JP2005060541A - Polycarbonate copolymer and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate copolymer having excellent heat resistance, excellent rigidity and improved hue. <P>SOLUTION: The polycarbonate copolymer powder composed of a polycarbonate copolymer the whole aromatic hydroxy components of which comprise 5-95 mol% fluorene-based bisphenol represented by general formula [1] [wherein, R<SP>1</SP>to R<SP>4</SP>are each independently a hydrogen atom, a 1-9C hydrocarbon group which may contain an aromatic group, or a halogen atom] and 95-5 mol% dihydroxy component represented by general formula [2] [wherein, R<SP>5</SP>to R<SP>8</SP>are each independently a hydrogen atom, a 1-9C hydrocarbon group which may contain an aromatic group, or a halogen atom; W is a single bond, a 1-20C hydrocarbon group which may contain an aromatic group, or O, S, SO, SO<SB>2</SB>, CO or COO group] is regulated so that the b-value of the solution obtained by dissolving 5 g powder of the polycarbonate copolymer in 50 ml methylene chloride in a shaded state may be ≤5.0. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polycarbonate resin having a good hue. More specifically, the present invention relates to a polycarbonate copolymer having excellent heat resistance and rigidity and improved hue.

  Conventionally, polycarbonate resins obtained by reacting bisphenol A with a carbonate precursor have been widely used in many fields as engineering plastics because of their excellent transparency, heat resistance, mechanical properties, and dimensional stability. 2. Description of the Related Art In recent years, the light and thin size of processed molded articles has progressed, and a polycarbonate resin having further improved heat resistance and rigidity has been demanded.

  In order to improve the heat resistance and rigidity of the polycarbonate resin, there is generally a method using bisphenols having a bulky structure that is difficult to move, and various polycarbonate resins have been proposed. Among them, a polycarbonate resin having a specific fluorene structure has been proposed (see, for example, Patent Documents 1 and 2). However, the polycarbonate resin having these structures is remarkably easily colored during the polymerization reaction, so that there is a problem that the hue of the molded product is yellowish.

Methods for solving this include a method of irradiating a polymer solution with visible light (see Patent Document 3) and a method of adding a metal deactivator and / or an active hydrogen-containing compound to the polymer solution (see Patent Document 4). Although proposed, these methods can improve the color of the film produced by the solution color and casting method, but can be applied to a molding method that gives a thermal history (injection molding method, compression molding method, melt extrusion method). When the molded product was prepared by the method, etc., the hue of the molded product could not be improved.
JP-A-11-174424 JP-A-8-134198 JP 2002-080580 A JP 2002-080734 A

  An object of the present invention is to provide a polycarbonate resin having excellent heat resistance, rigidity and good hue. Good hue is preferable for using the resin for optical path conversion parts such as lenses, prisms and optical fibers, reflow soldering parts, and optical members such as optical disks. Moreover, it is preferable also when giving arbitrary colors to resin.

  As a result of intensive research aimed at achieving this object, the present inventor achieved the above object by controlling the conditions for producing a polycarbonate copolymer using a specific dihydric phenol within a specific range. The present invention has been found.

  That is, according to the present invention, 5 to 95 mol% of the wholly aromatic dihydroxy component is represented by the following general formula [1],

［式中、Ｒ^１〜Ｒ^４は夫々独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲン原子である。］で表されるフルオレン系ビスフェノール、好ましくは９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９５〜５モル％が下記一般式［２］

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ], Preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 95 to 5 mol% is represented by the following general formula [2]

［式中、Ｒ^５〜Ｒ^８は夫々独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲンであり、Ｗは単結合、炭素原子数１〜２０の芳香族基を含んでもよい炭化水素基、Ｏ、Ｓ、ＳＯ、ＳＯ_２、ＣＯ又はＣＯＯ基である。］
で表されるジヒドロキシ成分からなるポリカーボネート樹脂であって、該ポリカーボネート樹脂のパウダー５ｇを塩化メチレン５０ｍｌに遮光状態にて溶解した溶液のｂ値が５．０以下であることを特徴とするポリカーボネート共重合体が提供される。溶液のｂ値は４．０以下であることが好ましく、更に好ましくは３．５以下である。

[Wherein, R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 9 carbon atoms, or a halogen, and W is a single bond, having 1 to 20 carbon atoms. Or a hydrocarbon group, O, S, SO, SO ₂ , CO or COO group which may contain an aromatic group. ]
A polycarbonate resin comprising a dihydroxy component represented by the formula (1), wherein a b value of a solution obtained by dissolving 5 g of the polycarbonate resin powder in 50 ml of methylene chloride in a light-shielded state is 5.0 or less. Coalescence is provided. The b value of the solution is preferably 4.0 or less, more preferably 3.5 or less.

  The aromatic polycarbonate copolymer of the present invention has 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as an aromatic dihydroxy component constituting it, 5 to 95 mol% of the total aromatic dihydroxy component, Preferably it is 10-95 mol%, More preferably, it is 30-85 mol%. If it is less than 5 mol%, it is not preferable because it is an unsatisfactory property as a heat-resistant material which is the object of the present invention.

  The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has a b value of preferably 6.0 or less, more preferably 5. measured by measuring a solution of 10 g in 50 ml of ethanol at an optical path length of 30 mm. 5 or less, more preferably 5.0 or less. When the b value is within the above range, a molded product formed from the obtained polycarbonate copolymer has a high hue and strength, and a stretched film property is also preferable.

  The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is usually obtained by the reaction of o-cresol and fluorenone. The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene having the specific b value can be obtained by performing a specific treatment to remove impurities. Specifically, after the reaction between o-cresol and fluorenone, unreacted o-cresol is distilled off, and the residue is dissolved in an alcohol, ketone, or benzene derivative solvent, and activated clay or activated carbon is added thereto. In addition, after filtration, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene purified by filtering the product crystallized from the filtrate can be obtained. Examples of impurities to be removed include 2,4′-dihydroxy form, 2,2′-dihydroxy form and impurities whose structure is unknown. The alcohol solvent used for such purification is preferably a lower alcohol such as methanol, ethanol, propanol or butanol, and the ketone solvent is preferably a lower aliphatic ketone such as acetone, methyl ethyl ketone, methyl isopropyl ketone or cyclohexanone and a mixture thereof. As the benzene derivative solvent, toluene, xylene, benzene and a mixture thereof are preferable. The amount of the solvent used is sufficient if the fluorene compound is sufficiently dissolved, and is usually about 2 to 10 times the amount of the fluorene compound. As the activated clay, a commercially available powdery or granular silica-alumina main component is used. Further, as the activated carbon, commercially available powdery or granular materials are used.

  The other dihydroxy component represented by the above general formula [2] used in the aromatic polycarbonate copolymer of the present invention may be any one that is usually used as a dihydroxy component of an aromatic polycarbonate. For example, hydroquinone, resorcinol 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4- Hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4- Droxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, α, α'-bis ( 4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, and the like. Among them, bisphenol A, bisphenol Z, bisphenol C, bisphenol E, Bisphenol M is preferred, and bisphenol A is particularly preferred.

  The aromatic polycarbonate copolymer preferably has a specific viscosity at 20 ° C. in a solution of the polymer in methylene chloride in the range of 0.2 to 1.2, more preferably in the range of 0.25 to 1.0. The range of .27 to 0.80 is more preferable. If the specific viscosity is within the above range, the strength of the molded product, particularly the sheet, is sufficiently strong, the melt viscosity and the solution viscosity are appropriate, and handling is easy and preferable.

  The polycarbonate copolymer of the present invention is produced by a reaction means known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. Next, basic means for these manufacturing methods will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Before using these solvents, it is necessary to remove oxygen in the solvent by adding nitrogen or the like or adding a reducing agent. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. During the reaction, it is necessary to always remove oxygen in the reaction solution by adding a reducing agent such as a method of blowing nitrogen or hydrosulfite. Further, it is necessary to carry out nitrogen aeration in the purification process.

  The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning.

  Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the aromatic polycarbonate copolymer of the present invention, monofunctional phenols that are usually used as a terminal terminator can be used in the polymerization reaction. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for molecular weight control, and the resulting aromatic polycarbonate copolymer has a monofunctional end. Since it is blocked by a group based on phenols, it is superior in thermal stability compared to other groups.

  Such monofunctional phenols only need to be used as a terminal terminator for aromatic polycarbonate resins, and are generally phenols or lower alkyl-substituted phenols, and monofunctional phenols represented by the following general formula: Can show.

［式中、Ａは水素原子、炭素数１〜９の直鎖または分岐のアルキル基あるいはアリールアルキル基であり、ｒは１〜５、好ましくは１〜３の整数である。］

[Wherein, A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or an arylalkyl group, and r is an integer of 1 to 5, preferably 1 to 3. ]

  Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

  Further, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic ester group as a substituent, or long chain alkyl carboxylic acid chlorides can be used, When these are used to block the ends of the aromatic polycarbonate copolymers, they not only function as end terminators or molecular weight regulators, but also improve the melt fluidity of the resin and facilitate molding processes. The physical properties are also improved. In particular, it has the effect of reducing the water absorption rate of the resin and is preferably used. These are represented by the following general formulas [Ia] to [Ih].

[In the general formulas [Ia] to [Ih], X represents —RO—, —R—CO—O—, or —R—O—CO—, wherein R represents a single bond or A divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, T represents a single bond or a bond similar to the above X, and n represents an integer of 10 to 50.
Q represents a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, p represents an integer of 0 to 4, Y represents 1 to 10 carbon atoms, preferably 1 to 1 carbon atoms. 5 is a divalent aliphatic hydrocarbon group, W ¹ is a hydrogen atom, —CO—R ¹⁷ , —CO—O—R ¹⁸ or R ¹⁹ , wherein R ¹⁷ , R ¹⁸ and R ¹⁹ are 1 to 10 carbon atoms, preferably 1 to 5 monovalent aliphatic hydrocarbon groups, 4 to 8 carbon atoms, preferably 5 to 6 monovalent alicyclic hydrocarbon groups or 6 to 15 carbon atoms, respectively. Preferably 6-12 monovalent | monohydric aromatic hydrocarbon group is shown.
a represents an integer of 4 to 20, preferably 5 to 10, m represents an integer of 1 to 100, preferably 3 to 60, particularly preferably 4 to 50, and Z represents a single bond or a carbon number of 1 to 10, preferably an 1-5 divalent aliphatic hydrocarbon group, ^{W 2} is a hydrogen atom, C1-10, preferably 1 to 5 monovalent aliphatic hydrocarbon group, having 4 to 8 carbon atoms, Preferably, it represents a monovalent alicyclic hydrocarbon group having 5 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms. ]

  Of these, the substituted phenols of [Ia] and [Ib] are preferable. As the substituted phenols of [Ia], those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, and octadecyl. Phenol, eicosylphenol, docosylphenol and triacontylphenol can be mentioned.

  Further, as the substituted phenols of [Ib], compounds in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

  In the substituted phenols or substituted benzoic acid chlorides represented by the above general formulas [Ia] to [Ig], the position of the substituent is generally preferably the p-position or the o-position, and a mixture of both is preferable.

  The monofunctional phenols are desirably introduced into at least 5 mol%, preferably at least 10 mol% of the terminals of the resulting aromatic polycarbonate copolymer, and the monofunctional phenols are used alone. Or you may use it in mixture of 2 or more types.

  Further, in the aromatic polycarbonate copolymer of the present invention, when 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is 60 mol% or more of the total aromatic hydroxy component, the fluidity of the resin Therefore, it is preferable to use the substituted phenols or substituted benzoic acid chlorides represented by the above general formulas [Ia] to [Ig] as a terminal terminator.

  The aromatic polycarbonate copolymer of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. . Moreover, the branched polycarbonate which copolymerized a small amount of trifunctional compounds may be sufficient.

  The aromatic polycarbonate copolymer of the present invention has a glass transition temperature of preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher.

  To the aromatic polycarbonate resin of the present invention, a modifying agent such as a mold release agent, a fluorescent brightening agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a coloring agent, an antistatic agent, an antibacterial agent, and the like are appropriately added. Can be used.

  The fluorescent whitening agent used in the present invention is not particularly limited as long as it is used for improving the color tone of a synthetic resin to white or bluish white, for example, stilbene, benzimidazole, naphthalimide, Examples include rhodamine-based, coumarin-based, and oxazine-based compounds.

  As the ultraviolet absorber used in the present invention, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a benzoxazine-based ultraviolet absorber, or a benzophenone-based ultraviolet absorber is used.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidomethyl). ) -5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2- (3'-tert-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis (4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3 ', 5'-bi) (Α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, 2- (3 ′, 5′-di-tert-amyl-2′-hydroxyphenyl) benzotriazole, 5-trifluoromethyl-2- (2 -Hydroxy-3- (4-methoxy-α-cumyl) -5-tert-butylphenyl) -2H-benzotriazole and the like.

  Among them, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidomethyl) -5′-methylphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3 '-Tert-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole is preferred, and 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole is more preferred.

  As the triazine-based ultraviolet absorber, hydroxyphenyltriazine-based, for example, trade name Tinuvin 400 (manufactured by Ciba Specialty Chemicals) is preferable.

  Examples of the benzoxazine-based ultraviolet absorber include 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazine-4-one, 2-phenyl-3,1-benzoxazine -4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2,2 ′ -Bis (3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one, 2,2'-m-phenylenebis (3,1- Benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6 or 1,5-naphthalene) ) Bis (3,1-benzoxazin-4-one) 1,3,5-tris (3,1-benzoxazin-4-on-2-yl) benzene and the like, among others, 2,2′-p-phenylenebis (3,1-benzoxazine-4- ON) is preferred.

  Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and the like can be mentioned, among which 2-hydroxy-4-n-octoxybenzophenone is preferable. These ultraviolet absorbers may be used alone or in combination of two or more.

  These ultraviolet absorbers are 0.01 to 5% by weight, preferably 0.02 to 3% by weight, particularly preferably 0.05, based on 100% by weight of the total amount of the polycarbonate resin and the ultraviolet absorber. ~ 2% by weight. If it is less than 0.01% by weight, the ultraviolet absorption performance is insufficient, and if it exceeds 5% by weight, the hue of the resin may be deteriorated.

  In the present invention, a bluing agent may be used. Examples of such a bluing agent include Macrolex Violet manufactured by Bayer Co., Ltd., Dialresin Violet manufactured by Mitsubishi Chemical Co., Ltd., Dial Resin Blue, Sand Co., Ltd. Terazole blue and the like are available, and the most suitable is macrolex violet. These bluing agents are preferably incorporated into the aromatic polycarbonate resin at a concentration of 0.1 to 3 ppm, more preferably 0.3 to 1.5 ppm, and most preferably 0.3 to 1.2 ppm.

  In the present invention, if necessary, the aromatic polycarbonate copolymer is blended with at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof. be able to. The amount of the phosphorus compound is preferably 0.0001 to 0.05% by weight, more preferably 0.0005 to 0.02% by weight, and 0.001 to 0.01 based on the aromatic polycarbonate copolymer. Weight percent is particularly preferred. By blending this phosphorus compound, the thermal stability of the aromatic polycarbonate copolymer is improved, and a decrease in molecular weight and a deterioration in hue during molding are prevented.

  The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, and esters thereof, preferably the following general formula

[Wherein, R ^{5 to} R ¹⁶ are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl. Represents an alkyl group having 1 to 20 carbon atoms such as octadecyl, an aryl group having 6 to 15 carbon atoms such as phenyl, tolyl and naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl and phenethyl; In the case where two alkyl groups are present, the two alkyl groups may be bonded to each other to form a ring. ]
At least one phosphorus compound selected from the group consisting of:

  Examples of the phosphorus compound represented by the formula (1) include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentae Sri diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol phosphite.

  Examples of the phosphorus compound represented by the formula (2) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like (3 ) The phosphorus compound represented by the formula includes tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, and the compound represented by the formula (4) Examples thereof include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Among these phosphorus compounds, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylene Phosphonite is preferably used.

  To the polycarbonate copolymer of the present invention, an antioxidant generally known for the purpose of antioxidant can be added. Examples thereof include phenolic antioxidants. Specifically, for example, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4- Loxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3.9 -Bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5 5) Undecane etc. are mentioned. The range of preferable addition amount of these antioxidants is 0.0001 to 0.05% by weight with respect to the polycarbonate copolymer.

  Furthermore, a higher fatty acid ester of a monohydric or polyhydric alcohol can be added to the aromatic polycarbonate copolymer of the present invention as necessary.

  The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Further, partial esters or total esters of such monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol. Examples thereof include monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, among which stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used. .

  The amount of ester of such alcohol and higher fatty acid is preferably 0.01 to 2% by weight, more preferably 0.015 to 0.5% by weight, more preferably 0.02 to 0.5% by weight based on the aromatic polycarbonate copolymer. More preferred is 0.2% by weight. If the blending amount is within this range, it is preferable that the release property is excellent and the release agent does not migrate and adhere to the metal surface.

  In the aromatic polycarbonate copolymer of the present invention, additives such as lubricants and fillers, other polycarbonate resins, and other thermoplastic resins may be added in a small amount within a range not impairing the object of the present invention.

  As a method for obtaining a molded product from the aromatic polycarbonate resin composition of the present invention, injection molding, extrusion molding, compression molding, injection compression molding, blow molding or the like is used. A method that is excellent in uniformity and that does not cause optical defects such as gels, brats, fish eyes, and scratches is preferred, and examples thereof include a melt extrusion method and a calendar method.

  The 2 mm thick molded plate molded using the aromatic polycarbonate copolymer of the present invention preferably has a YI value of 6.0 or less. Further, it is preferably 4.5 or less, and particularly preferably 3.5 or less. When the YI value is larger than 6.0, the hue is bad and it is difficult to use as an optical molded product.

  A molded product produced by such a method has a good hue, and also has high heat resistance and rigidity. Therefore, the molded product is suitably used for an optical molded product with little warpage and excellent color tone.

  The polycarbonate copolymer of the present invention has excellent heat resistance and rigidity, and has a very good hue when this polycarbonate copolymer powder is dissolved in methylene chloride in a light-shielded state. Molded articles made using this polycarbonate copolymer have a much improved hue compared to conventional molded articles, can be used as optical molded articles, and the industrial effects brought about by the present invention are exceptional. .

The following examples further illustrate the present invention. The part in an Example is a weight part and% is weight%. The evaluation was based on the following method.
(1) Specific viscosity: 0.7 g of polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.
(2) Glass transition temperature (Tg): Measured at a heating rate of 20 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd.
(3) BCF monomer solution b value: 10 g of a sample was dissolved in 50 ml of ethanol and measured with a color difference meter 300A by Nippon Denshoku Co., Ltd. in a sample tube having an optical path length of 30 mm.
(4) Powder solution b value: 5 g of polycarbonate copolymer powder was dissolved in 50 ml of methylene chloride in a light-shielded state, and measured using a color difference meter 300A by Nippon Denshoku Co., Ltd. with a sample tube having an optical path length of 30 mm.
(5) Molded product YI value: Using a N-20C injection molding machine manufactured by JSW, a sample plate having a thickness of 2 mm was prepared by injection molding at the cylinder temperature and the mold temperature shown in Table 1. The yellowness (YI) of this sample plate was measured using a spectrocolorimeter SE-2000 (light source: C / 2) manufactured by Nippon Denshoku Co., Ltd.

[Example 1]
In a thermometer, stirrer, and vented reactor, 21540 parts of ion-exchanged water and 4930 parts of 48% aqueous sodium hydroxide solution were bubbled with nitrogen for 30 minutes, and the b value in an ethanol solution was 3.0. , 9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) 3231 parts, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1949 parts and 15 parts of hydrosulfite were dissolved, 14530 parts of methylene chloride was added, and 2200 parts of phosgene was blown in at a temperature of 15 to 25 ° C. for 60 minutes with stirring under a nitrogen stream. After completion of phosgene blowing, 115.4 parts of p-tert-butylphenol and 705 parts of 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts of triethylamine was added and stirred at 28-33 ° C. for 1 hour to complete the reaction. did. After completion of the reaction, the product was diluted with methylene chloride, washed with water in a nitrogen stream, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, The methylene chloride was evaporated to obtain 5460 parts of a white polymer having a BCF to BPA ratio of 50:50, a specific viscosity of 0.282, and a Tg of 195 ° C. (yield 95%).

  Tris (2,4-di-tert-butylphenyl) phosphite 0.050% and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate were added to the polycarbonate resin powder. 010% and pentaerythritol tetrastearate 0.030% were added, and pelletized using a φ30 mm single screw extruder with a vent, and a molded product was prepared using this. The evaluation results are shown in Table 1.

[Example 2]
The ratio of BCF to BPA is the same as in Example 1 except that the amount of BCF used in Example 1 is 1292 parts, the amount of BPA used is 3118 parts, and the amount of p-tert-butylphenol used is 102.6 parts. 4770 parts (yield 96%) of a white polymer having a molar ratio of 20:80 were obtained. This polymer had a specific viscosity of 0.370 and a Tg of 170 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this pellet. The results are shown in Table 1.

[Example 3]
The ratio of BCF to BPA is the same as in Example 1 except that the amount of BCF used in Example 1 is 4523 parts, the amount of BPA used is 1169 parts, and the amount of p-tert-butylphenol used is 128.2 parts. 5840 parts (yield 93%) of polymer with a molar ratio of 70:30 were obtained. The white polymer had a specific viscosity of 0.258 and Tg of 213 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this pellet. The results are shown in Table 1.

[Example 4]
5650 parts of white polymer (yield 98%) having a molar ratio of BCF to BPA of 50:50 in the same manner as in Example 1 except that the amount of hydrosulfite used in Example 1 was 50 parts. Obtained. This polymer had a specific viscosity of 0.280 and a Tg of 195 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this pellet. The results are shown in Table 1.

[Example 5]
32320 parts of ion-exchanged water and 4320 parts of 48% sodium hydroxide were put in the same apparatus as in Example 1, and after bubbling with nitrogen for 30 minutes, 2828 parts of BCF, α, α′-bis (4-hydroxyphenyl)- 2589 parts of m-diisopropylbenzene (hereinafter sometimes abbreviated as “BPM”) and 13 parts of hydrosulfite are dissolved, 12720 parts of methylene chloride are added, and phosgene is added at 15 to 20 ° C. with stirring under a nitrogen stream. 2000 parts were blown in 60 minutes. After completion of phosgene blowing, 112.2 parts of p-tert-butylphenol and 617 parts of 48% aqueous sodium hydroxide solution were added to emulsify, and 3.8 parts of triethylamine was added, followed by stirring at 28 to 33 ° C. for 1 hour to complete the reaction. did. This was treated in the same manner as in Example 1 to obtain 5450 parts of a white polymer having a molar ratio of BCF to BPM structural unit of 50:50 (yield 92%). This polymer had a specific viscosity of 0.285 and a Tg of 178 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this pellet. The results are shown in Table 1.

[Comparative Example 1]
In the same apparatus as in Example 1, 21540 parts of ion-exchanged water and 4930 parts of 48% sodium hydroxide aqueous solution were added, and bubbling with nitrogen was not performed. 4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as “BCF”) 3231 parts, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1949 And 15 parts of hydrosulfite were dissolved, 14530 parts of methylene chloride was added, and nitrogen aeration was not performed, but 2200 parts of phosgene was blown in at 15 to 25 ° C. for 60 minutes with stirring. After completion of phosgene blowing, 115.4 parts of p-tert-butylphenol and 705 parts of 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts of triethylamine was added and stirred at 28-33 ° C. for 1 hour to complete the reaction. did. After completion of the reaction, the product was diluted with methylene chloride, washed with water without nitrogen aeration, then acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, a kneader was used. To obtain 5290 parts of a yellowish white polymer having a BCF to BPA molar ratio of 50:50, a specific viscosity of 0.278, and a Tg of 195 ° C. (90% yield). . This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this pellet. The results are shown in Table 1.

[Comparative Example 2]
After irradiating the methylene chloride solution of the polycarbonate resin prepared in Comparative Example 1 with a 400 W high-pressure mercury lamp (manufactured by Hitachi Lighting Co., Ltd.) (main wavelength: 350 to 500 nm) for 1 hour, The methylene chloride was evaporated to obtain a white polymer having a molar ratio of BCF to BPA of 50:50, a specific viscosity of 0.278, and a Tg of 195 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this pellet. The results are shown in Table 1.

[Comparative Example 3]
32320 parts of ion-exchanged water and 4320 parts of 48% sodium hydroxide were placed in the same apparatus as in Example 1, and bubbling with nitrogen was not performed, but 2828 parts of BCF, 2589 parts of BPM and 13 parts of hydrosulfite were dissolved, and methylene chloride 12720 After adding a part, nitrogen aeration was not performed but 2000 parts of phosgene was blown in for 15 minutes at 15 to 20 ° C. with stirring. After completion of phosgene blowing, 112.2 parts of p-tert-butylphenol and 617 parts of 48% aqueous sodium hydroxide solution were added to emulsify, and 3.8 parts of triethylamine was added, followed by stirring at 28 to 33 ° C. for 1 hour to complete the reaction. did. After completion of the reaction, the product was diluted with methylene chloride, washed with water without carrying out nitrogen bubbling, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, The methylene chloride was evaporated with a kneader to obtain 5440 parts of a yellowish white polymer having a molar ratio of BCF to BPM constitutional unit of 50:50. This polymer was dissolved again in 21760 parts of methylene chloride, and 272 parts of methanol was added thereto and stirred. After the yellow color of the solution faded, the methylene chloride was evaporated with a kneader to obtain 5030 parts of a white polymer ( Yield 85%). This polymer had a specific viscosity of 0.287 and a Tg of 178 ° C. This polymer resin powder was pelletized in the same manner as in Example 1, and a molded product was produced using this pellet. The results are shown in Table 1.

Claims (10)

5 to 95 mol% of the total aromatic dihydroxy component is represented by the following general formula [1],

[Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. Is a fluorene-based bisphenol represented by
95-5 mol% is the following general formula [2]

[Wherein, R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond, having 1 to 1 carbon atoms. A hydrocarbon group optionally containing 20 aromatic groups, an O, S, SO, SO ₂ , CO or COO group. ]
Wherein the b value of a solution obtained by dissolving 5 g of a powder of the polycarbonate copolymer in 50 ml of methylene chloride in a light-shielded state is 5.0 or less. Polycarbonate copolymer powder.   The polycarbonate copolymer powder according to claim 1, wherein the fluorene-based bisphenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.   3. The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has a b value of 6.0 or less measured by measuring a solution of 10 g in 50 ml of ethanol at an optical path length of 30 mm. The polycarbonate copolymer powder according to any one of the above.   The compound represented by the general formula [2] is 2,2-bis (4-hydroxyphenyl) propane and / or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene. The polycarbonate copolymer powder according to any one of 2 above.   The polycarbonate copolymer pellet produced by extruding the polycarbonate copolymer powder in any one of Claims 1-4.   The polycarbonate copolymer powder or pellet according to any one of claims 1 to 5, wherein a b value of a 2 mm-thick molded plate molded using the polycarbonate copolymer powder or pellet is 3 or less. .   A molded article comprising the polycarbonate copolymer powder or pellets according to any one of claims 1 to 6.   Molded products are pickup lenses, camera lenses, microarray lenses, projector lenses and Fresnel lenses, optical path conversion parts such as prisms and optical fibers, reflow soldering parts, optical disks, plastic mirrors, various cases, trays or containers. The molded article according to claim 7.   A film or sheet comprising the polycarbonate copolymer powder or pellets according to any one of claims 1 to 6.   The film or sheet according to claim 9, wherein the film or sheet is a retardation film, a plastic substrate, a protective film for an optical disc, a light guide plate, or a diffusion plate.