TW201011056A - Copolycarbonate copolymer and process for producing the same, resin composition and shaping product - Google Patents

Abstract

The present invention provides a copolycarbonate copolymer and a resin composition which shaping products may be used for transparent optical devices, particularly optical devices such as lens, optical conductor, optical disc, etc., and methods for manufacturing the same. The copolycarbonate copolymer contains repeat units represented by general formulas (I) (II), tin content (as element) is less than 0.5ppm. In the general formula (I), R and R represent an alkyl having 1 to 6 carbon atom(s) separately. X is one of a single key, an alkylidene group (-CnH2n-) having 1 to 8 carbon atom(s), an alkylidene group (CnH2n=) having 2 to 8 carbon atoms, a cycle alkylidene group (-CnH(2n-2)-) having 5 to 15 carbon atoms, a cycle alkylidene group (CnH(2n-2)=) having 5 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, -CO- and a group represented by formula (III-1) or formula (III-2). R and R represent an alkyl having 1 to 3 carbon atom(s) separately. Y represents an alkylidene group (-CnH2n-) containing a straight chain having 2 to 15 carbon atoms or a branched chain. a to d is an integer from 0 to 4 separately, n is an integer from 2 to 200.

Description

[Technical Field] The present invention relates to a polycarbonate copolymer excellent in color tone and durability during high-temperature molding, a method for producing the same, a resin composition containing the copolymer, and a molded article, and a molded article thereof. It can be used in the field of transparent optical members, especially optical members such as lenses, photoconductors, and optical discs. ^ [Prior Art] Polycarbonate (hereinafter abbreviated as PC) copolymer is mainly produced by using bisphenol A as a raw material, and PC copolymer is constantly required to be improved in various characteristics. A PC made of bisphenol A or the like is excellent in transparency, heat resistance, and mechanical properties (especially, impact resistance), and is used in a wide range of applications. However, when the molded article of the PC is used for an optical component such as a lens, a light guide plate or a compact disc, there is a disadvantage that fluidity is low and a desired molded article cannot be obtained, and it is desired to further improve fluidity, and various modified polycarbonates have been proposed. 〇 For example, in the method of improving the fluidity, there is a method of changing the structure of the PC copolymer by performing copolymerization, modification of the end of the molecular chain, and the like. For example, a PC copolymer having a molecular chain end modified with a long-chain alkyl group is disclosed (for example, Patent Document 1 for reference). However, in the terminally modified p c copolymer obtained by this method, the site where the fluidity is improved is only the terminal portion of the molecular chain, the introduction amount of the long-chain alkyl group is limited, and the degree of fluidity improvement is insufficient. Further, in Patent Document 2, a polycarbonate copolymer obtained by copolymerization of polytetramethylene glycol (PTMG)-bis(4-benzoic acid vinegar 201011056) is disclosed. In addition to remarkably improving the fluidity at the time of molding, the copolymer is excellent in thermal stability and can be obtained as a molding material in accordance with a wide range of molding conditions. However, the polybutylene glycol-bis(4-hydroxybenzoate) described in Patent Document 2 is continuously produced by copolymerization to produce a polycarbonate copolymer, and the copolymer is formed at a high temperature exceeding 320 °C. When used under the conditions, there is a problem of yellowing. In general, the yellowing of various polycarbonate copolymers mostly causes impurities from the comonomer to remain in the polycarbonate copolymer. However, since the comonomers used in the respective copolymers or their use conditions are different, the impurities or methods of use vary depending on the comonomer, and it is difficult to solve the yellowing problem of various polycarbonate copolymers (patent Documents 3 to 6). Such yellowing, although the high forming temperature is also the cause, the influence of the catalyst contained in the copolymer is also large. In the production of a phenol-modified diol which is a raw material of a polycarbonate copolymer, in particular, when a tin-based catalyst is used, a conventional raw material purification step (for example, Patent Document 7 is referred to) or a polycarbonate purification step (for example, a patent) Reference 8), which cannot be completely removed, is a polycarbonate copolymer produced by continuously polymerizing the phenol-modified diol by an interfacial polymerization method or a melt polymerization method, and is derived from a tin system in a range of several ppm to several tens of ppm. Catalyst tin compound. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-247947 (Patent Document 3) JP-A-2005-247947 (Patent Document 3) JP-A-2004-3 1 5747 (Patent Document 4) JP-A-2005-336332 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and is provided for use in the production of a polycarbonate copolymer using a phenol-modified diol, which is used in the obtained PC copolymer. The method for producing a polycarbonate copolymer, a resin composition, a molded article, and a copolymer of a high-purity phenol-modified diol having improved heat stability at a high temperature is intended. [Means for Solving the Problem] As a result of efforts to solve the above problems, the present inventors have found that it is possible to solve the above problem by controlling the impurity content of the synthetic raw material derived from the polycarbonate copolymer represented by the general formula (I) described later. problem. The present invention has been accomplished based on the relevant knowledge. That is, the present invention provides the following: (1) A polycarbonate copolymer characterized by the following general formula (I) and (if) 201011056 [Chemical Formula 1]

[W and R2 are each independently and represent an alkyl group having 1 to 6 carbon atoms. X is a single G bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or -S. -, -SO-, -S02-, -Ο-, -CO- or the following formula (III-1) or the following formula (III-2)

Any of the indicated bonds. R3 and R4 are each independently and represent an alkyl group having 1 to 3 carbon atoms. Y is a linear or branched carbon number of 2 to 15, and an alkylene group of the chain. a to d are each independently, an integer of 0 to 4, η is an integer of 2 to 200, and the repeating unit is represented, and the tin content (as an element) is 〇.5 ppm or less, and (2) the aggregation of the above (1) A method for producing a carbonate copolymer, which is synthesized in the presence of a tin-based catalyst, using a phenol-modified diol treated with an aqueous phosphoric acid solution or a solid adsorbent as a comonomer, (3) as described above ( 2) A method for producing a polycarbonate copolymer, wherein the tin content (as an element) in the phenol-modified diol is 10 ppm or less. (4) A polycarbonate resin composition comprising 1 part by mass of the polycarbonate copolymer of the above (1) and 0.01 to 0.5 parts by mass of an antioxidant, ❹ (5) as the above (4) The carbonate resin composition in which the yellow index (YO of 1.5 or less, and (6)) of the molded article is characterized by being formed of the resin composition of the above (4) or (5). According to the present invention, by setting the tin content in the polycarbonate copolymer to 0.5 ppm or less, yellowing due to molding at a high temperature can be reduced, and discoloration in the durability test can be reduced, and as a result, a good molded article can be obtained. [Best Mode for Carrying Out the Invention] The polycarbonate (PC) copolymer of the present invention is a polycarbonate obtained by copolymerizing a phenol-modified diol, and can be produced by a conventional production method called an interfacial polymerization method. It can be produced by a method of reacting a carbonate precursor such as a divalent phenol, a phenol-modified diol, or phosgene. Specifically, for example, an acid acceptor or a molecular weight adjustment is known in an inert solvent such as dichloromethane. In the presence of the agent, and then necessary Adding a catalyst or a -9 - 201011056 branching agent to react a carbonate precursor such as a divalent phenol, a phenol-modified diol, and phosgene. The PC copolymer has the following general formulas (I) and (II) Repeat unit. [Chemical 3]

In the above general formulas (I) and (II), R1 and R2 are each independently and represent an alkyl group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, and -S- And -SO-, -so2-, -Ο-, -CO- or any of the bonds represented by the following formula (III-1) or the following formula (III-2).

R3 and R4 are each independently and represent an alkyl group having 1 to 3 carbon atoms, and Y is a linear or branched alkyl group having 2 to 15 carbon atoms. a to d are each independent, and represent an integer of 0 -10- 201011056 to 4' η is an integer of 2 to 200, preferably 6 to 70. The alkyl group of R1 to R4 may be either linear or branched. Specific examples of the alkyl group of R1 and R2, such as methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, tert-butyl, η-pentyl, isopentyl, Η-hexyl, isohexyl, and the like. Specific examples of the alkyl group of R3 and R4 include a methyl group, an ethyl group, an η-propyl group, and an isopropyl group. Further, R1 and R2 are each independently and may be a cyclic hydrocarbon group such as a cyclopentyl group or a cyclohexyl group. Examples of the alkylene group having 1 to 8 carbon atoms of X include a methyl group, an ethylene group, a propylene group, a butyl group, a pentylene group, and a hexylene group. Examples of the alkylidene group having 2 to 8 carbon atoms of X include ethylidene and isopropylidene. Examples of the cycloalkylene group having 5 to 15 carbon atoms of X include a cyclopentylene group and a cyclohexylene group. The cyclocyl group having a carbon number of 5 to 15 in X may, for example, be φ such as a cyclopentylene group or a cyclohexylene group. The divalent phenol is, for example, a compound represented by the following general formula (la). 5 (R2)b (R1)a (la) Η°-〇-χ-<〇>'〇Η In the general formula (la), R1 and R2, a, b, and X are the same as described above. -11 - 201011056 Although there are various kinds of divalent phenols represented by the above general formula (la), it is preferable to use 2,2-bis(4-hydroxyphenyl)propane (commonly known as ··diacid A). Examples of the bisphenol other than bisphenol A include bis(hydroxyaryl) hydrocarbons, bis(ylaryl)cyclo hydrocarbons, dihydroxyaryl ethers, dihydroxydiaryl sulfides, and dihydroxy groups. Aryl sulfoximines, dihydroxydiaryl fluorenes, di-terminated diphenyls, dihydroxydiaryl fluorenes, dihydroxy diols, and other types, such as bis(4-hydroxyphenyl) Diphenylmethane, 4,4'-[1,3-phenylenebis(methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-nonanone, 1,5 - bis(4-hydroxyphenylthio)-2,3-dioxolene and an α,ω-bishydroxyphenylpolydimethyloxane compound. These divalent phenols may be used singly or in combination of two or more. The molecular weight modifier is generally used in a polymerizer which can be used for a PC resin. Specifically, 'monovalent phenol' such as phenol, 〇-η-butyl phenol, mn-butyl, ρ-η-butyl hydrazine, hydrazine-isobutyl ketone, m-isobutyl acid, ρ-isobutyl Base, 〇-t-butyl hydrazine, mt-butyl hydrazine, pt-butyl fluorene, 〇-η-pentyl hydrazine, mn-pentyl acid, pn-pentyl hydrazine, ο-η-hexyl Mn-hexylphenol 'p-η-hexylphenol, pt-octylphenol, anthracene-cyclohexylphenol, cyclohexylphenol, p-cyclohexylphenol, anthracene-phenylphenol, m-phenylphenol, p-phenyl Phenol, ο-η-nonylphenol, m-nonylphenol, pn-nonylphenol, fluorene-cumylphenol, m-isopropylphenol, p-cumylphenol, 〇-naphthyl Phenol, m-naphthyl phenol, P-naphthyl phenol; 2,5-di-t-butyl phenol; 2,4-di-t-butyl phenol; 3,5-di-t-butyl phenol; 2,5-diisopropylphenylphenol; 3,5-diisopropylphenylphenol: P-cresol, bromophenol, tribromophenol, having an average carbon number of 12 to 35 in the ortho, meta or para position a linear or branched alkyl monoalkylphenol; 9-(4- -12- 201011056 hydroxyphenyl)-9-(4-methoxyphenyl)anthracene; 9-(4-hydroxyl -3-methylphenyl)-9-(4-methoxy-3-methylphenyl)indole; 4-(1-adamantyl) Wait. Among these monovalent phenols, P-t-butylphenol, p-cumylphenol, p-phenylphenol or the like is preferably used. As the catalyst for the interfacial polymerization method, it is preferred to use a phase-shifting catalyst such as a tertiary amine or a salt thereof, a quaternary ammonium salt, a quaternary rust salt or the like. a tertiary amine such as triethylamine, tributylamine, hydrazine, hydrazine dimethylcyclohexylamine, pyridine, dimethyl φ aniline, etc., and a tertiary amine salt, such as a salt of a tertiary amine Acid salts, bromates, and the like. A quaternary ammonium salt such as trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, four Examples of the quaternary phosphonium salt such as butyl ammonium bromide and the quaternary phosphonium salt include tetrabutyl chlorinated scale and tetrabutyl brominated scale. These catalysts may be used singly or in combination of two or more. Among the above catalysts, a tertiary amine is preferred, and particularly triethylamine is preferred. Inert organic solvents, various. For example, dichloromethane (dichloromethane): chloroform; carbon tetrachloride; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane ; 1,1,2_trichloroethane; m2-tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane; chlorinated hydrocarbons such as chlorobenzene or toluene, acetophenone Wait. These organic solvents may be used singly or in combination of two or more. Of these, especially methylene chloride is preferred. For the branching agent, for example, stilbene (4-hydroxyphenyl)ethane; 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]benzene can also be used. Ethylene] bisphenol; hydrazine 1, 〇[', 〇["-para (4-hydroxyphenyl)-1,3,5-triisopropylbenzene; 1-[α-methyl-α -(4,-hydroxyphenyl)ethyl]-4_[α,,α,_bis-13- 201011056 (4"-p-phenylphenyl)ethyl]benzene; having more than 3 fluoroglycine, trimellitic acid A compound of a functional group such as an acid or a ruthenium bis(anthracene-cresol). The phenol-modified diol used in the present invention is represented by the following general formula (Ila).

In the formula (Ila), wherein R3 and R4 are each independently, it is an alkyl group having 1 to 3 carbon atoms, and Y is a linear or branched alkyl group having 2 to 15 carbon atoms. c and d are each independently, an integer of 0 to 4, and η is an integer of 2 to 450. The alkyl group represented by R3 and R4 may, for example, be a methyl group, an ethyl group, an η-propyl group or an isopropyl group. When R3 is a complex number, the plural R3s may be the same or different from each other. When R4 is a complex number, the plural R4s may be the same or different from each other. The alkylene group having a linear or branched chain having 2 to 15 carbon atoms represented by Υ may, for example, be an ethylene group, a propylene group, a butyl group, an isobutylene group, a pentylene group or an isopentylene group. An alkylidene residue such as an alkylene group, an ethylene group, a propylene group, an isopropylidene group, a butylene group, an isobutylene group, a pentylene group or an isopentylene group. η is preferably 2 to 200, more preferably 6 to 70. The phenol-modified diol represented by the above general formula (Ila) is a general formula (IV) or a general formula (V) -14 - 201011056 7 Ο HC^-

OH (IV) (R3)c

(R4)d (7) A compound derived by subjecting a hydroxybenzoic acid or an alkyl ester thereof to an esterification reaction or a transesterification reaction with a polyether diol described later. In the above general formula (V) and general formula (IV), R3 is an alkyl group having 1 to 3 carbon atoms. c is an integer from 0 to 4. The alkyl group having 1 to 3 carbon atoms is the aforementioned one. In the general formula (V), R4 is an alkyl group having 1 to 3 carbon atoms, and R5 is an alkyl group having 1 to 10 carbon atoms. d is an integer from 0 to 4. The alkyl group having 1 to 10 carbon atoms and the above-mentioned alkyl group having 1 to 3 carbon atoms may, for example, be η-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl or octyl. a hydroxybenzoic acid represented by the above general formula (IV) such as 2-ethylhexyl or fluorenyl, such as p-hydroxybenzoic acid, m-hydroxybenzoic acid, hydrazine-hydroxybenzoic acid (salicylic acid), and the like The alkyl group having a carbon number of 1 to 3 is substituted on the benzene ring. The alkyl hydroxybenzoic acid alkyl ester represented by the above general formula (V), for example, represented by P-hydroxybenzoic acid methyl ester, p-hydroxybenzoic acid ethyl ester, and P-hydroxybenzoic acid η-propyl ester example. Ί5- 201011056 The polyether diol is represented by ΗΟ-(Υ-Ο) η-Η [Υ is the same as described in the general formula (II)], and is a linear or branched form having a repeating carbon number of 2-15. The alkyl ether is formed. Specifically, for example, polyethylene glycol 'polypropylene glycol, polybutylene glycol, and the like. Polybutylene glycol is particularly preferred from the viewpoint of availability and hydrophobicity. The repeating number η of the ether portion of the polyether diol is from 2 to 200, preferably from 6 to 70. When η is 2 or more, the efficiency in copolymerizing a phenol-modified diol is good, and when η is 70 or less, there is an advantage that the heat resistance of the PC copolymer is small. The esterification or transesterification of the hydroxybenzoic acid or its alkyl ester with the polyether diol is carried out in the presence of a tin-based catalyst. The amount of the tin-based catalyst used is generally about 1 to 10% by mass, preferably about 0.05 to 5% by mass, more preferably about 0.1 to 3, based on the hydroxybenzoic acid or the alkyl hydroxybenzoic acid alkyl ester. About % by mass. When the amount is 0.01% by mass or more, sufficient reaction activity can be obtained, and when it is 10% by mass or less, side reactions can be suppressed, and the amount of the phosphoric acid aqueous solution or the solid adsorbent to be described later can be reduced, and the obtained phenol-modified diol can be obtained. Less tin content. It is necessary to purify the phenol-modified diol obtained by these methods to reduce the tin content. Specifically, by purifying the crude reaction liquid containing the phenol-modified diol by using an aqueous phosphoric acid solution or a solid adsorbent, the tin content in the phenol-modified diol can be lowered by using the phenol-modified diol. The above-described interfacial polymerization method can obtain a polycarbonate copolymer of the present invention having a tin content (as an element) of 0.5 ppm or less. In the treatment of the aqueous phosphoric acid solution, the crude reaction product obtained by the esterification reaction or the transesterification reaction is diluted with phosphoric acid and a non-mixable organic solvent, such as di-16-201011056. The extraction causes the tin compound-like impurities from the tin-based catalyst to be extracted from the phosphoric acid layer, thereby reducing the content in the target compound. The concentration of the aqueous phosphoric acid solution is preferably 5 to 4% by mass, more preferably 1.0 to 10% by mass, most preferably 2 to 5% by mass. The phosphoric acid concentration of 0.5% by mass or more or more ensures the extraction efficiency of impurities such as tin compounds. When the phosphoric acid concentration is 10% by mass or less, it is possible to prevent the high-concentration phosphorus-containing wastewater from being generated and to protect the environment, and to prevent the economical reduction of φ caused by the use of an aqueous phosphoric acid solution of a necessary amount or more. The capacity of the aqueous phosphoric acid solution is preferably 26% by volume or less in the total capacity. When the amount is 26% by volume or less, in the liquid-liquid extraction, the extraction efficiency of the tin compound derived from the tin-based catalyst can be prevented by the organic layer being the dispersed phase and the aqueous phosphoric acid solution being the continuous phase. The tin content (as an element) in the phenol-modified diol is 10 ppm or less, preferably 5 ppm or less. In the treatment of the solid adsorbent, the crude reaction product obtained by the esterification reaction or the transesterification reaction is diluted with a dichloromethane-like organic solvent, and then the φ solid adsorbent is dispersed therein to adsorb the tin compound-like impurities from the tin-based catalyst. Further, the content of the target compound can be lowered. As the solid adsorbent, a composite adsorbent composed of activated clay, acid clay, ion exchange resin, chelating resin, activated carbon, cerium oxide, magnesium oxide, alumina or the like can be used. For the commercial products of the adsorbent, for example, Mizukalife F-2G (made by Mizusawa Chemical Industry Co., Ltd., cerium oxide/magnesium oxide adsorbent), Mizukalife P-Ι (made by the company, cerium oxide, magnesium oxide adsorbent) 〕, galleon earthV2 [same company, active clay soil adsorbent], -17- 201011056

MizukasorbC-l [manufactured by the company, sand dioxide adsorbent], SA-l [made by Japan Activated White Earth Co., Ltd., activated clay adsorbent], R15 [made by Japan Activated White Earth Co., Ltd., activated clay adsorbent], Qiel KW700SL (manufactured by Kyowa Chemical Industry Co., Ltd., cerium oxide alumina-based adsorbent), Baine A [made by Japan EnviroChemicals. Ltd., activated carbon-based adsorbent], CR1 1 [manufactured by Nippon Sekisui Co., Ltd., chelate resin]. In particular, the tin compound of Mizukalife F-2G [made by Mizusawa Chemical Industry Co., Ltd.] and Mizukalife P-1 [same] is excellent in adsorption performance, and is preferable. In the treatment operation of the solid adsorbent, the solid adsorbent may be charged in the column, and the crude reaction product may be passed through the charging layer to adsorb impurities such as tin compounds derived from the tin-based catalyst. It is also possible to carry out a method of distilling off the inside of the reaction and distilling off excess raw material (for example, hydroxybenzoic acid or an alkyl ester thereof) in the latter stage of the reaction. Further, in order to efficiently remove the hydroxybenzoic acid of the impurity, the treatment may be carried out as a treatment for the aqueous phosphoric acid solution or as a pretreatment for the treatment of the solid adsorbent. The weakly basic aqueous solution is used in a pH of from 8 to 1, preferably from 8 to 1 0. When the pH is less than 8, the extraction of the hydroxybenzoic acid is insufficient, and when the pH is larger than 1, the comonomer is hydrolyzed. As the weakly alkaline aqueous solution, an alkali metal (sodium, potassium or the like) or an alkali earth metal (magnesium, calcium or the like) hydroxide or an aqueous solution of a carbonate or a hydrogencarbonate can be used. The treatment of the aqueous phosphoric acid solution, the treatment of the solid adsorbent, and the extraction of the weak aqueous solution can be carried out at room temperature or by heating to about 30 to 40 ° C. 201011056. The treatment operation of the aqueous phosphoric acid solution, the treatment of the solid adsorbent, and the extraction treatment of the aqueous alkaline solution may each be carried out several times. In the production step of the PC copolymer, the phenol-modified diol is preferably a user of a dichloromethane solution in order to prevent deterioration thereof. When it cannot be used as a dichloromethane solution, it can be used as an aqueous alkali solution such as NaOH. In the PC copolymer, the amount of copolymerization of the phenol-modified diol is increased, although the fluidity is improved, the heat resistance is lowered. Therefore, the copolymerization amount φ of the phenol-modified diol is preferably selected in consideration of the balance between the desired fluidity and heat resistance. When the amount of the phenol-modified diol is more than 40% by mass, as shown in JP-A-62-79222, it is an elastomer, and it is not suitable for the same application as a general PC resin. In order to maintain heat resistance of 100 ° C or more, the amount of the phenol-modified diol residue contained in the PC copolymer is 1 to 30% by mass, preferably 1 to 20% by mass, more preferably 1 in the present invention. ~15% by mass. The PC copolymer of the present invention has a viscosity of 30 to 71 [equivalent to Mv (viscosity average molecular weight) = 10,000 to 28, 100], preferably 37 to 62 [phase φ when Μν = 13,100 to 24,100]. The same applies to the PC copolymer composition described later. When the viscosity is 30 or more, the mechanical properties are good, and the viscosity is 70 or less, whereby the copolymerization effect of the comonomer can be favorably exhibited. Further, in order to exhibit high fluidity, a large amount of comonomer is required. However, if the viscosity is 71 or less, there is no problem that the heat resistance is greatly lowered for the use of the comonomer. Further, the viscosity is determined according to ISO 1628-4 (1999). The PC copolymer of the present invention has a flow enthalpy (Q値) of 280 〇C of 3〇xl (T2mL/sec or more, more preferably 4〇xlO_2mL/sec or more. Flow enthalpy (Q値) is based on JIS K 7 2 10, the melt viscosity 'flow enthalpy of -19-201011056 measured by the overhead flow tester is 30x 10_2mL / sec or more, the melt viscosity of the pc copolymer does not become too high. The same applies to the PC copolymer composition described later. The PC copolymer composition of the present invention is a composition containing 100 parts by mass of the above-mentioned PC copolymer and containing an antioxidant of 〇.01 to 〇·5 parts by mass. The antioxidant is, for example, an arylphosphine system, a phosphite system, a phosphate system or a hindered phenol system. Further, the PC copolymer composition of the present invention may be a composition of a mixture of other PC resins having a tin content (as an element) of 55 ppm or less. Moreover, when such a PC copolymer composition is used for a light guide plate or an optical lens, it is preferable to use an acrylic resin having a molecular weight of about 1,000 to 100,000 in order to increase the light transmittance, and in addition to the acrylic resin, A PC-based resin composition having an alicyclic epoxy compound or a polyoxyalkylene compound having one or more selected from the group consisting of an alkoxy group, a vinyl group and a phenyl group is more preferable. As the other PC resin to be blended in the PC copolymer of the present invention, a PC resin having a commercially available tin content (as an element) of 55 ppm or less can be used. The amount of the other _PC resin is preferably from 300 parts by mass or less, more preferably from 10 to 200 parts by mass, per 100 parts by mass of the PC copolymer, from the viewpoint of not impairing the effects of the present invention. The acrylic resin is a polymer which is at least one selected from the group consisting of monomer units of acrylic acid, acrylate, acrylonitrile and derivatives thereof, and is a single polymer or a copolymer with styrene, butadiene or the like. . Specifically, for example, polyacrylic acid, polymethyl methacrylate (PMMA), polyacrylonitrile, ethyl acrylate-2-chloroethyl copolymer, acrylic acid-η-butyl-20-[Chemical 9]

201011056 Base-acrylonitrile copolymer, acrylonitrile-styrene copolymer, acrylonitrile copolymer, acrylonitrile-butadiene-phenethyl copolymer, and the like. Polymethyl methacrylate (PMMA) is suitable for use in these applications. The acrylic resin has a molecular weight of about 1,000 to 10,000, and 10,000 to 60,000. When the molecular weight is from 1,000 to 100,000, the phase separation between the other PC resin and the acrylic resin does not occur at the time of molding, so that the molded article can obtain sufficient transparency. Polymethacrylic acid 0 PMMA ) can be used, but it is generally preferred to use a methyl methacrylate monomer in the presence of a peroxide or a coupling initiator. The amount of the acrylic resin to be mixed with the pc of the present invention is 100 parts by mass of the PC composition of the other PC resin mixed with the PC copolymer of the present invention, and is usually about 0.01 to 1 part by mass, 0.05 to 0.5 part by mass, more preferably Preferably, it is 0.1 to 0.3 parts by mass. When the amount of the acryl is 0 or more, the transparent φ ' of the molded article is at most 1 part by mass, and the properties can be improved without impairing other desired physical properties. An alicyclic epoxy compound refers to an alicyclic epoxy group, that is, a cyclo compound in which an epoxy group having 1 atom of oxygen is added to a bond in the aliphatic ring. Specifically, it is preferred to use a tetracycline. 11_ 1 5 8 364 is expressed by the following formulas (1) to (10). (1) • Butadiene, especially the 2 polymer and too fast, methyl ester (the nitrogen-based block polymer and copolymer are preferably acid-based, and the lipid-like fat is maintained.) 201011056 10°〇RI ch2occ=ch2 IIο 11 °〇RI CH2〇C(CH2)5〇CC=CH2ο ο (3) In the general formulae (2) and (3), R is a hydrogen atom or a methyl group. [1 2]

【化1 3】

,C0[0(CH2)5C0]a0CH2 C0[0(CH2)5C0]b0CH2

(5) In the general formula (5), 'a and b are each an integer of 0 to 10, and a+b is an integer of 1 to 10. -22- x>° 201011056 14 CH2C0[0(CH2)5C0]a0CH2 x>° CH-C0[0(CH2)5C0]b0CH2 CH-C0[0(CH2)5C0]c0CH2 x>° (6)

CH2C0[0(CH2)5C0]d0CH2 x>° In the general formula (6), a, b, c, and d are integers of 0 to 10, respectively, and a+b+c+d is an integer of 1 to 10. [化1 5]

In the general formula (7), a, b and c are each an integer of 0 to 10, and a + b + c is an integer of 1 to 10. -23- 201011056

(8) In the general formula (8), η is an integer of 1 to l〇. [化1 7]

R

(9) ❹ In the general formula (9), R is a hydrogen atom or an alkane having a carbon number of 1 to 6 as described above.

In the general formula (10), η is an integer of 1 to 10, and R is a residue of a compound having an active hydrogen group like trimethylolpropane. The amount of the above-mentioned alicyclic epoxy compound is usually from about 1 to 1 part by mass, preferably from 0.02 to 0.2 part by mass, per 100 parts by mass of the PC copolymer composition. The amount of addition is 0.01 parts by mass or more, and the effect of addition is obtained. When the amount is 1 part by mass or less, phase separation is not caused, and transparency can be obtained. A polysiloxane compound is a compound selected from alkoxy groups (for example, methoxy group, -24-201011056 ethoxy group), a vinyl group, and a phenyl group in a polysiloxane compound. The reactive polyoxo compound of the above functional group is, for example, an organic polyoxane. The polyoxyalkylene compound is a compound which is used as a stabilizer in the PC resin composition. When it is combined with a polyoxyalkylene compound, it is possible to prevent yellowing due to thermal deterioration during molding, poor appearance such as silver strips, and air bubbles. The amount of the polyoxyalkylene compound to be blended is usually from 0.01 to 3 parts by mass, preferably from 0.05 to 2 parts by mass, based on 1 part by mass of the polycarbonate copolymer. When it is 0.01 mass φ or more, the effect of addition is obtained, and when it is 3 parts by mass or less, turbidity does not occur in the molded article. In addition to the above respective components, the resin composition of the present invention may be blended with various additives without damaging the effects of the present invention. For example, an ultraviolet absorber such as a benzotriazole-based or benzophenone-based, a light stabilizer such as a hindered amine, an internal lubricant such as an aliphatic carboxylic acid ester, a paraffin wax, an eucalyptus oil, or a polyethylene wax is often difficult to use. A flammable agent, a flame retardant, a release agent, an antistatic agent, a colorant, and the like. [Embodiment] [Embodiment] Next, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to these examples. Further, the amount of impurities in each of the examples was measured by the following method. [Production Example 1 - Synthesis of polybutylene glycol-bis(4-hydroxybenzoate)] -25- 201011056 Introduced in a reaction vessel having a stirrer, a thermometer, a reflux condenser, a raw material supply port, and a gas introduction pipe Nitrogen, supplied with polybutyl ether glycol [PTMG, Mn (number average molecular weight) = 2000] 100 parts by mass and 15.8 parts by mass of methyl p-hydroxybenzoate and dibutyltin oxide as a tin-based catalyst. After the mass fraction was heated to 220 ° C, the resulting methanol was distilled off to carry out a transesterification reaction. After completion of the reaction, the reaction system was depressurized, and excess methyl P-hydroxybenzoate was distilled off to obtain a crude reaction product. The crude reaction product was dissolved in dichloromethane to give a solution having a concentration of 20% by mass. 20 parts by volume of a 0.1 mol% sodium hydrogencarbonate aqueous solution was added to 80 parts by volume of the dichloromethane solution, and the mixture was stirred and mixed at 20 ° C for 30 minutes in a stirred tank with a separator to form a P-hydroxy group of the impurities formed in the reaction. After the benzoic acid was extracted into the aqueous phase, the dichloromethane phase was taken up by standing. 25 parts by volume of 3.5% by mass phosphoric acid aqueous solution was added to 75 parts by volume of the dichloromethane phase, and the mixture was stirred and mixed in 2 (TC for 180 minutes) to extract the tin compound from the tin-based catalyst to water. After the reaction, the dichloromethane phase was taken out by static separation. Further, 25 parts by volume of a 3.5% by mass phosphoric acid aqueous solution was added to 75 parts by volume of the dichloromethane phase, and the mixture was stirred at 20 ° C for 180 minutes in a stirred tank with a separator. After mixing, the tin compound from the tin-based catalyst is extracted into the aqueous phase, and then the dichloromethane phase is taken out by standing. In order to remove a trace amount of phosphoric acid in the dichloromethane phase, pure water is added to 75 parts by volume of the dichloromethane phase. The volume fraction was stirred and mixed at 20 ° C for 60 minutes in a stirred tank with a separator, and the phosphoric acid was extracted into the aqueous phase, and then the dichloromethane phase was taken out by standing. -26- 201011056 Concentration under reduced pressure 'to obtain a polybutylene glycol-bis(4-hydroxybenzoate) of a phenol-modified diol [hereinafter abbreviated as PTMG-BHB }. The following HP LC (High Speed Liquid Chromatograph) Quantification, quantification of tin and quantification of phosphate ions It was confirmed that the p-hydroxybenzoic acid in PTMG-BHB was less than 10 ppm by mass, the methyl p-hydroxybenzoate was 0.2% by mass, and the tin (as the element and the same below) was less than 2 ppm, and phosphorus (as an element, the same as the element) 3 ppm. [Production Example 2 - Synthesis of polybutylene glycol-bis(4-hydroxybenzoate)] Substituting PTMG of Mn = 2000, using polybutylene glycol (Mn = 1 000 ) ' p-hydroxyl The methyl benzoate was 3 丨 6 parts by mass, and each obtained PTMG-BHB as in Production Example 1 '. Quantification by the following HPLC (high-speed liquid chromatography), quantification of tin, and quantification of phosphate ions confirmed that PTMG- The p-hydroxybenzoic acid in BHB is less than 1 〇 mass ppm, the methyl p-hydroxybenzoate is 0.2% by mass, the tin is less than 2 ppm, and the phosphorus is less than 2 ppm. [Production Example 3] Substituting 3.5% by mass of aqueous phosphoric acid solution as mass% In addition to the aqueous phosphoric acid solution, PTMg_bhb is obtained as in the production of (four)i. Quantification of the following HpLc (high-speed liquid chromatograph) _ ^ * quantification of tin and quantification of phosphate ions confirm that PTMG-BHB has not been irrigated by a certain anti-μ Benzoic acid does not reach 10 mass ppm ' -27- 201011056 p - 0.2% by mass, tin is iOppm, and the amount is less than 2 ppm. [Production Example 4] PTMG-oxime was obtained as in Production Example 1 except that a 3.5% by mass phosphoric acid aqueous solution was used instead of 5 〇 mass% phosphoric acid aqueous solution. The quantification of the high-speed liquid chromatograph, the quantification of tin, and the quantification of the phosphate ion confirmed that the P_hydroxybenzoic acid was less than 10 ppm by mass, the p-hydroxybenzoic acid methyl vinegar was 0.2% by mass, the tin was 5 ppm, and the pity was 4 ppm. [Production Example 5] A crude reaction product was obtained in the same manner as in Example 1 except that excess P-hydroxybenzoic acid methyl ester was distilled off. The crude reaction product was dissolved in dichloromethane to prepare a solution having a concentration of 20% by mass, and 5% by mass of Mizukalife F-2G (manufactured by Mizusawa Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred and mixed at 20 ° C for 3 hours. After the tin compound was adsorbed, it was filtered under reduced pressure using a filter membrane having a pore size of 0.2 jwm, and F-2G was filtered off. 20 parts by volume of a 0.1 mol% aqueous solution of sodium hydrogencarbonate was added to 80 parts by volume of the obtained dichloromethane solution, and the mixture was stirred and mixed at 20 ° C for 30 minutes in a stirred tank with a separator to form an impurity in the reaction. After the hydroxybenzoic acid was extracted into the aqueous phase, the dichloromethane phase was taken up by standing. In order to remove a trace amount of sodium in the methylene chloride phase, 25 parts by volume of pure water was added to a 75-volume part of the dichloromethane phase, and the mixture was stirred at 20 201011056 ° C for 60 minutes with a stirring tank with a separator to make sodium. After extraction to the aqueous phase, the dichloromethane phase was taken up by standing. The dichloromethane phase was concentrated under reduced pressure to give phenol-modified diol of PTMG-BHB. It was confirmed by the following HPLC (high-speed liquid chromatograph) quantification and tin quantification that ρ-hydroxybenzoic acid in PTMG-BHB was less than 10 ppm by mass of ρ-hydroxybenzoic acid methyl ester of 0.2% by mass and tin of 5 ppm. φ [Production Example 6] PTMG-BHB was obtained as in Production Example 1 except that the tin compound derived from the tin-based catalyst was extracted with a phosphoric acid aqueous solution. It was confirmed by the following HPLC (high-speed liquid chromatograph) quantification and tin quantification that ρ-hydroxybenzoic acid in PTMG-BHB was less than 10 mass ppm, and p-based benzoic acid methyl ester was 〇·3 mass%, tin. It is I90ppm. [Production Example 7] PT In place of the 5% by mass aqueous phosphoric acid solution, the 5% by mass of the aqueous phosphoric acid solution was used. As in Production Example 1, PTMG-BHB was obtained. The following HPLC (high-speed liquid chromatograph) and tin quantification confirmed that P-hydroxybenzoic acid in ptmG-BHB was less than 10 ppm by mass, methyl p-hydroxybenzoate was 0.3% by mass, tin was 70 ppm, and phosphorus was not Up to 2ppm. <Quantification of HPLC (High Speed Liquid Chromatography)> Based on the following conditions: HPLC (High Speed Liquid Chromatography), p-hydroxybenzoic acid and P-hydroxybenzoic acid methyl ester standards -29- 201011056 Quantitative. Pipe column: ODS-3 column temperature manufactured by GL SCIENCES INC. Solvent: 0.5 mass% mixture of aqueous acid solution and acetonitrile (capacity ratio 1: 2) Flow rate: 1.0 ml/min <Quantification of tin in comonomer > (1) Pretreatment of the sample PTMG-BHB was weighed in a platinum crucible: 1.0 g, and 0.8 ml of concentrated sulfuric acid was added thereto and heated to dryness, at 550. (: After 10 hours of treatment, ashing. After adding potassium bismuth hydrogen sulfate 5 5 g, heating with a burner, adding 3 ml of 6 ml/liter hydrochloric acid, heating, and dissolving and dissolving the ash. (2) Determination After the above acid decomposing solution was allowed to cool, the solution was allowed to have a capacity of 25 ml, and the solution was further diluted to 5 times by ICP-OES (high frequency derivatization combined with electro-optic luminescence spectrometry) device [SII NanoTechnology Inc., SPS 5100 Quantification is carried out. The luminescence spectroscopic analysis is based on JIS K0116. <Quantification of tin in polycarbonate> (1) Sample preparation: 3.0 gram of polycarbonate was weighed in a platinum dish, and concentrated sulfur was added thereto - 201011056 3.0 ml of acid was heated and dried, and then treated and ashed at 550 ° C for 10 hours. Add 0.1 gram of lithium tetraborate anhydrate and lithium fluoride in a mass ratio of 9:1, and 30 minutes at 930t. After the treatment, an aqueous solution of tartaric acid (5 g of tartaric acid, 40 ml of nitric acid, and 500 ml of water were mixed and dissolved, and water was added thereto to make the whole volume of 100 ml) 15 ml, and the mixture was heated and stirred to prepare an alkali-melting solution. ) The above alkaline solution was allowed to stand to a volume of 25 ml, and the solution was further diluted to 2.5 times. The solution was quantified by an ICP-OES apparatus (SPS 5100 manufactured by SII NanoTechnology Inc.). The luminescence spectroscopic analysis was based on JIS K0116 <> PTMG-BHB: 10g was weighed into a Squibb type separatory funnel made of Teflon (Dongyulu trademark) with a capacity of 20 ml. Add 10 ml of purified dichloromethane (:*1) and shake to make PTMG- BHB was dissolved. 10 ml of pure water was added thereto, and the phosphoric acid ions in the sample were extracted into water using a shaker at a rate of 240 times/min., and the phosphate ions were extracted into the water. After standing and separating into an organic layer and an aqueous layer, In the aqueous layer, the amount of scaly acid ions was quantified by an ion chromatograph apparatus (Dionex Corp., DX-120). The standard solution was a phosphoric acid standard solution. The ion chromatograph was based on JIS K0127. -31 - % 201011056 * Refined dichloride Methane: Methylene chloride and pure water were placed in a Squibb type separatory funnel made of Teflon (registered trademark). The methylene chloride was washed with pure water by shaking. This operation was carried out until the extracted pure water was ionized. Analytical device analysis no longer detects phosphoric acid Methylene chloride obtained was used as a purified dichloromethane. [Example P-1] (1) Polycarbonate (PC) oligomer synthesis step & added to a 5.6% by mass aqueous sodium hydroxide solution The bisphenol A (BPA) which was subsequently dissolved was 2,000 ppm by mass of sodium disulfoxide sulfonate. Here, BPA was dissolved so that the BPA concentration became 13.5% by mass to prepare a BPA aqueous sodium hydroxide solution. The above-mentioned BPA sodium hydroxide aqueous solution was continuously passed at a flow rate of 15 liters/hour and dichloromethane at a flow rate of 15 liters/hour in a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m, while making phosgene 4.0 kg/ The flow of hours passes continuously. The tubular reactor has a cover portion, and cooling water is passed through the outer cover to maintain the temperature of the reaction liquid @ 40 ° C or lower. The reaction liquid sent from the tubular reactor was continuously introduced into a tank reactor having a 4 liter-liter internal separator with a back-wing, and then the aqueous solution of BP A was 2.8 liter/hour. A 25 mass% sodium hydroxide aqueous solution was supplied at a flow rate of 0.64 liter/hr, water of 17 liter/hr, and 1 mass% of triethylamine aqueous solution at a rate of 0.64 liter/hr, and the reaction was carried out at 29 to 32 °C. The reaction liquid was continuously taken out from the tank type reactor, and the aqueous phase was separated and removed by standing, and a dichloromethane phase was taken. The thus obtained polycarbonate-32-201011056 vinegar oligomer solution had an oligomer concentration of 3 29 g/liter and a chloroformic acid concentration of 0.74 m/d. (2) Polymerization step of PC copolymer The PC oligomer obtained in the above synthesis step was used in 20 liters/hour, dichloromethane at 12 liters/hour, and PTMG-BHB obtained in Synthesis Example 1 in 4% by mass of dichloromethane. The solution was supplied to T.KPIPELINE HOMO MIXER 2SL type at a flow rate of 8 68 kg/hr, 3% by mass aqueous triethylamine at 400 ml/hr and 6.4% by mass aqueous sodium hydroxide solution at φ 2.3 kg/hr [PRIMIX (shares) The system was subjected to preliminary polymerization at a number of revolutions of 3000 rpm to obtain a preliminary polymerization liquid. Next, the 20% by mass methylene chloride solution of the preliminary polymerization liquid and PTBP (p-tert-butylphenol) was added at 960 g/hr, and the BPA dissolved in a 6.4% by mass aqueous sodium hydroxide solution was added to an aqueous solution having a concentration of 8.8% by mass. 14.lkg/hour was supplied to T.KPIPELINE HOMO MIXER Model 2SL [manufactured by PRIMIX Co., Ltd.], and emulsified at a number of revolutions of 3000 rpm to obtain φ to an emulsion. Next, the emulsion was introduced into a second reactor with two orifices (orifice plates) having three holes of 0.8 mm in diameter, and inserted into a pore-flow mixer of a 19.05 mm (3/4 inch) pipe. The polymerization was carried out in a 50 liter stirrer blade three-stage column type agitating tank to the outer cover of the third reactor. The cooling water flowing at 15 °C in the outer casing was made to have a polymerization liquid outlet temperature of 30T:. The polymerization liquid overflowed by the above-mentioned column reactor and the dichloromethane for dilution were continuously supplied at 11 liters/hr in a 50 liter dilution tank equipped with a stir bar type stirring blade. Next, the emulsion liquid obtained from the dilution tank was introduced into a KCC centrifugal extractor (trade name, manufactured by Kawasaki Heavy Industries Co., Ltd., internal volume 4 liters, rotor diameter 430 mm) by centrifugal extraction at a number of revolutions of 3000 rpm, and separated. Water layer and organic layer. (3) Alkali washing step

The organic layer obtained by the above centrifugal extractor and 7.8 liter/hr of a 0.03 mol/liter sodium hydroxide aqueous solution were supplied to a T. KPIPELINE HOMO MIXER 2SL type (manufactured by PRIMIX Co., Ltd.), and stirred and mixed at 3 000 rpm. The mixture from the outlet of the homogenizer was introduced into a centrifugal extraction A, and centrifugal extraction was carried out at a number of revolutions of 300 rpm to separate the aqueous layer from the organic layer. Then, the emulsion obtained from the dilution tank was introduced into a KCC centrifugal extractor (trade name, manufactured by Kawasaki Heavy Industries Co., Ltd., internal volume 4 liters, rotor diameter 430 mm), and then centrifugally extracted at a number of revolutions of 3000 rpm to separate the water layer and the organic layer. The layer, the organic layer is then supplied to the acid wash step. (4) The acid washing step is to supply the organic layer obtained from the centrifugal extraction machine of the alkali washing step and the 0.2 mol/liter aqueous hydrochloric acid solution to _ liter of _ T. KPIPELINE HOMO MIXER 2 SL [PRIMIX (shares) ), mixed with 300 Or pm. The mixed liquid from the outlet of the homogenizer is introduced into the stationary separation tank to separate the aqueous layer from the organic layer, and the organic layer is then supplied to the first water washing step. (5) First water washing step The organic layer obtained by the centrifugal extractor and pure water were supplied to T. KPIPELINE HOMO MIXER 2SL type (manufactured by PRIMIX Co., Ltd.) at 7.8 liter/hr, and stirred and mixed at 3000 rpm. After the mixture of -34-201011056 from the outlet of the homogenizer is introduced into the centrifugal extractor, centrifugal extraction is performed at a number of revolutions of 3000 rpm, and the aqueous layer and the organic layer are separated, and the organic layer is then supplied to the second water washing step (6). In the procedure, the organic layer obtained by the centrifugal extractor and pure water were supplied to T. KPIPELINE HOMO MIXER Model 2SL (manufactured by PRIMIX) at 7.8 liter/hr, and the mixture was stirred and mixed at 3000 rpm. The mixed liquid from the outlet of the homogenizer was introduced into a centrifugal extractor, and then centrifuged at 3,000 rpm to separate the aqueous layer and the organic layer to obtain a purified polycarbonate dichloromethane solution (organic layer). (7) Concentration and drying step The purified polycarbonate dichloromethane solution was concentrated and pulverized, and the obtained sheet was dried under reduced pressure at 105 °C. The properties of the obtained polycarbonate copolymer are as follows. The amount of the PTMG-BHB residue was determined by NMR to be 4.0% by mass. The viscosity measured according to IS01628-4 (1999) is 37·0 (Μν = ❿ 13100). [Example Ρ - 2] A 40% by mass methylene chloride solution of PTMG-BHB obtained in Production Example 2 was used at 434 kg/hour, in place of the 40 mass% dichloromethane solution of PTMG-BHB obtained in Production Example 1, at 868 kg/hr. A polycarbonate copolymer was obtained in the same manner as in Example P-1 except for the hour. [Examples P-3 to P-5 and Comparative Examples P-1 and P-2] -35- 201011056 In addition to the PTMG-BHB obtained in Production Example 1, except for PTMG - Β Η B obtained in Production Examples 3 to 7. A polycarbonate copolymer was obtained in the same manner as in Example P-1. The physical properties of the polycarbonate copolymers obtained in Examples Ρ-1 to Ρ-5 and Comparative Examples P-1 and Ρ-2 are shown in Table 1.

Table 1 Residue amount (% by mass) Viscosity tin content (ppm) Example P-1 4.0 37.0 <0.1 Example P - 2 4.0 37.1 <0.1 Example P - 3 4.0 36.9 0.4 Example P - 4 4.0 37.0 0.2 Example P-5 4.0 37.0 0.2 Comparative Example P -1 4.0 36.9 7.0 Comparative Example P - 2 4.0 37.0 2.5

1 part by mass of the polycarbonate copolymer obtained in Example 1-1, 0.05 parts by mass of ADK STAB ΡΕΡ-36 (trade name, manufactured by ADEKA) with an antioxidant, and extruded through a vent hole of 40 mm φ The machine was granulated at a resin temperature of 260 ° C to obtain granules. Using the obtained pellets, a 35 mm x 25 mm x 2 mm flat plate was injection-molded under the following molding conditions. <Forming conditions> Molding machine: Toshiba Machine Co., Ltd., EC40N (trade name) -36- 201011056 Forming machine cylinder temperature: 340° C Retention time in the cylinder: 10 pieces of the molded product after the 13th shot was taken, and the yellow index (YI) was measured by the average of the average enthalpy. The results are shown in Table 2. The method of determining YI is as follows. <YI> 0 A 2.0 mm-thick molded article was produced by injection molding, and was measured by a spectrophotometer Σ90 manufactured by Nippon Denshoku Industries Co., Ltd., and a measurement method of a measurement area of 3 〇φ and a C2 light source. [Application Examples 2 to 5] 75 parts by mass of the polycarbonate copolymers obtained in Examples P-2 to P-5 were used in combination with TAFLON FN1500 (trade name 'Bis-A polycarbonate, manufactured by Idemitsu Kosan Co., Ltd., VN = 39.5] 25 parts by mass, antioxidant ADK _ STAB PEP-36 [trade name, (share) ADΕΚA system] 0.05 parts by mass, 40mm φ extruder with venting holes, granulation at a resin temperature of 260 ° C Get granules. The other part was measured for YI in the same manner as in Application Example 1. [Application of Comparative Examples 1 to 2] The polycarbonate copolymer obtained in the above Example P-1 was used in the same manner as in Application Example 1 except that the polycarbonate copolymer obtained in Comparative Examples pl to P-2 was used. YI. -37-201011056 [Application Example 6] 75 parts by mass of the polycarbonate copolymer obtained in Example P-1 was used in combination with TAFLON FN 1 5 00 [trade name, Bis-A polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd., VN=39.5] 25 parts by mass, ADK STAB PEP-36 (trade name, ADEKA) of antioxidants 0.0 5 parts by mass, DIANALBR83 [trade name, manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 40000] 0.1 parts by mass, KR51 1 (trade name, Shin-Etsu Chemical Co., Ltd., methoxy and vinyl organic oxirane) 0.1 parts by mass, CEL2021P [trade name, manufactured by Daicel Chemical Industry Co., Ltd.) 0.05 parts by mass of the alicyclic epoxy resin represented by the formula (1) was granulated at a resin temperature of 260 ° C through a 40 mm φ extruder equipped with a vent hole to obtain granules. Using the obtained pellets, YI was measured in the same manner as in Application Example 1. YI is 0.9

[Table 2] Table 2 YI Application Example 1 1.0 Application Example 2 1.0 Application Example 3 1.1 Application Example 4 1.0 Application Example 5 1.0 Application Example 6 0.9 Application Comparison Example 1 2.3 Application Comparison Example 2 1.7 -38- 201011056 [Industrial Applicability] The molded article of the polycarbonate copolymer having a low tin content obtained by the present invention is suitably used as a transparent optical member, particularly in the field of optical members such as lenses, photoconductors, and optical disks.

-39-

Claims (1)

201011056 VII. Patent application 1) Polycarbonate copolymer characterized by repeating units expressed by the following general formulas (Ο and (π), and tin content (containing in elemental form) at 0.5 ppm By 'p, 【1' (Rl)a (Rz)b (I) Lu I gin, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -S〇2, -〇-, -CO- or any of the following formulas (πi i) or the following formula (ΠΙ_2), (IIM) 〇π〇- R3 and R4 each independently represent an alkyl group having 1 to 3 carbon atoms, and Υ is a linear or branched alkyl group having 2 to 15 carbon atoms, and a to d are each independently an integer of 0 to 4, η It is an integer from 2 to 200]. 2. The method for producing a polycarbonate copolymer according to the first aspect of the invention, wherein the phenol-modified second is synthesized in the presence of a tin-based catalyst and treated with a phosphoric acid aqueous solution -40-201011056 or a solid adsorbent. The alcohol is used as a comonomer. 3. The method for producing a polycarbonate copolymer according to the second aspect of the invention, wherein the tin content (in the form of an element) in the phenol-modified diol is 1 Oppm or less. A polycarbonate resin composition comprising 100 parts by mass of the polycarbonate copolymer of claim 1 and 0.01 to 0.5 part by mass of an antioxidant. φ 5. The polycarbonate resin composition of claim 4, wherein the molded article has a yellow index (YI) of 1.5 or less. 6. A molded article characterized by being formed from a resin composition of claim 4 or 5. 201011056 IV Designated representative circle: (1) The designated representative circle of this case is: None (2) The symbol of the symbol of this representative circle is simple: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none