JP2005060628A - Polycarbonate resin with excellent reflow resistance - Google Patents

Abstract

［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、９５〜５モル％が下記一般式［２］
【化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原子であり、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得られたポリカーボネート共重合体であって、ポリマー末端のクロロホーメート基に基づく塩素量が１０ｐｐｍ以下であり、かつポリマー末端の水酸基量が２５０ｐｐｍ以下であることを特徴とするリフロー耐性に優れた芳香族ポリカーボネート樹脂。
【選択図】 なしPROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin having a specific structure having excellent heat resistance and rigidity and excellent hue.
5 to 95 mol% of the wholly aromatic dihydroxy component is represented by the following general formula [1]
[Chemical 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. The fluorene-based bisphenol represented by the formula: 95-5 mol% is represented by the following general formula [2]
[Chemical 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. ]
A polycarbonate copolymer obtained from a dihydroxy component represented by the formula, wherein the chlorine content based on the chloroformate group at the polymer end is 10 ppm or less, and the hydroxyl content at the polymer end is 250 ppm or less. Aromatic polycarbonate resin with excellent reflow resistance.
[Selection figure] None

Description

  The present invention relates to an aromatic polycarbonate resin. More specifically, the present invention relates to an aromatic polycarbonate resin 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.

  This polycarbonate resin usually contains a very small amount of chloroformate groups and hydroxyl groups at the end of the molecular chain, but if these are contained in a large amount, deterioration of hue, metal corrosion resistance, hydrolysis resistance, etc. will be reduced, causing problems during use. Various methods for solving these problems have been proposed (see, for example, Patent Documents 1, 2, 3, and 4).

On the other hand, 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 polycarbonates have been proposed. Among them, a polycarbonate resin having a specific fluorene structure has been proposed (see, for example, Patent Documents 5 and 6). However, although the polycarbonate resin having these structures is excellent in heat resistance, refractive index, and rigidity, there is a problem that the above-mentioned chloroformate group is contained in a large amount at the molecular chain terminal, and the hue deteriorates, particularly in a reflow furnace. When processing at high temperatures, the hue deteriorates, the metal corrosion resistance, the hydrolysis resistance, etc. decrease, which may cause problems during use.
JP-A-61-87724 JP 2000-204148 A JP 63-97627 A Japanese Patent No. 3116386 JP-A-11-174424 JP-A-8-134198

  An object of the present invention is to provide an aromatic polycarbonate resin having a specific structure having excellent heat resistance and rigidity and excellent hue.

  As a result of intensive research aimed at achieving this object, the present inventor, as a result, in an aromatic polycarbonate copolymer using a specific dihydric phenol, an aromatic polycarbonate copolymer having a small number of chloroformate groups at the molecular chain ends and few hydroxyl groups. The inventors have found that the above object can be achieved by synthesizing a coalescence, and have reached the present invention.

  That is, according to the present invention, 5 to 95 mol% of the 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得られたポリカーボネート共重合体であって、ポリマー末端のクロロホーメート基に基づく塩素原子量が１０ｐｐｍ以下であり、かつポリマー末端の水酸基量が２５０ｐｐｍ以下であることを特徴とするリフロー耐性に優れた芳香族ポリカーボネート樹脂が提供される。

[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 copolymer obtained from a dihydroxy component represented by the formula: wherein the chlorine atom amount based on the chloroformate group at the polymer terminal is 10 ppm or less, and the hydroxyl group content at the polymer terminal is 250 ppm or less. An aromatic polycarbonate resin excellent in reflow resistance is provided.

  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 20-85 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.

  In order to obtain the aromatic polycarbonate copolymer of the present invention, the purity of the 9,9-bis (4-hydroxy-3-methylphenyl) fluorene used is preferably 99.0% or more, more preferably Preferably it is 99.5% or more, more preferably 99.9% or more. When the purity is within the above range, the content of the chloroformate group and hydroxyl group at the polymer terminal of the obtained polycarbonate copolymer is small, and the molded product formed therefrom is preferable because of good hue and the like. In addition, there is little change in hue during high-temperature processing using a reflow furnace or the like. The purity of the dihydroxy component represented by the general formula [2] is preferably 99.0% or more.

  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 is sufficiently strong, the melt viscosity and the solution viscosity are appropriate, and the handling is easy and preferable.

  The aromatic 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. However, as described above, in order to obtain the aromatic polycarbonate copolymer of the present invention, it is necessary to use the fluorene-based bisphenol having the purity described above.

  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. 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.

  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.

  In the aromatic polycarbonate resin of the present invention, the chlorine content based on the chloroformate group at the polymer terminal is 10 ppm or less, and the hydroxyl content at the polymer terminal is 250 ppm or less. The amount of chlorine based on the chloroformate group at the end of the polymer is preferably 5 ppm or less, and more preferably 2 ppm or less. Further, the hydroxyl amount of the polymer terminal is preferably 200 ppm or less, and more preferably 100 ppm or less. If the amount of chlorine atom based on the chloroformate group at the polymer end exceeds 10 ppm and the amount of hydroxyl group at the polymer end exceeds 250 ppm, the hue of the polycarbonate resin deteriorates, corrodes metals, and promotes deterioration of the resin. Therefore, it is not preferable. The hue of the polycarbonate resin is preferably 3.0 or less, more preferably 2.0 or less, and most preferably 1.5 or less when measured with a 2 mm-thick molded piece.

  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 brightener 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 , Rhodamine-based, coumarin-based, and oxazine-based compounds. The compounding amount of the optical brightener is 0.0005 to 0.1 parts by weight, preferably 0.001 to 0.05 parts by weight, and more preferably 0.000 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin of the present invention. 005 to 0.02 parts by weight. If the blending amount is less than 0.0005 parts by weight, a sufficient effect of improving the color tone cannot be obtained. In addition, the cost is increased.

  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, blow molding or the like is used, and as a method for producing a film or sheet, it is excellent in thickness uniformity, gel, A method that does not cause optical defects such as butts, fish eyes, and scratches is preferable, and examples thereof include a melt extrusion method and a calender method.

  A molded product produced by such a method has high light transmittance, and also has high heat resistance and rigidity, so that it is suitably used for an optical molded product with little warpage and excellent color tone.

  The aromatic polycarbonate resin of the present invention has high optical transparency, excellent heat resistance and rigidity, excellent hue, and excellent metal corrosion resistance. It is suitable for prisms, optical fibers, optical films, liquid crystal displays, backlight type light diffusion plates for liquid crystal televisions, or light guide plates used in scanners, and the industrial effects brought about by the present invention are particularly remarkable.

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) Monomer purity: HPLC analysis was performed with a gradient program at 40 ° C. and 280 nm using a mixture of eluent acetonitrile / 0.2% acetic acid water and acetonitrile on a column of Develosil ODS-MG manufactured by Nomura Chemical. The measurement was performed by injecting 10 μl of a solution of 3 mg of the sample in 10 ml of acetonitrile, and the ratio of the peak area of the main component to the total peak area was expressed in%.
(2) Specific viscosity: 0.7 g of polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.
(3) Glass transition temperature (Tg): Measured by DuPont 910 DSC.
(4) Analysis of trace amount of chlorine: About 0.5 g of polymer is precisely weighed, methylene chloride is added and dissolved therein, and 4- (p-nitrobenzyl) pyridine (manufactured by Wako Pure Chemicals, reagent special grade) of 0. 1 ml of 5 g / l methylene chloride solution was added to make the total volume 10 ml. The absorbance was measured at a wavelength of 440 nm using a spectrophotometer (Hitachi Co., Ltd. U-3000). Separately, a calibration curve was prepared using a methylene chloride solution of phenyl chlorocarbonate (manufactured by Wako Pure Chemicals, reagent grade), and the amount of trace chlorine derived from the chloroformate group in the sample was quantified. The limit of quantification was 0.2 ppm vs. solid content in terms of chlorine content.
(5) Amount of terminal hydroxyl groups: About 0.2 g of polymer is placed in a 25 ml volumetric flask and accurately weighed, and then about 10 ml of methylene chloride is added and dissolved. After dissolution, 10 ml of titanium tetrachloride solution and 4 ml of acetic acid solution are added and filled to the mark with methylene chloride. Here, the titanium tetrachloride solution was added to 20 ml of titanium tetrachloride and 0.2 g of acetic acid in a 500 ml volumetric flask and filled to the mark with methylene chloride. The acetic acid solution was added to 10 g of acetic acid in a 100 ml volumetric flask and marked with methylene chloride. Created to fill the line. After thoroughly shaking the sample solution, the absorbance at 500 nm was measured using water as a blank, and the amount of hydroxyl group was calculated.
(6) Total light transmittance: A molded piece having a thickness of 2 mm was measured using Nippon Denshoku Co., Ltd. MDH-300A in accordance with ASTM D-1003.
(7) Molded piece b value: A molded piece having a thickness of 2 mm was measured using a color difference meter SE2000 of Nippon Denshoku Co., Ltd., and an average value of 20 measured values was defined as a molded piece b value.
(8) Aluminum deposition cloudiness: Aluminum deposited on a 50 × 90 × 2 mm sample plate with a vacuum deposition apparatus manufactured by Daia Vacuum Engineering Co., Ltd. to a thickness of 100 nm and left in a 160 ° C. atmosphere for 24 hours. The change of the film was observed. When the clouded aluminum film was found to be cloudy, it was rated as x.
(9) Reflow resistance: A test piece having a thickness of 1.0 mm, a width of 10 mm, and a length of 20 mm prepared by injection molding was dried at 120 ° C. for 10 hours under reduced pressure. This test piece was processed by an infrared-hot air combined type reflow furnace (manufactured by Asahi Engineering Co., Ltd., TPF-20L). The heating temperature pattern was set so that the peak temperature was 5 seconds at 250 ° C. after heating at 150 ° C. for 60 seconds, and the presence or absence of a change in hue of the molded piece after the reflow treatment was visually evaluated. The case where there was no change in hue was indicated as “◯”, and the case where there was a change was indicated as “X”.

[Example 1]
Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 19580 parts of ion-exchanged water and 4486 parts of 48% aqueous sodium hydroxide solution were added, and 9,9-bis (4-hydroxy-3-methyl) having a purity of 99.9%. Phenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene” or “BCF”) 2349.7 parts, purity 99.9% 2,2-bis (4-hydroxyphenyl) propane (hereinafter “bisphenol A”) (It may be abbreviated as “BPA”) After dissolving 215.9 parts and 13 parts of hydrosulfite, add 13210 parts of methylene chloride, and then add 2000 parts of phosgene at 15 to 25 ° C. with stirring for 60 minutes. And blown. After completion of phosgene blowing, a solution prepared by dissolving 104.9 parts of p-tert-butylphenol in 500 parts of methylene chloride and 640.8 parts of a 48% aqueous sodium hydroxide solution were added, and after emulsification, 7.4 parts of triethylamine was added and 28 to 28 The reaction was terminated by stirring at 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove polycarbonate. A solution with a concentration of 20% was obtained. The polycarbonate obtained by removing the solvent from this solution had a molar ratio of biscresol fluorene and bisphenol A of 40:60. The specific viscosity of this polymer was 0.312, Tg was 189 ° C., the amount of trace chlorine based on chloroformate groups in the polymer was 0.3 ppm, and the amount of hydroxyl groups was 70.7 ppm. To 100 parts of this polymer, 0.05 part of tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate (0.01 parts) and stearic acid monoglyceride (0.05 parts) are mixed, and the extruder temperature is 280 to 320 ° C., the die temperature is 290 to 330 ° C., and the vacuum degree of the vent portion is 2.7 kPa. Hold and melt extruded and pelletized. The pellets were dried at 120 ° C. for 4 hours, and then injection molded into 50 × 90 × 2 mm test pieces. This product had a total light transmittance of 89% and a b value of 1.4. When aluminum was vapor-deposited on this and heat-treated, and the surface condition was visually evaluated, there was no cloudiness. Further, there was no change in the hue of the molded piece after the reflow treatment. The results are shown in Table 1.

[Example 2]
The ratio of biscresol fluorene to bisphenol A was 70 in molar ratio as in Example 1 except that the amount of biscresol fluorene used in Example 1 was 411.9 parts and the amount of bisphenol A used was 1062.9 parts. : 30 was obtained. This polymer had a specific viscosity of 0.262 and Tg of 215 ° C. The polymer was pelletized in the same manner as in Example 1, and the results of molding evaluation are shown in Table 1.

[Example 3]
A polymer having a molar ratio of biscresol fluorene to bisphenol A of 40:60 was obtained in the same manner as in Example 1 except that the purity of biscresol fluorene of Example 1 was 99.2%. This polymer had a specific viscosity of 0.296 and Tg of 189 ° C. The polymer was pelletized in the same manner as in Example 1, and the results of molding evaluation are shown in Table 1.

[Comparative Example 1]
A polymer having a molar ratio of biscresol fluorene to bisphenol A of 40:60 was obtained in the same manner as in Example 1 except that the purity of biscresol fluorene of Example 1 was 98.5%. This polymer had a specific viscosity of 0.301 and Tg of 189 ° C. The polymer was pelletized in the same manner as in Example 1, and the results of molding evaluation are shown in Table 1.

[Comparative Example 2]
A polymer having a molar ratio of biscresol fluorene to bisphenol A of 70:30 was obtained in the same manner as in Example 2 except that the purity of biscresol fluorene of Example 2 was 98.5%. This polymer had a specific viscosity of 0.259 and a Tg of 215 ° C. The polymer was pelletized in the same manner as in Example 1, and the results of molding evaluation are shown in Table 1.

Claims (8)

5 to 95 mol% of the 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. ]
A polycarbonate copolymer obtained from a dihydroxy component represented by the formula, wherein the chlorine content based on the chloroformate group at the polymer end is 10 ppm or less, and the hydroxyl content at the polymer end is 250 ppm or less. Aromatic polycarbonate resin with excellent reflow resistance.   The aromatic polycarbonate resin according to claim 1, wherein the fluorene-based bisphenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.   The aromatic polycarbonate resin according to claim 1 or 2, wherein the 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has a purity measured by HPLC of 99.0% or more.   The compound represented by the general formula [2] is 2,2-bis (4-hydroxyphenyl) propane and / or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene. 2. An aromatic polycarbonate resin according to 2.   A molded article comprising the aromatic polycarbonate resin according to claim 1.   Molded products include 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, lamp reflectors, various cases, trays or The molded article according to claim 5, which is a container.   A film or sheet comprising the aromatic polycarbonate resin according to claim 1.   The film or sheet according to claim 7, wherein the film or sheet is a retardation film, a plastic substrate, a protective film for an optical disk, a light guide plate, or a diffusion plate.