CN101608016B - Polycarbonate copolymer, method for producing same, resin composition, and molded article - Google Patents

Abstract

[R¹和R²各自独立地表示碳原子数1～6的烷基。X为单键、碳原子数1～8的亚烷基(-C_nH_2n-)、碳原子数2～8的亚烷基(C_nH_2n＝)、碳原子数5～15的环亚烷基(-C_nH_2n-2-)、碳原子数5～15的环亚烷基(C_nH_2n-2＝)、-S-、-SO-、-SO₂-、-O-、-CO-或下式(III-1)或下式(III-2)所示的基团的任意一种。R³和R⁴各自独立地表示碳原子数1～3的烷基。Y表示含碳原子数2～15的直链或含支链的亚烷基(-C_nH_2n-)。a～d各自为独立的0～4的整数，n为2～200的整数]。[化2]

The present invention provides a polycarbonate copolymer whose molded products can be used for transparent optical components, particularly optical components such as lenses, light guides, and optical disks, and a resin composition and a manufacturing method thereof. A polycarbonate copolymer and a molded article formed by molding the polycarbonate composition, the polycarbonate copolymer having repeating units represented by the following general formulas (I) and (II), and a tin content (as an element ) below 0.5ppm, [Chemical 1]

[R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. X is a single bond, an alkylene group with 1 to 8 carbon atoms (-C _n H _2n -), an alkylene group with 2 to 8 carbon atoms (C _n H _2n =), and a ring with 5 to 15 carbon atoms. Alkylene group (-C _n H _2n-2 -), cycloalkylene group with 5 to 15 carbon atoms (C _n H _2n-2 =), -S-, -SO-, -SO ₂ -, -O -, -CO-, or any one of the groups represented by the following formula (III-1) or the following formula (III-2). R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms. Y represents a linear or branched alkylene group containing 2 to 15 carbon atoms (-C _n H _2n -). a to d are each independent integers from 0 to 4, and n is an integer from 2 to 200]. [Chemicalization 2]

Description

Polycarbonate copolymer, method for producing same, resin composition, and molded article

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 which can be used for transparent optical parts, especially lenses and light guides , CD and other optical components. the

Background technique

Polycarbonate (hereinafter sometimes referred to as PC) copolymer is mainly made of bisphenol A, and the improvement of various properties of PC copolymer has never stopped. PC produced from bisphenol A or the like is widely used in various applications because of its excellent transparency, heat resistance, and mechanical properties (especially impact resistance). However, there is a disadvantage that when the molded article of PC is used for optical components such as lenses, light guide plates, and optical disks, satisfactory molded articles cannot be obtained due to low fluidity. In order to further improve fluidity, various improved polycarbonates have also been proposed. the

For example, as a method of improving fluidity, a method of changing the structure of a PC copolymer by modifying copolymerization and molecular chain terminals has been proposed. For example, there has been proposed a PC copolymer in which a molecular chain terminal is modified with a long-chain alkyl group (for example, refer to Patent Document 1). the

However, in the end-modified PC copolymer obtained by this method, since the site for improving fluidity is limited to the terminal part of the molecular chain, the amount of introduction of long-chain alkyl groups is limited, and it cannot be said that the degree of fluidity improvement is sufficient. the

In addition, Patent Document 2 proposes a polycarbonate copolymer obtained by copolymerizing polytetramethylene glycol-bis(4-hydroxybenzoate). Since this copolymer has significantly improved fluidity during molding and is excellent in thermal stability, it can be used as a molding raw material under various molding conditions, resulting in a good optical molded article. the

However, there is a problem that continuous production of the polycarbonate copolymer obtained by copolymerizing poly-1,4-butanediol-bis(4-hydroxybenzoate) described in the above-mentioned Patent Document 2 cannot be carried out at a high temperature exceeding 320° C. When this copolymer is used under molding conditions, yellowing occurs. the

Generally, there are many reasons for the yellowing of various polycarbonate copolymers because impurities derived from comonomers remain in the polycarbonate copolymer. However, since the comonomer used for each copolymer and its use status are different, the impurity and usage method are also different for each comonomer, and it is difficult to solve various polycarbonate copolymerization problems. The problem of object yellowing (Patent Documents 3-6). the

This kind of yellowing is also caused by the high molding temperature, but it is also greatly affected by the catalyst contained in the copolymer. When producing a phenol-modified diol as a polycarbonate copolymer raw material, especially when a tin-based catalyst is used, in the conventional raw material purification process (for example, refer to Patent Document 7) and the polycarbonate purification process (for example, , referring to Patent Document 8), which is not completely removed, and the polycarbonate copolymer of the phenol-modified diol produced by continuous polymerization such as an interfacial polymerization method and a melt polymerization method, will have a few ppm to tens of ppm Tin compounds of tin catalysts. the

Patent Document 1: JP-A-2003-96180 Gazette

Patent Document 2: JP-A-2005-247947 Gazette

Patent Document 3: JP-A-2004-315747 Gazette

Patent Document 4: JP-A-2005-336332 Gazette

Patent Document 5: JP-A-2006-28391 Gazette

Patent Document 6: JP-A-2007-70392 Gazette

Patent Document 7: JP-A-2005-232287 Gazette

Patent Document 8: Japanese Unexamined Patent Publication No. 1-96212

Contents of the invention

In view of the foregoing, the present invention aims to provide: when producing a polycarbonate copolymer using a phenol-modified diol, use a high-purity phenol-modified diol that can improve the thermal stability of the resulting PC copolymer at high temperatures, A polycarbonate copolymer, a resin composition, a molded article, and a method for producing the copolymer are obtained. the

In order to solve the above-mentioned problems, the inventors of the present invention have found that the above-mentioned problems can be solved by controlling the content of impurities derived from the synthesis raw materials of the polycarbonate copolymer represented by the following general formula (I) through intensive studies. The present invention has been accomplished based on the corresponding findings. the

That is, the present invention provides:

(1) a polycarbonate copolymer, it is characterized in that,

It has repeating units represented by the following general formulas (I) and (II), and the tin content (as an element) is below 0.5ppm,

[chemical 1]

[R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms (-C _n H _2n -) (alkylene), an alkylene group having 2 to 8 carbon atoms (C _n H _2n =) (alkylidene), a carbon atom Cycloalkylene (-C _n H _2n-2 -) (cycloalkylene) with 5 to 15 carbon atoms, cycloalkylene (C _n H _2n-2 =) (cycloalkylene) with 5 to 15 carbon atoms, -S- , -SO-, -SO ₂ -, -O-, -CO-, or any one of the groups represented by the following formula (III-1) or the following formula (III-2).

[chemical 2]

R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms. Y represents a linear or branched alkylene group (-C _n H _2n -) having 2 to 15 carbon atoms. a to d are each an independent integer of 0 to 4, and n is an integer of 2 to 200].

(2) The method for producing a polycarbonate copolymer described in (1) above is characterized in that, as a comonomer, a compound synthesized in the presence of a tin-based catalyst and treated with an aqueous phosphoric acid solution or a solid adsorbent is used. phenolic modified diols. the

(3) The method for producing a polycarbonate copolymer as described in (2) above, wherein the content of tin (as an element) in the phenol-modified diol is 10 ppm or less. the

(4) A polycarbonate resin composition containing 100 parts by mass of the polycarbonate copolymer described in (1) above and 0.01 to 0.5 parts by mass of an antioxidant. the

(5) The polycarbonate resin composition as described in said (4) whose yellowness index (YI) of a molded article is 1.5 or less. the

(6) A molded article molded from the resin composition described in (4) or (5) above. the

According to the present invention, by controlling the tin content in the polycarbonate copolymer to 0.5 ppm or less, yellowing during molding at high temperature can be reduced, and discoloration in durability tests can be reduced, resulting in good molded products. the

Detailed ways

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. That is, it can be produced by a method of reacting carbonate precursors such as dihydric phenol, phenol-modified diol, and phosgene. the

Specifically, for example, in an inert solvent such as dichloromethane, in the presence of known acid acceptors and molecular weight regulators, a catalyst or a branching agent is added as needed, so that dihydric phenols, phenol-modified diols, and Carbonyl chloride and other carbonate precursors react. The PC copolymer has repeating units represented by the following general formulas (I) and (II). the

[chemical 3]

In the above general formulas (I) and (II), [R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms (-C _n H _2n -), an alkylene group having 2 to 8 carbon atoms (C _n H _2n =), a ring having 5 to 15 carbon atoms Alkylene group (-C _n H _2n-2 -), cycloalkylene group having 5 to 15 carbon atoms (C _n H _2n-2 =), -S-, -SO-, -SO ₂ -, -O -, -CO-, or any one of the groups represented by the following formula (III-1) or the following formula (III-2).

[chemical 4]

R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms. Y represents a linear or branched alkylene group (-C _n H _2n -) having 2 to 15 carbon atoms. a to d are each an independent integer of 0 to 4, and n is an integer of 2 to 200, preferably an integer of 6 to 70.

The alkyl groups of R ¹ to R ⁴ may be linear or branched. Specific examples of alkyl groups for R ^{and R} include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, and isopentyl. , n-hexyl, isohexyl, etc.

Specific examples of the alkyl group for ^R3 and ^R4 include methyl, ethyl, n-propyl, and isopropyl.

In addition, R ¹ and R ² may be independently cyclic hydrocarbon groups such as cyclopentyl or cyclohexyl.

Examples of the alkylene group (-C _n H _2n -) having 1 to 8 carbon atoms in X include methylene, 1,2-ethylene, 1,3-propylene, 1,4 -Butylene, 1,5-pentylene, 1,6-hexylene, etc.

Examples of the alkylene group (C _n H _2n =) having 2 to 8 carbon atoms in X include ethylene group, isopropylidene group and the like.

Examples of the cycloalkylene group (-C _n H _2n-2 -) having 5 to 15 carbon atoms in X include cyclopentylene and cyclohexylene. Examples of the cycloalkylene group (C _n H _2n-2 =) having 5 to 15 carbon atoms in X include cyclopentylene and cyclohexylene. Examples of the dihydric phenol include compounds represented by the following general formula (Ia).

[Chemical 5]

R ¹ and R ² , a and b, and X in the general formula (Ia) are the same as above.

There are many kinds of dihydric phenols represented by the above general formula (Ia), and 2,2-bis(4-hydroxyphenyl)propane (commonly known as: bisphenol A) is particularly suitable. Examples of bisphenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiarylsulfides, Dihydroxydiarylsulfoxides, dihydroxydiarylsulfones, dihydroxydiphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes, in addition, bis(4- hydroxyphenyl) diphenylmethane, 4,4'-[1,3-phenylenebis(1-methylethylene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9 - Anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxopentene, and α,ω-dihydroxyphenylpolydimethylsiloxane compounds, etc. These dihydric phenols may be used alone or in combination of two or more. the

As the molecular weight regulator, any kind can be used as long as it is generally used for PC resin polymerization. Specifically, as a monohydric phenol, for example, phenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, o-tert-butyl phenylphenol, m-tert-butylphenol, p-tert-butylphenol, o-n-pentylphenol, m-n-pentylphenol, p-n-pentylphenol, o-n-hexylphenol, m-n-hexylphenol, p-n-hexylphenol, p-tert Octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-n-nonylphenol, m-nonylphenol, p-n-nonylphenol , o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,5-di-tert-butylphenol; 2,4-di-tert Butylphenol; 3,5-di-tert-butylphenol; 2,5-diisopropylphenol; 3,5-diisopropylphenol; p-cresol, bromophenol, tribromophenol, average carbon number 12 ~35 mono-alkylphenols with linear or branched alkyl groups in the ortho, meta or para positions; 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl )fluorene; 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene; 4-(1-adamantyl)phenol and the like. Among these monohydric phenols, p-tert-butylphenol, p-isopropylphenol, p-phenylphenol, etc. are preferably used. the

As the catalyst of the interfacial polymerization method, an interphase transfer catalyst, for example, a tertiary amine or a salt thereof, a quaternary ammonium salt, a quaternary phosphonium salt, or the like can be preferably used. Examples of tertiary amines include triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, dimethylaniline, etc. In addition, examples of tertiary amine salts include these tertiary Amine hydrochloride, bromate, etc. As the quaternary ammonium salt, for example, trimethylbenzyl ammonium chloride, triethylbenzyl ammonium chloride, tributyl benzyl ammonium chloride, trioctyl methyl ammonium chloride, tetrabutyl ammonium chloride, bromide Tetrabutylammonium etc., as a quaternary phosphonium salt, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, etc. are mentioned, for example. These catalysts may be used alone or in combination of two or more. Among the above catalysts, tertiary amines are preferred, especially triethylamine. the

There are many kinds of inert organic solvents. For example, dichloromethane; chloroform; carbon tetrachloride; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; , 2-trichloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane; chlorinated hydrocarbons such as chlorobenzene, toluene, benzene ethyl ketone etc. These organic solvents may be used alone or in combination of two or more. Among them, dichloromethane is particularly suitable. the

As a branching agent, for example, 1,1,1-tris(4-hydroxyphenyl)ethane; 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1- Methylethyl]phenyl]ethylene]bisphenol; α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene; 1-[α-methyl Base-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene; phloroglucinol, trimellitic acid, indigo Compounds with three or more functional groups such as red di(o-cresol). the

The phenol-modified diol used in the present invention is represented by the following general formula (IIa). the

[chemical 6]

In the general formula (IIa), in the formula, ^R3 and ^R4 each independently represent an alkyl group with 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group with 2 to 15 carbon atoms (- C _n H _2n -). c and d are each independent integers of 0-4, and n is an integer of 2-450.

Examples of the alkyl group represented by ^R3 and ^R4 include methyl, ethyl, n-propyl and isopropyl. When there are multiple ^R3s , the multiple ^R3s may be the same or different, and when there are multiple ^R4s , the multiple ^R4s may be the same or different. Examples of straight-chain or branched-chain alkylene groups (-C _n H _2n -) having 2 to 15 carbon atoms represented by Y include 1,2-ethylene, 1,3-propylene , 1,4-butylene, 1,4-isobutylene, 1,5-pentylene and 1,5-isopentylene and other alkylene groups (-C _n H _2n -), ethylene, Alkylene (C _n H _2n =) residues such as propylene, isopropylene, butylene, isobutylene, pentylene and isopentylene. n is preferably 2-200, more preferably 6-70.

The phenol-modified diol represented by the above-mentioned general formula (IIa) is esterified by hydroxybenzoic acid or its alkyl ester represented by the following general formula (IV) or general formula (V) and the polyether diol described later. Compounds derived from chemical reactions or transesterification reactions. the

[chemical 7]

[chemical 8]

In the above general formula (V) and general formula (IV), R ³ represents an alkyl group having 1 to 3 carbon atoms. c is an integer of 0-4. The alkyl group having 1 to 3 carbon atoms is the same as above.

In the general formula (V), R ⁴ represents an alkyl group having 1 to 3 carbon atoms. R ⁵ represents an alkyl group having 1 to 10 carbon atoms. d is an integer of 0-4. Examples of the alkyl group having 1 to 10 carbon atoms include n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, Octyl, 2-ethylhexyl, decyl, etc.

Examples of the hydroxybenzoic acid represented by the above general formula (IV) include p-hydroxybenzoic acid, m-hydroxybenzoic acid, ortho-hydroxybenzoic acid (salicylic acid), and those having 1 to 1 carbon atoms on their benzene rings. Substituted substances of the alkyl group of 3, etc. the

Representative examples of the alkyl esters of hydroxybenzoic acid represented by the above general formula (V) include methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate and n-propyl p-hydroxybenzoate. the

Polyether diol is represented by HO-(YO) _n -H [Y is the same as the group described in general formula (II)], and is composed of repeating straight-chain or branched-chain alkanes with 2 to 15 carbon atoms. base ether composition. Specifically, polyethylene glycol, polypropylene glycol, poly-1,4-butylene glycol, etc. are mentioned. From the viewpoint of easy availability and hydrophobicity, poly-1,4-butylene glycol is particularly preferable.

The repetition number n of the ether part of polyether diol is 2-200, Preferably it is 6-70. When n is 2 or more, the efficiency of copolymerization of phenol-modified diol is good, and when n is 70 or less, there is an advantage that the heat resistance of the PC copolymer decreases less. the

The esterification reaction or transesterification reaction of hydroxybenzoic acid or its alkyl ester and polyether diol is carried out in the presence of a tin catalyst. the

The usage-amount of a tin catalyst is about 0.01-10 mass % normally about hydroxybenzoic acid or hydroxybenzoic acid alkyl ester, Preferably it is about 0.05-5 mass %, More preferably, it is about 0.1-3 mass %. By being more than 0.01% by mass, sufficient reactivity can be obtained, and by being below 10% by mass, side reactions can be suppressed, and the amount of phosphoric acid aqueous solution or solid adsorbent used can be reduced to further reduce the resulting phenol modification. Tin content in diols. the

Refining is necessary for the phenol-modified diols obtained by these methods to reduce the tin content. Specifically, the tin content in the phenol-modified diol can be reduced by using a phosphoric acid aqueous solution or a solid adsorbent to wash the crude reaction liquid containing the phenol-modified diol. The above-mentioned interfacial polymerization method can obtain the polycarbonate copolymer of the present invention with a tin content (as an element) below 0.5 ppm. the

When treating with an aqueous phosphoric acid solution, the crude reaction product obtained by the esterification reaction or transesterification reaction can be diluted with phosphoric acid and an immiscible organic solvent, such as methylene chloride, and extracted from tin by liquid-liquid extraction. Catalyst-like tin compounds and other impurities are extracted into the phosphoric acid layer, thereby reducing the content of the target compound. The concentration of the phosphoric acid aqueous solution is preferably 0.5 to 40% by mass, more preferably 1.0 to 10% by mass, and most preferably 2 to 5% by mass. By making the phosphoric acid concentration 0.5% by mass or more, the extraction efficiency of impurities such as tin compounds can be ensured. By keeping the phosphoric acid concentration at 10% by mass or less, it is possible to prevent high-concentration phosphorous-containing wastewater from being generated and to protect the environment, and it is also possible to prevent unnecessary excessive use of phosphoric acid aqueous solution and economical decline. the

The volume of the phosphoric acid aqueous solution used is preferably 26% by volume or less of the total volume. When it is 26% by mass or less, since the organic layer is a dispersed phase and the aqueous phosphoric acid solution is a continuous phase during liquid-liquid extraction, it is possible to prevent a decline in the extraction efficiency of tin compounds derived from tin-based catalysts. The tin content (as an element) in the phenol-modified diol is 10 ppm or less, preferably 5 ppm or less. the

In the solid adsorbent treatment, the crude reaction product obtained by the esterification reaction or the transesterification reaction is diluted with an organic solvent such as methylene chloride, and the solid adsorbent is dispersed in it to adsorb impurities such as tin compounds derived from tin-based catalysts, In this way, the content of the target compound can be reduced. the

As the solid adsorbent, a composite adsorbent composed of activated clay, acid clay, ion exchange resin, chelate resin, activated carbon, silica, magnesia, alumina, etc. can be used. Commercially available products of the adsorbent include, for example, Mizukaraif F-2G (manufactured by Mizusawa Chemical Industry Co., Ltd., silica-magnesia-based adsorbent), Mizukaraif P-1 (manufactured by the above company, silica-magnesia-based adsorbent). Magnesium oxide-based adsorbent), Gareon Ass V2 (manufactured by the above-mentioned company, activated clay-based adsorbent), Mizukasorbu C-1 (manufactured by the above-mentioned company, silica-based adsorbent), SA-1 (Nippon Active Clay Co., Ltd. production, activated clay-based adsorbent), R15 (manufactured by Japan activated clay company, activated clay-based adsorbent), キヨ一ワ一ド KW700SL (manufactured by Kyowa Chemical Industry Co., Ltd., silica-alumina-based adsorbent), Bailu A ( Japan Enbiro Chemical Co., Ltd., activated carbon adsorbent), CR11 (manufactured by Japan Water Refining Co., Ltd., chelating resin). Mizukaraif F-2G (manufactured by Mizusawa Chemical Industry Co., Ltd.) and Mizukaraifu P-1 (same) are particularly preferable because they have excellent adsorption performance for tin compounds. the

When treating with a solid adsorbent, it is also possible to fill the column with a solid adsorbent and pass the crude reaction product through the packed layer to adsorb impurities such as tin compounds derived from the tin-based catalyst. the

It is also possible to properly reduce the pressure in the system at the later stage of the reaction to distill off excess raw materials (for example, hydroxybenzoic acid or its alkyl ester). the

In addition, in order to effectively remove impurity hydroxybenzoic acids, as the pretreatment of the above-mentioned phosphoric acid aqueous solution treatment or solid adsorbent treatment operation, it can also be extracted by weak alkali aqueous solution. the

The pH of the weak base aqueous solution is 8-11, preferably 8-10 is used. If the pH is lower than 8, the extraction of hydroxybenzoic acids will be insufficient, and if the pH exceeds 11, the comonomer will be hydrolyzed. the

As the weakly alkaline aqueous solution, aqueous solutions of hydroxides, carbonates, bicarbonates, etc. of alkali metals (sodium, potassium, etc.) or alkaline earth metals (magnesium, calcium, etc.) can be used. the

The treatment operation of phosphoric acid aqueous solution, the treatment operation of solid adsorbent and the extraction of weak base aqueous solution can be carried out at normal temperature, or can be carried out by heating to about 30-40°C. The treatment operation of the phosphoric acid aqueous solution, the treatment operation of the solid adsorbent, and the extraction treatment of the weak alkali aqueous solution can each be repeated multiple times. the

In the production process of the PC copolymer, it is preferable to use a dichloromethane solution as much as possible in order to prevent deterioration of the phenol-modified diol. When dichloromethane solution cannot be used, alkaline aqueous solution such as NaOH can be used. the

In the PC copolymer, increasing the copolymerization amount of phenol-modified diol will improve the fluidity, but the heat resistance will decrease. Therefore, the copolymerization amount of the phenol-modified diol is preferably selected according to a desired balance between fluidity and heat resistance. If the copolymerization amount of the phenol-modified diol exceeds 40% by mass, as shown in JP-A-62-79222, it will become an elastic body and may not be suitable for the same application as general PC resins. In order to maintain heat resistance above 100°C, the amount of phenol-modified diol residues contained in the PC copolymer is 1 to 30% by mass in the present invention, preferably 1 to 20% by mass, more preferably 1 to 15% by mass. quality%. the

The PC copolymer of the present invention has a relative viscosity of 30 to 71 [corresponding to Mv (viscosity average molecular weight) = 10,000 to 28,100], preferably 37 to 62 [corresponding to Mv = 13,100 to 24,100]. The same applies to the PC copolymer composition described later. When the relative viscosity is 30 or more, the mechanical properties are good, and when the relative viscosity is 70 or less, the copolymerization effect of the comonomer can be exhibited well. In addition, a large amount of comonomer is required to express high fluidity, and if the specific viscosity is 71 or less, the use of comonomer does not significantly reduce heat resistance. In addition, the relative viscosity is measured according to ISO1628-4 (1999). the

The PC copolymer of the present invention has a flow value (Q value) at 280°C of preferably not less than 30×10 ^-2 mL/sec, more preferably not less than 40×10 ^-2 mL/sec. The flow value (Q value) is the melt viscosity measured using an overhead flow rate detector in accordance with JIS K7210. When the flow value (Q value) is 30×10 ^-2 mL/s 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 this invention is a composition containing 0.01-0.5 mass parts of antioxidants with respect to 100 mass parts of PC copolymers. the

Examples of antioxidants include arylphosphines, phosphites, phosphoric acid esters, hindered phenols, and the like. the

In addition, the PC copolymer composition of the present invention may be a composition mixed with other PC resins having a tin content (as an element) of 0.5 ppm or less. the

In addition, when using these PC copolymer compositions for light guide plates, optical lenses, etc., in order to increase the light transmittance, it is preferable to add an acrylic resin with a molecular weight of about 1,000 to 100,000, and it is more preferable to add an acrylic resin in addition to the acrylic resin. , A PC-based resin composition containing an alicyclic epoxy compound or one or more polysiloxane compounds selected from the group consisting of alkoxy groups, vinyl groups, and phenyl groups. the

As other PC resins added to the PC copolymer of the present invention, commercially available resins having a tin content (as an element) of 0.5 ppm or less can be used. The amount of other PC resins added is preferably 300 parts by mass or less, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the PC copolymer, from the viewpoint of not impairing the effects of the present invention. the

Acrylic resin refers to a polymer with at least one monomer unit selected from acrylic acid, acrylate, acrylonitrile and its derivatives as a repeating unit, and is a polymer alone or combined with styrene, butadiene, etc. copolymer. Specifically, polyacrylic acid, polymethyl methacrylate (PMMA), polyacrylonitrile, ethyl acrylate-2-chloroethyl acrylate copolymer, n-butyl acrylate-acrylonitrile copolymer, acrylonitrile- Styrene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, etc. Among them, polymethyl methacrylate (PMMA) is particularly suitably used. the

The molecular weight of the propylene resin is about 1000-100,000, preferably 20,000-60,000. If the molecular weight is 1,000 to 100,000, the phase separation between the PC copolymer, other PC resins, and propylene-based resins will not occur too quickly during molding, so the molded products have sufficient transparency. As polymethyl methacrylate (PMMA), known substances can be used, and in general, it is preferable to perform bulk polymerization of methyl methacrylate monomer in the presence of peroxides and azo-based polymerization initiators And manufacture. the

The amount of the propylene-based resin added is usually about 0.01 to 1 part by mass for 100 parts by mass of the PC copolymer of the present invention or a PC copolymer composition in which other PC resins are mixed in the PC copolymer of the present invention. Preferably it is 0.05-0.5 mass part, More preferably, it is 0.1-0.3 mass part. When the amount of the propylene-based resin added is 0.01 parts by mass or more, the transparency of the molded article can be improved, and if it is 1 part by mass or less, the transparency can be maintained without impairing other desired physical properties. the

As an alicyclic epoxy compound, it refers to a cycloaliphatic compound having an alicyclic epoxy group, that is, an epoxy group obtained by adding an oxygen atom to a vinyl bond in an aliphatic ring, specifically The ones represented by the following formulas (1) to (10) shown in JP-A-11-158364 are applied. the

[Chemical 9]

[chemical 10]

[chemical 11]

In the general formulas (2) and (3), R is a hydrogen atom or a methyl group. the

[chemical 12]

[chemical 13]

In general formula (5), a and b are each an integer of 0-10, and a+b is an integer of 1-10. the

[chemical 14]

In general formula (6), a, b, c, and d are each an integer of 0-10, and a+b+c+d is an integer of 1-10. the

[chemical 15]

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

[chemical 16]

In general formula (8), n is an integer of 1-10. the

[chemical 17]

In the general formula (9), R is a hydrogen atom or the above-mentioned alkyl group having 1 to 6 carbon atoms. the

[chemical 18]

In general formula (10), n is an integer of 1 to 10, and R is a residue of a compound having an active hydrogen group such as trimethylolpropane. the

The addition amount of each said alicyclic epoxy compound is about 0.01-1 mass part normally with respect to 100 mass parts of PC copolymer compositions, Preferably it is 0.02-0.2 mass part. By making this addition amount more than 0.01 parts by mass, the effect of addition can be obtained, and by making it less than 1 part by mass, phase separation will not occur and transparency will be obtained. the

The polysiloxane compound is a reactive silicon compound that introduces at least one functional group selected from alkoxy (for example, methoxy, ethoxy), vinyl and phenyl in a silicon compound, such as There are polyorganosiloxane, etc. This polysiloxane compound is a compound that functions as a stabilizer in the PC resin composition. Adding a polysiloxane compound can prevent yellowing caused by thermal deterioration during molding, and appearance of silver (silver bars) etc. Defective, air bubbles mixed. The amount of the polysiloxane compound added is usually about 0.01 to 3 parts by mass, preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the polycarbonate copolymer. If it is 0.01 parts by mass or more, the effect of addition can be exhibited, and if it is less than 3 parts by mass, cloudiness or the like will not occur in molded products. the

In addition to the above-mentioned components, various additives may be added to the resin composition of the present invention as needed within a range not impairing the effects of the present invention. For example, UV absorbers such as benzotriazoles and benzophenones; photostabilizers such as hindered amines; aliphatic carboxylic acid esters, paraffins, silicone oils, polyvinyl waxes, etc. Lubricants; commonly used flame retardants, flame retardant additives, release agents, antistatic agents, colorants, etc. the

Example

The present invention will be further specifically described below through examples and comparative examples, but the present invention is not limited to these examples. In addition, the amount of impurities in each example was measured by the following method. the

[Production Example 1 - Synthesis of poly-1,4-butanediol-bis(4-hydroxybenzoate)]

Nitrogen gas is introduced into a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a raw material supply port, and a gas introduction pipe, and 100 parts by mass of poly-1,4-butanediol [PTMG, Mn (number average molecular weight)=2000 ], 15.8 parts by mass of methyl p-hydroxybenzoate, and 0.05 parts by mass of dibutyltin oxide as a tin-based catalyst were heated to 220° C., and transesterification was carried out while distilling off the generated methanol. After completion of the reaction, the inside of the reaction system was reduced in pressure, and excess methyl p-hydroxybenzoate was distilled off to obtain a crude reaction product. the

The crude reaction product was dissolved in dichloromethane to obtain a solution having a concentration of 20% by mass. In 80 parts by volume of this dichloromethane solution, add 20 parts by volume of 0.1 mol% aqueous sodium bicarbonate solution, stir and mix for 30 minutes at 20°C in a stirring tank with a baffle, and the impurities generated by the aqueous phase extraction reaction para-hydroxy Benzoic acid is then separated by standing, taking the dichloromethane phase. the

In the dichloromethane phase of 75 parts by volume, add 25 parts by volume of 3.5% by mass aqueous phosphoric acid solution, stir and mix for 180 minutes at 20° C. in a stirring tank with a baffle, extract the tin compound derived from the tin catalyst in the aqueous phase, and then Separated by standing, the dichloromethane phase was taken. the

In the dichloromethane phase of 75 parts by volume again, add 25 parts by volume of 3.5% by mass phosphoric acid aqueous solution, stir and mix for 180 minutes at 20° C. in a stirring tank with a baffle, and extract the tin compound derived from the tin catalyst in the aqueous phase, It was then separated by standing and the dichloromethane phase was taken. the

In order to remove trace amounts of phosphoric acid in the dichloromethane phase, add 25 parts by volume of pure water to 75 parts by volume of the dichloromethane phase, stir and mix for 60 minutes at 20°C in a stirring tank with a baffle, and extract phosphoric acid in the water phase, It was then separated by standing and the dichloromethane phase was taken. the

The dichloromethane phase was concentrated under reduced pressure to obtain a phenol-modified diol, namely poly-1,4-butanediol-bis(4-hydroxybenzoate) [hereinafter referred to as PTMG-BHB]. the

By the following HPLC (high performance liquid chromatography) quantification, quantification of tin, and quantification of phosphate ions, it was confirmed that p-hydroxybenzoic acid in PTMG-BHB was less than 10 mass ppm, methyl p-hydroxybenzoate was 0.2 mass%, tin (as an element, the same below) is less than 2 ppm, and phosphorus (as an element, the same below) is 3 ppm. the

[Production Example 2 - Synthesis of poly-1,4-butanediol-bis(4-hydroxybenzoate)]

PTMG-BHB was obtained in the same manner as in Production Example 1, except that poly-1,4-butanediol (Mn=1000) was used instead of PTMG of Mn=2000 and methyl p-hydroxybenzoate was 31.6 parts by mass. By the following HPLC (high performance liquid chromatography) quantification, quantification of tin, and quantification of phosphate ions, it was confirmed that p-hydroxybenzoic acid in PTMG-BHB was less than 10 mass ppm, methyl p-hydroxybenzoate was 0.2 mass%, tin It is less than 2 ppm, and phosphorus is less than 2 ppm. the

[Manufacturing example 3]

Except having used 1.0 mass % phosphoric acid aqueous solution instead of 3.5 mass % phosphoric acid aqueous solution, it carried out similarly to manufacture example 1, and obtained PTMG-BHB. By the following HPLC (high performance liquid chromatography) quantification, quantification of tin, and quantification of phosphate ions, it was confirmed that p-hydroxybenzoic acid in PTMG-BHB was less than 10 mass ppm, methyl p-hydroxybenzoate was 0.2 mass%, tin It is 10ppm, and phosphorus is less than 2ppm. the

[Manufacturing example 4]

Except having made 5.0 mass % phosphoric acid aqueous solution instead of 3.5 mass % phosphoric acid aqueous solution, it carried out similarly to manufacture example 1, and obtained PTMG-BHB. By the following HPLC (high performance liquid chromatography) quantification, quantification of tin, and quantification of phosphate ions, it was confirmed that p-hydroxybenzoic acid was less than 10 mass ppm, methyl p-hydroxybenzoate was 0.2 mass%, tin was 5 ppm, and phosphorus was 4ppm. the

[Manufacturing example 5]

The operation until excess methyl p-hydroxybenzoate was distilled off was the same as in Example 1 to obtain a crude reaction product. the

The crude reaction product was dissolved in dichloromethane to prepare a solution with a concentration of 20% by mass, and 5% by mass of Mizukaraifu F-2G (manufactured by Mizusawa Chemical Industry Co., Ltd.) was added thereto, stirred and mixed at 20° C. for 3 hours, and the tin compound was adsorbed. Then, filter under reduced pressure using a membrane filter with a pore size of 0.2 μm, and filter F-2G. the

In 80 parts by volume of the resulting dichloromethane solution, add 20 parts by volume of 0.1 mol% sodium bicarbonate aqueous solution, stir and mix for 30 minutes at 20°C in a stirring tank with a baffle, and extract the impurities generated in the reaction by aqueous phase That is, p-hydroxybenzoic acid is then separated by standing to take the dichloromethane phase. the

In order to remove traces of sodium in the dichloromethane phase, add 25 parts by volume of pure water to the 75 parts by volume of dichloromethane phase, stir and mix for 60 minutes at 20°C in a stirring tank with a baffle, extract the sodium in the aqueous phase, and then Separated by standing, the dichloromethane phase was taken. the

The dichloromethane phase was concentrated under reduced pressure to obtain a phenol-modified diol, namely PTMG-BHB. By the following HPLC (high performance liquid chromatography) quantification and tin quantification, it was confirmed that p-hydroxybenzoic acid in PTMG-BHB was less than 10 mass ppm, methyl p-hydroxybenzoate was 0.2 mass%, and tin was 5 ppm. the

[Manufacturing example 6]

PTMG-BHB was obtained in the same manner as in Production Example 1, except that the tin compound derived from the tin-based catalyst was not extracted using an aqueous phosphoric acid solution. By the following HPLC (high performance liquid chromatography) quantification and tin quantification, it was confirmed that p-hydroxybenzoic acid in PTMG-BHB was less than 10 mass ppm, methyl p-hydroxybenzoate was 0.3 mass%, and tin was 190 ppm. the

[Manufacturing example 7]

Except having made 0.5 mass % phosphoric acid aqueous solution instead of 3.5 mass % phosphoric acid aqueous solution, it carried out similarly to manufacture example 1, and obtained PTMG-BHB. By the following HPLC (high performance liquid chromatography) quantification and quantification of tin, it was confirmed that p-hydroxybenzoic acid in PTMG-BHB was less than 10 mass ppm, methyl p-hydroxybenzoate was 0.3 mass%, tin was 70 ppm, and phosphorus was Less than 2ppm. the

<HPLC (high performance liquid chromatography) quantification>

Quantification was performed by HPLC (high performance liquid chromatography) under the following conditions, based on a calibration curve prepared from standard products of p-hydroxybenzoic acid and p-hydroxybenzoic acid methyl ester. the

(Chromatograph) column: ODS-3 manufactured by GL Cyence Co., Ltd.

(Chromatography) column temperature: 40°C

Solvent: a mixture of 0.5% by mass phosphoric acid aqueous solution and acetonitrile (volume ratio 1:2)

Flow rate: 1.0ml/min

<Quantitative amount of tin in comonomer>

(1) Pretreatment of samples

Weigh 1.0g of PTMG-BHB in a platinum (Pt) crucible, add 0.8ml of concentrated sulfuric acid, let it heat and dry, then treat it at 550°C for 10 hours, and ash it. the

Add 0.5 g of potassium hydrogen sulfate, heat with a combustion furnace, add 3 ml of 6 mol/l hydrochloric acid, and heat to decompose and dissolve the ash. the

(2) Determination

After the above-mentioned acid decomposition solution was left to cool, the solution was constant volume to 25ml, and then diluted 5 times, and this solution was manufactured in an ICP-OES (high-frequency inductively coupled plasma luminescent spectroscopic analysis) device (Esairiai NanoTechnologi Co., Ltd., SPS5100) quantification. Luminescence spectroscopic analysis is based on JIS K0116. the

<The quantification of tin in polycarbonate>

(1) Pretreatment of samples

Weigh 3.0 g of polycarbonate in a platinum dish, add 3.0 ml of concentrated sulfuric acid, heat and dry it, then treat it at 550° C. for 10 hours, and ash it. the

Add 0.1g of lithium tetraboric anhydride and lithium fluoride at a mass ratio of 9:1, and treat at 930°C for 30 minutes, then add 15ml of tartaric acid in nitric acid (mix and dissolve 5g of tartaric acid, 40ml of nitric acid, and 500ml of water, then add water, the overall constant volume is 1000ml), heated and stirred to prepare an alkali-dissolving solution. the

(2) Determination

After the above alkaline solution was left to cool, the volume was adjusted to 25 ml, and then diluted 2.5 times, and the solution was quantified by ICP-OES (manufactured by Esairai Nanotechnology Co., Ltd., SPS5100). Luminescence spectroscopic analysis is based on JIS K0116. the

<Quantification of Phosphorus>

10 g of PTMG-BHB was weighed using a Teflon (registered trademark) ski-bolt with a capacity of 200 ml. the

Add 100ml of refined dichloromethane ( ^* 1), shake to dissolve PTMG-BHB. Add 10ml of pure water, vibrate at a speed of 240 times/min for 30 minutes with a vibrator, and extract the phosphate ions in the sample into the water.

The organic layer and the aqueous layer were separated by standing, and then the aqueous layer was collected, and the amount of phosphate ions was quantified by an ion chromatograph (manufactured by Dionex Corp., DX-120). As the standard solution, phosphoric acid standard solution was used. the

The ion chromatogram is based on JIS K0127. the

^* Purification of dichloromethane: dichloromethane and pure water were shaken in a Teflon (registered trademark) ski blot, and the dichloromethane was washed with pure water. This was done until the ion chromatographic device analyzed the extracted water and phosphate ions were no longer detected. The obtained dichloromethane was used as purified dichloromethane.

[Example P-1]

(1) Polycarbonate (PC) oligomer synthesis process

In an aqueous solution of sodium hydroxide having a concentration of 5.6% by mass, 2,000 ppm by mass of sodium dithionite was added to bisphenol A (BPA) to be dissolved later, and BPA was dissolved in this solution so that the concentration of BPA was 13.5% by mass to prepare BPA. aqueous sodium hydroxide solution. In a tubular reactor with an internal diameter of 6mm and a tube length of 30m, the aqueous sodium hydroxide solution and dichloromethane of the above-mentioned BPA were continuously fed into the above-mentioned BPA at a flow rate of 40l/hour and 15l/hour respectively, and simultaneously with a flow rate of 4.0kg/hour. into carbonyl chloride. The tubular reactor has a jacket part, and cooling water is passed into the jacket to keep the temperature of the reaction solution below 40°C. the

The reaction solution sent from the tubular reactor is continuously introduced into a tank reactor with a retreating wing, an internal volume of 40l, and a baffle plate, and then supplies the aqueous sodium hydroxide solution of BPA at a flow rate of 2.8l/hour, at a rate of 0.07l/ A 25% by mass sodium hydroxide aqueous solution was supplied at an hourly flow rate, water was supplied at a flow rate of 17 l/hour, and a 1 mass% triethylamine aqueous solution was supplied at a flow rate of 0.64 l/hour, and the reaction was performed at 29 to 32°C. Continuously extract the reaction solution from the tank reactor, let it stand still to separate and remove the water phase, and collect the dichloromethane phase. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 329 g/l and a chloroformate group concentration of 0.74 mol/l. the

(2) Polymerization process of PC copolymer

Supply to T.K PIPELINE HOMO MIXER 2SL type (manufactured by Primix Corporation) at a flow rate of 20 liters/hour: PC oligomer obtained in the above synthesis process, methylene chloride at a flow rate of 12 liters/hour, synthesis example of 868 kg/hour 1 The 40 mass % methylene chloride solution of the obtained PTMG-BHB, the 3 mass % triethylamine aqueous solution of 400 ml/hour flow rate, and the 6.4 mass % sodium hydroxide aqueous solution of 2.3 kg/ hour flow rate are prepared under the rotating speed of 3000 rpm Polymerize to obtain a preliminary polymerization solution. the

Next, to the T.K PIPELINE emulsifying homogenizer 2SL type (manufactured by Primix Corporation): 960 g/hour flow rate of the preliminary polymerization solution and PTBP (p-tert-butylphenol) 20% by mass dichloromethane solution; 14.1 kg/hour flow rate An aqueous solution obtained by dissolving BPA in a 6.4% by mass sodium hydroxide aqueous solution so as to have a concentration of 8.8% by mass. Emulsification was carried out at a rotational speed of 3000 rpm to obtain an emulsion. Next, the emulsion is introduced into the second reactor, which is equipped with a jacket, and has two orifice plates with three holes with a diameter of 0.8 mm inserted into a 19.05 mm (3/4 inch) pipe. The reactor was supplied to the third reactor, which was a tower-type stirred tank with a jacketed 50 l paddle-blade three-stage, and polymerized. Cooling water at 15°C flows through the jacket, and the outlet temperature of the polymerization solution is set at 30°C. the

To a 50-liter dilution tank equipped with paddle-type stirring blades, the polymerization liquid overflowed from the above-mentioned tower reactor and dichloromethane for dilution were continuously supplied at a flow rate of 11 liters/hour. Next, the emulsion obtained by the dilution tank is introduced into a K.C.C centrifugal extractor (trade name, manufactured by Kawasaki Heavy Industries, with an internal volume of 4 l and a rotor diameter of 430 mm), and centrifugal extraction is carried out at 3000 rpm to separate the aqueous layer and the organic layer. the

(3) Alkali cleaning process

Supply to T.K PIPELINE emulsifying homogenizer 2SL type (manufactured by Primix Corporation) at a flow rate of 7.8 l/hour: the organic layer obtained by the above-mentioned centrifugal extractor and 0.03 mol/l sodium hydroxide aqueous solution are stirred and mixed at a rotation speed of 3000 rpm . From the outlet of the emulsification homogenizer, the mixed solution is introduced into a centrifugal extractor, and the centrifugal extraction is carried out at a speed of 3000 rpm, and the aqueous layer and the organic layer are separated. Next, the emulsion obtained by the dilution tank is introduced into a K.C.C centrifugal extractor (trade name, manufactured by Kawasaki Heavy Industries, with an internal volume of 4 liters and a rotor diameter of 430 mm), and centrifugal extraction is carried out at 3000 rpm to separate the aqueous layer and the organic layer, and the organic layer is then Supplied to the pickling process. the

(4) Pickling process

Supply to T.K PIPELINE Emulsifying Homogenizer 2SL (manufactured by Primix Corporation) at a flow rate of 7.8 l/hour: The organic layer obtained from the centrifugal extractor in the alkali cleaning process and 0.2 mol/l hydrochloric acid aqueous solution are carried out at a rotation speed of 3000 rpm Stir to combine. The mixed solution was introduced from the outlet of the emulsification homogenizer into a static separation tank, and the water layer and the organic layer were separated, and the organic layer was then supplied to the first water washing step. the

(5) The first washing process

The organic layer obtained from the centrifugal extractor and pure water were supplied to T.K PIPELINE emulsifying homogenizer 2SL type (manufactured by Primix Co., Ltd.) at 7.8 l/hour, and stirred and mixed at a rotation speed of 3000 rpm. The mixed liquid was introduced into a centrifugal extractor from the outlet of the emulsification homogenizer, and centrifugal extraction was performed at 3000 rpm to separate the aqueous layer and the organic layer, and the organic layer was then supplied to the second water washing step. the

(6) The second washing process

The organic layer obtained from the centrifugal extractor and pure water were supplied to T.K PIPELINE emulsifying homogenizer 2SL type (manufactured by Primix Co., Ltd.) at 7.8 l/hour, and were stirred and mixed at a rotation speed of 3000 rpm. From the outlet of the emulsification homogenizer, the mixed solution is introduced into the centrifugal extractor, and the centrifugal extraction is carried out with a rotating speed of 3000rpm, and the aqueous layer and the organic layer are separated to obtain a dichloromethane solution (organic layer) of refined polycarbonate. the

(7) Concentration and drying process

The dichloromethane solution of the purified polycarbonate was concentrated and pulverized, and the obtained flakes were dried at 105° C. under reduced pressure. The properties of the obtained polycarbonate copolymer were as follows. The amount of PTMG-BHB residues determined by NMR was 4.0% by mass. The relative viscosity measured according to ISO 1628-4 (1999) is 37.0 (Mv=13100). the

[Embodiment P-2]

With the 40 mass % dichloromethane solution 434kg/ hour flow rate of the PTMG-BHB that manufacture example 2 obtains, replace the 40 mass % methylene chloride solution 868kg/ hour flow rate of the PTMG-BHB that manufacture example 1 obtains, in addition with embodiment In the same manner as P-1, a polycarbonate copolymer was obtained. the

[Example P-3～P-5 and comparative example P-1, P-2]

A polycarbonate copolymer was obtained in the same manner as in Example P-1 except that the PTMG-BHB obtained in Production Examples 3 to 7 was used instead of the PTMG-BHB obtained in Production Example 1. Table 1 shows the physical properties of the polycarbonate copolymers obtained in Examples P-1 to P-5 and Comparative Examples P-1 and P-2. the

[Table 1]

Table 1

the Residue amount (mass%) Relative 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

[Application example 1]

Mix 100 parts by mass of the polycarbonate copolymer obtained in Example P-1, 0.05 parts by mass of ADEKA STAP PEP-36 (trade name, manufactured by ADEKA Corporation) as an antioxidant, and extrude through a 40mm diameter port equipped with a vent hole (outlet). machine, and granulate at a resin temperature of 260°C to obtain granules. Using the obtained pellets, a flat plate of 35 mm x 25 mm x 2 mm was injection molded according to the following molding conditions. the

<forming conditions>

Forming machine: manufactured by Toshiba Machine Co., Ltd., EC40N (trade name)

Forming barrel temperature: 340°C

Retention time in cylinder: 10 minutes

Five molded articles after the 13th shot were collected, and the yellowness index (YI) was measured for each, and the average value was obtained. The results are shown in Table 2. The method of measuring YI is as follows. the

<YI>

A molded product having a thickness of 2.0 mm was produced by injection molding, and measured by a transmission method with a measurement area of 30φ and a C2 light source with a spectrophotometer Σ90 manufactured by Nippon Denshoku Industries Co., Ltd. the

[Application example 2~5]

Mix 75 parts by mass of the polycarbonate copolymer obtained in Examples P-2 to P-5, 25 parts by mass of Tufflon FN1500 (trade name, Bis-A polycarbonate manufactured by Idemitsu Kosan Co., Ltd., VN=39.5), 0.05 parts by mass of Adecastab PEP-36 (trade name, manufactured by ADEKA Corporation) as an antioxidant was pelletized at a resin temperature of 260° C. through a 40 mmφ extruder equipped with a vent hole (outlet) to obtain pellets. Others are the same as in application example 1, YI is measured. the

[Applied Comparative Example 1~2]

Pellets were obtained and YI was measured in the same manner as in Application Example 1 except that the polycarbonate copolymers obtained in Comparative Examples P-1 to P-2 were used instead of the polycarbonate copolymers obtained in Example P-1. the

[Application example 6]

Mix 75 parts by mass of the polycarbonate copolymer obtained in Example P-1, 25 parts by mass of Teflon FN1500 (trade name, Bis-A polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd., VN=39.5), 0.05 parts by mass of As an antioxidant, Adecastab PEP-36 (trade name, manufactured by ADEKA Corporation), 0.1 parts by mass of DYANA BR83 (trade name, manufactured by Mitsubishi Rayon Co., acrylic resin, molecular weight 40000), 0.1 parts by mass of KR511 ( Trade name, manufactured by Shin-Etsu Silicone Co., Ltd., organosiloxane having a methoxy group and a vinyl group), 0.05 parts by mass of Ceroxide 2021P (trade name, manufactured by Daicel Chemical Co., Ltd., an alicyclic compound represented by the above formula (1) Epoxy resin) was pelletized at a resin temperature of 260° C. through a 40 mmφ extruder equipped with a vent hole (outlet) to obtain pellets. the

Using the obtained pellets, YI was measured in the same manner as in Application Example 1. YI is 0.9. the

[Table 2]

Table 2

the 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 Comparative Example 1 2.3 Application Comparative Example 2 1.7

industry availability

The molded article of the polycarbonate copolymer with a low tin content obtained by the present invention is suitable for use in the field of transparent optical components, especially optical components such as lenses, light guides, and optical discs. the

Claims (4)

1. a Copolycarbonate is characterized in that,

It possess following general formula (I) and (II) shown in repeating unit, form below 0.5ppm and by the interfacial polymerization copolymerization as the content of the tin of element,

[changing 1]

In the formula, R ¹And R ²The alkyl that represents independently of one another carbonatoms 1～6, X represent the alkylidene group-C of singly-bound, carbonatoms 1～8 _nH _2n-, the alkylidene group C of carbonatoms 2～8 _nH _2n=, the ring alkylidene group-C of carbonatoms 5～15 _nH _2n-2-, the ring alkylidene group C of carbonatoms 5～15 _nH _2n-2=,-S-,-SO-,-SO ₂-,-O-,-any one of the group shown in CO-or following formula (III-1) or the following formula (III-2),

[changing 2]

R ³And R ⁴The alkyl that represents independently of one another carbonatoms 1～3, Y represent the straight chain of carbon atom quantity 2～15 or contain the alkylidene group-C of side chain _nH _2n-, a～d is 0～4 integer independently of one another, n is 2～200 integer,

The amount of contained phenol modification diol residue is 1～30 quality % in the multipolymer,

And described multipolymer is 30～71 according to the reduced viscosity that ISO 1628-4 (1999) measures.

2. the manufacture method of Copolycarbonate claimed in claim 1, it is characterized in that, as comonomer, what use is phenol modification glycol synthetic in the presence of tin class catalyzer, that processed with phosphate aqueous solution or solid adsorbent, and in the described phenol modification glycol as the content of the tin of element below 10ppm.

3. poly carbonate resin composition wherein, contains the Copolycarbonate of claim 1 of 100 mass parts and the oxidation inhibitor of 0.01～0.5 mass parts.

4. molding that is shaped and forms by resin combination claimed in claim 3.