Polycarbonate copolymer and molded article comprising same

Abstract

Provided is a polycarbonate copolymer characterized by containing a constituent unit (A-1) represented by formula (A-1) (in the formula, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1-6 carbon atoms, or a halogen atom, and n represents an integer of 1-4) and a constituent unit (B-1) represented by formula (B-1) (in the formula, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1-6 carbon atoms, or a halogen atom, and n represents an integer of 1-4) in an amount of 70 mol% or more relative to the total constituent units. (In formula (1), R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, R2 represents a hydrogen atom, a substituted or unsubstituted aryl group, R3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted aryl group, X represents a single bond or a divalent group represented by formula (X-1), R5 and R6 each independently represent a hydrogen atom or a methyl group, Z represents a group that bonds to a carbon atom to form an optionally substituted alicyclic hydrocarbon having 6-12 carbon atoms. The proportion of the constituent unit (A-1) in all constituent units is 15-60 mol%, and the polycarbonate copolymer has excellent scratch resistance, heat resistance, amine resistance and moldability. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin having excellent scratch resistance, heat resistance, and moldability, and being able to suppress polymer decomposition under conditions of exposure to an alkaline environment containing amines. In addition, the present invention relates to a polycarbonate resin molded product (sheet, film, etc.) suitable for manufacturing an automotive interior decoration part. Furthermore, the present invention relates to an automotive interior decoration part having excellent scratch resistance, heat resistance, moldability, and amine resistance, which is composed of a polycarbonate resin having specific structural units. Background Art

[0002] Polyurethane foam is made of polyol and polyisocyanate as main raw materials, and is formed by mixing a blowing agent, a foam stabilizer, a catalyst, a colorant, etc., and foaming while resinizing. In particular, in the automotive field, it is widely used in seat cushions, door trims, headrests, armrests, steering wheels, floor ceilings, and other sound-absorbing and vibration-damping materials, cushioning materials, sunshades, etc. It is known that tertiary amine compounds used as catalysts are indispensable substances in the resinization, foaming, and expansion reactions of polyurethane foam, but the amine catalyst gradually volatilizes from the polyurethane foam after production, causing discoloration and whitening of other interior decorative parts.

[0003] In addition, in the automotive field, the paint-free interior parts are being studied for the purpose of reducing environmental load and improving production efficiency, and paint-free materials that do not require coating treatment for the purpose of protecting the surface are required. Therefore, such paint-free materials need to have scratch resistance and amine resistance.

[0004] Polycarbonate resins are used as engineering plastics in a wide range of fields, such as housings of electrical and electronic equipment, automobile interior and exterior parts, building materials, furniture, musical instruments, and sundries, due to their excellent transparency, impact resistance, heat resistance, and dimensional stability. Furthermore, compared with inorganic glass, polycarbonate resins have a lower specific gravity, can be lightweight, and have excellent productivity, so they are used for windows of automobiles, etc.

[0005] Furthermore, sheets and films using polycarbonate resins are widely used as various display devices and protective parts for automobile interiors by subjecting them to additional secondary processing such as coating, lamination, and surface modification.

[0006] However, polycarbonate resins that have not been subjected to coating treatment have the following problems: if exposed to an alkaline environment containing amines, the polymer decomposes and the surface of the molded product turns white. Furthermore, the pencil hardness of polycarbonate resin measured according to JIS K5600-5-4 General Test Methods for Coatings - Part 5: Mechanical Properties of Coatings - Section 4: Scratch Hardness (Pencil Method) is only about 2B, and as an uncoated material, there is a problem that the surface is easily scratched.

[0007] Therefore, it is described that polycarbonate and copolycarbonate containing 2,2-bis(4-hydroxy-3-methylphenyl)propane as a constituent unit have excellent scratch resistance (for example, Patent Documents 1 to 5). Although such polycarbonate resin has improved scratch resistance, it is inferior in heat resistance.

[0008] Therefore, it is known that polycarbonate resins obtained by copolymerizing 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimide alone or with bisphenol A have high heat resistance. (For example, Patent Documents 6 to 9) Although the polycarbonate resins have improved heat resistance, they have the problem of poor amine resistance. Furthermore, polycarbonate resins having a glass transition temperature exceeding 200°C have poor fluidity during molding, causing poor appearance and yellowing of the molded products, and thus poor moldability.

[0009] Therefore, there is no polycarbonate resin that is excellent in scratch resistance, heat resistance, amine resistance, and moldability.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application Laid-Open No. 64-069625

[0013] Patent Document 2: Japanese Patent Application Laid-Open No. 08-183852

[0014] Patent Document 3: Japanese Patent Application Laid-Open No. 08-034846

[0015] Patent Document 4: Japanese Patent Application Publication No. 2002-117580

[0016] Patent Document 5: Japanese Patent Application Publication No. 2003-252978

[0017] Patent Document 6: Japanese Patent Application Laid-Open No. 06-82624

[0018] Patent Document 7: Japanese Patent Application No. 2009-517537

[0019] Patent Document 8: Japanese Patent Application No. 2009-517530

[0020] Patent Document 9: Japanese Patent Application Publication No. 2005-290378 Summary of the invention

[0021] An object of the present invention is to provide a polycarbonate resin having excellent scratch resistance, heat resistance, amine resistance and moldability. Another object of the present invention is to provide a polycarbonate resin molded article particularly suitable for automobile interior parts.

[0022] The present inventors unexpectedly found that the above-mentioned object can be achieved even with a polycarbonate resin by containing a specific structural unit. Based on this finding, the present invention was completed as a result of further studies.

[0023] That is, according to the present invention, the following (Configuration 1) to (Configuration 13) can be provided.

[0024] (Composition 1)

[0025] A polycarbonate copolymer comprising 70 mol% or more of a structural unit (A-1) represented by the following formula (A-1) and a structural unit (B-1) represented by the following formula (B-1) based on all structural units, wherein the proportion of the structural unit (A-1) in all structural units is 15 to 60 mol%.

[0026]

[0027] (In the formula, R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and n represents an integer of 1 to 4.)

[0028]

[0029] (wherein, R3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X is a single bond or a divalent group represented by the following formula (X-1),

[0030]

[0031] R5 and R6 each independently represent a hydrogen atom or a methyl group, and Z represents a group that is bonded to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms that may have a substituent.

[0032] (Composition 2)

[0033] The polycarbonate copolymer according to Configuration 1, wherein the repeating unit (A-1) represented by the formula (A-1) is a repeating unit represented by the following formula (A-1-1).

[0034]

[0035] (In the formula, R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

[0036] (Composition 3)

[0037] The polycarbonate copolymer according to configuration 1 or 2, wherein the repeating unit (B-1) represented by the formula (B-1) is a repeating unit represented by the following formula (B-1-1).

[0038]

[0039] (Wherein, R9 and R 10 Each independently represents a hydrogen atom or a methyl group, and Y represents at least one group among the divalent groups represented by the following formula (Y-1).

[0040]

[0041] (Composition 4)

[0042] A polycarbonate copolymer characterized by comprising 70 mol% or more of a structural unit (A-2) represented by the following formula (A-2) and a structural unit (B-2) represented by the following formula (B-2) based on all structural units, wherein the proportion of the structural unit (A-2) in all structural units is 15 to 75 mol%.

[0043]

[0044] (In the formula, R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom, and n represents an integer of 1 to 4.)

[0045]

[0046] (W represents a single bond, at least one divalent organic residue selected from the following formulae (W-1) to (W-3), or any bond of the following formula (W-4); x and y each independently represent 0 or an integer of 1 to 4; R3 and R4 each independently represent a halogen atom, or an organic residue selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkyloxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms.)

[0047]

[0048] (In the formula, R5, R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

[0049]

[0050] (Wherein, R9 and R 10 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms. )

[0051]

[0052] (Where R 11and R 12 Each independently represents a hydrogen atom or a methyl group, and Z represents a group that is bonded to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms which may have a substituent.

[0053]

[0054] (Composition 5)

[0055] The polycarbonate copolymer according to Configuration 4, wherein the repeating unit (A-2) represented by the formula (A-2) is a repeating unit represented by the following formula (A-2-1).

[0056]

[0057] (Where R 13 and R 14 Each independently represents an alkyl group having 1 to 6 carbon atoms. )

[0058] (Composition 6)

[0059] The polycarbonate copolymer according to configuration 4 or 5, wherein the repeating unit (B-2) represented by the formula (B-2) is a repeating unit represented by the following formula (B-2-1).

[0060]

[0061] (Where R 15 and R 16 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents a single bond or at least one divalent group represented by the following formula (X-2).

[0062]

[0063] (Composition 7)

[0064] The polycarbonate copolymer according to configuration 1 or 4, wherein the glass transition temperature is 130 to 200°C.

[0065] (Composition 8)

[0066] The polycarbonate copolymer according to configuration 1 or 4, wherein the indentation hardness measured according to the instrumented micro-indentation hardness test for measuring the hardness of plastics described in ISO / TS19278 is 200 to 400 (N / mm 2 ) and the pencil hardness measured according to the scratch hardness (pencil method) described in JIS K5600-5-4 is 3H or more.

[0067] (Composition 9)

[0068] The polycarbonate copolymer according to configuration 1 or 4, wherein the viscosity average molecular weight is 15,000 to 40,000.

[0069] (Composition 10)

[0070] A molded article is obtained by injection molding the polycarbonate copolymer described in configuration 1 or 4.

[0071] (Composition 11)

[0072] A sheet or film obtained by extrusion molding the polycarbonate copolymer described in configuration 1 or 4.

[0073] (Composition 12)

[0074] An automobile interior component using the molded article of structure 10.

[0075] (Composition 13)

[0076] An automobile interior component using the sheet or film of configuration 11.

[0077] The polycarbonate copolymer of the present invention and the molded articles thereof are excellent in scratch resistance, heat resistance, amine resistance and moldability, and in particular, do not require coating treatment, and are suitable for interior decorative parts of automobiles such as lamp lenses for interior lighting, instrument covers for displays, instrument letter plates, various switch covers, display covers, thermal control panels, instrument panels, central instrument panels, central panels, interior lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Figure 1 This is the proton NMR of 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine obtained in Synthesis Example A-2-1. DETAILED DESCRIPTION

[0079] Hereinafter, the present invention will be described in detail.

[0080] (Method 1)

[0081] <Polycarbonate copolymer (polycarbonate resin)>

[0082] The polycarbonate copolymer of the present invention (hereinafter, sometimes referred to as a polycarbonate resin) is substantially composed of a structural unit (A-1) represented by the following formula (A-1) and a structural unit (B-1) represented by the following formula (B-1).

[0083]

[0084] (In the formula, R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and n represents an integer of 1 to 4.)

[0085]

[0086] (wherein, R3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X is a single bond or a divalent group represented by the following formula (X-1),

[0087]

[0088] R5 and R6 each independently represent a hydrogen atom or a methyl group, and Z represents a group that is bonded to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms that may have a substituent.

[0089] Here, "substantially" means a ratio of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol% in 100 mol% of all structural units excluding the terminals.

[0090] In the structural unit (A-1) represented by the above formula (A-1), R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. n is preferably an integer of 1 or 2, and particularly preferably an integer of 1.

[0091] Examples of the dihydric phenol from which the structural unit (A-1) is derived include 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimide and 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimide. The most preferred dihydric phenol is 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimide.

[0092] In the polycarbonate resin of the present invention, the ratio of the structural unit (A-1) relative to 100 mol% of all structural units is 15 to 60 mol%, preferably 20 to 55 mol%, and more preferably 30 to 50 mol%. If the ratio of the structural unit (A-1) exceeds the upper limit, although the heat resistance is improved, the moldability and amine resistance are poor, which is not preferred. When the ratio of the structural unit (A-1) is less than the lower limit, the heat resistance and scratch resistance are poor, which is not preferred.

[0093] In the structural unit (B-1) represented by the above formula (B-1), substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms for R3 and R4 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, n-hexyl, n-heptyl, n-octyl, etc., and substituted or unsubstituted aryl groups include, for example, phenyl, benzyl, tolyl, 4-methylphenyl, naphthyl, etc. R3 and R4 are preferably hydrogen atoms, methyl, ethyl, n-propyl, 4-methylphenyl, more preferably hydrogen atoms, methyl groups, and particularly preferably hydrogen atoms.

[0094] In addition, the bonding position of R3 and R4 in the above formula (B-1) is preferably the 5-position relative to X.

[0095] In the above formula (B-1), R5 and R6 of X each independently represent a hydrogen atom or a methyl group, preferably a methyl group, and particularly preferably an isopropylidene group in which R5 and R6 are methyl groups.

[0096] In the above formula (B-1), Z is bonded to the carbon atom to which the two phenyl groups are bonded to form a substituted or unsubstituted divalent alicyclic hydrocarbon having 6 to 12 carbon atoms. Examples of the divalent alicyclic carbon ring include cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclododecylidene or adamantylidene and other cycloalkylidene groups (preferably having 4 to 12 carbon atoms), and examples of the substituted group include these groups having a methyl substituent or an ethyl substituent. Among them, cyclohexylidene, methyl-substituted cyclohexylidene, and cyclododecylidene are preferred.

[0097] The dihydric phenol from which the structural unit (B-1) is derived is preferably 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes referred to as bisphenol C), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (hereinafter sometimes referred to as bisphenol OCZ), and 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes referred to as bisphenol OCTMC). Bisphenol C, bisphenol OCZ, and bisphenol OCTMC are more preferred. The most preferred dihydric phenol is bisphenol C.

[0098] In the polycarbonate resin of the present invention, the ratio of the structural unit (B-1) relative to 100 mol% of all the structural units is preferably 40 to 85 mol%, more preferably 45 to 80 mol%, and most preferably 50 to 70 mol%. If the ratio of the structural unit (B-1) is within the above range, the balance among heat resistance, scratch resistance, amine resistance, and moldability is excellent, and therefore it is preferred.

[0099] Furthermore, according to the present invention, a carbonate bond repeating unit derived from another dihydric phenol as a dihydric phenol may be copolymerized unless the object and characteristics of the present invention are impaired. Representative examples of the other dihydric phenols include hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A), 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, Hexane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, 1,1'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, 1,1'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxydiphenyl ester, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, etc. These can be used alone or in combination of two or more. The most preferred dihydric phenol is bisphenol A. The content of these other dihydric phenols is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, particularly preferably 5 mol% or less, based on 100 mol% of all structural units.

[0100] (Method 2)

[0101] <Polycarbonate copolymer (polycarbonate resin)>

[0102] The polycarbonate copolymer of the present invention is substantially composed of a carbonate copolymer, wherein the carbonate copolymer comprises 70 mol% or more of a structural unit (A-2) represented by the following formula (A-2) and a structural unit (B-2) represented by the following formula (B-2) based on all structural units.

[0103]

[0104] (In the formula, R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom, and n represents an integer of 1 to 4.)

[0105]

[0106] (W represents a single bond, at least one divalent organic residue selected from the following formulae (W-1) to (W-3), or any bond of the following formula (W-4); x and y each independently represent 0 or an integer of 1 to 4; R3 and R4 each independently represent a halogen atom, or an organic residue selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkyloxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms.)

[0107]

[0108] (In the formula, R5, R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

[0109]

[0110] (Wherein, R9 and R 10 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms. )

[0111]

[0112] (Where R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, and Z represents a group that is bonded to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms which may have a substituent.

[0113]

[0114] The ratio of the structural unit (A-2) in all structural units is 15 to 75 mol%.

[0115] Here, "substantially" means a ratio of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol% in 100 mol% of all structural units excluding the terminals.

[0116] In the structural unit (A-2) represented by the above formula (A-2), R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom, preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. In addition, n is an integer of 1 to 4, preferably an integer of 1 to 2, and most preferably an integer of 1.

[0117] Examples of the dihydric phenol from which the structural unit (A-2) is derived include 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimide and 2-phenyl-3,3-bis(4-hydroxy-3-isopropylphenyl)phthalimide. The most preferred dihydric phenol is 2

[0118] -phenyl-3,3-bis(4-hydroxy-3-methylphenyl)benzo[c]pyrrolidone.

[0119] In the polycarbonate resin of the present invention, the ratio of the structural unit (A-2) relative to 100 mol% of all structural units is 15 to 75 mol%, preferably 20 to 70 mol%, preferably 25 to 60 mol%, and more preferably 30 to 50 mol%. If the ratio of the structural unit (A-2) exceeds the above upper limit, the heat resistance is improved, but the moldability and amine resistance are poor, so it is not preferred. When the ratio of the structural unit (A-2) is less than the above lower limit, the heat resistance and scratch resistance are poor, so it is not preferred.

[0120] Among the structural units (B-2) represented by the above formula (B-2), repeating units represented by the following formula (B-2-1) are preferred.

[0121]

[0122] (Where R 15 and R 16 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X represents a single bond or at least one divalent group represented by the following formula (X-2).

[0123]

[0124] In the structural unit (B-2) represented by the above formula (B-2), examples of compounds from which the structural unit in which W is a single bond is derived include 4,4′-biphenol and 4,4′-bis(2,6-dimethyl)diphenol.

[0125] Examples of the compound from which W is derived as a constituent unit of the formula (W-1) include α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (generally referred to as "bisphenol M"), and α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene.

[0126] Examples of the compound from which W is derived as a structural unit of the above formula (W-2) include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

[0127] Examples of the compound from which W is a constituent unit of the formula (W-3) include 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes referred to as bisphenol OCTMC), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (hereinafter sometimes referred to as bisphenol OCZ), 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis( 3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-2-phenyl)-1-phenylethane, 1,1-bis(4-hydroxy-2-chlorophenyl)ethane , 2,2-bis(4-hydroxyphenyl)propane (hereinafter, sometimes referred to as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter, sometimes referred to as bisphenol C), 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-ethylphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(3-methyl-4-hydroxyphenyl)decane and 1,1-bis(2,3-dimethyl-4-hydroxyphenyl)decane.

[0128] Examples of the compound from which W is derived as a structural unit of any one of the formula (W-4) include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, and bis(3,5-dimethyl-4-hydroxyphenyl)sulfone.

[0129] Among the above dihydric phenols, bisphenol M is preferred in the case of formula (W-1), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene is preferred in the case of formula (W-2), bisphenol OCZ, bisphenol OCTMC, bisphenol A, and bisphenol C are preferred in the case of formula (W-3), and 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide is preferred in the case of formula (W-4).

[0130] As the dihydric phenol from which the structural unit (B-2) is derived, bisphenol C, bisphenol OCZ, and bisphenol OCTMC are more preferred, and bisphenol C is the most preferred dihydric phenol.

[0131] In the polycarbonate resin of the present invention, the ratio of the structural unit (B) relative to 100 mol% of all the structural units is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, further preferably 40 to 75 mol%, and most preferably 50 to 70 mol%. If the ratio of the structural unit (B-2) is within the above range, the balance of heat resistance, scratch resistance, amine resistance, and moldability is excellent, so it is preferred.

[0132] Furthermore, according to the present invention, a carbonate bond repeating unit derived from another dihydric phenol as the dihydric phenol may be further copolymerized unless the object and characteristics of the present invention are impaired. Representative examples of the other dihydric phenols include 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, resorcinol substituted with an alkyl group having 1 to 3 carbon atoms, 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol, 1-(4-hydroxyphenyl)-1,3,3-trimethylindan-5-ol, 6,6'-dihydroxy-3,3,3',3'-tetramethylspiroindan, 1-methyl-1,3-bis(4-hydroxyphenyl)-3-isopropylcyclohexane, 1-methyl-2-(4-hydroxyphenyl)-3-[1-(4-hydroxyphenyl)isopropyl]cyclohexane, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, and ethylene glycol bis(4-hydroxyphenyl) ether. These may be used alone or in combination of two or more. The content of these other dihydric phenols is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, particularly preferably 5 mol% or less, based on 100 mol% of all structural units.

[0133] <Method for producing polycarbonate copolymer (polycarbonate resin)>

[0134] The polycarbonate copolymer (polycarbonate resin) of (mode 1) and (mode 2) used in the present invention is obtained by reacting dihydric phenol with carbonate precursor. As the reaction method, interfacial polycondensation, melt transesterification, solid phase transesterification of carbonate prepolymer and ring-opening polymerization of cyclic carbonate compounds etc. can be enumerated. In the case of interfacial polycondensation, a capping agent of monohydric phenol is usually used. In addition, it can be a branched polycarbonate formed by polymerization of 3 functional components, and then it can also be a copolymerized polycarbonate formed by copolymerization of aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and vinyl monomer.

[0135] For example, the reaction using phosgene as a carbonate precursor is usually carried out in the presence of an acid binding agent and a solvent. As an acid binding agent, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine can be used. As a solvent, for example, a halogenated hydrocarbon such as dichloromethane or chlorobenzene can be used. In addition, in order to promote the reaction, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. At this time, the reaction temperature is usually 0 to 40°C, and the reaction time is a few minutes to 5 hours.

[0136] For example, the transesterification reaction using carbonic acid diester as a carbonate precursor is carried out by heating and stirring a predetermined ratio of aromatic dihydroxy components and carbonic acid diester under an inert gas atmosphere, and distilling out the generated alcohol or phenol. The reaction temperature varies according to the boiling point of the generated alcohol or phenol, and is usually in the range of 120 to 300°C. The reaction is decompressed from its initial stage, and the generated alcohol or phenol is distilled out while completing the reaction. In addition, in order to promote the reaction, a catalyst used in a conventional transesterification reaction can also be used. As the carbonic acid diester used in the above-mentioned transesterification reaction, for example, diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc. can be cited. Among these, diphenyl carbonate is particularly preferred.

[0137] As the end-capping agent, commonly used monofunctional phenols can be used. In particular, in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as end-capping agents to adjust the molecular weight. In addition, since the ends of the obtained aromatic polycarbonate resin are end-capped with groups based on monofunctional phenols, the thermal stability is excellent compared to a case where this is not the case. Specific examples of the above-mentioned monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, p-long-chain alkylphenol, etc.

[0138] The polycarbonate resin of the present invention preferably contains a structural unit (T) represented by the following formula (T) at the terminal. The inclusion of the structural unit (T) at the terminal improves fluidity.

[0139]

[0140] (In formula (T), l represents an integer of 0 or 1, and R5 represents an alkyl group having 5 to 20 carbon atoms.)

[0141] The content (molar fraction) of the structural unit (T) represented by the above formula (T) in all structural units in the polycarbonate resin is preferably 0.01 mol% or more, more preferably 0.01 to 10 mol%, and further preferably 0.1 to 10 mol%. Within the above range, the glass transition temperature does not become too high, the fluidity is excellent, and the mechanical properties (such as not becoming brittle) are also excellent.

[0142] In the structural unit (B) represented by the above formula (2), R5 is preferably an alkyl group having 8 to 20 carbon atoms, and more preferably an alkyl group having 10 to 18 carbon atoms.

[0143] The polycarbonate resin used in the present invention can be copolymerized with an aliphatic diol as needed. For example, isosorbide: 1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, cyclohexane-1,4-diol, ...2-diol, 1,2-diol, 1,4-diol, 1,2-diol, 1,4- cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bis(cyclohexyl)-4,4'-diol, spirodiol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxydicyclohexyl and poly(ethylene glycol).

[0144] The polycarbonate resin used in the present invention may be copolymerized with fatty acids as needed, for example, 1,10-dodecanedioic acid (DDDA), adipic acid, adipic acid, isophthalic acid, 1,3-phthalic acid, terephthalic acid, 1,4-phthalic acid, 2,6-naphthalene dicarboxylic acid, 3-hydroxybenzoic acid (mHBA) and 4-hydroxybenzoic acid (pHBA).

[0145] The polycarbonate resin used in the present invention comprises polyester carbonates obtained by copolymerizing aromatic or aliphatic (including alicyclic) difunctional carboxylic acids. The aliphatic difunctional carboxylic acids are preferably α, ω-dicarboxylic acids. As aliphatic difunctional carboxylic acids, for example, linear saturated aliphatic dicarboxylic acids such as sebacic acid (decane dioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid and eicosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid can be preferably cited. These carboxylic acids can be copolymerized within the range that does not hinder the purpose. The polycarbonate resin of the present invention can also copolymerize the constituent units containing polyorganosiloxane units as needed.

[0146] The polycarbonate resin used in the present invention may be copolymerized with a constituent unit containing a trifunctional or higher polyfunctional aromatic compound to form a branched polycarbonate as required. As the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate, preferably, there can be exemplified triphenols such as 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol and 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The constituent units derived from the polyfunctional aromatic compound account for preferably 0.03 to 1.5 mol %, more preferably 0.1 to 1.2 mol %, and particularly preferably 0.2 to 1.0 mol % of the total 100 mol % of the constituent units derived from other binary components.

[0147] In addition, the branched structural unit can be derived not only from a polyfunctional aromatic compound, but also from a side reaction such as that produced during a polymerization reaction using a melt transesterification method without using a polyfunctional aromatic compound. 1 It was calculated by H-NMR measurement.

[0148] The viscosity average molecular weight (Mv) of the polycarbonate copolymer (polycarbonate resin) of (Mode 1) and (Mode 2) of the present invention is preferably 15,000 to 40,000, more preferably 15,500 to 35,000, further preferably 16,000 to 30,000, and particularly preferably 17,000 to 25,000. Polycarbonate resins having a viscosity average molecular weight less than the above lower limit may not have sufficient toughness for practical use. On the other hand, polycarbonate resins having a viscosity average molecular weight exceeding the above upper limit require high molding processing temperatures or require special molding methods, and therefore have poor versatility. Furthermore, sometimes the injection speed dependency tends to increase due to an increase in melt viscosity, and the yield rate is reduced due to poor appearance, etc.

[0149] The viscosity average molecular weight of the polycarbonate resin in the present invention is calculated as follows: First, the specific viscosity (η) calculated by the following formula is obtained from a solution obtained by dissolving 0.7 g of the polycarbonate resin in 100 ml of dichloromethane at 20° C. using an Ostwald viscometer. SP ),

[0150] Specific viscosity (η SP )=(t-t0) / t0

[0151] [t0 is the falling seconds of dichloromethane, t is the falling seconds of the sample solution]

[0152] According to the calculated specific viscosity (η SP ) The viscosity average molecular weight Mv is calculated by the following mathematical formula.

[0153] η SP / c=[η]+0.45×[η] 2 c (where [η] is limiting viscosity)

[0154] [η] = 1.23 × 10 -4 Mv 0.83

[0155] c=0.7

[0156] <Components other than polycarbonate copolymer (polycarbonate resin)>

[0157] The polycarbonate copolymer (polycarbonate resin) of (Aspect 1) and (Aspect 2) of the present invention may contain a mold release agent, a heat stabilizer, an ultraviolet absorber, a flow improver, an antistatic agent, and other known functional agents within a range that does not impair the effects of the present invention.

[0158] (i) Release agent

[0159] The polycarbonate resin of the present invention can be used in combination with a release agent within a range that does not impair the effects of the present invention. Examples of release agents include fatty acid esters, polyolefin waxes (polyethylene waxes, 1-olefin polymers, etc., and substances modified with compounds containing functional groups such as acid-modified ones can also be used), fluorine compounds (fluorine oils represented by polyfluoroalkyl ethers, etc.), paraffin waxes, beeswax, etc. Among these, fatty acid esters are preferred in terms of ease of acquisition, demolding properties, and transparency. The proportion of the release agent contained is preferably 0.005 to 0.5 parts by weight, more preferably 0.007 to 0.4 parts by weight, and further preferably 0.01 to 0.3 parts by weight relative to 100 parts by weight of the polycarbonate resin. When the content is above the lower limit of the above range, the effect of improving demolding properties can be clearly exerted, and when it is below the upper limit, adverse effects such as mold contamination during molding are reduced, so it is preferred.

[0160] The fatty acid ester used as the preferred release agent among the above is further described in detail. The fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol of dihydric or higher. In addition, the number of carbon atoms of the alcohol is preferably in the range of 3 to 32, and more preferably in the range of 5 to 30. As the monohydric alcohol, for example, dodecanol, tetradecanol, hexadecanol, octadecyl alcohol, eicosanol, tetracosanol, hexacosanol and triacontanol can be exemplified. As the polyol, pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol and mannitol can be cited. Among the fatty acid esters, polyols are more preferred.

[0161] On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. As the aliphatic carboxylic acid, for example, saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, eicosanoic acid and docosanoic acid (behenic acid), and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid and cetylene acid can be cited. Among the above, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. The aliphatic carboxylic acid is usually manufactured from natural oils and fats such as animal fats and fats (bean oil and lard, etc.) and vegetable fats and fats (palm oil, etc.), so these aliphatic carboxylic acids are usually a mixture of other carboxylic acid components containing different carbon atoms. Therefore, the aliphatic carboxylic acid is also manufactured from the natural oils and fats in the manufacture, and is composed of the form of a mixture containing other carboxylic acid components. The acid value of the fatty acid ester is preferably 20 or less (can be substantially 0). However, in the case of a full ester (Full Ester), it is preferred to contain a large amount of free fatty acid in order to improve the mold release property. From this point of view, the acid value of the full ester is preferably in the range of 3 to 15. In addition, the iodine value of the fatty acid ester is preferably 10 or less (can be substantially 0). These properties can be obtained by the method specified in JIS K 0070.

[0162] The above-mentioned fatty acid ester can be any one of partial ester and full ester. From the aspect of better demoulding property and durability, partial ester is preferred, and monoglyceride is particularly preferred. In monoglyceride, the monoester of glycerol and fatty acid is the main component. As preferred fatty acid, saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, montanic acid and lauric acid, unsaturated fatty acids such as oleic acid, linoleic acid and sorbic acid can be cited. It is particularly preferred that the monoglyceride of stearic acid, behenic acid and palmitic acid is the main component. It should be noted that the fatty acid is synthesized from natural fatty acids, which is a mixture as described above. In such a case, the ratio of the monoglyceride in the fatty acid ester is also preferably more than 60 weight %.

[0163] Should be explained, from the aspect of heat stability, partial ester is more than the situation of full ester difference.In order to improve the heat stability of this partial ester, partial ester is preferably following sodium metal content: preferably less than 20ppm, more preferably less than 5ppm, further preferably less than 1ppm.Sodium metal content is less than the fatty acid partial ester of 1ppm and can utilize molecular distillation etc. to purify and manufacture after making fatty acid partial ester by common method as early as possible.

[0164] Specifically, there are following methods, etc.: after removing gaseous components and low-boiling substances by a nozzle-type degassing device, use a falling film (Falling Film) formula distillation apparatus to remove polyol components such as glycerol under the conditions of distillation temperature 120~150 ℃, vacuum 0.01~0.03kPa, further use a centrifugal molecular distillation apparatus to obtain highly purified fatty acid partial esters as distillate components under the conditions of distillation temperature 160~230 ℃, vacuum 0.01~0.2Torr, and sodium metal can be removed in the form of distillation residue. By repeatedly carrying out molecular distillation to the resulting distillate components, purity can also be further improved to obtain fatty acid partial esters with further less sodium metal content. In addition, it is also important to fully clean the molecular distillation apparatus in advance, and to prevent the pollution of the sodium metal component from the external environment by improving air tightness, etc. This fatty acid ester can be obtained from a professional (for example, Riken Vitamin Co., Ltd.).

[0165] (ii) Phosphorus stabilizer

[0166] The polycarbonate resin of the present invention is preferably further mixed with various phosphorus stabilizers for the main purpose of improving the thermal stability during its molding process. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters. Furthermore, the phosphorus stabilizer contains a tertiary phosphine.

[0167] Specifically, examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri(octadecyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl) phosphite, tris(diisopropylphenyl) phosphite, tris(di-n-butyl ... bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc.

[0168] Furthermore, as other phosphite compounds, phosphite compounds having a cyclic structure that react with dihydric phenols may be used. Examples thereof include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite.

[0169] Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl mono-o-biphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferred.

[0170] Examples of the phosphite compound include tetrakis(2,4-di-tert-butylphenyl)-4,4'-

[0171] Biphenylene diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphite, bis(2,4-di-tert-butylphenyl) The phosphite compound is preferably tetrakis(di-tert-butylphenyl)-biphenylene diphosphite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphite. The phosphite compound is preferably used in combination with the phosphite compound having an aryl group substituted with two or more alkyl groups.

[0172] Examples of the phosphonate compound include dimethyl phenylphosphonate, diethyl phenylphosphonate, and dipropyl phenylphosphonate.

[0173] Examples of the tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, tripentylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0174] The above-mentioned phosphorus stabilizer can be used not only alone but also in combination of two or more. Among the above-mentioned phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferred. Particularly preferred are tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. In addition, the use of these together with phosphoric acid compounds is also a preferred mode.

[0175] (iii) Hindered phenol stabilizer (antioxidant)

[0176] The polycarbonate resin of the present invention may be blended with a hindered phenol stabilizer for the main purpose of improving its thermal stability and heat aging resistance during molding. Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, β-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionic acid n-octadecyl ester, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4

[0177] -(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylenebis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-butylidenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol phenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl] terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2, 2'-Thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyoxycinnamic amide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]ethyl isocyanurate, 1,3,5-tris-2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. These are all easily available. The above hindered phenol antioxidants can be used alone or in combination of two or more.

[0178] The amount of the above-mentioned (ii) phosphorus stabilizer and / or (iii) hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, and further preferably 0.005 to 0.1 part by weight relative to 100 parts by weight of the polycarbonate resin. If the amount of the stabilizer is too small compared to the above range, it is difficult to obtain a good stabilization effect, and if it exceeds the above range, it may sometimes cause a decrease in the physical properties of the material and mold contamination during molding.

[0179] The polycarbonate resin of the present invention may also be appropriately used with other antioxidants other than the above-mentioned hindered phenol antioxidants. Examples of the other antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate) and glycerol-3-stearyl thiopropionate. The amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0180] (iv) UV absorber

[0181] The polycarbonate used in the present invention may contain an ultraviolet absorber. Specifically, as the ultraviolet absorber of the present invention, for example, benzophenone-based, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid (sulfoxy)benzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid trihydrobenzophenone, 2,2'-dihydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid trihydro ... Hydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0182] As the ultraviolet absorber, specifically, for the benzotriazole series, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzotriazole oxazine-4-one) and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, etc., copolymers of 2-(2'-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, copolymers of 2-(2'-hydroxy-5-acryloyloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, etc. having a 2-hydroxyphenyl-2H-benzotriazole skeleton, etc.

[0183] As the ultraviolet absorber, specifically, for the hydroxyphenyl triazine series, for example, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methoxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethoxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propoxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butoxyphenol can be exemplified. Furthermore, compounds in which the phenyl group of the above-exemplified compounds is replaced with 2,4-dimethylphenyl, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol, can be exemplified.

[0184] As the ultraviolet absorber, specifically, for the cyclic iminoester type, for example, 2,2'-p-phenylenebis(3,1-benzo Oxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzo Oxazine-4-one) and 2,2'-(2,6-naphthalene)bis(3,1-benzo Oxazine-4-one) etc.

[0185] Examples of the ultraviolet absorber include cyanoacrylate-based agents such as 1,3-bis-[(2′-cyano-3′,3′-diphenylacryl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryl)oxy]benzene.

[0186] Furthermore, the ultraviolet absorber may also be a polymer type ultraviolet absorber obtained by copolymerizing the ultraviolet absorbing monomer and / or the light stabilizing monomer having a hindered amine structure with a monomer such as (meth) alkyl acrylate by adopting the structure of a monomer compound capable of free radical polymerization. As the ultraviolet absorbing monomer, preferably, there can be exemplified compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylate.

[0187] Among the above, benzotriazole and hydroxyphenyltriazine are preferred from the perspective of ultraviolet absorption, and cyclic iminoester and cyanoacrylate are preferred from the perspective of heat resistance and color tone. The above ultraviolet absorbers may be used alone or in the form of a mixture of two or more.

[0188] The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 2 parts by weight, further preferably 0.04 to 1 part by weight, and particularly preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate resin.

[0189] (v) Flow Improver

[0190] The polycarbonate resin of the present invention may contain a flow improver within the scope of not impairing the effect of the present invention. As the flow improver, preferably styrene oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomers), polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomers), highly branched and hyperbranched aliphatic polyester oligomers, terpene resins and polycaprolactones can be exemplified.

[0191] As the flow improver, fatty acid esters are preferred. The fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids.

[0192] The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having a valence of more than two valences. In addition, the number of carbon atoms of the alcohol is preferably in the range of 3 to 32, and more preferably in the range of 5 to 30. Examples of the monohydric alcohol include dodecanol, tetradecanol, hexadecanol, octadecyl alcohol, eicosanol, tetracosanol, hexacosanol, and triacontanol. Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Monohydric alcohols are more preferred among fatty acid esters.

[0193] On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, eicosanoic acid, and docosanoic acid (behenic acid), and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetylene acid. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred.

[0194] The fatty acid ester may be either a partial ester or a full ester, but is preferably a monoester from the viewpoint of better flow-improving properties, and preferably a monoester of a monohydric alcohol and an aliphatic carboxylic acid.

[0195] The flow improver is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1 to 10 parts by weight relative to 100 parts by weight of the polycarbonate resin. Fatty acid esters are particularly preferred, and the composition ratio is particularly preferably 1 to 5 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0196] (vi) Antistatic agent

[0197] The polycarbonate resin of the present invention may be blended with an antistatic agent for the main purpose of improving antistatic properties. As the antistatic agent, sulfonic acid Salts, phosphites, caprolactone polymers, etc., preferably sulfonic acid As the sulfonic acid Specific examples of the salt include tetrabutyl dodecylsulfonate , Tetrabutyl dodecylbenzenesulfonate , tributyloctyl dodecylbenzenesulfonate , Tetraoctyl dodecylbenzenesulfonate , Tetraethyl Octadecylbenzenesulfonate , tributylmethyl dibutylbenzenesulfonate , triphenyl dibutylnaphthylsulfonate , trioctyl methyl diisopropylnaphthalenesulfonate Among them, tetrabutyl dodecylbenzenesulfonate is preferred from the perspective of compatibility with polycarbonate and easy availability. The amount of the antistatic agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, further preferably 0.3 to 2.0 parts by weight, and particularly preferably 0.5 to 1.8 parts by weight, relative to 100 parts by weight of the polycarbonate resin. When the amount is 0.1 parts by weight or more, an antistatic effect can be obtained, and when it is 5.0 parts by weight or less, the transparency and mechanical strength are excellent, silver streaks and peeling will not occur on the surface of the molded product, and it is not easy to cause poor appearance.

[0198] The polycarbonate resin of the present invention may further contain various additives such as a bluing agent, a fluorescent dye, a flame retardant, and a dye pigment, etc. These may be appropriately selected and contained within a range not impairing the effects of the present invention.

[0199] The bluing agent is preferably contained in the polycarbonate resin in an amount of 0.05 to 3.0 ppm (weight ratio). Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR from Bayer and Polysynthren blue RLS from Clariant.

[0200] Examples of fluorescent dyes (including fluorescent whitening agents) include coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, xanthene fluorescent dyes, xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthene fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. The amount of the fluorescent dye (including fluorescent whitening agents) added is preferably 0.0001 to 0.1 parts by weight relative to 100 parts by weight of the polycarbonate resin.

[0201] As flame retardants, for example, sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants can be cited. Among these, sulfonic acid metal salt flame retardants are preferred. The amount of the flame retardant is usually preferably 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight, relative to 100 parts by weight of the polycarbonate resin.

[0202] The polycarbonate resin composition of the present invention may contain other components in addition to the above-mentioned components as long as the effects of the present invention are not significantly impaired. If other components are given as examples, resins other than polycarbonate resins may be given. It should be noted that other components may be contained alone or in any combination and proportion. As other resins, for example, thermoplastic polyester resins such as polyethylene terephthalate (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer Styrene resins such as polystyrene-based resins (AES resin); polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin; polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin); polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin), etc.

[0203] The method of adding additives to the polycarbonate resin of the present invention is not particularly limited, and a known method can be used. As the most common method, the following method can be cited: after premixing the polycarbonate resin and the additive, the mixture is put into an extruder for melt kneading, the extruded strands are cooled, and the strands are cut by a granulator to produce a granular molding material.

[0204] The extruder in the above method can utilize any one of a uniaxial extruder and a twin-axial extruder, but from the viewpoint of productivity and kneadability, a twin-axial extruder is preferred. As a representative example of the twin-axial extruder, ZSK (Werner & Pfleiderer company system, trade name) can be cited. As a specific example of the same type, TEX (Japan Steel Works, Ltd. system, trade name), TEM (Toshiba Machine Co., Ltd. system, trade name), KTX (Kobe Steel, Ltd. system, trade name) etc. can be cited. As an extruder, an extruder with an exhaust port that can degas the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. It is preferably provided to efficiently discharge the generated moisture and volatile gas from the exhaust port to the outside of the extruder. A vacuum pump. In addition, a screen for removing foreign matter mixed in the extrusion raw material, etc., can also be arranged in the area in front of the die portion of the extruder to remove foreign matter from the resin composition. Examples of the mesh include a metal mesh, a screen changer, and a sintered metal plate (disc filter, etc.).

[0205] Furthermore, the additive may be supplied to the extruder independently, but is preferably premixed with the resin raw material as described above. Examples of the premixing device include a Nauta mixer, a V-type mixer, a Henschel mixer, a mechanochemical device, and an extrusion mixer. A more preferred method is a method in which, for example, a part of the raw resin and the additive are mixed with a high-speed mixer such as a Henschel mixer to prepare a masterbatch, and then the masterbatch is mixed with the remaining total amount of the resin raw material with a non-high-speed mixer such as a Nauta mixer.

[0206] The resin extruded from the extruder is directly cut and granulated, or the filament bundle is cut and granulated by a granulator after forming the filament bundle. In the case where it is necessary to reduce the influence of external dust, etc., it is preferred to purify the atmosphere around the extruder. Furthermore, in the manufacture of the granules, it is preferred to use various methods that have been proposed in the polycarbonate resin for optical disks to narrow the shape distribution of the particles, further reduce the miscut objects, further reduce the fine powder generated during transportation or conveying, and reduce the bubbles (vacuum bubbles) generated inside the filament bundle and particles. In order to reduce miscutting, the following methods can be cited: temperature management of the linear object when cutting by the granulator, blowing of ion wind when cutting, appropriate front angle of the granulator and appropriate combination of release agent, and filtering the mixture of the cut particles and water to separate the particles from water and miscut objects. For example, an example of this measurement method is disclosed in Japanese Patent Publication No. 2003-200421. Through these formulations, high cycle molding and reduction of the proportion of defects such as silver streaks can be achieved.

[0207] The amount of miscutting in the molding material (particles) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, miscutting refers to a powder or granule that is finer than particles of the desired size that pass through a JIS standard sieve with a mesh size of 1.0 mm. The shape of the particles can be a general shape such as a cylinder, a prism, and a sphere, but a cylinder (including an elliptical cylinder) is more preferred, and the diameter of the cylinder is preferably 1.5 to 4 mm, more preferably 2 to 3.5 mm. The ratio of the short diameter to the long diameter in the elliptical cylinder is preferably 60% or more, more preferably 65% ​​or more. On the other hand, the length of the cylinder is preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

[0208] <Characteristics of polycarbonate copolymer (polycarbonate resin)>

[0209] The polycarbonate copolymers (polycarbonate resins) of (Aspect 1) and (Aspect 2) of the present invention can suppress polymer decomposition in an alkaline environment containing amines. As a result of various studies, it has been found that in the depolymerization reaction of polycarbonate based on amine compounds, the amine compounds act on the carbonate bonds of the polycarbonate, and depolymerization proceeds while generating carbamate oligomers as intermediates.

[0210] Therefore, in (mode 1), in order to suppress the reaction between the amine compound and the carbonate bond, it was found that the substituent of the aromatic ring plays a role of steric hindrance to the carbonate bond by being composed of the structural unit (B-1) represented by the above formula (B-1). It was also found that the polycarbonate copolymer (polycarbonate resin) in (mode 1) of the present invention is composed of the structural unit (A-1) represented by the above formula (A-1) and the structural unit (B-1) represented by the above formula (B-1) in a specific ratio, and has an excellent balance of scratch resistance, heat resistance and moldability while maintaining amine resistance.

[0211] In addition, in (mode 2), in order to suppress the reaction between the amine compound and the carbonate bond, it was found that the substituent of the aromatic ring plays a role of steric hindrance to the carbonate bond by being composed of the structural unit (A-2) represented by the above formula (A-2). It was also found that the polycarbonate copolymer (polycarbonate resin) in (mode 2) of the present invention is composed of the structural unit (A-2) represented by the above formula (A-2) and the structural unit (B-2) represented by the above formula (B-2) in a specific ratio, and has an excellent balance of scratch resistance, heat resistance and moldability while maintaining amine resistance.

[0212] The glass transition temperature of the polycarbonate copolymer (polycarbonate resin) of (Aspect 1) and (Aspect 2) of the present invention is preferably 130 to 200° C., more preferably 135 to 195° C., further preferably 140 to 190° C., and particularly preferably 145 to 180° C. When the glass transition temperature is at least the above lower limit, heat resistance is excellent, and when it is at most the above upper limit, molding is easy without excessively high molding temperature.

[0213] The polycarbonate copolymer (polycarbonate resin) of (Aspect 1) and (Aspect 2) of the present invention preferably has an indentation hardness of 200 to 400 (N / mm 2 ), more preferably 210 to 350 (N / mm 2 ), more preferably 220 to 300 (N / mm 2 ). If the indentation hardness is less than the above lower limit, the scratch resistance may be poor. If the indentation hardness exceeds the above upper limit, the material may become very brittle. The indentation hardness can be measured based on ISO / TS19278 by using a dynamic ultra-micro hardness tester (Shimadzu Corporation, model DUH-210S) to measure the relationship between load and indentation depth on the surface of the resin molded product in real time.

[0214] The polycarbonate copolymer (polycarbonate resin) of (Aspect 1) and (Aspect 2) of the present invention preferably has a pencil hardness of 3H or more measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4. In the wear resistance test of "scratching" the surface of a molded product with a human fingernail, a pencil hardness of 3H or more is less likely to scratch, so it is preferred. The pencil hardness decreases in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with 9H being the hardest and 6B being the softest.

[0215] <Amine resistance and amine compounds used in polyurethane foam formation>

[0216] Regarding the polycarbonate copolymers (polycarbonate resins) of (Mode 1) and (Mode 2) of the present invention, when a soft polyurethane foam for a seat cushion material is cut into a shape of 50 mm in length and width and 5 mm in thickness, and is sealed in a glass sealed container together with a molded article of the polycarbonate copolymer, and left in a hot air dryer set at 85° C. for 1000 hours, if there is no change in the appearance of the test piece, it is preferred that the test piece has excellent amine resistance.

[0217] Polyurethane resin is usually produced by reacting polyol and polyisocyanate in the presence of a catalyst and a blowing agent, surfactant, flame retardant, crosslinking agent, etc. as required. Many metal compounds and tertiary amine compounds are known to be used as catalysts in the production of polyurethane resin. These catalysts are used in large quantities in industry by being used alone or in combination. In the production of polyurethane foam using water, low-boiling point organic compounds or both as blowing agents, tertiary amine compounds are particularly widely used among these catalysts from the perspective of excellent productivity and moldability. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N,N,N',N'-tetramethylhexanediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylethylenediamine, bis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N',N'-trimethylaminoethylpiperazine, N,N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, and N,N-dimethylethanolamine.

[0218] <Polycarbonate resin molded products, automotive interior parts>

[0219] The method for producing a molded article from the polycarbonate copolymer (polycarbonate resin) of (Form 1) and (Form 2) of the present invention is not particularly limited, and any molding method generally used for polycarbonate resins can be used. Examples thereof include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding such as gas-assisted molding, molding using an insulating mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, and the like. In addition, a molding method using a hot runner method can also be used.

[0220] In addition, the polycarbonate resin of the present invention can also be obtained into a sheet-like or film-like molded product by a melt extrusion method, a solution casting method (casting method), and the like. The specific method of the melt extrusion method can be, for example, the following method: the polycarbonate resin is quantitatively supplied to an extruder, heated and melted, and the molten resin is extruded from the front end of a T-die onto a mirror-finished roller in a sheet-like shape, and is extracted while being cooled using a plurality of rollers, and is cut into an appropriate size or wound up at the time of solidification. The specific method of the solution casting method can be, for example, the following method: the polycarbonate resin is dissolved in dichloromethane, and the obtained solution (concentration 5% to 40%) is cast from a T-die onto a mirror-finished stainless steel plate, and the sheet is peeled off while passing through an oven with staged temperature control, and the solvent is removed, and then cooled and wound up.

[0221] Furthermore, the polycarbonate resin of the present invention can also be molded to form a laminate. As a method for preparing the laminate, any method can be used, and it is particularly preferred to use a thermocompression bonding method or a coextrusion method. As the thermocompression bonding method, any method can be used, and it is preferred to use, for example, a method of thermocompression bonding a polycarbonate resin sheet using a laminator or a press, and a method of thermocompression bonding immediately after extrusion. In particular, a method of continuously thermocompressing a polycarbonate resin sheet immediately after extrusion is industrially advantageous.

[0222] Furthermore, the polycarbonate copolymers (polycarbonate resins) of (Mode 1) and (Mode 2) of the present invention are used as automotive interior decoration parts due to their excellent scratch resistance, heat resistance, amine resistance and moldability. Examples of automotive interior decoration parts include lamp lenses for interior lighting, instrument covers for display, instrument letter plates, various switch covers, display covers, thermal control panels, instrument panels, central instrument panels, central panels, interior lamp lenses, various display devices such as head-up displays, protective components, light-transmitting components, etc. In addition, since the automotive interior decoration parts of the present invention have the above-mentioned characteristics, they have the advantage that polycarbonate resin molded products can be used directly without coating treatment.

[0223] Example

[0224] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples. In the following Examples and Comparative Examples, the methods for measuring various properties are as follows.

[0225] (1) Composition ratio

[0226] 40 mg of a polycarbonate resin (copolymer) was dissolved in 0.6 ml of a deuterated chloroform solution and measured using a 400 MHz nuclear magnetic resonance device manufactured by JEOL Ltd. 1 The composition ratio of the polycarbonate resin (copolymer) was calculated from the area integration ratio of the characteristic spectrum peaks of each structural unit in the H-NMR spectrum.

[0227] (2) Viscosity average molecular weight

[0228] The viscosity average molecular weight of the polycarbonate resin is measured and calculated by the following method. First, the polycarbonate resin pellets obtained by extrusion are mixed with 30 times the weight of dichloromethane to dissolve it, and the soluble components are collected by diatomaceous earth filtration. Then, after removing the solvent from the obtained solution, the obtained solid is fully dried, and the specific viscosity (η) of the solution at 20°C is measured based on the solution obtained by dissolving 0.7 g of the solid in 100 ml of dichloromethane. sp ). Then, Mv calculated from the following formula was used as the viscosity average molecular weight.

[0229] η sp / c=[η]+0.45×[η] 2 c

[0230] [η] = 1.23 × 10 -4 Mv 0.83

[0231] η sp : Specific viscosity

[0232] η: limiting viscosity

[0233] c: constant (=0.7)

[0234] Mv: viscosity average molecular weight

[0235] (3) Glass transition temperature

[0236] The measurement was performed using a thermal analysis system DSC-2910 manufactured by TA Instruments in accordance with JIS K7121 under the conditions of a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) and a temperature increase rate of 20° C. / min.

[0237] (4) Pencil hardness

[0238] The obtained polycarbonate resin was press-molded using a hot press molding machine ((compression molding machine manufactured by Shinto Metal Industries Co., Ltd.: SFV-10, vacuum pump unit: GXD-360) to obtain a disc-shaped resin plate with a thickness of about 3 mm. The press molding conditions are: mold temperature 150-350°C, primary pressure: 1 MPa (30 seconds), secondary pressure: 1.5 MPa (12 minutes). Using this resin plate, based on the scratch hardness (pencil method) described in JIS K5600-5-4, in a constant temperature room with an atmosphere temperature of 23°C, a pencil was kept at an angle of 45 degrees relative to the surface of the resin plate while applying a load of 750g, and the surface state was visually observed for evaluation.

[0239] Load: 750g

[0240] Measuring speed: 50mm / min

[0241] Measuring distance: 7mm

[0242] Pencil: Hi-uni, Mitsubishi Pencil

[0243] (5) Indentation hardness (Hit)

[0244] The obtained polycarbonate resin was pressed and molded using a hot press molding machine ((Compression molding machine manufactured by Shinto Metal Industries, Ltd.: SFV-10, vacuum pump unit: GXD-360) to obtain a disc-shaped resin plate with a thickness of about 3 mm. The pressing molding conditions are: mold temperature 150-350°C, primary pressure: 1 MPa (30 seconds), secondary pressure: 1.5 MPa (12 minutes). Using this resin plate, based on the instrumented micro-indentation hardness test for measuring plastic hardness described in ISO / TS19278, a dynamic ultra-micro hardness tester (Shimadzu Corporation, model DUH-210S) was used to measure the relationship between the load and the indentation depth on the surface of the resin plate in real time, and the indentation hardness (N / mm 2 ).

[0245] (Measurement conditions)

[0246] Measuring indenter: Berkovich indenter (made of diamond)

[0247] Test force: 500mN

[0248] Minimum test force: 4.9mN

[0249] Load / unload time: 30sec

[0250] Load holding time: 40 sec

[0251] Uninstall hold time: 0sec

[0252] Number of trials: 5

[0253] (Calculation method of indentation hardness)

[0254] Indentation hardness (Hit) is measured by measuring the resistance to semi-permanent deformation or damage. Indentation hardness is calculated by the following formula.

[0255] Hit=F max / A p

[0256] F max : Maximum test force

[0257] A p : The projected area of ​​the indenter and the test piece

[0258] A p =23.96×h c 2 (In the case of a triangular cone indenter (115°))

[0259] h c =h max -ε(h max -h r )

[0260] ε=3 / 4(in the case of triangular pyramid)

[0261] h r : The intercept of the tangent line of the unloading curve at Fmax of the test force-depth curve and the depth axis

[0262] (6) Amine resistance

[0263] Using a mold with a cavity surface having an arithmetic mean roughness (Ra) of 0.03 μm, a three-stage mold plate with a width of 50 mm, a length of 90 mm, and a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate was molded using a J-75E3 injection molding machine manufactured by Nippon Steel Works, Ltd. at a barrel temperature of 300°C and a mold temperature of 80°C with a holding time of 20 seconds and a cooling time of 20 seconds. The soft polyurethane foam used in the material of the car seat cushion was cut into a shape of 50 mm in length and width and 5 mm in thickness using a cutter, and was sealed in a glass sealed container together with the three-stage mold plate. After being placed in a hot air dryer set at 85°C for 1000 hours, the appearance of the test piece was visually observed.

[0264] (7) Formability

[0265] The flow length was evaluated using an injection molding machine EC100N2-2Y manufactured by Toshiba Machine Co., Ltd. and an Archimedean spiral flow mold (flow path thickness 2 mm, flow path width 8 mm) under the conditions of a cylinder temperature of 330° C., a mold temperature of 100° C., and an injection pressure of 100 MPa.

[0266] The judgment method is ○: spiral flow length is more than 20 cm, △: spiral flow length is more than 10 cm and less than 20 cm, ×: spiral flow length is less than 10 cm.

[0267] (8) 1H-NMR measurement

[0268] The compound obtained in Synthesis Example A-2-1 was measured using the following apparatus and solvent.

[0269] Device: JNM-AL400 (400MHz) manufactured by NEC Corporation

[0270] Solvent: (CD3)2SO

[0271] (9) High performance liquid chromatography (HPLC)

[0272] The measurement was performed using a high performance liquid chromatograph Chromaster manufactured by Hitachi under the measurement conditions described in the following Table 1. In Synthesis Example A-2-1, unless otherwise specified, % is an area percentage value corrected by removing the solvent in HPLC.

[0273] [Table 1]

[0274]

[0275] (10)MVR

[0276] The resin composition (pellets) was dried at 80°C for 4 hours, and then the MVR (melt volume rate) was measured at a temperature of 300°C and a load of 2.16 kgf using a method in accordance with ISO1133. The amount of polymer (cm 3 )express.

[0277] (11) Saturated water absorption

[0278] According to JIS K7209:2000, 3 g of a sample was dissolved in dichloromethane, and the dichloromethane was evaporated. The resulting cast film was dried at 50°C for 24 hours, immersed in water at 25°C, and the weight was measured. The water absorption was determined from the following formula.

[0279] Water absorption rate (%) = {(resin weight after water absorption - resin weight before water absorption) / resin weight before water absorption} × 100

[0280] The water absorption was measured over time, and the water absorption when the equilibrium value was reached was determined as the saturated water absorption.

[0281] (Method 1)

[0282] [Example A-1-1]

[0283] 5032 parts of 48% sodium hydroxide aqueous solution and 14030 parts of ion exchange water were placed in a reactor equipped with a thermometer, a stirrer and a reflux cooler, 1177 parts of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimide (manufactured by OG Co., Ltd., hereinafter referred to as PPPBP), 3067 parts of bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter referred to as BPC) and 8.5 parts of hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved therein, and then 16550 parts of dichloromethane were added, and 2000 parts of phosgene were blown into the mixture at 15 to 25° C. for about 90 minutes under stirring. After the blowing of phosgene was completed, 3355 parts of 48% sodium hydroxide aqueous solution and 67 parts of p-tert-butylphenol were added, stirring was resumed, and 4 parts of triethylamine was added after emulsification, and stirring was further performed at 28 to 35° C. for 1 hour to terminate the reaction.

[0284] After the reaction is completed, the product is diluted with dichloromethane and washed with water, and then hydrochloric acid is added to adjust the acidity and washed with water, and then the water washing is repeated until the conductivity of the aqueous phase is substantially the same as that of ion exchange water, thereby obtaining a dichloromethane solution of a polycarbonate resin. Next, the solution is passed through a filter with a mesh of 0.3 μm, and then dripped into warm water in a kneader with an isolation chamber having a foreign matter removal port in the bearing part, and the polycarbonate resin is flaked while distilling off the dichloromethane, and then the liquid-containing flakes are crushed and dried to obtain powders.

[0285] Then, 0.05 parts by weight of Adekastab PEP-36A (manufactured by ADEKA, phosphorus stabilizer), 0.05 parts by weight of Irganox 1076 (manufactured by Ciba Specialty Chemicals, hindered phenol antioxidant), 0.1 parts by weight of RIKESTAR EW-400 (manufactured by Riken Vitamins, fatty acid ester), and 0.3 parts of KEMISORB 79 (manufactured by Chemipro Chemicals, benzotriazole ultraviolet absorber) were added to 100 parts by weight of the powder, and after uniformly mixing, the powder was melt-kneaded and extruded using a vented twin-screw extruder [KTX-46 manufactured by Kobe Steel, Ltd.] while degassing, to obtain polycarbonate resin composition pellets. Various evaluations were performed using the pellets, and the results are described in Table 2.

[0286] [Example A-1-2]

[0287] The results of evaluation using the pellets are shown in Table 2.

[0288] [Example A-1-3]

[0289] The results of evaluation using the pellets are shown in Table 2.

[0290] [Example A-1-4]

[0291] The results of evaluation using the pellets are shown in Table 2.

[0292] [Example A-1-5]

[0293] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-1 except that 1766 parts of PPPBP and 63 parts of p-tert-butylphenol were used and 3103 g of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (manufactured by OG, hereinafter referred to as BP-OCZ) was used instead of BPC. The results of evaluation using the pellets are shown in Table 2.

[0294] [Example A-1-6]

[0295] A polycarbonate resin composition pellet was obtained by the same method as in Example A-1-1 except that 1766 parts of PPPBP, 2300 parts of BPC, 67 parts of p-tert-butylphenol, and 506 parts of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (manufactured by OG, hereinafter referred to as BP-OCTMC) were used. The results of evaluation using the pellet are shown in Table 2.

[0296] [Comparative Example A-1-1]

[0297] The results of evaluation using the pellets are shown in Table 3.

[0298] [Comparative Example A-1-2]

[0299] The results of evaluation using the pellets are shown in Table 3.

[0300] [Comparative Example A-1-3]

[0301] Table 3 shows the results of the evaluation using bisphenol A polycarbonate resin pellets (Panlite L-1225Z100M manufactured by Teijin).

[0302] [Comparative Example A-1-4]

[0303] The polycarbonate resin composition pellets were obtained by the same method as in Example A-1-1 except that 1177 parts of PPPBP, 2732 parts of bisphenol A (Mitsui Chemicals) instead of BPC, and 67 parts of p-tert-butylphenol were used.

[0304] [Comparative Example A-1-5]

[0305] The results of evaluation using the pellets are shown in Table 3.

[0306] [Comparative Example A-1-6]

[0307] The results of evaluation using the pellets are shown in Table 3.

[0308] [Table 2]

[0309]

[0310] [Table 3]

[0311]

[0312] [Example A-1-7]

[0313] In a reactor equipped with a thermometer, a stirrer, and a reflux cooler, 302.98 parts by weight of ion exchange water and 181.27 parts by weight of a 25% sodium hydroxide aqueous solution were placed under a nitrogen atmosphere, 27.07 parts by weight of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimide (manufactured by Shanxi Liuqing ■■, hereinafter referred to as PPPBP) as a dihydric phenol, 70.54 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (manufactured by Honshu Chemical, hereinafter referred to as BPC), and 0.197 parts by weight of hydrogen sulfite were dissolved, 357.69 parts by weight of dichloromethane were added, and 41.66 parts by weight of phosgene were blown into the mixture at 18 to 20° C. for 60 minutes while stirring. Then, 25.90 parts by weight of a 25% sodium hydroxide aqueous solution and 2.718 parts by weight of 4-dodecylphenol (manufactured by Sigma·Aldrich, hereinafter referred to as 4DDP) were added and stirred. 0.082 parts by weight of triethylamine was added during the process, and then stirring was continued at 25-30°C for 1.5 hours to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with dichloromethane and repeatedly washed with ion exchange water. When the washing liquid was neutral, it was washed with acidic hydrochloric acid water. Then, it was repeatedly washed with ion exchange water. When the conductivity of the aqueous phase was approximately the same as that of the ion exchange water, it was added dropwise to warm water kept at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was filtered and dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. The polycarbonate resin was melt-mixed and extruded to obtain polycarbonate resin particles. Various evaluations were performed using the particles, and the results are recorded in Table 4.

[0314] [Example A-1-8]

[0315] The results of evaluation using the pellets are shown in Table 4.

[0316] [Example A-1-9]

[0317] The results of evaluation using the pellets are shown in Table 4.

[0318] [Example A-1-10]

[0319] The polycarbonate resin pellets were obtained by the same method as in Example A-1-7 except that 3.138 parts by weight of 3-pentadecylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as 3PDP) was used instead of 2.718 parts by weight of 4DDP.

[0320] [Example A-1-11]

[0321] The results of evaluation using the pellets are shown in Table 4, except that 3.138 parts by weight of 3-pentadecylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as 3PDP) was used instead of 2.718 parts by weight of 4DDP.

[0322] [Example A-1-12]

[0323] The results of evaluation using the pellets are shown in Table 4, except that 3.138 parts by weight of 3-pentadecylphenol (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as 3PDP) was used instead of 2.718 parts by weight of 4DDP.

[0324] [Table 4]

[0325]

[0326] [Example A-1-13]

[0327] The obtained polycarbonate resin flakes were pulverized and dried in the same manner as in Example A-1-1 to obtain a powder.

[0328] Then, 2 parts by weight of Spermaceti (made by NOF Corporation, cetyl myristate), 0.05 parts by weight of Irganox 1076 (made by Ciba Specialty Chemicals, hindered phenol antioxidant), and 0.05 parts by weight of Irgafos 168 (made by BASF, phosphorus stabilizer) were added to 100 parts by weight of the powder, and after uniformly mixing, the powder was melt-kneaded and extruded using a vented twin-screw extruder [KTX-46 made by Kobe Steel Co., Ltd.] while degassing the powder to obtain polycarbonate resin composition pellets. Various evaluations were performed using the pellets, and the results are recorded in Table 5.

[0329] [Example A-1-14]

[0330] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-13 except that 2 parts by weight of Unister M-B96R (fatty acid monoester) was used instead of 2 parts by weight of Spermaceti (made by NOF Corporation, cetyl myristate).

[0331] [Example A-1-15]

[0332] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-13 except that 2 parts by weight of Unister M-9676 (NOF Corporation, stearyl stearate) was used instead of 2 parts by weight of Spermaceti (NOF Corporation, cetyl myristate).

[0333] [Example A-1-16]

[0334] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-13 except that 2 parts by weight of Unister M-2222SL (behenyl behenate, manufactured by NOF Corporation) was used instead of 2 parts by weight of Spermaceti (manufactured by NOF Corporation, cetyl myristate).

[0335] [Example A-1-17]

[0336] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-13 except that 2 parts by weight of Unister E-275 (ethylene glycol distearate, manufactured by NOF Corporation) was used instead of 2 parts by weight of Spermaceti (manufactured by NOF Corporation, cetyl myristate).

[0337] [Example A-1-18]

[0338] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-13 except that 2 parts by weight of Unister H-476D (pentaerythritol distearate, manufactured by NOF Corporation) was used instead of 2 parts by weight of Spermaceti (manufactured by NOF Corporation, cetyl myristate).

[0339] [Example A-1-19]

[0340] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-13 except that 2 parts by weight of Unister H-476 (pentaerythritol tetrastearate, manufactured by NOF Corporation) was used instead of 2 parts by weight of Spermaceti (manufactured by NOF Corporation, cetyl myristate).

[0341] [Example A-1-20]

[0342] The obtained polycarbonate resin flakes were pulverized and dried in the same manner as in Example A-1-8 to obtain a powder.

[0343] Then, 2 parts by weight of Spermaceti (made by NOF Corporation, cetyl myristate), 0.05 parts by weight of Irganox 1076 (made by Ciba Specialty Chemicals, hindered phenol antioxidant), and 0.05 parts by weight of Irgafos 168 (made by BASF, phosphorus stabilizer) were added to 100 parts by weight of the powder, and after uniformly mixing, the powder was melt-kneaded and extruded using a vented twin-screw extruder [KTX-46 made by Kobe Steel Co., Ltd.] while degassing the powder to obtain polycarbonate resin composition pellets. Various evaluations were performed using the pellets, and the results are described in Table 6.

[0344] [Example A-1-21]

[0345] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-20 except that 2 parts by weight of Unister M-9676 (NOF Corporation, stearyl stearate) was used instead of 2 parts by weight of Spermaceti (NOF Corporation, cetyl myristate).

[0346] [Example A-1-22]

[0347] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-20 except that 2 parts by weight of Unister M-2222SL (behenyl behenate, manufactured by NOF Corporation) was used instead of 2 parts by weight of Spermaceti (manufactured by NOF Corporation, cetyl myristate). Various evaluations were performed using the pellets, and the results are shown in Table 6.

[0348] [Example A-1-23]

[0349] The obtained polycarbonate resin flakes were pulverized and dried in the same manner as in Example A-1-11 to obtain a powder.

[0350] Then, 2 parts by weight of Spermaceti (made by NOF Corporation, cetyl myristate), 0.05 parts by weight of Irganox 1076 (made by Ciba Specialty Chemicals, hindered phenol antioxidant), and 0.05 parts by weight of Irgafos 168 (made by BASF, phosphorus stabilizer) were added to 100 parts by weight of the powder, and after uniformly mixing, the powder was melt-kneaded and extruded using a vented twin-screw extruder [KTX-46 made by Kobe Steel Co., Ltd.] while degassing the powder to obtain polycarbonate resin composition pellets. Various evaluations were performed using the pellets, and the results are described in Table 6.

[0351] [Example A-1-24]

[0352] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-23 except that 2 parts by weight of Unister M-9676 (NOF Corporation, stearyl stearate) was used instead of 2 parts by weight of Spermaceti (NOF Corporation, cetyl myristate).

[0353] [Example A-1-25]

[0354] Polycarbonate resin composition pellets were obtained by the same method as in Example A-1-23 except that 2 parts by weight of Unister M-2222SL (behenyl behenate, manufactured by NOF Corporation) was used instead of 2 parts by weight of Spermaceti (manufactured by NOF Corporation, cetyl myristate). Various evaluations were performed using the pellets, and the results are shown in Table 6.

[0355] [Table 5]

[0356]

[0357] [Table 6]

[0358]

[0359] (Method 2)

[0360] [Synthesis Example A-2-1]

[0361] After adding 150 g (0.4 mol) of o-cresolphthalein (produced by Tokyo Chemical Industry) and 826 g (8.9 mol) of aniline (produced by Fujifilm Wako Pure Chemical Industries, Ltd.), 86 mL (1.0 mol) of 36% concentrated hydrochloric acid (produced by Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added dropwise. After the addition was completed, the reaction solution was heated to 160±5°C while distilling off water. The progress of the reaction was tracked by HPLC, and stirring was continued until the o-cresolphthalein of the raw material was almost gone. After the reaction was completed, the reaction solution was cooled to room temperature, and then ethyl acetate was added, and the solution was separated and washed with 5% aqueous hydrochloric acid solution to remove unreacted aniline, and the washing was continued until the water layer became neutral. The light yellow crystals obtained when the organic layer was concentrated were recrystallized with toluene / methanol (v / v=10 / 1), and then 137 g of white crystals of the target 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimide (hereinafter referred to as PCP-BP) were obtained, and the yield was 75%. The obtained PCP-BP is passed through 1 H-NMR analysis confirmed that it was the target compound (ref. Figure 1 ). In addition, the purity was 98.3% as a result of HPLC measurement.

[0362] [Example A-2-1]

[0363] A reactor equipped with a thermometer, a stirrer and a reflux cooler was charged with 5032 parts of a 48% sodium hydroxide aqueous solution and 14030 parts of ion exchange water, and 1261 parts of PCP-BP obtained in Synthesis Example 1, 3067 parts of bisphenol C (manufactured by Honshu Chemical Industry, hereinafter referred to as BPC) and 8.7 parts of hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved therein, and then 16550 parts of dichloromethane were added, and 2000 parts of phosgene were blown into the mixture at 15 to 25° C. for about 90 minutes under stirring. After the blowing of phosgene was completed, 3355 parts of a 48% sodium hydroxide aqueous solution and 67 parts of p-tert-butylphenol were added, stirring was resumed, and 4 parts of triethylamine were added after emulsification, and stirring was further performed at 28 to 35° C. for 1 hour to terminate the reaction.

[0364] After the reaction is completed, the product is diluted with dichloromethane and washed with water, and then hydrochloric acid is added to adjust the acidity and washed with water, and then the water washing is repeated until the conductivity of the aqueous phase is substantially the same as that of ion exchange water, thereby obtaining a dichloromethane solution of a polycarbonate resin. Next, the solution is passed through a filter with a mesh of 0.3 μm, and then dripped into warm water in a kneader with an isolation chamber having a foreign matter removal port in the bearing part, and the polycarbonate resin is flaked while distilling off the dichloromethane, and then the liquid-containing flakes are crushed and dried to obtain powders.

[0365] Then, 0.05 parts by weight of Adekastab PEP-36A (manufactured by ADEKA, phosphorus stabilizer), 0.05 parts by weight of Irganox 1076 (manufactured by Ciba Specialty Chemicals, hindered phenol antioxidant), 0.1 parts by weight of RIKESTAR EW-400 (manufactured by Riken Vitamins, fatty acid ester), and 0.3 parts of KEMISORB 79 (manufactured by Chemipro Chemicals, benzotriazole ultraviolet absorber) were added to 100 parts by weight of the powder, and after uniformly mixing, the powder was melt-kneaded and extruded using a vented twin-screw extruder [KTX-46 manufactured by Kobe Steel, Ltd.] while degassing, to obtain polycarbonate resin composition pellets. Various evaluations were performed using the pellets, and the results are described in Table 7.

[0366] [Example A-2-2]

[0367] The results of evaluation using the pellets are shown in Table 7.

[0368] [Example A-2-3]

[0369] The results of evaluation using the pellets are shown in Table 7.

[0370] [Example A-2-4]

[0371] The results of evaluation using the pellets are shown in Table 7.

[0372] [Example A-2-5]

[0373] The results of evaluation using the pellets are shown in Table 7, except that 3153 parts of PCP-BP and 63 parts of p-tert-butylphenol were used and 1707 g of bisphenol A was used instead of BPC.

[0374] [Example A-2-6]

[0375] A polycarbonate resin composition pellet was obtained by the same method as in Example A-2-1 except that 1892 parts of PCP-BP and 67 parts of p-tert-butylphenol were used and 3103 parts of bisphenol OCZ (manufactured by OG Co., Ltd., hereinafter sometimes referred to as BP-OCZ) was used instead of BPC. The evaluation results using the pellet are shown in Table 7.

[0376] [Example A-2-7]

[0377] A polycarbonate resin composition pellet was obtained by the same method as in Example A-2-1 except that 1892 parts of PCP-BP, 383 parts of BPC, 58 parts of p-tert-butylphenol and 3037 parts of bisphenol OCTMC (manufactured by OG Co., Ltd., hereinafter sometimes referred to as BP-OCTMC) were used. The results of evaluation using the pellet are shown in Table 7.

[0378] [Comparative Example A-2-1]

[0379] Polycarbonate resin composition pellets were obtained by the same method as in Example A-2-1 except that BPC was not used and PCP-BP was replaced with 5886 parts of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimide (manufactured by OG, hereinafter referred to as PPPBP) and 67 parts of p-tert-butylphenol. The results of evaluation using the pellets are shown in Table 8.

[0380] [Comparative Example A-2-2]

[0381] The results of evaluation using the pellets are shown in Table 8.

[0382] [Comparative Example A-2-3]

[0383] Table 8 shows the results of the evaluation using bisphenol A polycarbonate resin pellets (Panlite L-1225Z100M manufactured by Teijin).

[0384] [Comparative Example A-2-4]

[0385] The polycarbonate resin composition pellets were obtained by the same method as in Example A-2-1 except that 1177 parts of PPPBP was used instead of PCP-BP, and 2732 parts of bisphenol A (Mitsui Chemicals) and 67 parts of p-tert-butylphenol were used instead of BPC. The evaluation results using the pellets are shown in Table 8.

[0386] [Comparative Example A-2-5]

[0387] The results of evaluation using the pellets are shown in Table 8.

[0388] [Comparative Example A-2-6]

[0389] The results of evaluation using the pellets are shown in Table 8.

[0390] [Comparative Example A-2-7]

[0391] The results of evaluation using the pellets are shown in Table 8, except that BPC was not used and 6305 parts of PCP-BP and 101 parts of p-tert-butylphenol were used.

[0392] [Table 7]

[0393]

[0394] [Table 8]

[0395]

[0396] Industrial Applicability

[0397] The polycarbonate resin of the present invention can be used for interior lighting lamp lenses, display instrument covers, instrument dials, various switch covers, display covers, thermal control panels, instrument panels, center instrument panels, center panels, interior lamp lenses, various display devices such as head-up displays, protective parts, light-transmitting parts and other automotive interior decoration parts without coating treatment.

Claims

1. A polycarbonate copolymer, characterized in that: The composition comprises 70 mol% or more of the constituent unit (A-1) represented by the following formula (A-1) and the constituent unit (B-1) represented by the following formula (B-1), with the proportion of the constituent unit (A-1) in the total constituent units being 15 to 60 mol%, In the formula, R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and n represents an integer of 1 to 4. In the formula, R3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group, and X is a single bond or a divalent group represented by the following formula (X-1), R5 and R6 each independently represent a hydrogen atom or a methyl group, and Z represents a group which is bonded to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms which may have a substituent.

2. The polycarbonate copolymer according to claim 1, wherein The repeating unit (A-1) represented by the formula (A-1) is a repeating unit represented by the following formula (A-1-1), In the formula, R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

3. The polycarbonate copolymer according to claim 1, wherein The repeating unit (B-1) represented by the formula (B-1) is a repeating unit represented by the following formula (B-1-1), In the formula, R9 and R 10 Each independently represents a hydrogen atom or a methyl group, and Y represents at least one divalent group represented by the following formula (Y-1).

4. A polycarbonate copolymer, characterized in that: The present invention comprises 70 mol% or more of the structural unit (A-2) represented by the following formula (A-2) and the structural unit (B-2) represented by the following formula (B-2) relative to all the structural units, and the ratio of the structural unit (A-2) in all the structural units is 15 to 75 mol%, In the formula, R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms or a halogen atom, and n represents an integer of 1 to 4. In the formula, W represents a single bond, at least one divalent organic residue selected from the following formulas (W-1) to (W-3), or any bond of the following formula (W-4); x and y are each independently 0 or an integer of 1 to 4; R3 and R4 are each independently a halogen atom, or an organic residue selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkyloxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms; In the formula, R5, R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, In the formula, R9 and R 10 each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, In the formula, R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, and Z represents a group which is bonded to a carbon atom to form an alicyclic hydrocarbon having 6 to 12 carbon atoms which may have a substituent.

5. The polycarbonate copolymer according to claim 1, wherein The repeating unit (A-2) represented by the formula (A-2) is a repeating unit represented by the following formula (A-2-1), In the formula, R 13 and R 14 Each independently represents an alkyl group having 1 to 6 carbon atoms.

6. The polycarbonate copolymer according to claim 1, wherein The repeating unit (B-2) represented by the formula (B-2) is a repeating unit represented by the following formula (B-2-1), In the formula, R 15 and R 16 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a single bond or at least one divalent group represented by the following formula (X-2), 7. The polycarbonate copolymer according to claim 1 or 4, wherein The glass transition temperature is 130-200°C.

8. The polycarbonate copolymer according to claim 1 or 4, wherein The indentation hardness measured according to the instrumented micro-indentation hardness test for measuring the hardness of plastics as described in ISO / TS19278 is 200N / mm 2 ~400N / mm 2 The pencil hardness measured by the scratch hardness based on the pencil method described in JIS K5600-5-4 is 3H or more.

9. The polycarbonate copolymer according to claim 1 or 4, wherein The viscosity average molecular weight is 15000 to 40000.

10. A molded article obtained by injection molding the polycarbonate copolymer according to claim 1 or 4.

11. A sheet or film obtained by extrusion molding the polycarbonate copolymer according to claim 1 or 4.

12. An automotive interior component using the molded article according to claim 10.

13. An automotive interior component using the sheet or film according to claim 11.

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