Polycarbonate resin composition

Abstract

To provide a polycarbonate resin composition having improved mechanical properties and excellent bending strength and impact resistance.SOLUTION: There is provided a polycarbonate resin composition which comprises 0.0001 to 0.3 pts.mass of a triaryl phosphate (B), 1 to 100 pts.mass of a fibrous filler (C) and at least one of the following (i) to (iv) in the following amount based on 100 pts.mass of a polycarbonate resin (A): (i) 0.0005 to 0.1 pts.mass of 2-4-di-tert-butylphenol, (ii) 0.0001 to 0.03 pts.mass of 2,2-bis(4-hydroxyphenyl)propane, (iii) 0.0005 to 0.05 pts.mass of 4-tert-butylphenol, (iv) 0.001 to 0.05 pts.mass of cumylphenol.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition excellent in flexural strength and impact resistance, and a molded article thereof. [Background technology]

[0002] Polycarbonate resin has excellent mechanical properties such as impact resistance, as well as excellent heat resistance and transparency, and is therefore widely used in a wide range of applications, including various optical components, electrical and electronic equipment components, automotive interior and exterior parts, office equipment components, sheets, machine parts, and building materials.

[0003] One method for improving the heat resistance of polycarbonate resin is to add a stabilizer. The stabilizers most commonly used in polycarbonate resin are aromatic phosphite stabilizers, and one of the most representative stabilizers is tris(2,4-di-tert-butylphenyl)phosphite. Many proposals have been made for polycarbonate resin compositions using this stabilizer. For example, Patent Document 1 proposes a method of using tris(2,4-dibutylphenyl)phosphite in combination with tris(nonylphenyl)phosphite.

[0004] Although tris(2,4-di-tert-butylphenyl)phosphite certainly has the effect of preventing the coloration and deterioration of polycarbonate resin, it has a problem of decreasing mechanical strength. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 10-60247 Summary of the Invention [Problem to be solved by the invention]

[0006] In order to improve the mechanical properties of polycarbonate resins, fillers are blended therein. An object (object) of the present invention is to provide a polycarbonate resin composition containing a filler, which has improved mechanical properties and is excellent in flexural strength and impact resistance. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted intensive research to achieve the above object, and as a result have found that a polycarbonate resin composition containing a specific triaryl phosphate compound, a specific compound having a phenol structure, and a fibrous filler in specific amounts has improved mechanical properties and is excellent in flexural strength and impact resistance, thereby completing the present invention. The present invention relates to the following polycarbonate resin composition and molded article.

[0008] 1. A polycarbonate resin composition comprising, relative to 100 parts by mass of a polycarbonate resin (A), 0.0001 to 0.3 parts by mass of a triaryl phosphate (B) represented by the following general formula (1), 1 to 100 parts by mass of a fibrous filler (C), and at least one of the following (i) to (iv) in the amounts specified below: (i) 0.0005 to 0.1 parts by mass of 2-4-di-tert-butylphenol (ii) 0.0001 to 0.03 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (iii) 0.0005 to 0.05 parts by mass of 4-tert-butylphenol (iv) 0.001 to 0.05 parts by mass of cumylphenol [ka] [In formula (1), R 1 ~R 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.] 2. The polycarbonate resin composition according to the above item 1, wherein the fibrous filler (C) is glass fiber, carbon fiber or a mixture thereof. 3. The polycarbonate resin composition according to item 2 above, wherein the glass fiber is at least one type selected from the group consisting of milled fiber, chopped strand and flat glass fiber. 4. In formula (1), R 1 ~R 5 4. The polycarbonate resin composition according to any one of 1 to 3 above, wherein at least one of the groups is an alkyl group having 1 to 12 carbon atoms. 5. In formula (1), R 1 , R 3 is an alkyl group having 1 to 12 carbon atoms, and R 2 , R 4 and R 5 5. The polycarbonate resin composition according to any one of the above 1 to 4, wherein is a hydrogen atom. 6. In formula (1), R 1 , R 3 is a tert-butyl group, and R 2 , R 4 and R 5 6. The polycarbonate resin composition according to any one of the above 1 to 5, wherein is a hydrogen atom. 7. The polycarbonate resin composition according to any one of 1 to 6 above, further comprising 0.001 to 0.3 part by mass of tris(2,4-di-tert-butylphenyl)phosphite per 100 parts by mass of the polycarbonate resin (A). 8. The polycarbonate resin composition according to any one of the above 1 to 7, wherein the polycarbonate resin (A) contains a recycled polycarbonate resin. 9. Pellets comprising the polycarbonate resin composition according to any one of 1 to 8 above. 10. A molded article made of the polycarbonate resin composition according to any one of 1 to 8 above. 11. A molded article obtained by molding the pellets described in 9 above. Effect of the Invention

[0009] The polycarbonate resin composition of the present invention has good mechanical properties, and is particularly excellent in flexural strength and impact resistance. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a conceptual diagram of an example of a glass fiber having a flat cross-sectional shape that is blended into a polycarbonate resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. In this specification, unless otherwise specified, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0012] The polycarbonate resin composition of the present invention is characterized by containing, relative to 100 parts by mass of a polycarbonate resin (A), 0.0001 to 0.3 parts by mass of a triaryl phosphate (B) represented by the above general formula (1), 1 to 100 parts by mass of a fibrous filler (C), and at least one of the following (i) to (iv) in the amounts described below: (i) 0.0005 to 0.1 parts by mass of 2-4-di-tert-butylphenol (ii) 0.0001 to 0.03 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (iii) 0.0005 to 0.05 parts by mass of 4-tert-butylphenol (iv) 0.001 to 0.05 parts by mass of cumylphenol

[0013] [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 the carbonate bonds are aromatic carbons, and aliphatic polycarbonate resins in which the carbons directly bonded to the carbonate bonds are aliphatic carbons, and either type can be used. Among them, aromatic polycarbonate resins are preferred as the polycarbonate resin (A) from the viewpoints of heat resistance, mechanical properties, electrical properties, etc.

[0014] Among the monomers that are 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; 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-tert-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-naphthylethan, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)dodecane, Bis(hydroxyaryl)alkanes such as;

[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-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane, Bis(hydroxyaryl)cycloalkanes such as;

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

[0019] 4,4'-dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; etc.

[0020] Among these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred. In particular, 2,2-bis(4-hydroxyphenyl)propane and 2,2-bis(3-methyl-4-hydroxyphenyl)propane are preferred from the standpoints of impact resistance and heat resistance. The aromatic dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0021] Among the monomers that are 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 adopted. Examples of the method include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. Among these, the interfacial polymerization and melt transesterification methods are preferred because they have a higher effect of improving resistance to moist heat, and the interfacial polymerization method is particularly preferred.

[0025] The molecular weight of the polycarbonate resin (A) is preferably 10,000 to 50,000, more preferably 10,000 to 40,000, of which 10,000 to 30,000, 10,000 to 26,000, and further 10,500 or more, 11,000 or more, particularly 11,500 or more, most preferably 12,000 or more, and further 24,000 or less, particularly preferably 20,000 or less. By making the viscosity average molecular weight equal to or more 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 making the viscosity average molecular weight equal to or less than the upper limit of the above range, the decrease in the flowability of the polycarbonate resin composition of the present invention can be suppressed and improved, and the molding processability can be improved to facilitate molding process. Two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, polycarbonate resins having a viscosity average molecular weight outside the above-mentioned preferable range may be mixed.

[0026] The viscosity average molecular weight (Mv) is calculated by using methylene chloride as a solvent, measuring the intrinsic viscosity [η] (unit: dl / g) at 25°C using an Ubbelohde viscometer, and calculating the value according to the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 The intrinsic viscosity [η] is the value calculated from the specific viscosity [η sp ] was measured and the value was calculated according to the following formula.

number

[0027] Furthermore, the polycarbonate resin (A) may be not only a virgin resin, but also a polycarbonate resin regenerated from a used product (so-called material recycled polycarbonate resin), or a polycarbonate resin produced from a polycarbonate resin that has been chemically decomposed and returned to its raw materials (so-called chemically recycled polycarbonate resin), and it is also preferable that the polycarbonate resin contains both a virgin resin and a recycled resin, or may be made of a recycled polycarbonate resin. The proportion of the 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%.

[0028] Preferred examples of used products include various sheet materials, optical recording media such as optical disks (CDs, DVDs), light guide plates, transparent vehicle components such as automobile window glass, automobile headlamp lenses, and windshields, containers such as water bottles, various cover materials, eyeglass lenses, soundproof walls, glass windows, corrugated sheets, and other building components. In addition, as recycled polycarbonate resins, crushed products obtained from non-conforming products, sprues, or runners during molding, or pellets obtained by melting these can also be used.

[0029] [Triaryl phosphate (B)] The polycarbonate resin composition of the present invention contains a triaryl phosphate (B) represented by general formula (1). In this specification, the aryl group means a group containing a monocyclic or polycyclic aromatic group, and particularly preferably means a phenyl group. [ka]

[0030] In formula (1), R 1 ~R 5are 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 preferable, and examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-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 preferable.

[0031] In formula (1), the three R on the aromatic ring 1 ~R 5 When two or more of are alkyl groups, the alkyl groups may be the same or different from each other. As the triaryl phosphate (B), R on each aromatic ring in formula (1) 1 ~R 5 At least one of them is preferably an alkyl group having 1 to 12 carbon atoms. In addition, R on each aromatic ring 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 It is more preferable that is a hydrogen atom.

[0032] Specific examples of the triaryl phosphate (B) 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, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl phosphate.

[0033] Among them, triaryl phosphate (B) is a compound represented by the formula (1) in which R on each aromatic ring 1 , R 3is a tert-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-tert-butylphenyl)phosphate.

[0034] The triaryl phosphate (B) may be used alone or in combination of two or more kinds.

[0035] The content of triaryl phosphate (B) is 0.0001 to 0.3 parts by mass relative to 100 parts by mass of polycarbonate resin (A). A resin composition containing such an amount is excellent in bending strength and impact resistance. The content of triaryl phosphate (B) is preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, 0.003 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.

[0036] [Fibrous filler (C)] The polycarbonate resin composition of the present invention contains a fibrous filler (C). By combining the triaryl phosphate (B) with the fibrous filler (C), it is possible to improve bending strength and impact resistance.

[0037] As the fibrous filler used in the present invention, any conventionally known filler can be used. Specific examples include glass fiber, carbon fiber, calcium silicate (wollastonite) fiber, alumina fiber, silica alumina fiber, potassium titanate fiber, ceramic fiber, etc. Among these, at least one selected from the group consisting of glass fiber, carbon fiber, wollastonite fiber, alumina fiber, and silica alumina fiber is preferable. Among these, glass fiber, carbon fiber, or a mixture thereof is preferable.

[0038] The glass fiber may have a cross-sectional shape of various irregular shapes in addition to the general circular shape. The average fiber diameter of such glass fiber is preferably 1 to 25 μm, more preferably 5 to 17 μm. If a glass fiber having an average fiber diameter of less than 1 μm is used, the moldability may be impaired, and if a glass fiber having an average fiber diameter of more than 25 μm is used, the appearance may be impaired or the reinforcing effect may be insufficient. In addition, as the glass fiber, a continuously wound glass roving, a chopped strand cut to a length (cut length) of 1 to 10 mm, a milled fiber pulverized to an average fiber length of about 10 to 500 μm, a glass fiber having a flat cross-sectional shape perpendicular to the length direction of the glass fiber (also called a flat glass fiber) or an elliptical glass fiber may be used, and these may be used in combination. In glass fibers having a flat cross-sectional shape, the length of the short side (1 in Figure 1) is the fiber diameter (sometimes called the long diameter), and in glass fibers having an elliptical cross-sectional shape, the length of the long axis of the ellipse is the fiber diameter. The use of glass fibers is preferred since it provides better impact resistance.

[0039] Carbon fibers are generally produced by burning acrylic fibers, petroleum or carbon-based special pitch, cellulose fibers, lignin, etc., and are available in various types such as flame-resistant, carbonaceous, and graphite, but the substrate is not particularly limited. The carbon fibers preferably have an average fiber diameter of 1 to 20 μm, more preferably 3 to 15 μm. If carbon fibers with an average fiber diameter of less than 1 μm are used, the moldability may be impaired, and if carbon fibers with an average fiber diameter of more than 20 μm are used, the appearance may be impaired and the reinforcing effect may be insufficient. Carbon fibers are preferred because they provide better tensile strength.

[0040] The average fiber diameter and average fiber length of the fibrous filler (C) can be determined, for example, by randomly selecting 50 fibrous fillers from 10 g of fibrous filler, measuring the fiber diameter and length of each fibrous filler by microscopic observation, and averaging the measurement results.

[0041] If necessary, the fibrous filler (C) may be subjected to a surface treatment such as coating with a fatty acid such as stearic acid or oleic acid, paraffin, wax, organic silane, organic titanate, epoxy resin, urethane resin, or the like.

[0042] The content of the fibrous filler (C) is 1 to 100 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). If the content of the fibrous filler (C) is less than 1 part by mass, the effect of improving the impact resistance and elastic modulus is insufficient, and if it exceeds 100 parts by mass, the appearance of the polycarbonate resin molded article may deteriorate. The content is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and preferably 90 parts by mass or less, particularly preferably 80 parts by mass or less.

[0043] [Polycarbonate oligomer] The polycarbonate resin composition of the present invention may contain a polycarbonate oligomer in order to improve the appearance and flowability of the molded article. The polycarbonate oligomer is, for example, a carbonate oligomer having a viscosity average molecular weight (Mv) of less than 10,000. The viscosity average molecular weight (Mv) of the polycarbonate oligomer is measured in the same manner as the viscosity average molecular weight (Mv) of the polycarbonate resin. The viscosity average molecular weight (Mv) of the polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and more preferably 3,000 or more, and is usually 9,500 or less, preferably 9,000 or less, and more preferably 8,000 or less. Furthermore, the polycarbonate oligomer contained is preferably 30% by mass or less of the polycarbonate resin. The polycarbonate oligomer is not particularly limited as long as it contains a -[OR-OC(=O)]- unit (wherein R is an organic group, preferably a hydrocarbon group, more preferably an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure) containing a carbonate bond in the molecular main chain. In this embodiment, the polycarbonate oligomer is preferably an aromatic polycarbonate oligomer, and more preferably a polycarbonate oligomer having a bisphenol skeleton. By adding a polycarbonate oligomer, the affinity between the polycarbonate resin (A) and the glass fiber tends to be improved.

[0044] [Compounds with phenol structure] The polycarbonate resin composition of the present invention contains at least one of the following compounds (i) to (iv) having a phenol structure in the following amount. (i) 0.0005 to 0.1 parts by mass of 2-4-di-tert-butylphenol (ii) 0.0001 to 0.03 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (iii) 0.0005 to 0.05 parts by mass of 4-tert-butylphenol (iv) 0.001 to 0.05 parts by mass of cumylphenol By containing at least one of the compounds having a phenol structure in the above specific amount together with the triaryl phosphate (B), the bending strength and impact resistance of the polycarbonate resin composition can be further improved.

[0045] Among the above, it is preferable to contain at least one of (i) 0.0005 to 0.1 parts by mass of 2,4-di-tert-butylphenol, (ii) 0.0001 to 0.03 parts by mass of 2,2-bis(4-hydroxyphenyl)propane, or (iii) 0.0005 to 0.05 parts by mass of 4-tert-butylphenol. By containing these together with the triaryl phosphate (B), the bending strength and impact resistance of the polycarbonate resin composition can be further improved. The content of the 2,4-di-tert-butylphenol is, relative to 100 parts by mass of the polycarbonate resin (A), preferably 0.001 part by mass or more, more preferably 0.003 part by mass or more, and particularly preferably 0.005 part by mass or more, and is preferably 0.08 part by mass or less, more preferably 0.07 part by mass or less, even more preferably 0.06 part by mass or less, and particularly preferably 0.05 part by mass or less.

[0046] The content of the 2,2-bis(4-hydroxyphenyl)propane is preferably 0.002 parts by mass or more, more preferably 0.003 parts by mass or more, even more preferably 0.004 parts by mass or more, and preferably 0.02 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A). The content of the 4-tert-butylphenol is 0.001 part by mass or more, more preferably 0.0012 parts by mass or more, further preferably 0.0015 parts by mass or more, and preferably 0.0035 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (A).

[0047] The content of cumylphenol (i.e., 2-(4-hydroxyphenyl)-2-phenylpropane, or 4-α-cumylphenol) is preferably 0.0012 parts by mass or more, more preferably 0.0015 parts by mass or more, and is preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, and particularly preferably 0.0035 parts by mass or less, per 100 parts by mass of polycarbonate resin (A).

[0048] [Tris(2,4-di-tert-butylphenyl)phosphite] The polycarbonate resin composition of the present invention preferably further contains tris(2,4-di-tert-butylphenyl)phosphite in an amount of 0.001 to 0.3 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). By containing tris(2,4-di-tert-butylphenyl)phosphite in such an amount in combination with the triaryl phosphate (B) and a compound having a phenol structure, the bending strength and impact resistance can be further improved.

[0049] The content of tris(2,4-di-tert-butylphenyl)phosphite is more preferably 0.002 parts by mass or more, of which 0.003 parts by mass or more, 0.004 parts by mass or more, and particularly preferably 0.005 parts by mass or more, and is more preferably 0.25 parts by mass or less, of which 0.2 parts by mass or less, 0.15 parts by mass or less, 0.13 parts by mass or less, and particularly preferably 0.10 parts by mass or less.

[0050] [Arylphosphines, arylphosphine oxides] It is also preferable that the polycarbonate resin composition of the present invention further contains an aryl phosphine or an aryl phosphine oxide.

[0051] Preferred examples of arylphosphines include triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris(p-tolyl)phosphine, tris(p-nonylphenyl)phosphine, tris(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl), diphenyl(β-ethylcarboxyethyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-fluorophenyl)phosphine, diphenylbenzylphosphine, diphenyl-β-cyanoethylphosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine, phenylnaphthylbenzylphosphine, and the like. Triarylphosphines are preferred, and triphenylphosphine and tritolylphosphine are preferred, with triphenylphosphine being particularly preferred.

[0052] The content of the arylphosphine when contained is preferably 0.001 to 0.3 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). The resin composition containing the arylphosphine in such an amount together with the triaryl phosphate (B) is superior in bending strength, tensile strength and impact resistance. The content of the arylphosphine is more preferably 0.005 parts by mass or more, among which 0.008 parts by mass or more, particularly preferably 0.01 parts by mass or more, and more preferably 0.25 parts by mass or less, among which 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, particularly preferably 0.04 parts by mass or less.

[0053] Preferred examples of the arylphosphine oxide include triphenylphosphine oxide, diphenylbutylphosphine oxide, diphenyloctadecylphosphine oxide, tris(p-tolyl)phosphine oxide, tris(p-nonylphenyl)phosphine oxide, tris(naphthyl)phosphine oxide, diphenyl(hydroxymethyl)phosphine oxide, diphenyl(acetoxymethyl)phosphine oxide, diphenyl(β-ethylcarboxyethyl)phosphine oxide, tris(p-chlorophenyl)phosphine oxide, tris(p-fluorophenyl)phosphine oxide, diphenylbenzylphosphine oxide, diphenyl-β-cyanoethylphosphine oxide, diphenyl(p-hydroxyphenyl)phosphine oxide, diphenyl-1,4-dihydroxyphenyl-2-phosphine oxide, and phenylnaphthylbenzylphosphine oxide. Triarylphosphine oxide is preferred, and triphenylphosphine oxide is particularly preferred.

[0054] The content of the arylphosphine oxide when contained is preferably 0.001 to 0.3 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). With such an amount, the resin composition containing the triaryl phosphate (B) in combination with each of the above-mentioned components can further improve bending strength, tensile strength and impact resistance. The content of the arylphosphine oxide is more preferably 0.002 parts by mass or more, particularly 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 more preferably 0.25 parts by mass or less, particularly preferably 0.2 parts by mass or less, 0.15 parts by mass or less, 0.13 parts by mass or less, particularly preferably 0.10 parts by mass or less.

[0055] [Styrene-based resin] The polycarbonate resin composition of the present invention also preferably contains a styrene-based resin. The styrene-based resin is preferably a resin obtained by polymerizing an aromatic vinyl monomer (b1) alone, or an aromatic vinyl monomer (b1) and, if necessary, one or more selected from other vinyl monomers (b2, b4) copolymerizable therewith and a rubber polymer (b3).

[0056] Examples of the aromatic vinyl monomer (b1) used in the styrene-based resin include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, and other styrene derivatives, with styrene being particularly preferred. These may be used alone or in combination of two or more.

[0057] As the other vinyl monomer copolymerizable with these aromatic vinyl monomers (b1), vinyl cyanide monomers (b2) are preferred, such as acrylonitrile and methacrylonitrile.

[0058] Examples of the copolymerizable monomer (b4) other than the vinyl cyanide monomer (b2) include aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, and dodecyl acrylate; aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate; methyl methacrylate, ethyl Examples of the methacrylic acid alkyl esters include methacrylic acid alkyl esters such as amyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, and dodecyl methacrylate; epoxy group-containing methacrylic acid esters such as glycidyl methacrylate; maleimide-based monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide; and α,β-unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid. Preferred are acrylic acid alkyl esters and methacrylic acid alkyl esters. These other monomers (b4) may be used alone or in combination of two or more.

[0059] The rubbery polymer (b3) copolymerizable with the aromatic vinyl monomer (b1) is preferably a rubber having a glass transition temperature of 10° C. or less. Specific examples of such rubbery polymers include diene rubber, acrylic rubber, ethylene-propylene rubber, silicone rubber, and composite rubber (IPN type rubber) having a structure in which a polyorganosiloxane rubber component and a polyalkyl(meth)acrylate rubber component are mutually entangled so as not to be separated, and preferably, diene rubber, acrylic rubber, etc. are mentioned. In this specification, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate", and the same applies to "(meth)acryl" and "(meth)acrylo".

[0060] Examples of diene rubbers include polybutadiene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene copolymers, polyisoprene, butadiene-isoprene copolymers, copolymers of ethylene, propylene and non-conjugated dienes such as ethylene-propylene-hexadiene copolymers, butadiene-lower alkyl ester copolymers of (meth)acrylic acid, and butadiene-styrene-lower alkyl ester copolymers of (meth)acrylic acid. Examples of the lower alkyl ester of (meth)acrylic acid include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. The proportion of lower alkyl ester of (meth)acrylic acid in the butadiene-lower alkyl ester of (meth)acrylic acid copolymer or butadiene-styrene-lower alkyl ester of (meth)acrylic acid copolymer is preferably 30 mass % or less of the amount of the rubber polymer.

[0061] Examples of the acrylic rubber include acrylic acid alkyl ester rubber, in which the number of carbon atoms of the alkyl group is preferably 1 to 8. Specific examples of the acrylic acid alkyl ester include ethyl acrylate, butyl acrylate, and hexyl acrylate. The acrylic acid alkyl ester rubber may optionally contain an ethylenically unsaturated monomer. Specific examples of such compounds include di(meth)acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth)acrylate, butadiene, and isoprene. The acrylic rubber further includes a core-shell type polymer having a crosslinked diene rubber as a core.

[0062] As for these rubbery polymers (b3), one type may be used alone, or two or more types may be used in combination.

[0063] The styrene-based resin is preferably composed of 50 to 100 mass% of the aromatic vinyl monomer component (b1), 0 to 30 mass% of the vinyl cyanide monomer component (b2), 0 to 30 mass% of the rubber-like polymer component (b3), and 0 to 30 mass% of other monomer components (b4). It is more preferable that the styrene-based resin is composed of 50 to 80 mass% of the aromatic vinyl monomer component (b1), 10 to 30 mass% of the vinyl cyanide monomer component (b2), 5 to 25 mass% of the rubber-like polymer component (b3), and 0 to 20 mass% of other monomer components (b4). It is further preferable that the styrene-based resin is composed of 55 to 70 mass% of the aromatic vinyl monomer component (b1), 15 to 25 mass% of the vinyl cyanide monomer component (b2), 10 to 25 mass% of the rubber-like polymer component (b3), and 0 to 5 mass% of other monomer components (b4).

[0064] Specific preferred examples of styrene-based resins include homopolymers of styrene, copolymers of styrene and (meth)acrylonitrile, copolymers of styrene and (meth)acrylic acid alkyl esters, copolymers of styrene, (meth)acrylonitrile and other copolymerizable monomers, as well as graft copolymers obtained by polymerizing styrene in the presence of rubber and graft copolymers obtained by graft polymerizing styrene and (meth)acrylonitrile in the presence of rubber. Further specific examples of the resin include polystyrene, high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), styrene-maleic anhydride copolymer (SMA resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), styrene-butadiene-styrene copolymer (SBS resin), hydrogenated styrene-butadiene-styrene copolymer (hydrogenated SBS), hydrogenated styrene-isoprene-styrene copolymer (SEPS), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin) and styrene-IPN type rubber copolymer, or mixtures thereof.

[0065] Among these, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), acrylonitrile-styrene-acrylic rubber copolymers (ASA resins), and acrylonitrile-ethylene propylene rubber-styrene copolymers (AES resins) are preferred, and among these, acrylonitrile-butadiene-styrene copolymers (ABS resins) and acrylonitrile-styrene copolymers (AS resins) are preferred, with acrylonitrile-butadiene-styrene copolymers (ABS resins) being particularly preferred.

[0066] The styrene resin can improve the fluidity of the resin composition. When the styrene resin is contained, the content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (A).

[0067] [Release agent] The resin composition of the present invention also 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.

[0068] Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic mono-, di- or tri-carboxylic acids. Here, the aliphatic carboxylic acid also includes alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, and more preferred are saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms. 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, tetralinic acid, montanic acid, adipic acid, and azelaic acid.

[0069] The aliphatic carboxylic acid in the ester of aliphatic carboxylic acid and alcohol can be, for example, the same as the aliphatic carboxylic acid. 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.

[0070] 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.

[0071] The above ester may contain an aliphatic carboxylic acid and / or alcohol as an impurity. The above ester may be a pure substance, or may be a mixture of a plurality of compounds. The aliphatic carboxylic acid and alcohol that are combined to form an ester may each be used alone or in any combination and ratio of two or more.

[0072] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly composed of myricyl palmitate), 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.

[0073] Examples of aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. The aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbons may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferred, and paraffin wax and polyethylene wax are more preferred. The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, but a mixture of substances having various constituent components and molecular weights can also be used as long as the main component is within the above range.

[0074] Examples of polysiloxane-based silicone oils include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

[0075] The above-mentioned release agents may be contained alone or in any combination and ratio of two or more kinds. The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (A). If the content of the release agent is less than the lower limit of the above range, the effect of releasability may be insufficient, and if the content of the release agent is more than the upper limit of the above range, there is a possibility that a decrease in hydrolysis resistance and mold contamination during injection molding may occur.

[0076] [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 carbon black), dyes, flame retardants, ultraviolet absorbers, impact resistance improvers, plasticizers, compatibilizers, etc. These additives may be contained alone or in combination of two or more.

[0077] In addition, the polycarbonate resin (A) may contain other resins other than the styrene-based resin. Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins; and polymethacrylate resins. As the other resins, polybutylene terephthalate resins are preferred. The other resins may not be contained, and even if they are contained, the amount is preferably less than 5 parts by mass per 100 parts by mass of the polycarbonate resin (A). When they are contained, one kind may be contained, or two or more kinds may be contained in any combination and ratio.

[0078] [Method for producing polycarbonate resin composition pellets] The kneading conditions for producing pellets from the polycarbonate resin composition of the present invention vary depending on the types and blending ratios of each component used in the polycarbonate resin composition. However, among the blending components of the polycarbonate resin composition, it is preferable to melt-knead the fibrous filler (C) separately from the other components. In particular, it is preferable to side-feed the fibrous filler (C) when melt-kneading using an extruder, and supply it from the middle of the extruder to the melt-kneaded product in which the other components such as the polycarbonate resin have been sufficiently melt-kneaded, and melt-knead the mixture. The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

[0079] The strands molten and extruded from the extruder are quenched in a water tank and cut using a pelletizer to obtain polycarbonate resin composition pellets.

[0080] The method for molding a molded article from polycarbonate resin composition pellets is not particularly limited, and a conventionally known molding method can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, etc. Among these, injection molding is particularly preferred.

[0081] The shape of the molded article is not particularly limited and can be appropriately selected depending on the application and purpose of the molded article. Examples include a case, a plate, a rod, a sheet, a film, a cylinder, an annular shape, a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow article, a frame shape, a box shape, a panel shape, and the like. EXAMPLES

[0082] The following were carried out in order to confirm the effects of the polycarbonate resin composition of the present invention, but the present invention should not be construed as being limited to the following examples. The components are shown in Tables 1 and 2 below.

[0083] [Table 1]

[0084] [Table 2]

[0085] (Examples 1 to 32, Comparative Examples 1 to 18) Of the above-mentioned components, the components except for the glass fiber and carbon fiber were blended in the ratios (parts by mass) shown in Table 3 below, and mixed in a tumbler for 20 minutes. After that, the glass fiber and carbon fiber were side-fed, and the mixture was melt-kneaded at a cylinder temperature of 280°C using a twin-screw extruder with a screw diameter of 25 mm ("TEX-25αIII" manufactured by Japan Steel Works, Ltd.), and pellets were obtained by strand cutting.

[0086] <Measurement of bar flow length> The pellets obtained above were dried at 120°C for 5 hours, and then injection molded into a barflow molded body with a width of 20 mm and a thickness of 2 mm using an injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd. (NEX80III: clamping force 80 tons) under conditions of cylinder setting temperature of 300°C, mold temperature of 100°C, injection pressure of 150 MPa, injection time of 5 seconds, and molding cycle of 40 seconds, and the flow length (unit: mm) of the molded body was evaluated.

[0087] The resin composition pellets obtained above were dried at 120°C for 5 hours, and then injection molded into ISO multipurpose test pieces (4 mm thick) using an injection molding machine (NEX80III) manufactured by Nissei Plastic Industrial Co., Ltd. under the following conditions: cylinder setting temperature 300°C, mold temperature 110°C, injection time 2 seconds, and molding cycle 50 seconds.

[0088] <Measurement of unnotched Charpy impact strength> Using the ISO multipurpose test pieces obtained by the above method, the unnotched Charpy impact strength (unit: kJ / m 2 ) was measured.

[0089] <Measurement of bending strength and tensile strength> Using the ISO multipurpose test pieces obtained by the above-mentioned method, the bending strength (unit: MPa) was measured in accordance with ISO 178, and the tensile strength (unit: MPa) was measured at 23°C in accordance with ISO standards 527-1 and 527-2.

[0090] The above evaluation results are shown in Tables 3 to 9 below.

[0091] [Table 3]

[0092] [Table 4]

[0093] [Table 5]

[0094] [Table 6]

[0095] [Table 7]

[0096] [Table 8]

[0097] [Table 9] [Industrial Applicability]

[0098] The polycarbonate resin composition of the present invention has improved mechanical properties, and is excellent in bending strength, tensile strength and impact resistance, and can therefore be suitably used for various molded articles. [Explanation of symbols]

[0099] 1 Short Side 2 Minor diameter

Claims

1. A polycarbonate resin composition comprising, per 100 parts by mass of a polycarbonate resin (A), 0.005 to 0.1 parts by mass of a triaryl phosphate (B) represented by the following general formula (1), 1 to 100 parts by mass of a fibrous filler (C), and at least one of the following components (i) to (iv), wherein the components (i) to (iv) are contained only in the amounts described below. (i) 0.0005 to 0.1 parts by mass of 2-4-di-tert-butylphenol (ii) 0.0001 to 0.03 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (iii) 0.0005 to 0.0035 parts by mass of 4-tert-butylphenol (iv) 0.001 to 0.0035 parts by mass of cumylphenol 【Chemistry 1】 [In formula (1), R １ ~R ５ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

2. 2. The polycarbonate resin composition according to claim 1, wherein the fibrous filler (C) is glass fiber, carbon fiber or a mixture thereof.

3. 3. The polycarbonate resin composition according to claim 2, wherein the glass fiber is at least one selected from the group consisting of milled fiber, chopped strand, and flat glass fiber.

4. In formula (1), R １ ~R ５ and at least one of them is an alkyl group having 1 to 12 carbon atoms.

5. In formula (1), R １ , R ３ is an alkyl group having 1 to 12 carbon atoms, and R ２ , R ４ and R ５ The polycarbonate resin composition according to claim 1 or 4, wherein is a hydrogen atom.

6. In formula (1), R １ , R ３ is a tert-butyl group, R ２ , R ４ and R ５ The polycarbonate resin composition according to claim 5, wherein is a hydrogen atom.

7. The polycarbonate resin composition according to claim 1, further comprising 0.001 to 0.3 parts by mass of tris(2,4-di-tert-butylphenyl)phosphite per 100 parts by mass of the polycarbonate resin (A).

8. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) contains a recycled polycarbonate resin.

9. A pellet comprising the polycarbonate resin composition according to claim 1 or 2.

10. A molded article comprising the polycarbonate resin composition according to claim 1 or 2.

11. A molded article obtained by molding the pellet according to claim 9.

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