatic saturated monohydric alcohols and aliphatic saturated polyhydric alcohols each having not more than 30 carbons are more preferred. Here, aliphatic is used as a term that also includes alicyclic compounds.

[0144] The contemplated alcohols can specifically exemplify octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentyl glycol, ditrimethylolpropane, and dipentaerythritol.

[0145] The ester can contain aliphatic carboxylic acids and / or alcohols as impurities. In addition, the ester can be one compound or can be a mixture of a plurality of compounds. For the aliphatic carboxylic acid that constitutes one ester by bonding therein, one aliphatic carboxylic acid or any combination of two or more in any ratio can be used, and for the alcohol that constitutes one ester by bonding therein, one alcohol or any combination of two or more in any ratio can be used.

[0146] Specific examples of the ester of aliphatic carboxylic acids and alcohols are beeswax (a mixture in which palmitic acid myricyl ester is a main component), stearic acid stearyl ester, behenic acid behenyl ester, behenic acid stearyl ester, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0147] The aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 can exemplify liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and C 3-12 Oligomers of α-olefins. The aliphatic hydrocarbon also includes alicyclic hydrocarbons. These hydrocarbons can be partially oxidized.

[0148] Among them, paraffin wax, polyethylene wax and partially oxidized polyethylene wax are preferred, and paraffin wax and polyethylene wax are more preferred.

[0149] The number average molecular weight of the aliphatic hydrocarbon is preferably not more than 5000.

[0150] The aliphatic hydrocarbon can be a single substance; however, a mixture of aliphatic hydrocarbons having various constituent components and / or molecular weights can be used as long as the main component is within the above range.

[0151] The silicone-based silicone oil can be exemplified by dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil and fluoroalkyl silicone, etc.

[0152] One releasing agent as described above can be included, or two or more of any combination in any ratio can be included.

[0153] The content of the releasing agent is usually at least 0.001 parts by mass, preferably at least 0.01 parts by mass, and usually not more than 2 parts by mass, preferably not more than 1 part by mass, more preferably not more than 0.5 parts by mass, 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 releasing agent is less than the lower limit of the range, the releasing effect can be unsatisfactory. On the other hand, when the content of the releasing agent exceeds the upper limit of the range, the hydrolysis resistance can be reduced and mold contamination during injection molding, etc. can occur.

[0154] [ultraviolet absorber]

[0155] The polycarbonate resin composition according to the present application preferably further comprises an ultraviolet absorber.

[0156] 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, oxanilide compounds, malonate compounds and hindered amine compounds. Among them, the organic ultraviolet absorbers are preferred, and the benzotriazole compounds are more preferred. By including the organic ultraviolet absorber, the resin composition according to the present application can provide advantageous transparency and advantageous mechanical properties.

[0157] The benzotriazole compound can be specifically exemplified by 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(alpha,alpha-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-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-5'- tert-octylphenyl)benzotriazole, and 2,2'-methylenebis[4-(l,l,3,3-tetramethylbutyl)-6-(2H- benzotriazol-2-yl)phenol], among which 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylenebis[4-(l,l,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] are preferred, and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole is particularly preferred.

[0158] The benzophenone compound can be specifically exemplified by 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.

[0159] The salicylate compound can be specifically exemplified by phenyl salicylate and 4-tert-butylphenyl salicylate.

[0160] The cyano acrylate compound can be specifically exemplified by 2-cyano-3,3-diphenyl acrylate ethyl ester and 2-cyano-3,3-diphenyl acrylate 2-ethylhexyl ester.

[0161] The oxalyl diamide compound can be specifically exemplified by 2-ethoxy-2'-ethyl oxanil.

[0162] The malonate compound is preferably an ester of 2-(alkylene)malonic acid, among which an ester of 2-(l-arylalkylene)malonic acid is more preferred.

[0163] When the ultraviolet absorber is contained, the content of the ultraviolet absorber is usually at least 0.05 parts by mass, preferably at least 0.1 parts by mass, and usually not more than 1 parts by mass, preferably not more than 0.5 parts by mass, 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 range, the improvement in weather resistance and light resistance can be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, for example, mold contamination and the like can occur and mold contamination can be caused.

[0164] One ultraviolet absorber can be contained, or two or more ultraviolet absorbers in any combination can be contained at any ratio.

[0165] [Additives and the like]

[0166] The polycarbonate resin composition according to the present application can contain additives other than the above, for example, additives such as a fluorescent whitening agent, a pigment (including titanium oxide and the like), a dye, a flame retardant, an impact resistance modifier, a plasticizer, and a compatibilizer, and the like. One of these additives or two or more of these additives can be contained.

[0167] Furthermore, a resin other than the polycarbonate resin (A) and the graft copolymer (B) can also be contained. Such additional resin can be exemplified by a thermoplastic polyester resin such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate; a styrene-based resin such as polystyrene resin (GPPS), high-impact polystyrene resin (HIPS), and acrylonitrile-styrene copolymer (AS resin); a polyolefin resin such as polyethylene resin and polypropylene resin; a polyamide resin; a polyimide resin; a polyetherimide resin; a polyurethane resin; a polyphenylene ether resin; a polyphenylene sulfide resin; a polysulfone resin; and a polymethacrylate resin.

[0168] When a resin other than the polycarbonate resin (A) and the graft copolymer (B) is contained, the content of the resin other than the polycarbonate resin (A) and the graft copolymer (B) is preferably not more than 20 parts by mass, more preferably not more than 10 parts by mass, still more preferably not more than 5 parts by mass, particularly not more than 3 parts by mass, relative to 100 parts by mass of the total mass of the polycarbonate resin (A) and the graft copolymer (B).

[0169] [Examples]

[0170] In order to confirm the effects of the polycarbonate resin composition according to the present application, the polycarbonate resin composition was produced as described below; however, the present application should not be construed as being limited to or by the following examples.

[0171] Table 1 below provides the components used.

[0172] [Table 1]

[0173]

[0174] (Examples 1 to 13 and Comparative Examples 1 to 9)

[0175] The above components were compounded in the proportions (parts by mass) shown in Table 2 or the like below and supplied to a twin-screw extruder ("TEM26SX" manufactured by Toshiba Machine Co., Ltd.), where they were kneaded at a screw rotation speed of 150 rpm, a discharge rate of 25 kg / hr, and a barrel temperature of 260°C, and extruded in the form of a strand from the front end of the extrusion nozzle. The strand thus obtained was quenched in a water tank, and then cut and pelletized with a pelletizer to obtain pellets of the polycarbonate resin composition.

[0176] <mvr>

[0177] The pellets obtained in the above manner were dried at 100°C for 5 hours, and then the MVR or melt volume rate (unit: g / 10 min) was measured according to ISO 1133 at a measurement temperature of 250°C and a load of 2.16 kgf.

[0178] <Notched Charpy Strength>

[0179] 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" manufactured by Nissei Plastic Industrial Co., LTD.) at a cylinder temperature of 260°C and a mold temperature of 60°C to obtain ISO multipurpose test pieces (4 mmt).

[0180] The ISO multipurpose test pieces (4 mmt) thus obtained were used to measure the notched Charpy strength (unit: kJ / m 2 ) according to ISO 179 at a temperature of 23°C.

[0181] <Heat Resistance DTUL (Load Deflection Temperature)>

[0182] According to ISO 75-1 and ISO 75-2, a constant bending load (1.80 MPa) was applied in the planar direction at the center of a 4 mm x 10 mm ISO multipurpose test piece (4 mmt), and then the temperature at which the deformation of the test piece at the center reached 0.34 mm as the temperature was raised at a constant rate was measured (unit: °C).

[0183] <Weather Resistance (ΔE)>

[0184] The pellets obtained were injection-molded using an injection molding machine "EC50SXII" manufactured by Toshiba Machine Co., Ltd. at a cylinder 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 length of 90 mm, and a thickness of 2 mm.

[0185] Using a xenon weather resistance tester ("Ci4000" manufactured by Atlas Electric Devices Company), a light source having a wavelength of 300 to 400 nm and an irradiation intensity of about 55 W / m 2 The plate-shaped molded articles thus obtained were subjected to light resistance treatment for 100 hours (or 200 hours for those containing carbon black). The hue of the plate-shaped molded articles before and after the light resistance treatment was measured using a spectrophotometer "SE6000" manufactured by Nippon Denshoku Industries Co., Ltd. under reflection conditions of D65 light source and 10° field of view, and the color difference ΔΕ was obtained for evaluation of light resistance.

[0186] The color difference ΔΕ is preferably not more than 7.5, or not more than 3.0 when containing carbon black.

[0187] The evaluation results are shown in Table 2 and the like below.

[0188] [Table 2]

[0189]

[0190] [Table 3]

[0191]

[0192] [Table 4]

[0193]

[0194] Industrial Applicability

[0195] The polycarbonate resin composition according to the present application exhibits high weather resistance and excellent impact resistance, heat resistance, and flowability (moldability), 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), wherein the graft copolymer (B) comprises an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2), and a diene rubber polymer component (b3); and 0.001 to 0.3 parts by mass of an arylphosphine oxide (C) and 0.001 to 0.3 parts by mass of a compound having a phenol structure (D), relative to 100 parts by mass of the total mass of (A) and (B). 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. 2 . The polycarbonate resin composition according to claim 1 , wherein the arylphosphine oxide (C) is triphenylphosphine oxide. 3 . The polycarbonate resin composition according to claim 1 , further comprising 0.001 to 0.3 parts by mass of an aryl phosphine (E) relative to 100 parts by mass of the total mass of (A) and (B). The polycarbonate resin composition according to claim 3 , wherein the aryl phosphine (E) is triphenylphosphine. 5 . Pellets of the polycarbonate resin composition according to claim 1 . 6 . A molded article comprising the polycarbonate resin composition according to claim 1 . 7 . A molded article comprising pellets of the polycarbonate resin composition according to claim 5 .

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