Polycarbonate resin components

Abstract

DEPCT6820 / 06 / 2568 Polycarbonate resin composition including: Polycarbonate resin (A) 55 to 90 percent By mass, with an average viscosity molecular weight of 17500 to 30000, branched copolymer (B)10 to 45 percent by mass containing the aromatic vinyl monomer (b1) component. Vinyl cyanide monomer (b2) and diene rubber polymer component (b3) and When compared to the combined mass of (A) and (B) which is 100 parts by mass, 0.001 to 0.3 parts by mass of Triaryl phosphate (C) is determined by the general formula (1) specifically and 0.001 to 0.3 parts by Mass of the phenolic compound (D) at which the phenolic compound (D) There is at least one type of 4-t-butylphenol, 2,4-di-t-butylphenol, 4-alpha-cumylphenol, and bisphenol. Phenol A;

Description

Polycarbonate resin composition

[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 thereof.

[0002] Polycarbonate resins have excellent mechanical properties such as impact resistance, and also have excellent heat resistance and transparency, and are therefore widely used in many applications such as various optical components, electrical and electronic equipment components, automobile interior and exterior components, office automation equipment components, sheets, machine components, building materials, etc. However, polycarbonate resins do not have sufficient weather resistance, and for example, when used outdoors or indoors under fluorescent light irradiation, discoloration or a decrease in strength of the product is observed, which has limited their use to some extent.

[0003] For this reason, various light stabilizers have been used alone or in combination, and it is known to incorporate ultraviolet absorbers such as benzotriazoles. However, when such ultraviolet absorbers are incorporated into polycarbonate resins, there is a problem that the color of the polycarbonate resin composition deteriorates due to thermal degradation during melt-kneading and molding. Furthermore, various additives have been incorporated to enhance functionality. For example, Patent Document 1 describes that a fiber-reinforced polycarbonate resin composition with excellent dimensional stability, mechanical strength, and fluidity can be obtained by mixing 5 to 15 mass% of triphenyl phosphate with 85 to 95 mass% of polycarbonate resin.

[0004] In recent years, with the rapid progress in the sophistication and performance of various devices, there has been a strong demand for polycarbonate resins, particularly for improved weather resistance.

[0005] Patent No. 3308657

[0006] An object (object) of the present invention is to provide a polycarbonate resin composition which has excellent weather resistance, good impact resistance, heat resistance and flowability (moldability).

[0007] The present inventors have conducted extensive research to achieve the above object and have found that a polycarbonate resin composition containing a small amount of a specific triaryl phosphate compound in a resin alloy with a graft polymer such as an ABS resin has good impact resistance and heat resistance as well as excellent weather resistance, and have thus completed the present invention. The present invention relates to the following polycarbonate resin composition and molded article.

[0008] 1. A polycarbonate resin composition comprising 55 to 90 mass% of a polycarbonate resin (A) having a viscosity average molecular weight of 17,500 to 30,000, and 10 to 45 mass% of a graft copolymer (B) comprising an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2), and a diene rubber polymer component (b3), relative to a total of 100 mass% of (A) and (B), and 0.001 to 0.3 mass parts of a triaryl phosphate (C) represented by the following general formula (1), and 0.001 to 0.3 mass parts of a compound (D) having a phenol structure, wherein the compound (D) having a phenol structure comprises at least one of 4-t-butylphenol, 2,4-di-t-butylphenol, 4-α-cumylphenol, and bisphenol A: [In formula (1), R １ ~R ５ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.] 2. In formula (1), R on each aromatic ring １ ~R ５ 3. The polycarbonate resin composition according to 1 above, wherein at least one of R on each aromatic ring is an alkyl group having 1 to 12 carbon atoms. １ , R ３ is an alkyl group having 1 to 12 carbon atoms, and R on each aromatic ring ２ , R ４ and R ５ 4. The polycarbonate resin composition according to the above item 1, wherein R on each aromatic ring in formula (1) is a hydrogen atom. １ , R ３ is a t-butyl group, and R on each aromatic ring ２ , R ４ and R ５is a hydrogen atom. 5. The polycarbonate resin composition according to the above 3, wherein the triaryl phosphate (C) contains at least one of triphenyl phosphate, tris-2,4-di-t-butyl phosphate, and tris-4-t-butyl phosphate. 6. The polycarbonate resin composition according to the above 1, further containing 0.001 to 0.3 parts by mass of triaryl phosphite (E) per 100 parts by mass of the total of (A) and (B). 7. Pellets of the polycarbonate resin composition according to any one of the above 1 to 6. 8. A molded article made from the polycarbonate resin composition according to any one of the above 1 to 6. 9. A molded article made from pellets of the polycarbonate resin composition according to the above 7.

[0009] The polycarbonate resin composition of the present invention has high weather resistance, and is excellent in impact resistance, heat resistance, and fluidity (moldability).

[0010] The present invention will be described in detail below with reference to embodiments and examples. In this specification, unless otherwise specified, the term "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0011] The polycarbonate resin composition of the present invention contains 55 to 90 mass% of a polycarbonate resin (A) having a viscosity average molecular weight of 17,500 to 30,000, and 10 to 45 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), relative to a total of 100 parts by mass of (A) and (B), and further contains 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 (E) having a phenol structure, wherein the compound (D) having a phenol structure contains at least one of 4-t-butylphenol, 2,4-di-t-butylphenol, 4-α-cumylphenol, and bisphenol A.

[0012] [Polycarbonate Resin (A)] The polycarbonate resin (A) used in the present invention is not particularly limited, and various types can be used. Polycarbonate resins can be classified into aromatic polycarbonate resins in which the carbons directly bonded to carbonate bonds are aromatic carbons, and aliphatic polycarbonate resins in which the carbons directly bonded to carbonate bonds are aliphatic carbons, and either can be used. Among these, aromatic polycarbonate resins are preferred as the polycarbonate resin (A) from the viewpoints of heat resistance, mechanical properties, electrical properties, etc.

[0013] Among the monomers that serve as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include: dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl;

[0014] dihydroxynaphthalenes 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;

[0015] 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;

[0016] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, Bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, 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-naphthyleethane, 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, bis(hydroxyaryl)alkanes such as 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;

[0017] 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, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-t-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-t-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane;

[0018] Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0019] Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; and the like.

[0020] Of these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly 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. The aromatic dihydroxy compounds may be used alone or in any combination and ratio of two or more.

[0021] Among the monomers serving as raw materials for polycarbonate resins, examples of carbonate precursors include carbonyl halides, carbonate esters, etc. The carbonate precursors may be used alone or in any combination and ratio of two or more.

[0022] Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds; and the like.

[0023] Specific examples of carbonate esters include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0024] The method for producing the polycarbonate resin (A) is not particularly limited, and any method can be used. Examples include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, and solid-phase transesterification of a prepolymer. Among these, the interfacial polymerization and melt transesterification methods are preferred because they have a higher effect of improving moist heat resistance, and the interfacial polymerization method is particularly preferred.

[0025] The molecular weight of the polycarbonate resin (A), expressed as a viscosity average molecular weight (Mv) calculated from the solution viscosity measured at 25°C using methylene chloride as a solvent, is preferably 10,000 to 50,000, more preferably 10,000 to 40,000, especially 10,000 to 30,000, or 10,000 to 26,000, and further preferably 10,500 or more, 11,000 or more, particularly 11,500 or more, most preferably 12,000 or more, and further preferably 24,000 or less, particularly preferably 20,000 or less. By setting the viscosity average molecular weight to be equal to or greater than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by setting the viscosity average molecular weight to be equal to or less than the upper limit of the above range, the decrease in flowability of the polycarbonate resin composition of the present invention can be suppressed and improved, and molding processability can be enhanced, allowing molding processability to be easily performed. Two or more polycarbonate resins having different viscosity average molecular weights may be mixed together, and in this case, polycarbonate resins having viscosity average molecular weights outside the above-mentioned preferred range may be mixed.

[0026] The viscosity average molecular weight [Mv] is determined by measuring the intrinsic viscosity [η] (unit: dl / g) at 25°C using methylene chloride as a solvent with an Ubbelohde viscometer, and then calculating the viscosity average molecular weight [Mv] using the Schnell viscosity formula, i.e., η = 1.23 × 10 －４ Mv ０．８３ The intrinsic viscosity [η] is the specific viscosity [η] at each solution concentration [C] (g / dl). ｓｐ ] was measured and the value was calculated according to the following formula.

[0027] In order to improve the appearance and flowability of the molded article, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Furthermore, the amount of the polycarbonate oligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[0028] Furthermore, the polycarbonate resin (A) may be not only a virgin raw material but also a polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin), and it is also preferable to contain both a virgin raw material and a recycled resin, or it may be made of a recycled polycarbonate resin. The proportion of recycled polycarbonate resin in the polycarbonate resin (A) is preferably 40% or more, 50% or more, 60% or more, or 80% or more, and particularly preferably 100%.

[0029] [Graft Copolymer (B)] The graft copolymer (B) contained in the polycarbonate resin composition of 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 comprises 40 to 80 mass% of the aromatic vinyl monomer component (b1), 10 to 30 mass% of the vinyl cyanide monomer component (b2), and 10 to 50 mass% of the diene rubber polymer component (b3), and may further contain 0 to 30 mass% of another monomer component (b4).

[0030] 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-t-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, etc., with styrene being particularly preferred. The proportion of the aromatic vinyl monomer component (b1) in 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, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less, based on 100% by mass of the graft copolymer (B).

[0031] Examples of the vinyl cyanide monomer component (b2) in the graft copolymer (B) include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. The proportion of the vinyl cyanide monomer component (b2) in 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, based on 100% by mass of the graft copolymer (B).

[0032] As the diene rubbery polymer component (b3) of the graft copolymer (B), for example, a rubber component such as polybutadiene, polyisoprene, or styrene-butadiene copolymer is used, and the proportion of the diene rubbery polymer component (b3) in the graft copolymer (B) is preferably in the range of 10 to 50 mass%, more preferably 13 mass% or more, even more preferably 14 mass% or more, particularly preferably 15 mass% or more, and more preferably 45 mass% or less, based on 100 mass% of the graft copolymer (B).

[0033] Furthermore, other copolymerizable monomer components (b4) may be copolymerized with these, and in this case, examples of the copolymerizable other 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, methoxypolyethylene glycol methacrylate, etc. The proportion of the other monomer component (b4) in the graft copolymer (B) is preferably in the range of 0 to 30% by mass, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly 3% by mass or less, and particularly preferably 2% by mass or less, based on 100% by mass of the graft copolymer (B).

[0034] 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, and the like, and among these, acrylonitrile-butadiene-styrene graft copolymer (ABS resin) is particularly preferred.

[0035] The graft copolymer (B) is usually produced by a method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and any of these methods can be used.

[0036] 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, and preferably 42% by mass or less, more preferably 40% by mass or less, based on 100% by mass of the total of the polycarbonate resin (A) and the graft copolymer (B). By having the content within this range, the resin composition can have excellent heat resistance and fluidity. If the amount of the graft copolymer (B) exceeds 45% by mass, the heat resistance decreases, and if it is less than 10% by mass, the fluidity decreases.

[0037] [Triaryl Phosphate (C)] The polycarbonate resin composition of the present invention contains a triaryl phosphate (C) represented by general formula (1). Here, the aryl group means a group containing an aromatic group, and particularly preferably means a phenyl group.

[0038] In formula (1), R １ ~R ５ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and as the alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 8 carbon atoms is preferred, and preferred examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms, is preferred.

[0039] In formula (1), R on the three aromatic rings １ ~R ５When two or more of R on each aromatic ring are alkyl groups, the alkyl groups may be the same or different from each other. １ ~R ５ It is preferable that at least one of R on each aromatic ring is an alkyl group having 1 to 12 carbon atoms. １ , R ３ is an alkyl group having 1 to 12 carbon atoms, and R on each aromatic ring ２ , R ４ and R ５ is more preferably a hydrogen atom.

[0040] Specific examples of the triaryl phosphate (C) include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, dicresyl phenyl phosphate, ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate, tripropyl phenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl phosphate.

[0041] The triaryl phosphate (C) is preferably triphenyl phosphate or tris(4-t-butylphenyl) phosphate. １ , R ３ is a t-butyl group, and R on each aromatic ring ２ , R ４ and R ５ is preferably a hydrogen atom, and particularly preferably tris(2,4-di-t-butylphenyl)phosphate.

[0042] The triaryl phosphate (C) may be used alone or in combination of two or more kinds.

[0043] The content of triaryl phosphate (C) is 0.001 to 0.3 parts by mass per 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer (B). A resin composition containing such an amount, together with a predetermined amount of the compound (D) having a phenol structure, exhibits excellent weather resistance and excellent hue. The content of triaryl phosphate (C) is preferably 0.002 parts by mass or more, more preferably 0.003 parts by mass or more, 0.004 parts by mass or more, particularly preferably 0.005 parts by mass or more, and also preferably 0.25 parts by mass or less, more preferably 0.2 parts by mass or less, 0.15 parts by mass or less, 0.13 parts by mass or less, particularly preferably 0.1 parts by mass or less.

[0044] [Compound (D) Having a Phenol Structure] The polycarbonate resin composition of the present invention contains a compound (D) having a phenol structure. The compound (D) having a phenol structure is a compound in which a hydroxy group is directly bonded to a benzene ring, and in the present invention, is 4-t-butylphenol, 2,4-di-t-butylphenol, 4-α-cumylphenol, or bisphenol A. Of these, 4-t-butylphenol, 4-α-cumylphenol, and 4-t-butylphenol are more preferred. The compound (D) having a phenol structure may contain one type alone, or two or more types.

[0045] The content of the compound (D) having a phenol structure is 0.001 to 0.03 parts by mass per 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer (B). When two or more types of compound (D1) having a phenol structure are contained, the content is the total amount of all of them. A resin composition containing the polycarbonate resin (A) and the graft copolymer (B) together with the triaryl phosphate (C) in such an amount exhibits excellent weather resistance, as well as excellent impact resistance, heat resistance, and fluidity (moldability).

[0046] The content of the compound (D) having a phenol structure, relative to 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer (B), is preferably 0.0015 parts by mass or more, more preferably 0.002 parts by mass or more, 0.003 parts by mass or more, particularly preferably 0.004 parts by mass or more, and is preferably 0.025 parts by mass or less, more preferably 0.02 parts by mass or less, 0.015 parts by mass or less, particularly preferably 0.013 parts by mass or less.

[0047] When 4-t-butylphenol is contained as the compound (D) having a phenol structure, the content is preferably 0.0012 to 0.01 parts by mass, more preferably 0.002 to 0.003 parts by mass, relative to 100 parts by mass of (A) and (B) combined. When 2,4-di-t-butylphenol is contained as the compound (D) having a phenol structure, the content is preferably 0.0012 to 0.01 parts by mass, more preferably 0.002 to 0.003 parts by mass, relative to 100 parts by mass of (A) and (B) combined. When 4-α-cumylphenol is contained, the content is preferably 0.0012 to 0.01 parts by mass, more preferably 0.002 to 0.003 parts by mass, relative to 100 parts by mass of (A) and (B) combined. 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, per 100 parts by mass of the total of (A) and (B).

[0048] 4-t-butylphenol, 2,4-di-t-butylphenol, 4-α-cumylphenol, or bisphenol A may be present in a free state as a by-product or used in the production of the polycarbonate resin (A), or as a by-product derived from a recycled polycarbonate resin, and the amount of such a compound is also included in the amount of the compound (D) having a phenol structure.

[0049] [Triaryl Phosphite (E)] The polycarbonate resin composition of the present invention preferably further contains a triaryl phosphite (E). Here, the aryl group means a group containing a monocyclic or polycyclic aromatic group, and particularly preferably means a phenyl group.

[0050] Preferred examples of the triaryl phosphite (E) include triphenyl phosphite, tris(p-tolyl)phosphite, tris(p-nonylphenyl)phosphite, tris(mononyl / dinonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(naphthyl)phosphite, tris(p-chlorophenyl)phosphite, tris(p-fluorophenyl)phosphite, diphenylbenzylphosphine, diphenyl(p-hydroxyphenyl)phosphite, diphenyl-1,4-dihydroxyphenyl-2-phosphite, and phenylnaphthylbenzylphosphine, with triphenyl phosphite and tris(2,4-di-t-butylphenyl)phosphine being particularly preferred.

[0051] When triaryl phosphite (E) is contained, its content is preferably 0.001 to 0.3 parts by mass per 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer (B). Resin compositions containing such an amount together with triaryl phosphate (C) also have superior hue. The aryl phosphine content is more preferably 0.005 parts by mass or more, even more preferably 0.008 parts by mass or more, and 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, 0.15 parts by mass or less, 0.1 parts by mass or less, 0.05 parts by mass or less, and particularly preferably 0.04 parts by mass or less.

[0052] [Phenol-Based Antioxidant] The polycarbonate resin composition of the present invention preferably further contains a phenol-based antioxidant, such as a hindered phenol-based antioxidant. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-t-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-t-butyl-a,a',a"-(mesitylene-2,4, 6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, and the like.

[0053] Among these, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate are particularly preferred. Note that the phenolic antioxidant may be contained alone or in any combination and ratio of two or more kinds.

[0054] When a phenolic antioxidant is contained, the content is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer (B). By setting the content of the phenolic antioxidant to be equal to or greater than the lower limit of the above range, the effect as a phenolic antioxidant can be sufficiently obtained. Furthermore, by setting the content of the phenolic antioxidant to be equal to or less than the upper limit of the above range, the effect does not plateau, which is economical.

[0055] [Release Agent] The resin composition of the present invention preferably contains a release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils.

[0056] Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, with saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms being more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetraliacontanoic acid, montanic acid, adipic acid, and azelaic acid.

[0057] The aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol can be, for example, the same as the aliphatic carboxylic acid described above. On the other hand, the alcohol can be, for example, a saturated or unsaturated monohydric or polyhydric alcohol. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferred, and an aliphatic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferred. Here, the term "aliphatic" is used to include alicyclic compounds.

[0058] Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol.

[0059] The ester may contain an aliphatic carboxylic acid and / or alcohol as an impurity. The ester may be a pure substance or a mixture of multiple compounds. The aliphatic carboxylic acid and alcohol that combine to form an ester may each be used alone or in any combination and ratio of two or more.

[0060] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0061] Examples of aliphatic hydrocarbons having a number-average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbons may be partially oxidized. Among these, paraffin wax, polyethylene wax, or partial oxides of polyethylene wax are preferred, with paraffin wax and polyethylene wax being more preferred. The number-average molecular weight of the aliphatic hydrocarbons is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, or a mixture of substances with various constituent components and molecular weights may be used as long as the main component is within the above-mentioned range.

[0062] Examples of polysiloxane-based silicone oils include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

[0063] The above-mentioned release agents may be contained alone or in any combination and ratio of two or more.

[0064] The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part 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 of the polycarbonate resin (A) and the graft copolymer (B). If the content of the release agent is less than the lower limit of the above range, the release effect may be insufficient, whereas if the content of the release agent is more than the upper limit of the above range, the hydrolysis resistance may decrease, and mold contamination during injection molding may occur.

[0065] [UV Absorber] The polycarbonate resin composition of the present invention preferably contains a UV absorber. Examples of UV absorbers include inorganic UV absorbers such as cerium oxide and zinc oxide; and organic UV absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, and hindered amine compounds. Among these, organic UV absorbers are preferred, and benzotriazole compounds are more preferred. By selecting an organic UV absorber, the transparency and mechanical properties of the resin composition of the present invention can be improved.

[0066] 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-t-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl- ... amyl)-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], etc., among which 2-(2'-hydroxy-5'-t-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'-t-octylphenyl)benzotriazole is particularly preferred.

[0067] 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-octoxybenzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0068] Specific examples of salicylate compounds include phenyl salicylate and 4-t-butylphenyl salicylate. Specific examples of cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenylacrylate and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate. Specific examples of oxanilide compounds include 2-ethoxy-2'-ethyloxalic acid bis-alinide. As the malonic acid ester compound, 2-(alkylidene)malonic acid esters are preferred, and 2-(1-arylalkylidene)malonic acid esters are more preferred.

[0069] When an ultraviolet absorber is contained, its content 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, per 100 parts by mass of the total 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 above range, the effect of improving weather resistance and light resistance may be insufficient, and if the content of the ultraviolet absorber is more than the upper limit of the above range, mold deposits or the like may occur, causing mold contamination. One type of ultraviolet absorber may be contained, or two or more types may be contained in any combination and ratio.

[0070] [Additives, etc.] The polycarbonate resin composition of the present invention may contain additives other than those described above, such as fluorescent whitening agents, pigments (including titanium oxide, etc.), dyes, flame retardants, impact modifiers, plasticizers, compatibilizers, etc. These additives may be contained alone or in combination of two or more.

[0071] Furthermore, other resins besides the polycarbonate resin (A) and the graft copolymer (B) may be contained. Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; styrene-based resins such as polystyrene resin (GPPS), high-impact polystyrene resin (HIPS), and 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. When other resins besides the polycarbonate resin (A) and the graft copolymer (B) are contained, the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer (B).

[0072] In order to confirm the effects of the polycarbonate resin composition of the present invention, polycarbonate resin compositions were prepared as follows, but the present invention should not be construed as being limited to the following examples. The components used are as shown in Table 1 below.

[0073]

[0074] Examples 1 to 17, Comparative Examples 1 to 8 The above-described components were blended in the ratios (parts by mass) shown in Table 2 below, fed to a twin-screw extruder ("TEM26SX" manufactured by Toshiba Machine Co., Ltd.), kneaded under conditions of a screw rotation speed of 150 rpm, a discharge rate of 25 kg / hour, and a barrel temperature of 260°C, and extruded in the form of strands from the tip of the extrusion nozzle. The strands were quenched in a water bath and cut and pelletized using a pelletizer to obtain pellets of a polycarbonate resin composition.

[0075] <MVR> The pellets obtained by the above method were dried at 100°C for 5 hours, and then MVR (melt volume rate, unit: g / 10 min) was measured in accordance with ISO 1133 under conditions of a measurement temperature of 250°C and a load of 2.16 kgf.

[0076] <Notched Charpy Strength> The pellets obtained by the above method were dried at 100°C for 5 hours, and then injection molded in an injection molding machine ("NEX80III" manufactured by Nissei Plastic Industrial Co., Ltd.) under conditions of a cylinder temperature of 260°C and a mold temperature of 60°C to produce ISO multipurpose test specimens (4 mmt). Using the obtained ISO multipurpose test specimens (4 mmt), the notched Charpy strength (unit: kJ / m) was measured at a temperature of 23°C in accordance with ISO Standard 179. ２ ) was measured.

[0077] <Heat Resistance DTUL (Deflection Temperature Under Load)> In accordance with ISO 75-1 and ISO 75-2, a constant bending load (1.80 MPa) was applied in the flatwise direction to the center of a 4 mm x 10 mm ISO multipurpose test piece (4 mmt), and the temperature was raised at a uniform rate to measure the temperature (unit: ° C.) when the strain at the center reached 0.34 mm.

[0078] <Weather resistance (ΔE)> The obtained pellets were injection molded using an injection molding machine "EC50SXII" manufactured by Toshiba Machine Co., Ltd. under conditions of a cylinder temperature of 260°C and a mold temperature of 60°C to obtain a plate-shaped molded product having a length of 90 mm, a width of 60 mm, and a thickness of 2 mm. The obtained plate-shaped molded product was subjected to a xenon weather test using light with a wavelength of 300-400 nm at a temperature of 89°C and an irradiation intensity of approximately 55 W / m ２The lightfastness treatment was carried out under the conditions of a treatment time of 100 hours (300 hours for titanium oxide-added systems), and the hue before and after the lightfastness treatment was measured using an SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. under D65, 10° field of view, and reflective conditions, and the color difference ΔE was calculated to evaluate the lightfastness. ΔE is preferably 7.5 or less. In the case of titanium oxide-added systems, it is preferably 1.4 or less.

[0079] The evaluation results are shown in Table 2 below.

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] The polycarbonate resin composition of the present invention has high weather resistance, and is excellent in impact resistance, heat resistance, and fluidity (moldability), and can therefore be suitably used for various molded articles.

Claims

DEPCT6820 / 06 / 25681. The composition of polycarbonate resins is: 55 to 90 percent by mass of polycarbonate resin (A) with an average viscosity molecular weight of 17500 to 30000; 10 to 45 percent by mass of branched copolymer (B) composed of an aromatic vinyl monomer component (b1), a vinyl cyanide monomer component (b2), and a diene rubber polymer component (b3); and, when compared to the total mass of (A) and (B) being 100 parts by mass, 0.001 to 0.3 parts by mass of triaryl phosphate (C), as determined by General formula(1) and 0.001 to 0.3 parts by mass of a phenolic compound(D) in which the phenolic compound(D) contains at least one of the 4-t-butylphenol, 2,4-di-t-butylphenol, 4-alpha-cumylphenol and bisphenol A[C1](chemical formula)(1)(in formula(1) R1 to R5 independently are hydrogen atoms or alkyl C1-2 groups).

2. The polycarbonate resin composition of claim 1 in which at least one of the R1 to R5 on each aromatic ring in formula(1) is an alkyl C1-12 group.3.The polycarbonate resin composition of claim 1 in which R1 and R3 on each aromatic ring in formula (1) are C1-12 alkyl groups and R2, R4 and R5 on each aromatic ring are hydrogen atoms.

4. The polycarbonate resin composition of claim 3 in which R1 and R3 on each aromatic ring in formula (1) are t-butyl groups and R2, R4 and R5 on each aromatic ring are hydrogen atoms.

5. The polycarbonate resin composition of claim 1 in which triaryl phosphate (C) contains at least one type of triphenyl phosphate, tris-2,4-di-t-butylphenyl phosphate. and tris-4-t-butylphenylphosphate 6. Polycarbonate resin composition of claim 1 incorporating an additional 0.001 to 0.3 parts by mass of triaryl phosphite (E) compared to the total mass of (A) and (B) which is 100 parts by mass.

7. Small spheres incorporated with any polycarbonate resin composition of claims 1 to 6.

8. Molded products incorporated with any polycarbonate resin composition of claims 1 to 6.

9. Molded products incorporated with small spheres of the polycarbonate resin composition of claim 7;