Polycarbonate copolymer and molded articles made therefrom

Abstract

To provide a polycarbonate resin that excels in scratch resistance, heat resistance, amine resistance and moldability.SOLUTION: A polycarbonate copolymer comprises a constituent unit (A) represented by formula (1) and a constituent unit (B) represented by bisphenol C, together constituting at least 70 mol% of all constituent units. In all the constituent units, the proportion of the constitutional unit (A) is 15-75 mol%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a polycarbonate resin that exhibits excellent scratch resistance, heat resistance, and moldability, and can suppress polymer degradation under conditions of exposure to a basic environment containing amines. Furthermore, this invention relates to polycarbonate resin molded articles (sheets, films, etc.) suitable for the manufacture of automotive interior parts. Moreover, this invention relates to automotive interior parts made of a polycarbonate resin having specific structural units, exhibiting excellent scratch resistance, heat resistance, moldability, and amine resistance. [Background technology]

[0002] Polyurethane foam is manufactured using polyols and polyisocyanates as the main raw materials, and is foamed while resinifying by mixing in foaming agents, foam stabilizers, catalysts, and colorants. It is widely used in the automotive sector, in particular, for seat cushions, door trims, headrests, armrests, steering wheels, sound-absorbing and vibration-damping materials for floors and ceilings, cushioning materials, sun visors, etc. Tertiary amine compounds used as catalysts are essential substances in the resinification and foaming / expansion reactions of polyurethane foam, but it is known that amine catalysts gradually volatilize from the polyurethane foam after manufacturing, causing discoloration and whitening of other interior parts.

[0003] Furthermore, in the automotive sector, the elimination of paint on interior components is being considered with the aim of reducing environmental impact and improving production efficiency. This has created a demand for paint-free materials that do not require surface protection coatings. Therefore, such paint-free materials require scratch resistance and amine resistance.

[0004] Polycarbonate resin is an engineering plastic with excellent transparency, impact resistance, heat resistance, and dimensional stability, and is used in a wide range of fields such as electrical and electronic equipment housings, automotive interior and exterior parts, building materials, furniture, musical instruments, and general merchandise. Furthermore, compared to inorganic glass, it has a lower specific gravity, allowing for weight reduction and superior productivity, making it suitable for use in automotive windows and other applications.

[0005] Furthermore, sheets and films made from polycarbonate resin are widely used as various display devices and protective components in automotive interiors after undergoing additional secondary processing such as coating, lamination, and surface modification.

[0006] However, a challenge with uncoated polycarbonate resin is that when exposed to a basic environment containing amines, the polymer decomposes, causing the surface of the molded product to whiten. Furthermore, the pencil hardness of polycarbonate resin measured according to JIS K5600-5-4 - General test methods for paints - Part 5: Mechanical properties of coating films - Section 4: Scratch hardness (pencil method) is only about 2B, which is a challenge for a paintless material as its surface is easily scratched.

[0007] Therefore, it has been described that polycarbonates and copolymers with 2,2-bis(4-hydroxy-3-methylphenyl)propane as a constituent unit have excellent scratch resistance. (For example, Patent Documents 1-5) While these polycarbonate resins have improved scratch resistance, their heat resistance is inferior.

[0008] Therefore, it is known that polycarbonate resins obtained by polymerization of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine alone or with bisphenol A have high heat resistance. (For example, Patent Documents 6-9) However, a problem with these polycarbonate resins is that although their heat resistance is improved, their amine resistance is poor. Furthermore, polycarbonate resins with a glass transition temperature exceeding 200°C have poor fluidity during molding, which causes poor appearance and yellowing of molded products, resulting in poor moldability. Therefore, a polycarbonate resin with excellent scratch resistance, heat resistance, amine resistance, and moldability does not yet exist. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 64-069625 [Patent Document 2] Japanese Patent Application Laid-Open No. 08-183852 [Patent Document 3] Japanese Patent Application Laid-Open No. 08-034846 [Patent Document 4] Japanese Patent Application Laid-Open No. 2002-117580 [Patent Document 5] Japanese Patent Application Laid-Open No. 2003-252978 [Patent Document 6] Japanese Patent Application Laid-Open No. 06-82624 [Patent Document 7] Japanese Patent Application Laid-Open No. 2009-517537 [Patent Document 8] Japanese Patent Application Laid-Open No. 2009-517530 [Patent Document 9] Japanese Patent Application Laid-Open No. 2005-290378 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] An object of the present invention is to provide a polycarbonate resin excellent in scratch resistance, heat resistance, amine resistance, and moldability. Another object of the present invention is to provide a polycarbonate resin molded product particularly suitable for automotive interior parts. [Means for Solving the Problems]

[0011] The present inventors have surprisingly found that even a polycarbonate resin can achieve the above object by containing a specific structural unit. As a result of further studies based on such findings, the present invention has been completed. That is, according to the present invention, the following (Configuration 1) to (Configuration 10) are provided.

[0012] (Configuration 1) A structural unit (A) represented by the following formula (1), and [Chemical Formula] (In the formula, R1 and R2 are each independently alkyl or halogen atoms having 1 to 6 carbon atoms, and n represents an integer from 1 to 4.) The constituent unit (B) is represented by the following formula (2) [ka] (In the formula, W represents a single bond, at least one divalent organic residue selected from the group consisting of formulas (3) to (5) below, or any bond in formula (6) below; x and y are each independently 0 or an integer from 1 to 4; and R3 and R4 are each independently a halogen atom, or an organic residue selected from the group consisting of 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 cycloalkoxy 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.) [ka] (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.) [ka] (In the formula, R9 and R 10 Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. [ka] (In the formula, R 11 and R 12 (Each of the three elements independently represents a hydrogen atom and a methyl group, while Z represents a group that forms an alicyclic hydrocarbon with 6 to 12 carbon atoms, which may be bonded to a carbon atom and have substituents.) [ka] A polycarbonate copolymer containing 70 mol% or more of the total constituent units, characterized in that the proportion of constituent unit (A) in the total constituent units is 15 to 75 mol%.

[0013] (Configuration 2) The polycarbonate copolymer according to claim 1, wherein the repeating unit (A) represented by formula (1) is a repeating unit represented by the following formula (7). [ka] (In the formula, R 13 and R 14 Each of these independently represents an alkyl group with 1 to 6 carbon atoms.

[0014] (Composition 3) The polycarbonate copolymer according to claim 1 or 2, wherein the repeating unit (B) represented by formula (2) is a repeating unit represented by the following formula (8). [ka] (In the formula, R 15 and R 16 Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X is a single bond or the following formula (9) [ka] (This represents at least one divalent group represented by .)

[0015] (Composition 4) A polycarbonate copolymer according to any one of the above 1 to 3, wherein the glass transition temperature is 130 to 200°C. (Composition 5) Indentation hardness measured in accordance with the instrumented microindentation hardness test for plastics described in ISO / TS19278 for hardness measurement is 200-400 (N / mm²). 2A polycarbonate copolymer according to any one of the above 1 to 4, wherein the pencil hardness measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4 is 3H or higher. (Composition 6) A polycarbonate copolymer according to any one of the above 1 to 5, wherein the viscosity-average molecular weight is 15,000 to 40,000. (Composition 7) A molded article obtained by injection molding a polycarbonate copolymer according to any one of items 1 to 6 above. (Composition 8) A sheet or film obtained by extruding a polycarbonate copolymer according to any one of items 1 to 6 above. (Composition 9) Automotive interior parts using the molded product described in item 7 above. (Composition 10) Automotive interior parts using the sheet or film described in item 8 above. [Effects of the Invention]

[0016] The polycarbonate copolymer and molded articles made therefrom of the present invention exhibit excellent scratch resistance, heat resistance, amine resistance, and moldability, and in particular do not require coating treatment. They are suitable for automotive interior parts such as lamp lenses for interior lighting, meter covers for display, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts. [Brief explanation of the drawing]

[0017] [Figure 1] This is the proton NMR spectrum of 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine obtained in Synthesis Example 1. [Modes for carrying out the invention]

[0018] The details of the present invention will be described below.

[0019] <Polycarbonate copolymer (polycarbonate resin)> The polycarbonate copolymer of the present invention (hereinafter sometimes referred to as polycarbonate resin) comprises a structural unit (A) represented by the following formula (1), and

[0020]

Chemical formula

[0021]

Chemical formula

[0022]

Chemical formula

[0023]

Chemical formula

[0024] [ka] (In the formula, R 11 and R 12 (Each of the three elements independently represents a hydrogen atom and a methyl group, while Z represents a group that forms an alicyclic hydrocarbon with 6 to 12 carbon atoms, which may be bonded to a carbon atom and have substituents.)

[0025] [ka]

[0026] This polycarbonate copolymer is substantially composed of a polycarbonate copolymer containing 70 mol% or more of the total constituent units, wherein the proportion of constituent unit (A) in the total constituent units is 15 to 75 mol%.

[0027] Here, "substantially" means that the proportion is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and most preferably 100 mol% of the total constituent units excluding the terminals.

[0028] In the constituent unit (A) represented by formula (1) above, R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms and a halogen atom, preferably an alkyl group having 1 to 4 carbon atoms, with a methyl group being the most preferred. Also, n is an integer from 1 to 4, preferably an integer from 1 to 2, with an integer of 1 being the most preferred.

[0029] Examples of divalent phenols that induce the constituent unit (A) include 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine and 2-phenyl-3,3-bis(4-hydroxy-3-isopropylphenyl)phthalimidine. The most preferred divalent phenol is 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine.

[0030] In the polycarbonate resin of the present invention, the ratio of constituent unit (A) to 100 mol% of all constituent 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 constituent unit (A) exceeds the above upper limit, heat resistance improves, but moldability and amine resistance deteriorate, which is undesirable. If the ratio of constituent unit (A) is below the above lower limit, heat resistance and scratch resistance deteriorate, which is undesirable.

[0031] In the constituent unit (B) represented by formula (2) above, it is preferable that it be a repeating unit represented by the following formula (8).

[0032] [ka] (In the formula, R 15 and R 16 Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X is a single bond or the following formula (9)

[0033] [ka] (This represents at least one divalent group represented by .)

[0034] Examples of compounds that induce a structural unit (B) in which W is a single bond, as represented by formula (2) above, include 4,4'-biphenol and 4,4'-bis(2,6-dimethyl)diphenol.

[0035] Examples of compounds that derive a structural unit where W is the one in formula (3) include α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (commonly referred to as "bisphenol M"), and α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene.

[0036] Examples of compounds that derive a structural unit in which W is the aforementioned formula (4) include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

[0037] Compounds that derive a structural unit where W is the above formula (5) 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), and 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 Ropane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4-bis(4-hydroxyphenyl)heptane, 2,Examples include 2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(3-methyl-4-hydroxyphenyl)decane, and 1,1-bis(2,3-dimethyl-4-hydroxyphenyl)decane.

[0038] Compounds that derive a structural unit in which W is any of the formulas (6) above 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.

[0039] Among the divalent phenols mentioned above, bisphenol M is preferred for formula (3), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene for formula (4), bisphenol OCZ, bisphenol OCTMC, bisphenol A, and bisphenol C for formula (5), and 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide for formula (6).

[0040] As the divalent phenol that induces the constituent unit (B), bisphenol C, bisphenol OCZ, and bisphenol OCTMC are more preferred, and the most preferred divalent phenol is bisphenol C.

[0041] In the polycarbonate resin of the present invention, the ratio of constituent unit (B) to 100 mol% of all constituent units is preferably 25 to 85 mol%, more preferably 30 to 80 mol%, even more preferably 40 to 75 mol%, and most preferably 50 to 70 mol%. A ratio of constituent unit (B) within the above range is preferable because it provides an excellent balance of heat resistance, scratch resistance, amine resistance, and moldability.

[0042] Furthermore, according to the present invention, carbonate bond repeating units derived from other divalent phenols may be copolymerized as divalent phenols, provided that the objectives and properties of the present invention are not impaired. Other typical examples of such divalent phenols include 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, resorcinol substituted with alkyl groups 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 can be used individually or in combination of two or more. These other divalent phenols are preferably present in amounts of 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, based on 100 mol% of the total constituent units.

[0043] The polycarbonate resin used in this invention is obtained by reacting a divalent phenol with a carbonate precursor. Reaction methods include interfacial polycondensation, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. In the case of interfacial polycondensation, monovalent phenol end-terminating agents are usually used. Furthermore, the polycarbonate may be a branched polycarbonate polymerized from trifunctional components, or a copolymerized polycarbonate obtained by copolymerizing aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and vinyl monomers.

[0044] In reactions using phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine. Examples of solvents include halogenated hydrocarbons such as methylene chloride and chlorobenzene. Catalysts such as tertiary amines or quaternary ammonium salts can also be used to accelerate the reaction. The reaction temperature is typically 0-40°C, and the reaction time is several minutes to 5 hours.

[0045] Transesterification reactions using, for example, diester carbonate as a carbonate precursor are carried out by heating and stirring a predetermined proportion of aromatic dihydroxy components with the diester carbonate under an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol. A catalyst commonly used in transesterification reactions can also be used to accelerate the reaction. Examples of diester carbonates used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

[0046] Monofunctional phenols, commonly used as end-terminating agents, can be used. In particular, in reactions using phosgene as a carbonate precursor, monofunctional phenols are generally used as end-terminating agents to adjust molecular weight, and the resulting polycarbonate resin has superior thermal stability compared to those that are not, because its ends are sealed by groups based on monofunctional phenols. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long-chain alkylphenols.

[0047] The polycarbonate resin used in the present invention can be copolymerized with aliphatic diols as needed. For example, isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecanedimethanol (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, cyclohex-1,4-ylenedimethanol, and Examples include lance-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'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).

[0048] The polycarbonate resin used in the present invention can be copolymerized with fatty acids as needed. Examples include 1,10-dodecanedionic acid (DDDA), adipic acid, hexanedionic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 3-hydroxybenzoic acid (mHBA), and 4-hydroxybenzoic acid (pHBA).

[0049] The polycarbonate resin used in the present invention includes a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of preferred aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that they do not impede the objective. The polycarbonate resin of the present invention may also be copolymerized with constituent units containing polyorganosiloxane units as needed.

[0050] The polycarbonate resin used in the present invention can also be copolymerized with structural units containing trifunctional or polyfunctional aromatic compounds as needed to form a branched polycarbonate. Suitable examples of trifunctional or polyfunctional aromatic compounds used in branched polycarbonates include tri,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 trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The constituent units derived from such polyfunctional aromatic compounds are 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 constituent units from other divalent components.

[0051] Furthermore, branched structural units may be derived not only from polyfunctional aromatic compounds, but also from side reactions that occur during polymerization reactions by molten transesterification, without the use of polyfunctional aromatic compounds. Regarding the proportion of such branched structures, 1 It can be calculated by 1H-NMR measurement.

[0052] The polycarbonate resin of the present invention preferably has a viscosity-average molecular weight (Mv) of 15,000 to 40,000, more preferably 15,500 to 35,000, even more preferably 16,000 to 30,000, and particularly preferably 17,000 to 25,000. Polycarbonate resins with a viscosity-average molecular weight below the above lower limit may not provide sufficient toughness for practical use. On the other hand, polycarbonate resins with a viscosity-average molecular weight exceeding the above upper limit require high molding temperatures or special molding methods, making them less versatile. Furthermore, the increased melt viscosity tends to increase the dependence on injection speed, which can lead to a decrease in yield due to appearance defects, etc.

[0053] The viscosity-average molecular weight of the polycarbonate resin in this invention is first calculated using the following formula: the specific viscosity (η) SP The viscosity of the solution was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SP The viscosity-average molecular weight (Mv) was calculated from the following formula. η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 -4 Mv 0.83 c = 0.7

[0054] <Components other than polycarbonate copolymer (polycarbonate resin)> The polycarbonate resin of the present invention may contain known functional agents such as mold release agents, heat stabilizers, ultraviolet absorbers, flow modifiers, and antistatic agents, to the extent that they do not impair the effects of the present invention.

[0055] (i) Release agent The polycarbonate resin of the present invention may be used in combination with a release agent, to the extent that it does not impair the effects of the present invention. Examples of release agents include fatty acid esters, polyolefin waxes (such as polyethylene wax and 1-alkene polymers, and those modified with functional group-containing compounds such as acid modification can also be used), fluorine compounds (such as fluorine oils represented by polyfluoroalkyl ethers), paraffin wax, and beeswax. Among these, fatty acid esters are preferred in terms of availability, release properties, and transparency. The proportion of the release agent to be included is preferably 0.005 to 0.5 parts by weight, more preferably 0.007 to 0.4 parts by weight, and even more preferably 0.01 to 0.3 parts by weight, per 100 parts by weight of the polycarbonate resin. When the content is above the lower limit of the above range, the effect of improving release properties is clearly exhibited, and when it is below the upper limit, adverse effects such as mold contamination during molding are reduced, which is preferable.

[0056] The fatty acid esters used as preferred release agents among those mentioned above will be described in more detail. Such fatty acid esters are esters of an aliphatic alcohol and an aliphatic carboxylic acid. Such aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol with two or more hydric properties. 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 such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in fatty acid esters.

[0057] On the other hand, aliphatic carboxylic acids are preferably those having 3 to 32 carbon atoms, and particularly preferably those having 10 to 22 carbon atoms. Examples of such aliphatic carboxylic acids include 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, eicosanic acid, and docosanic acid (behenic acid), as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Saturated aliphatic carboxylic acids are especially preferred. Since such aliphatic carboxylic acids are usually produced from natural oils and fats such as animal fats (beef tallow and lard, etc.) and vegetable oils (palm oil, etc.), these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, the production of aliphatic carboxylic acids also consists of mixtures produced from such natural oils and fats containing other carboxylic acid components. The acid value of fatty acid esters is preferably 20 or less (may take substantially 0). However, in the case of full esters, it is preferable to contain at least some free fatty acids to improve release properties, and in this respect, the acid value of full esters is preferably in the range of 3 to 15. The iodine value of fatty acid esters is also preferably 10 or less (may take substantially 0). These properties can be determined by the method specified in JIS K 0070.

[0058] The aforementioned fatty acid esters may be either partial esters or full esters, but partial esters are preferred in terms of better mold release properties and durability, and glycerin monoesters are particularly preferred. Glycerin monoesters mainly consist of glycerin and a fatty acid monoester, and suitable fatty acids include saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, montanic acid, and lauric acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and sorbic acid, with glycerin monoesters of stearic acid, behenic acid, and palmitic acid being particularly preferred. Such fatty acids are synthesized from natural fatty acids and, as described above, are mixtures. Even in such cases, it is preferable that the proportion of glycerin monoester in the fatty acid ester be 60% by weight or more.

[0059] Furthermore, partial esters are often inferior to full esters in terms of thermal stability. To improve the thermal stability of such partial esters, it is preferable that the sodium metal content of the partial ester be less than 20 ppm, more preferably less than 5 ppm, and even more preferably less than 1 ppm. Fatty acid partial esters with a sodium metal content of less than 1 ppm can be produced by producing fatty acid partial esters by conventional methods and then purifying them by molecular distillation or the like.

[0060] Specifically, one method involves removing gaseous and low-boiling-point substances using a spray nozzle degassing apparatus, then removing polyhydric alcohols such as glycerin using a drip-film distillation apparatus at a distillation temperature of 120-150°C and a vacuum of 0.01-0.03 kPa, and finally obtaining high-purity fatty acid partial esters as distillates using a centrifugal molecular distillation apparatus at a distillation temperature of 160-230°C and a vacuum of 0.01-0.2 Torr. Sodium metal can be removed as a distillation residue. By repeatedly performing molecular distillation on the obtained distillates, the purity can be further increased, and fatty acid partial esters with even lower sodium metal content can be obtained. It is also important to prevent contamination from the external environment by thoroughly cleaning the inside of the molecular distillation apparatus using appropriate methods beforehand and by improving airtightness. Such fatty acid esters are available from specialized suppliers (e.g., Riken Vitamin Co., Ltd.).

[0061] (ii) Phosphate stabilizers The polycarbonate resin of the present invention preferably contains various phosphorus-based stabilizers, primarily for the purpose of improving its thermal stability during molding. Examples of such phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Furthermore, such phosphorus-based stabilizers may include tertiary phosphines.

[0062] Specifically, examples of phosphite compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl 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(di-iso-propylphenyl) phosphite, and tris(di-n-butylphenyl) phosphite. Examples include tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

[0063] Furthermore, other phosphite compounds that react with divalent phenols to form cyclic structures can also be used. Examples 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.

[0064] Examples of phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, with triphenyl phosphate and trimethyl phosphate being preferred.

[0065] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis Examples include (2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, with tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite being preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. Such phosphonite compounds can be used in combination with phosphite compounds having an aryl group substituted with two or more alkyl groups, and this is preferable.

[0066] Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0067] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0068] The above phosphorus-based stabilizers can be used not only individually but also in combination of two or more. Among the above phosphorus-based 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'-biphenylenediphosphonite, and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. Combinations of these with phosphate compounds are also preferred.

[0069] (iii) Hindered phenol stabilizers (antioxidants) The polycarbonate resin of the present invention may be blended with a hindered phenol-based stabilizer primarily for the purpose of improving its thermal stability during molding and its resistance to heat aging. Examples of such hindered phenol-based stabilizers include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert- Butyl-4-hydroxybenzylphosphonate 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'-dimethylene-bis(6-α-methylbenzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert- Butylphenol), 2,2'-Butylidene-bis(4-methyl-6-tert-butylphenol), 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol), 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-methyl6-(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'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(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-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydro Examples include xy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. All of these are readily available. The above hindered phenol antioxidants can be used individually or in combination of two or more.

[0070] The amount of (ii) phosphorus-based stabilizer and / or (iii) hindered phenol-based antioxidant described above is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight, and even more preferably 0.005 to 0.1 parts by weight, per 100 parts by weight of polycarbonate resin. If the amount of stabilizer is too little compared to the above range, it will be difficult to obtain a good stabilization effect, and if it is too much compared to the above range, it may conversely lead to a decrease in the physical properties of the material or contamination of the mold during molding.

[0071] The polycarbonate resin of the present invention may also be used with other antioxidants besides the above-mentioned hindered phenol-based antioxidants, as appropriate. Examples of such other antioxidants include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. The amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight per 100 parts by weight of the polycarbonate resin.

[0072] (iv) UV absorbers The polycarbonate used in this invention may contain an ultraviolet absorber. Specific examples of UV absorbers of the present invention include, among others, benzophenone-based 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-bendyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridebenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0073] Specifically, examples of UV absorbers include benzotriazole-based benzotriazoles such as 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-benzotriazole-2-yl)phenol], 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, and 2-(2-hydroxy-5-tert-octylphenyl) Examples of polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton include 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer.

[0074] Examples of UV absorbers include, specifically, hydroxyphenyltriazine compounds such as 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butyloxyphenol. Furthermore, examples include compounds in which the phenyl group of the above example compounds has been replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol.

[0075] Examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one).

[0076] Examples of UV absorbers include cyanoacrylate-based 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0077] Furthermore, the above-mentioned ultraviolet absorber may also be a polymer-type ultraviolet absorber obtained by copolymerizing such ultraviolet-absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate, by adopting the structure of a monomer compound that can be radically polymerized. Suitable examples of the above-mentioned ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.

[0078] Among the above, benzotriazole and hydroxyphenyltriazine types are preferred in terms of ultraviolet absorption capacity, while cyclic iminoester and cyanoacrylate types are preferred in terms of heat resistance and hue. The above ultraviolet absorbers may be used individually or as a mixture of two or more.

[0079] The amount of ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 2 parts by weight, even more preferably 0.04 to 1 part by weight, and particularly preferably 0.05 to 0.5 parts by weight per 100 parts by weight of polycarbonate resin.

[0080] (v) Flow modifiers The polycarbonate resin of the present invention may contain a flow modifier to the extent that it does not impair the effects of the present invention. Suitable examples of such flow modifiers include styrene oligomers, polycarbonate oligomers (including highly branched, hyperbranched, and cyclic oligomer types), polyalkylene terephthalate oligomers (including highly branched, hyperbranched, and cyclic oligomer types), highly branched and hyperbranched aliphatic polyester oligomers, terpene resins, and polycaprolactone. The amount of such flow modifier is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and even more preferably 2 to 15 parts by weight per 100 parts by weight of the polycarbonate resin. Polycaprolactone is particularly preferred, and the composition ratio is particularly preferably 2 to 7 parts by weight per 100 parts by weight of the polycarbonate resin. The molecular weight of polycaprolactone is expressed as a number-average molecular weight and ranges from 1,000 to 70,000, preferably 1,500 to 40,000, more preferably 2,000 to 30,000, and even more preferably 2,500 to 15,000.

[0081] (vi) Antistatic agents The polycarbonate resin of the present invention may be blended with an antistatic agent primarily for the purpose of improving its antistatic properties. Suitable antistatic agents include phosphonium sulfonates, phosphite esters, caprolactone polymers, etc., with phosphonium sulfonates being preferred. Specific examples of such phosphonium sulfonates include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate, tributylmethylphosphonium dibutylbenzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, and trioctylmethylphosphonium diisopropylnaphthylsulfonate. Among these, tetrabutylphosphonium dodecylbenzenesulfonate is preferred due to its compatibility with polycarbonate and ease of availability. The amount of antistatic agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, even more preferably 0.3 to 2.0 parts by weight, and particularly preferably 0.5 to 1.8 parts by weight per 100 parts by weight of polycarbonate resin. At 0.1 parts by weight or more, an antistatic effect is obtained, and at 5.0 parts by weight or less, excellent transparency and mechanical strength are achieved, and silvering or peeling does not occur on the surface of the molded product, making it less likely to cause appearance defects.

[0082] The polycarbonate resin of the present invention may also contain various additives such as bluing agents, fluorescent dyes, flame retardants, and dyes and pigments. These can be appropriately selected and included as long as they do not impair the effects of the present invention.

[0083] The bluing agent is preferably present in the polycarbonate resin at a concentration of 0.05 to 3.0 ppm (by weight). Representative examples of bluing agents include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polysynthrene Blue RLS.

[0084] Examples of fluorescent dyes (including fluorescent whitening agents) include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiaidine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. The amount of fluorescent dye (including fluorescent whitening agent) blended is preferably 0.0001 to 0.1 parts by weight per 100 parts by weight of polycarbonate resin.

[0085] Examples of flame retardants include metal sulfonate salt-based flame retardants, halogen-containing compound-based flame retardants, phosphorus-containing compound-based flame retardants, and silicon-containing compound-based flame retardants. Among these, metal sulfonate salt-based flame retardants are preferred. The amount of flame retardant added is usually preferably 0.01 to 1 part by weight, and more preferably in the range of 0.05 to 1 part by weight, per 100 parts by weight of polycarbonate resin.

[0086] The polycarbonate resin composition of the present invention may contain other components as appropriate, insofar as they do not significantly impair the effects of the present invention. Examples of other components include resins other than polycarbonate resin. The other components may be present as a single component, or as two or more components in any combination and ratio. Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); styrene resins such as 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), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin); polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), and 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); and polymethacrylate resin (PMMA resin).

[0087] The method for incorporating additives into the polycarbonate resin of the present invention is not particularly limited, and known methods can be used. The most commonly used method involves pre-mixing the polycarbonate resin and additives, then feeding them into an extruder for melt-kneading, cooling the extruded threads, and cutting them with a pelletizer to produce pellet-shaped molding material.

[0088] In the above method, either a single-screw extruder or a twin-screw extruder can be used, but a twin-screw extruder is preferred from the viewpoint of productivity and kneading ability. A typical example of such a twin-screw extruder is the ZSK (Werner & Pfleiderer, trade name). Specific examples of similar types include the TEX (Japan Steel Works, Ltd., trade name), TEM (Toshiba Machine Co., Ltd., trade name), and KTX (Kobe Steel, Ltd., trade name). The extruder should preferably have a vent that can remove moisture from the raw material and volatile gases generated from the molten, kneaded resin. A vacuum pump is preferably installed in the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. It is also possible to install a screen in the zone in front of the extruder die to remove foreign matter mixed into the extrusion raw material, thereby removing foreign matter from the resin composition. Examples of such screens include wire mesh, screen changers, and sintered metal plates (disc filters, etc.).

[0089] Furthermore, while additives can be supplied to the extruder independently, it is preferable to pre-mix them with the resin raw materials as described above. Examples of means for such pre-mixing include Nauter mixers, V-type blenders, Henschel mixers, mechanochemical devices, and extruder mixers. A more preferable method is to first mix a portion of the raw resin and the additive with a high-speed agitator such as a Henschel mixer to create a master compound, and then mix this master compound with the remaining entire amount of resin raw materials with a slower agitator such as a Nauter mixer.

[0090] The resin extruded from the extruder is either directly cut and pelletized, or strands are formed and then cut in a pelletizer to form pellets. If it is necessary to reduce the influence of external dust and other contaminants, it is preferable to purify the atmosphere around the extruder. Furthermore, in the production of such pellets, it is preferable to use various methods already proposed for polycarbonate resins for optical discs to narrow the shape distribution of the pellets, further reduce miscuts, further reduce fine powder generated during transportation or shipping, and reduce air bubbles (vacuum bubbles) generated inside the strands and pellets. Methods for reducing miscuts include temperature control of the thread during cutting in the pelletizer, blowing ionized air during cutting, optimizing the scoop angle of the pelletizer, and appropriate blending of release agents, as well as a method of filtering a mixture of cut pellets and water to separate the pellets from the water and miscuts. An example of a measurement method is disclosed, for example, in Japanese Patent Application Publication No. 2003-200421. These formulations can increase the molding cycle and reduce the rate of defects such as silver.

[0091] The amount of miscuts in the molding material (pellets) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, miscuts refer to finer particles than the pellets of the desired size that pass through a JIS standard sieve with a mesh size of 1.0 mm. The shape of the pellets can be general shapes such as cylinders, prismatics, and spheres, but more preferably cylinders (including elliptical cylinders), and the diameter of such cylinders is preferably 1.5 to 4 mm, more preferably 2 to 3.5 mm. In elliptical cylinders, the ratio of the minor axis to the major axis 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.

[0092] <Properties of polycarbonate copolymer (polycarbonate resin)> The polycarbonate resin of the present invention can suppress polymer degradation in a basic environment containing amines. Through various studies, it was found that the depolymerization reaction of polycarbonate by amine compounds proceeds with the amine compound acting on the carbonate bonds of polycarbonate, generating carbamic acid ester oligomers as intermediates. Therefore, in order to suppress the reaction of amine compounds on carbonate bonds, it was found that by being composed of the constituent unit (A) represented by formula (1) above, the substituent on the aromatic ring plays a role in steric hindrance to the carbonate bonds.

[0093] Furthermore, it has been found that the polycarbonate resin of the present invention, by comprising the constituent unit (A) represented by formula (1) and the constituent unit (B) represented by formula (2) in specific proportions, maintains amine resistance while exhibiting an excellent balance of scratch resistance, heat resistance, and moldability.

[0094] The polycarbonate resin of the present invention preferably has a glass transition temperature of 130 to 200°C, more preferably 135 to 195°C, even more preferably 140 to 190°C, and particularly preferably 145 to 180°C. If the glass transition temperature is above the lower limit, it exhibits excellent heat resistance, and if it is below the upper limit, it does not require excessively high molding temperatures, making molding easier.

[0095] The polycarbonate resin of the present invention has an indentation hardness of 200-400 (N / mm²) as measured in accordance with the instrumented micro-indentation hardness test for plastics described in ISO / TS19278. 2 Preferably, it is 210-350 (N / mm²). 2 It is more preferable that the value be 220-300 (N / mm²). 2It is even more preferable that the indentation hardness is below the above lower limit. If the indentation hardness is below the above upper limit, the scratch resistance may be poor. If the indentation hardness is above the above upper limit, the material may become extremely brittle. Indentation hardness can be measured in real time on the surface of the resin molded product using a dynamic ultramicrohardness tester (Shimadzu Corporation, model DUH-210S) based on ISO / TS 19278, by measuring the relationship between load and indentation depth.

[0096] The polycarbonate resin of the present invention preferably has a pencil hardness of 3H or higher, as measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4. A pencil hardness of 3H or higher is preferable because it makes the molded product surface less susceptible to scratches in abrasion resistance tests where the surface is "scratched" with a human fingernail. 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.

[0097] <Amine compounds used for amine resistance and polyurethane foam formation> The polycarbonate resin of the present invention is preferable because it exhibits excellent amine resistance, when a molded product of the resin is cut from a soft urethane foam used in seat cushions into a shape of 50 mm in length and width and 5 mm in thickness, both are sealed in a glass airtight container, and left for 1,000 hours in a hot air dryer set to 85°C, and the appearance of the test piece does not change.

[0098] Polyurethane resins are generally produced by reacting polyols and polyisocyanates in the presence of a catalyst and, if necessary, a blowing agent, surfactant, flame retardant, crosslinking agent, etc. Numerous metal compounds and tertiary amine compounds are known to be used as catalysts in the production of polyurethane resins. These catalysts are widely used industrially, either alone or in combination. In the production of polyurethane foams using water, low-boiling point organic compounds, or both, as blowing agents, tertiary amine compounds, in particular, are widely used among these catalysts due to their superior productivity and moldability. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N,N,N',N'-tetramethylhexanediamine, N,N,N',N'-tetramethylpropanediamine, 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.

[0099] <Polycarbonate resin molded products, automotive interior parts> The manufacturing method for forming molded articles from polycarbonate resin according to the present invention is not particularly limited, and any molding method commonly used for polycarbonate resin can be arbitrarily employed. Examples include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding using insulated molds, molding using rapidly heated molds, foam molding (including supercritical fluids), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, and press molding. Furthermore, a molding method using a hot runner system can also be used.

[0100] Furthermore, the polycarbonate resin of the present invention can also be used to produce sheet-like or film-like molded articles by methods such as melt extrusion and solution casting (casting). A specific method of melt extrusion involves, for example, supplying a fixed amount of polycarbonate resin to an extruder, heating and melting it, extruding the molten resin in a sheet-like form from the tip of a T-die onto a mirror-polished roll, taking it up while cooling it with multiple rolls, and then cutting or winding it to an appropriate size once it has solidified. A specific method of solution casting involves, for example, casting a solution (concentration 5% to 40%) of polycarbonate resin dissolved in methylene chloride from a T-die onto a mirror-polished stainless steel plate, peeling the sheet while passing it through an oven with gradually controlled temperatures, removing the solvent, and then cooling and winding it up.

[0101] Furthermore, the polycarbonate resin of the present invention can also be molded into a laminate. Any method can be used to manufacture the laminate, but it is particularly preferable to use a thermocompression method or a co-extrusion method. Any method can be used for thermocompression, but for example, a method of thermocompressing polycarbonate resin sheets with a laminating machine or press machine, or a method of thermocompression immediately after extrusion is preferred, and a method of continuously thermocompressing the polycarbonate resin sheet immediately after extrusion is particularly industrially advantageous.

[0102] Furthermore, the polycarbonate resin of the present invention is used as an automotive interior component because it has excellent scratch resistance, heat resistance, amine resistance, and moldability. Examples of automotive interior components include lamp lenses for interior lighting, meter covers for display, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective components, and light-transmitting components. In addition, because the automotive interior components of the present invention have the above-mentioned properties, they have the advantage of being usable as polycarbonate resin molded products without the need for coating treatment. [Examples]

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the measurement methods for each characteristic are as follows.

[0104] (1) Composition ratio 40 mg of polycarbonate resin (polymer) is dissolved in 0.6 ml of deuterated chloroform solution, and then subjected to a JEOL 400 MHz nuclear magnetic resonance spectrometer. 1 The 1H-NMR spectrum was measured, and the composition ratio of the polycarbonate resin (polymer) was calculated from the area integral ratio of the characteristic spectral peaks of each constituent unit.

[0105] (2) Viscosity average molecular weight The viscosity-average molecular weight of the polycarbonate resin was measured and calculated using the following method. First, polycarbonate resin pellets obtained by extrusion were mixed with 30 times their weight in methylene chloride and dissolved, and the soluble components were collected by Celite filtration. After removing the solvent from the resulting solution, the resulting solid was thoroughly dried, and the specific viscosity (η) of the solution at 20°C was calculated from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride. sp The viscosity was measured. Then, the Mv calculated by the following formula was taken as the viscosity-average molecular weight. η sp / c=[η]+0.45×[η] 2 c [η] = 1.23 × 10 -4 Mv 0.83 η sp :Specific viscosity η: Intrinsic viscosity c: Constant (=0.7) Mv: Viscosity average molecular weight

[0106] (3) Glass transition temperature The thermal analysis was performed using a TA Instruments DSC-2910 system under JIS K7121 conditions: nitrogen atmosphere (nitrogen flow rate: 40 ml / min), heating rate: 20°C / min.

[0107] (4) Pencil hardness The obtained polycarbonate resin was press-molded using a hot press molding machine (Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to obtain a disc-shaped resin plate with a thickness of approximately 3 mm. The press molding conditions were: mold temperature 150-350°C, primary pressure: 1 MPa (30 seconds), secondary pressure: 1.5 MPa (12 minutes). Using this resin plate, the scratch hardness (pencil method) described in JIS K5600-5-4 was evaluated by drawing a line on the surface of the resin plate with a pencil at a 45-degree angle and a load of 750 g in a constant temperature room at an ambient temperature of 23°C, and visually observing the surface condition. Load: 750g Measurement speed: 50mm / min Measurement distance: 7mm Pencil: Mitsubishi Pencil Hi-uni

[0108] (5) Hardness of indentation (Hit) The obtained polycarbonate resin was press-molded using a hot press molding machine (Shinto Metal Industries Co., Ltd., compression molding machine: SFV-10, vacuum pump unit: GXD-360) to obtain a disc-shaped resin plate with a thickness of approximately 3 mm. The press molding conditions were: mold temperature 150-350°C, primary pressure: 1 MPa (30 seconds), secondary pressure: 1.5 MPa (12 minutes). Using this resin plate, the relationship between load and indentation depth was measured in real time on the surface of the resin plate using a dynamic micro-hardness tester (Shimadzu Corporation, model DUH-210S) based on the instrumented micro-indentation hardness test for plastics described in ISO / TS19278, and the indentation hardness (N / mm²) was determined. 2 ) was measured. (Measurement conditions) Measuring indenter: Berkovich indenter (made of diamond) Test force: 500mN Minimum test force: 4.9 mN Loading / unloading time: 30sec Load holding time: 40sec Unloading holding time: 0sec Number of tests: 5 (Method for calculating indentation hardness) Indentation hardness (Hit) measures the resistance to semi-permanent deformation or damage. Indentation hardness is calculated using the following formula: Hit=F max / A p F max : Maximum test force A p : Projected area where the indenter and the test specimen are in contact A p = 23.96 × h c 2 (In the case of a triangular pyramidal indenter (115°)) h c =h max -ε(h max -h r ) ε = 3 / 4 (in the case of a triangular pyramid) h r : The intercept where the tangent line of the unloading curve at Fmax of the force-depth curve intersects the depth axis.

[0109] (6) Amine resistance Using a mold with a cavity surface having an arithmetic mean roughness (Ra) of 0.03 μm, a three-tiered plate with a width of 50 mm, a length of 90 mm, and thicknesses of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate side was molded using a J-75E3 injection molding machine manufactured by Japan Steel Works, under conditions of cylinder temperature of 300°C and mold temperature of 80°C, with a holding pressure time of 20 seconds and a cooling time of 20 seconds. Soft polyurethane foam used as cushioning material for automobile seats was cut using a cutter into a shape of 50 mm x 50 mm and a thickness of 5 mm, and sealed together with the three-tiered plate in a glass airtight container. The specimens were left in a hot air dryer set to 85°C for 1000 hours, after which the appearance of the test pieces was visually observed.

[0110] (7) Formability Flow length was evaluated using an Archimedes spiral flow mold (flow channel thickness 2 mm, flow channel width 8 mm) manufactured by Toshiba Machine Co., Ltd., with an injection molding machine EC100N2-2Y. The conditions were cylinder temperature 330°C, mold temperature 100°C, and injection pressure 100 MPa. The criteria for evaluation were as follows: ○: 20cm or more, △: 10cm or more but less than 20cm, ×: less than 10cm.

[0111] (8)1H-NMR measurement The compounds obtained in Synthesis Example 1 were measured using the following apparatus and solvent. Equipment: JEOL JNM-AL400 (400MHz) Solvent: (CD3)2SO

[0112] (9) High-performance liquid chromatography (HPLC) Measurements were performed using a Hitachi Chromaster high-performance liquid chromatography system under the measurement conditions listed in Table 1 below. In Synthesis Example 1, unless otherwise specified, percentages represent area percentages corrected for the absence of solvent in HPLC.

[0113] [Table 1]

[0114] [Synthesis Example 1] 150 g (0.4 mol) of orthocresolphthalein (manufactured by Tokyo Chemical Industry Co., Ltd.) and 826 g (8.9 mol) of aniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged, and then 86 mL (1.0 mol) of 36% concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added dropwise. After the addition was complete, the reaction mixture was heated to 160 ± 5°C while the water was removed by distillation. The progress of the reaction was monitored by HPLC, and stirring was continued until the orthocresolphthalein was almost completely eliminated. After the reaction was complete, the reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was separated and washed with 5% hydrochloric acid aqueous solution to remove unreacted aniline. Further washing with water was continued until the aqueous layer became neutral. The pale yellow crystals obtained from the concentration of the organic layer were recrystallized in toluene / methanol (v / v=10 / 1) to obtain 137 g of white crystals of the target product, 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine (hereinafter referred to as PCP-BP), in a yield of 75%. 1 The substance was identified by H-NMR analysis (see Figure 1). HPLC analysis revealed a purity of 98.3%.

[0115] [Example 1] In a reactor equipped with a thermometer, stirrer, and reflux condenser, 5,032 parts of 48% sodium hydroxide aqueous solution and 14,030 parts of deionized water were charged. 1,261 parts of PCP-BP obtained in Synthesis Example 1, 3,067 parts of bisphenol C (manufactured by Honshu Chemical Co., Ltd., hereinafter referred to as BPC), and 8.7 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries Co., Ltd.) were dissolved in these mixtures. Then, 16,550 parts of methylene chloride were added, and under stirring, 2,000 parts of phosgene were blown in over approximately 90 minutes at 15-25°C. After the phosgene blowing was complete, 3,355 parts of 48% sodium hydroxide aqueous solution and 67 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 4 parts of triethylamine were added. The reaction was then completed by stirring for 1 hour at 28-35°C.

[0116] After the reaction was complete, the product was diluted with methylene chloride and washed with water. Then hydrochloric acid was added to make it acidic, and the mixture was washed with water again. The washing was repeated until the conductivity of the aqueous phase was approximately the same as that of deionized water, to obtain a methylene chloride solution of polycarbonate resin. Next, this solution was passed through a filter with a mesh size of 0.3 μm, and then dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing section. The polycarbonate resin was flakebed while the methylene chloride was removed by distillation, and the liquid-containing flakes were subsequently crushed and dried to obtain a powder.

[0117] Subsequently, to 100 parts by weight of the powder, 0.05 parts by weight of ADEKA PEP-36A (a phosphorus-based stabilizer), 0.05 parts by weight of Irganox 1076 (a hindered phenol-based antioxidant manufactured by Ciba Specialty Chemicals), 0.1 parts by weight of Rikestar EW-400 (a fatty acid ester manufactured by Riken Vitamin Co., Ltd.), and 0.3 parts of Chemisorb 79 (a benzotriazole-based ultraviolet absorber manufactured by Chemipro Chemical Co., Ltd.) were added and uniformly mixed. After that, the powder was melt-kneaded and extruded while degassing using a vented twin-screw extruder [KTX-46 manufactured by Kobe Steel, Ltd.] to obtain polycarbonate resin composition pellets. Various evaluations were performed using these pellets, and the results are shown in Table 2.

[0118] [Example 2] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that the composition consisted of 2,207 parts PCP-BP, 492 parts BPC, and 79 parts p-tert-butylphenol. The results of evaluation using these pellets are shown in Table 2.

[0119] [Example 3] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that the composition consisted of 3,153 parts PCP-BP, 1,917 parts BPC, and 63 parts p-tert-butylphenol. The results of evaluation using these pellets are shown in Table 2.

[0120] [Example 4] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that the composition consisted of 4,414 parts PCP-BP, 1,150 parts BPC, and 157 parts p-tert-butylphenol. The results of evaluation using these pellets are shown in Table 2.

[0121] [Example 5] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that 3,153 parts of PCP-BP and 63 parts of p-tert-butylphenol were used, and 1,707 g of bisphenol A was used instead of BPC. The results of evaluation using these pellets are shown in Table 2.

[0122] [Example 6] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that 1,892 parts of PCP-BP and 67 parts of p-tert-butylphenol were used, and 3,103 parts of bisphenol OCZ (manufactured by O.G. Co., Ltd., hereinafter sometimes referred to as BP-OCZ) were used instead of BPC. The results of evaluation using these pellets are shown in Table 2.

[0123] [Example 7] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that 1,892 parts of PCP-BP, 383 parts of BPC, 58 parts of p-tert-butylphenol, and an additional 3,037 parts of bisphenol OCTMC (manufactured by O.G. Co., Ltd., hereinafter sometimes referred to as BP-OCTMC) were used. The results of evaluation using these pellets are shown in Table 2.

[0124] [Comparative Example 1] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that BPC was not used, and instead of PCP-BP, 5,886 parts of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (manufactured by O.G., hereinafter referred to as PPPBP) and 67 parts of p-tert-butylphenol were used. The results of evaluation using these pellets are shown in Table 3.

[0125] [Comparative Example 2] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that PCP-BP was not used, and 3,834 parts of BPC and 63 parts of p-tert-butylphenol were used instead. The results of evaluation using these pellets are shown in Table 3.

[0126] [Comparative Example 3] Table 3 shows the results of the evaluation using bisphenol A type polycarbonate resin pellets (Teijin Panlite L-1225Z100M).

[0127] [Comparative Example 4] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that 1,177 parts of PPPBP were used instead of PCP-BP, and 2,732 parts of bisphenol A (manufactured by Mitsui Chemicals) and 67 parts of p-tert-butylphenol were used instead of BPC. The results of evaluation using these pellets are shown in Table 3.

[0128] [Comparative Example 5] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that the composition consisted of 5,044 parts PCP-BP, 767 parts BPC, and 70 parts p-tert-butylphenol. The results of evaluation using these pellets are shown in Table 3.

[0129] [Comparative Example 6] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that the composition consisted of 63 parts PCP-BP, 45 parts BPC3, and 70 parts p-tert-butylphenol. The results of evaluation using these pellets are shown in Table 3.

[0130] [Comparative Example 7] Polycarbonate resin composition pellets were obtained using the same method as in Example 1, except that BPC was not used, and 6,305 parts of PCP-BP and 101 parts of p-tert-butylphenol were used. The results of evaluation using these pellets are shown in Table 3.

[0131] [Table 2]

[0132] [Table 3] [Industrial applicability]

[0133] The polycarbonate resin of the present invention does not require coating treatment and can be used in automotive interior parts such as lamp lenses for interior lighting, meter covers for display, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts.

Claims

1. The constituent unit (A) represented by the following formula (7), and 【Chemistry 1】 (In the formula, R13 and R14 each independently represent an alkyl group having 1 to 6 carbon atoms.) The constituent unit (B) is represented by the following formula (2) 【Chemistry 2】 (In the formula, W represents a single bond, at least one divalent organic residue selected from the group consisting of formulas (3) to (5) below, or any of the bonds in formula (6) below, x and y are each independently 0 or an integer from 1 to 4, R ３ and R ４ Each of these independently represents an organic residue selected from the group consisting of a halogen atom, or 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 cycloalkoxy 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. 【Transformation 3】 (In the formula, R ５ , R ６ , R ７ and R ８ Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. 【Chemistry 4】 (In the formula, R ９ and R １０ Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. 【Transformation 5】 (wherein, R １１ and R １２ each independently represents a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon having 6 to 12 carbon atoms which may have a substituent and is bonded to a carbon atom.) 【Transformation 6】 A polycarbonate copolymer containing 70 mol% or more of the total constituent units, characterized in that the proportion of constituent unit (A) in the total constituent units is 15 to 75 mol%.

2. The polycarbonate copolymer according to claim 1, wherein R13 and R14 in formula (7) represent methyl groups.

3. The polycarbonate copolymer according to claim 1, wherein the repeating unit (B) represented by formula (2) is a repeating unit represented by the following formula (8). 【Transformation 7】 (In the formula, R １５ and R １６ Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X is a single bond or the following formula (9) 【Transformation 8】 (This represents at least one divalent group represented by .)

4. The polycarbonate copolymer according to claim 1, wherein the glass transition temperature is 130 to 200°C.

5. An indentation hardness of 200-400 (N / mm²) measured in accordance with the instrumented micro-indentation hardness test for plastics described in ISO / TS19278 for hardness measurement. ２ The polycarbonate copolymer according to claim 1, wherein the hardness is within the range of ) and the pencil hardness measured in accordance with the scratch hardness (pencil method) described in JIS K5600-5-4 is 3H or higher.

6. The polycarbonate copolymer according to claim 1, wherein the viscosity-average molecular weight is 15,000 to 40,000.

7. A molded article obtained by injection molding a polycarbonate copolymer according to any one of claims 1 to 6.

8. A sheet or film obtained by extruding a polycarbonate copolymer according to any one of claims 1 to 6.

9. Automotive interior part using the molded product of claim 7.

10. Automotive interior component using the sheet or film according to claim 8.

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