JP2005119124A - Injection molding method for polycarbonate copolymer and molded product molded thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product comprising a polycarbonate copolymer having excellent heat resistance and good appearance. <P>SOLUTION: In this injection molding method for the polycarbonate copolymer composed of a fluorene bisphenol wherein 5-95 mol% of a wholly-aromatic dihydroxy component is represented by a specific general structural formula [e.g., 9,9-bis(4-hydroxy-3-methylphenyl)fluorene] and 95-5 mol% thereof is a hydroxy component represented by a specific general structural formula (e.g., hydroquinone), the polycarbonate copolymer is dried under a condition of 105≤Td≤Tg-10 when the glass transition temperature of the polycarbonate copolymer is Tg(°C), the drying temperature of pellets is Td(°C), the temperature of the resin in a cylinder is Tc(°C) and the temperature of a mold of Tm(°C) before molded under conditions of 381-20,900/Tg≤Tc≤485-17,000/Tg and 0.458 Tg≤Tm≤Tg-10. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for injection molding of a polycarbonate copolymer and a molded article formed thereby. More particularly, the present invention relates to a method for molding a molded article having a good appearance from a polycarbonate copolymer having excellent heat resistance, and a molded article molded thereby.

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.
In recent years, the progress of miniaturization and miniaturization has progressed, and a polycarbonate resin having further improved heat resistance has been demanded.

  In order to improve the heat resistance 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, polycarbonate resins having these structures have low melt flowability due to their heat resistance, and many conjugated structures in the molecule tend to cause burns, making it extremely difficult to obtain molded articles with good appearance. Met.

JP-A-11-174424 JP-A-8-134198

  An object of the present invention is to provide a molded article having excellent heat resistance and good appearance.

  As a result of intensive research aimed at achieving this object, the present inventor dried aromatic polycarbonate copolymer pellets synthesized using a specific dihydric phenol under specific conditions, It was found for the first time that the above object was achieved by molding within the molding conditions, and the present invention was achieved.

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であり、
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. Is a fluorene-based bisphenol represented by
95-5 mol% is 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なるポリカーボネート共重合体の成形方法であって、該ポリカーボネート共重合体のガラス転移温度をＴｇ（℃）、該ポリカーボネート共重合体ペレットの乾燥温度をＴｄ（℃）、射出成形機のシリンダ内の樹脂温度をＴｃ（℃）、射出成形機の金型温度をＴｍ（℃）としたとき、
１０５ ≦ Ｔｄ ≦ Ｔｇ−１０
の条件下で乾燥した後、下記式の条件下で成形することを特徴とするポリカーボネート共重合体の射出成形法により、良好な外観の成形品を得ることができる。
３８１−２０９００／Ｔｇ ≦ Ｔｃ ≦ ４８５−１７０００／Ｔｇ
０．４５８Ｔｇ ≦ Ｔｍ ≦ Ｔｇ−１０

[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 comprising a dihydroxy component represented by the formula: a polycarbonate copolymer having a glass transition temperature of Tg (° C.), a polycarbonate copolymer pellet having a drying temperature of Td (° C.), injection When the resin temperature in the cylinder of the molding machine is Tc (° C.) and the mold temperature of the injection molding machine is Tm (° C.),
105 ≦ Td ≦ Tg−10
After drying under the above conditions, a molded article having a good appearance can be obtained by an injection molding method of a polycarbonate copolymer characterized by molding under the conditions of the following formula.
381-20900 / Tg ≦ Tc ≦ 485-17000 / Tg
0.458 Tg ≦ Tm ≦ Tg−10

  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. If b value is in the said range, the molded object formed from the obtained polycarbonate copolymer will become favorable, and it is 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 and removing impurities. Specifically, after the reaction between o-cresol and fluorenone, unreacted o-cresol is distilled off, and then 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, the purified product can be obtained by filtering the crystallized product from the filtrate to obtain 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. 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 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.

  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 is appropriately added with a modifying agent such as a release agent, a fluorescent brightening agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a coloring agent, an antistatic agent, and an antibacterial agent. 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.

  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.

“Molding” in the present invention refers to a method of obtaining a molded product by temporarily melting a resin and adjusting it to a desired shape, followed by cooling and solidification, such as injection molding and injection compression molding.
When molding the polycarbonate copolymer of the present invention, the form of the resin may be powder, pellets, etc., and is not particularly restricted, but the uniformity of the dispersion of additives and fillers, and the oxygen molding machine cylinder From the viewpoint of suppressing the carry-in to the inside, it is preferable to use pellets with an extruder in advance.

When molding the polycarbonate copolymer of the present invention, when the glass transition temperature of the polycarbonate copolymer is Tg (° C.) and the drying temperature of the polycarbonate copolymer pellet is Td (° C.),
105 ≦ Td ≦ Tg−10
It is preferable to mold after drying under the above conditions. More preferably,
115 ≦ Td ≦ Tg-15
It is. If the Td is less than 105 ° C., the moisture in the resin cannot be sufficiently removed, which causes decomposition of the resin and generation of silver, making it difficult to obtain a molded article having a good appearance. On the other hand, when Td is Tg−10 ° C. or higher, the resin is thermally deteriorated during drying, which causes a deterioration of the hue of the molded product, making it difficult to obtain a molded product with a good appearance. The drying time is preferably 3 to 12 hours, and more preferably 5 to 10 hours.

When molding the polycarbonate copolymer of the present invention, when the copolymer resin temperature in the cylinder of the injection molding machine is Tc (° C.),
381-20900 / Tg ≦ Tc ≦ 485-17000 / Tg
It is preferable to mold in this range. Tc Tc <381-20900 / Tg
In this case, since the melt fluidity of the resin is lowered, it becomes difficult to form a good molded product, which is not preferable. on the other hand,
Tc> 485-17000 / Tg
In this case, the resin is thermally decomposed to cause burns or silver, which makes it difficult to obtain a molded article having a good appearance, and also causes a decrease in physical properties accompanying a decrease in molecular weight, which is not preferable.

When molding the polycarbonate copolymer of the present invention, when the mold temperature of the injection molding machine is Tm (° C.),
0.458 Tg ≦ Tm ≦ Tg−10
It is preferable to mold in this range.
Tm <0.458Tg
In this case, since the melt fluidity of the resin is lowered, it becomes difficult to form a good molded product, which is not preferable. on the other hand,
Tm> Tg-10
In this case, since the molten resin is not cooled and solidified, it is difficult to obtain a molded article having a good appearance.

  When the polycarbonate copolymer pellets of the present invention are molded, it is preferable to mold them while allowing an inert gas to flow into the hopper of the molding machine. When inert gas is not allowed to flow into the molding machine hopper, the oxygen of the molding machine brings oxygen into the molding machine, causing the molten resin and oxygen to react at high temperatures, resulting in oxidative degradation of the resin. This is not preferable. Examples of the inert gas include nitrogen, carbon dioxide, helium, and argon, and nitrogen is particularly preferable.

  The inflow method of the inert gas in the present invention is not limited to any form as long as the polycarbonate copolymer is supplied into the molding machine cylinder and the accompanying air is replaced with an inert gas. The oxygen concentration in the nitrogen gas as the inert gas is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 5 ppm or less. The nitrogen gas supply source as an inert gas is not particularly limited, such as a commercially available nitrogen gas cylinder, industrially available industrial nitrogen, separation membrane type, PSA type nitrogen gas generator, etc. Oxygen can be removed from the flowing out inert gas and reused.

  The flow rate of the inert gas depends on the screw diameter of the molding machine or the extruder, the screw rotation speed, the material supply speed, and the inert gas supply method, but it may be supplied in the range of 0.01 to 100 L / min. preferable. More preferably, it is 0.1-10 L / min.

  Molded products manufactured by this method have high heat resistance, high rigidity, good hue and appearance, and optical path conversion of lenses such as pickup lenses, camera lenses, microarray lenses, projector lenses and Fresnel lenses, prisms and optical fibers. It is suitably used for parts, reflow soldered parts, optical disks, plastic mirrors, various cases, trays, containers, and the like.

  The polycarbonate copolymer of the present invention is a resin that has excellent heat resistance and rigidity and can greatly improve the properties of conventional polycarbonates. By molding this resin under a specific range of drying conditions and molding conditions, it is possible to obtain a molded article having a good appearance and hue for the first time. Therefore, the industrial effect brought about by the present invention is 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) b value of monomer solution: 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 with an optical path length of 30 mm.
(4) Sample plate appearance: After drying the pellets under the conditions shown in Table 1, a sample plate having a thickness of 2 mm was formed under the conditions shown in Table 1 using an injection molding machine [SG-150 manufactured by Sumitomo Heavy Industries, Ltd.]. Injection molded. At that time, “○” indicates that molding is possible and no silver is generated, “×” indicates that molding is possible but silver is occurring, and “XX” indicates that molding is impossible. "
(5) Sample plate hue: The yellowness (YI) of the sample plate molded in (4) was measured using a spectrocolorimeter SE-2000 (light source: C / 2) manufactured by Nippon Denshoku Co., Ltd.
(6) Residence test: When molding in the same manner as in (4), the sample plate was molded after retaining for 10 minutes in the cylinder of the molding machine. The specific viscosity, appearance, and hue of this sample plate were evaluated in the same manner as (1), (4), and (5).

[Preparation of Polycarbonate Copolymer-Part 1]
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts of ion-exchanged water and 4930 parts of 48% aqueous sodium hydroxide solution were added, and the b value in the ethanol solution was 3.0. 1,292 parts of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”), 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 3118 parts and 15 parts of hydrosulfite were dissolved, 14530 parts of methylene chloride was added, and 2200 parts of phosgene was blown in at 15 to 25 ° C. with stirring for 60 minutes. After the completion of phosgene blowing, 102.6 parts of p-tert-butylphenol and 705 parts of a 48% aqueous sodium hydroxide solution were added, 5.9 parts of triethylamine was added, and the reaction was terminated by stirring at 28 to 33 ° C. for 1 hour. After completion of the reaction, the product was diluted with methylene chloride, washed with water, 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, As a result, 4720 parts of white polymer having a molar ratio of BCF to BPA of 20:80, a specific viscosity of 0.347, and a Tg of 168 ° C. were obtained (95% yield).

  To this polycarbonate resin granular material, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite 0.050%, octadecyl-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate (0.030%) and stearic acid monoglyceride (0.030%) were added, and polycarbonate copolymer pellets (EX-PC1) were prepared using a vented φ30 mm single screw extruder.

[Preparation of Polycarbonate Copolymer-Part 2]
The ratio of BCF to BPA was the same as in Example 1 except that the amount of BCF used in Example 1 was 3231 parts, the amount of BPA used was 1949 parts, and the amount of p-tert-butylphenol used was 128.2 parts. 5190 parts (yield 90%) of polymer with a molar ratio of 50:50 were obtained. This polymer had a specific viscosity of 0.280 and a Tg of 195 ° C. The polymer resin particles were pelletized in the same manner as in Example 1 to prepare polycarbonate copolymer pellets (EX-PC2).

[Preparation of Polycarbonate Copolymer-3]
In the same manner as in Example 1, except that the amount of BCF used in Example 1 was 4523 parts, the amount of BPA used was 1169 parts, and cumylphenol was 174.0 parts instead of p-tert-butylphenol. The polymer 5950 parts (yield 95%) having a molar ratio of 70:30 was obtained. This polymer had a specific viscosity of 0.267 and Tg of 215 ° C. This polymer resin powder was pelletized in the same manner as in Example 1 to prepare a polycarbonate copolymer pellet (EX-PC3).

[Examples 1-5, Comparative Examples 1-5]
Each pellet of EX-PC1, EX-PC2 and EX-PC3 obtained above is dried at the temperature shown in Table 1 for 8 hours, and then an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.) is used. Then, a sample plate for measurement was injection molded under the conditions of cylinder temperature and mold temperature shown in Table 1. The presence / absence of inflow of nitrogen into the molding machine hopper during molding is also shown in Table 1 (nitrogen inflow 1 L / min). Table 2 shows the evaluation results of these sample plates.

Claims (7)

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. ]
A polycarbonate copolymer comprising a dihydroxy component represented by the formula: a polycarbonate copolymer having a glass transition temperature of Tg (° C.), a polycarbonate copolymer pellet having a drying temperature of Td (° C.), injection When the resin temperature in the cylinder of the molding machine is Tc (° C.) and the mold temperature of the injection molding machine is Tm (° C.),
105 ≦ Td ≦ Tg−10
A method for injection molding a polycarbonate copolymer, which is dried under the following conditions and then molded under the conditions of the following formula.
381-20900 / Tg ≦ Tc ≦ 485-17000 / Tg
0.458 Tg ≦ Tm ≦ Tg−10   2. The polycarbonate copolymer injection molding method according to claim 1, wherein the molding is performed while an inert gas is allowed to flow into a hopper of a molding machine.   The method for injection molding a polycarbonate copolymer according to claim 1 or 2, wherein the fluorene-based bisphenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.   The b-value of the 9,9-bis (4-hydroxy-3-methylphenyl) fluorene measured in an optical path length of 30 mm of a solution obtained by dissolving 10 g in 50 ml of ethanol is 6.0 or less. An injection molding method for a polycarbonate copolymer 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. 5. A method for injection molding a polycarbonate copolymer according to any one of 4 above.   A molded article molded by the polycarbonate copolymer injection molding method according to claim 1.   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 product according to claim 6.