JP2005107380A - Optical member and aromatic polycarbonate resin suitable for its manufacture - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical member having excellent heat resistance and rigidity and less changes in the appearance such as internal haze. <P>SOLUTION: The optical member is made of an aromatic polycarbonate resin comprising a component expressed by general formula [1] and a specified dihydroxy component and has ≤10 ppm content of alkali metal compounds. As the optical member made of the aromatic polycarbonate resin has high transmitting property, excellent heat resistance and rigidity, and less changes in the appearance such as haze, the resin is suitable for an optical member such as a lens, prism, optical fiber, optical film, liquid crystal display, light diffusing plate in a backlight system of a liquid crystal TV set, and light guide plate used for a scanner. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an optical member such as a lens molded from an aromatic polycarbonate resin. More specifically, the present invention relates to an optical member such as a lens made of an aromatic polycarbonate resin having excellent heat resistance and rigidity and having a small change in appearance such as cloudiness.

  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. Since it is particularly excellent in transparency, it has many uses as an optical member, and is used for applications such as lenses and mirrors.

  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 polycarbonates have been proposed. Among them, a polycarbonate resin having a specific fluorene structure has been proposed (see, for example, Patent Documents 1 and 2).

  On the other hand, it is generally known that polycarbonate resin is easy to absorb moisture and is not high in hydrolysis resistance. When used in optical members, problems such as deterioration of mechanical properties and surface appearance have been seen, and its improvement (See, for example, Patent Documents 3 and 4).

JP-A-11-174424 JP-A-8-134198 JP 2000-80261 A Japanese Patent Laid-Open No. 10-60247

  An object of the present invention is to provide an optical member such as a lens made of an aromatic polycarbonate resin having a specific structure having excellent heat resistance and rigidity and having a small change in appearance such as internal fogging.

  As a result of intensive research aimed at achieving this object, the present inventor has controlled the content of the alkali metal compound contained in the aromatic polycarbonate resin synthesized using a specific dihydric phenol to a specific amount or less. The inventors have found that the above object can be achieved, 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なる芳香族ポリカーボネート樹脂であって、アルカリ金属化合物の含有量が、アルカリ金属原子として１０ｐｐｍ以下であることを特徴とする芳香族ポリカーボネート樹脂より形成されるそれへの入射光線とそれからの出射光線とが、その光路において変化を賦与されるような透明樹脂製光学部材が提供される。

[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. ]
An incident light incident on an aromatic polycarbonate resin comprising an aromatic polycarbonate resin, wherein the content of the alkali metal compound is 10 ppm or less as an alkali metal atom. A transparent resin optical member is provided in which a change in the optical path of the light beam and the light beam emitted therefrom is provided.

  In the aromatic polycarbonate resin of the present invention, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as an aromatic dihydroxy component constituting the aromatic polycarbonate resin is preferably 5-95 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 other dihydroxy component represented by the above general formula [2] used in the aromatic polycarbonate resin 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-hydroxy) Phenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydride) Xylphenyl) -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, etc., among which bisphenol A, bisphenol Z, bisphenol C, bisphenol E, bisphenol M And bisphenol A is particularly preferable.

  The aromatic polycarbonate resin 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. However, in order to prepare the aromatic polycarbonate resin of the present invention, it is preferable to wash the concentrated methylene chloride phase again with ion-exchanged water after washing with water conventionally performed in the purification step.

  A method of mixing an organic solvent solution of an aromatic polycarbonate resin with water to form a dispersed phase and then obtaining an organic solvent solution of the aromatic polycarbonate resin by centrifugation is also preferably employed.

  The content of the aromatic polycarbonate resin in the organic solvent solution of the aromatic polycarbonate resin is preferably 4 to 25% by weight, and more preferably 6 to 15% by weight. The amount of water used is preferably 5 to 95% by volume when the total volume of the organic solvent solution of aromatic polycarbonate resin and water is 100% by weight, and 15 to 85% by volume. Is more preferable. In order to increase the extraction efficiency of the compound into the aqueous phase, the droplet diameter in the dispersed phase is preferably 100 μm or less, more preferably 50 μm or less, which is vigorously mixed and stirred. Is achieved.

  There is no restriction | limiting in particular as an apparatus used in order to form this disperse phase, The thing of various forms is used suitably. Specifically, for example, a static mixer such as a slew mixer, a static mixer, or a static in-pipe mixer can be suitably used, and an orifice mixer, a stirring tank, or the like can also be used by selecting operating conditions. Here, the static mixer refers to an apparatus that can insert a compact element having a liquid dividing action into a pipe and form fine dispersed droplet particles having the above particle diameter in a short residence time. .

  The operating conditions of this static mixer for forming a dispersed phase having the desired dispersed droplet diameter cannot be defined unconditionally because it varies depending on the type of the apparatus used. For example, the tube speed is 0.5 m / second or more. It is preferable that the number of elements is the number necessary to make the dispersed droplet diameter within the predetermined value range, for example, usually 5 to 16 elements.

  The method is not particularly limited, and any of a continuous method, a batch method, and a semi-continuous method is possible, but a continuous method can be preferably used from the viewpoint of productivity and operability.

  The mixed solution thus formed with the dispersed phase is then subjected to a centrifugal separation process. There is no particular limitation on the apparatus used for the centrifugal separation process as long as it can generate a centrifugal force of 300 G or more, preferably 700 G or more, and saturates moisture in oil by high centrifugal force with respect to a strong emulsion. Various devices can be used as long as they are separable to almost the amount, and particularly a centrifugal extractor capable of performing extraction and separation can be suitably used. Any of the continuous method, the batch method, and the semi-continuous method can be applied as the method of the centrifugal separation treatment, and the continuous method can be particularly preferably employed.

  In addition, the formation of the dispersed phase and the centrifugal separation treatment can be continuously performed in the same apparatus, which is more preferably employed. Specific examples include a centrifugal extractor with a perforated plate (Utrex EP-02 manufactured by Hitachi, Ltd., KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.).

  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 resin of the present invention, monofunctional phenols which 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 controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol. Since it is blocked by a group based on, it is superior in thermal stability compared to those not.

  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 end of an aromatic polycarbonate resin, they not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as physical properties. Will also be 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 total terminal of the obtained aromatic polycarbonate resin. You may mix and use seeds or more.

  In the aromatic polycarbonate resin 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 is lowered. 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 resin 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.

  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, based on the total amount of the aromatic polycarbonate resin and the ultraviolet absorber as 100% by weight. 0.05 to 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 blended in an aromatic polycarbonate resin 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 resin may contain at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof. it can. 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% by weight based on the aromatic polycarbonate resin. Is particularly preferred. By blending this phosphorus compound, the thermal stability of the aromatic polycarbonate resin 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 aromatic polycarbonate resin 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 the preferable addition amount of these antioxidants is 0.0001 to 0.05% by weight with respect to the aromatic polycarbonate resin.

  Furthermore, higher fatty acid esters of mono- or polyhydric alcohols can be added to the aromatic polycarbonate resin 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 the ester of alcohol and higher fatty acid is preferably 0.01 to 2% by weight, more preferably 0.015 to 0.5% by weight, and 0.02 to 0.02% by weight based on the aromatic polycarbonate resin. 2% by weight is more preferred. 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 resin of the present invention, additives such as lubricants and fillers, other polycarbonate resins, and other thermoplastic resins may be added in a small proportion within a range not impairing the object of the present invention.

  In the aromatic polycarbonate resin of the present invention, the specific viscosity at 20 ° C. in a solution dissolved in methylene chloride is preferably in the range of 0.2 to 1.2, more preferably in the range of 0.25 to 1.0, and A 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 resin 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.

The aromatic polycarbonate resin of the present invention preferably has high hydrolysis resistance when the content of the alkali metal compound is 10 ppm or less as an alkali metal atom. Preferably, it is 5 ppm or less, and more preferably 3 ppm or less. Such an alkali metal compound is one whose aqueous solution or extracted water is neutral or basic. For example, sodium, potassium nitrate, sulfate, oxide, hydroxide, carbonate, fatty acid salt, salt of aromatic dihydroxy compound, halide, specifically, NaCl, KCl, NaBr, KBr, _NaOH, KOH, and the like _{Na 2 SO 4, K 2 SO} 4. Further, glass, mica and zeolite containing alkali metal or alkaline earth metal are also included. Of these, the Na and / or K content is preferably 10 ppm or less, more preferably 5 ppm or less, and most preferably 3 ppm or less.

  The optical member in the present invention refers to lenses, prisms, light guide plates, optical waveguides, and the like, which are optical elements that are components for optical equipment. Specifically, the lens has two spherical or aspherical refractive surfaces and can transmit light, and is not particularly limited as long as it satisfies this. For example, a spherical lens, Examples include aspherical lenses, Fresnel lenses, and microarray lenses.

  In addition, the prism refers to a molded body having two or more polished surfaces that are not parallel but at an angle, and is not particularly limited as long as it satisfies this, but an example is given. For example, right-angle prisms, poro prisms, amic prisms, pentagonal prisms, doubless prisms, Hensolt prisms, Sprenggo prisms, mailer prisms, Wollaston prisms, tilted prisms, and Abbe prisms.

  The optical member formed from the aromatic polycarbonate copolymer in the present invention is molded by an arbitrary method such as an injection molding method, a compression molding method, an injection compression molding method, an extrusion molding method, or a solution casting method. In view of ease of molding and cost, it is particularly preferable to mold by an injection molding method or an injection compression molding method.

  An optical member such as a lens manufactured by such a method has high light transmittance, high heat resistance, high rigidity, and little change in appearance such as internal fogging, so that it is suitably used for electronic and electrical equipment.

  In the aromatic polycarbonate resin of the present invention, the optical member formed therefrom has high light transmittance, excellent heat resistance and rigidity, and little change in appearance such as cloudiness, so that the lens, prism, It is suitable for an optical member such as an optical fiber, an optical film, a liquid crystal display, a backlight type light diffusion plate of a liquid crystal television, or a light guide plate used in a scanner, and 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) Alkali metal content: 100 ml of water is added to 100 ml of methylene chloride solution in which 10 g of aromatic polycarbonate resin is dissolved, and the mixture is sufficiently stirred with a homomixer. It was measured.
(2) Glass transition temperature (Tg): Measured by a DuPont 910 type DSC measuring apparatus under a nitrogen stream of 40 mL / min under a temperature rising condition of 20 ° C./min.
(3) Viscosity average molecular weight (Mv): The intrinsic viscosity of polycarbonate resin obtained from bisphenol A by dissolving 0.7 g of polycarbonate resin in 100 mL of methylene chloride and inserting the specific viscosity (η _sp ) measured at 20 ° C. into the following equation: It was calculated in terms of
η _sp /c=[η]+0.45×[η] ² c
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
([Η] is intrinsic viscosity, c = 0.7)
(4) Wet heat evaluation of polycarbonate resin: 100 g of polycarbonate resin was put in a petri dish, covered, and treated for 11 hours in an autoclave under saturated steam conditions at 120 ° C.
(5) Evaluation of fog resistance of lens: After drying polycarbonate resin at 120 ° C. for 4 hours, cylinder temperature is set to 320 to 350 ° C. and mold temperature is set to 115 to 140 ° C. using an N-20C injection molding machine manufactured by JSW Corporation. A plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.8 mm, and a focal length of 2.0 mm was injection molded. The lens was treated for 11 hours in an autoclave under saturated steam conditions at 120 ° C., and then the appearance was visually evaluated. Those with no change in appearance such as internal cloudiness were marked with “◯”, and those with change were marked with “X”.

[Example 1]
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 22148 parts of ion-exchanged water and 4109 parts of 48% aqueous sodium hydroxide, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter referred to as “bis”). After dissolving 1165 parts of cresol fluorene (sometimes abbreviated as “cresol fluorene”), 2800 parts of 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as “bisphenol A”) and 13 parts of hydrosulfite After adding 15670 parts of methylene chloride, 1815 parts of phosgene was blown in at a temperature of 15 to 25 ° C. with stirring for 60 minutes. After completion of phosgene blowing, a solution obtained by dissolving 92 parts of p-tert-butylphenol in 330 parts of methylene chloride and 633 parts of a 48% aqueous sodium hydroxide solution were added. After emulsification, 5 parts of triethylamine was added and stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product was diluted with methylene chloride and washed with water. After acidification with hydrochloric acid, washing was repeated until the aqueous phase became almost neutral. Subsequently, the methylene chloride phase was concentrated to obtain a solution having a polycarbonate concentration of 10%, and the same amount of ion-exchanged water was added, followed by washing with water until the alkali metal content in the aqueous phase became 1 ppm or less. After dehydration, methylene chloride was removed to obtain a polymer having a molar ratio of biscresol fluorene to bisphenol A of 20:80 (polymer yield 97%). 0.1 wt% of “Irgafos 168” manufactured by Ciba Specialty Chemicals was added to this polymer, and extruded at 300 ° C. with a 30φ single screw extruder to be pelletized. The glass transition temperature (Tg) was 165 ° C., and the viscosity average molecular weight (Mv) was 18,500. When this pellet was analyzed by an ion chromatograph, 1.5 ppm of sodium ion was detected. Using this pellet, a plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.8 mm, and a focal length of 2.0 mm was injection-molded using an N-20C injection molding machine manufactured by JSW Corporation. When the lens and the pellet were subjected to a wet heat treatment, the Mv decreased by 400 to 18,100. In addition, no change was observed in the lens appearance. The results are shown in Table 1.

[Example 2]
The ratio of biscresol fluorene to bisphenol A is 50:50 in the same manner as in Example 1 except that the amount of biscresol fluorene used in Example 1 is 3058 parts and the amount of bisphenol A used is 1845 parts. A polymer was obtained (yield 96%). 0.1 wt% of “Irgafos 168” manufactured by Ciba Specialty Chemicals was added to this polymer, and extruded at 300 ° C. with a 30φ single screw extruder to be pelletized. The glass transition temperature (Tg) was 197 ° C., and the viscosity average molecular weight (Mv) was 15,500. When this pellet was analyzed by ion chromatography, 0.9 ppm of sodium ion was detected. When a lens was manufactured in the same manner as in Example 1 and wet heat treatment was performed in the same manner, Mv decreased by 200 and was 15,300. In addition, no change was observed in the lens appearance. The results are shown in Table 1.

[Example 3]
Ion exchange water 35315 parts, 48% sodium hydroxide 3920 parts were put in the same apparatus as in Example 1, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (abbreviated as bisphenol M) 2955 parts, After dissolving 3228 parts of biscresol fluorene and 14 parts of hydrosulfite, 12775 parts of methylene chloride was added, and 1946 parts of phosgene was blown in at 45 ° C. with stirring for 15 minutes. After the completion of phosgene blowing, 109 parts of p-tert-butylphenol and 711 parts of a 48% sodium hydroxide aqueous solution were added and emulsified, and 4.55 parts of triethylamine was added, followed by stirring at 28 to 33 ° C. for 1 hour to complete the reaction. After completion of the reaction, the product was diluted with methylene chloride and washed with water. After acidification with hydrochloric acid, washing was repeated until the aqueous phase became almost neutral. Subsequently, the methylene chloride phase and the aqueous phase were centrifuged by applying a centrifugal force of 1000 G or more at maximum. After dehydration, methylene chloride was removed to obtain a polymer having a molar ratio of bisphenol M to biscresol fluorene units of 50:50 (yield 98%). 0.1 wt% of “Irgafos 168” manufactured by Ciba Specialty Chemicals was added to this polymer, and extruded at 300 ° C. with a 30φ single screw extruder to be pelletized. The glass transition temperature (Tg) was 180 ° C., and the viscosity average molecular weight (Mv) was 13,200. When this pellet was analyzed by ion chromatography, 1.2 ppm of sodium ion was detected. When a lens was manufactured in the same manner as in Example 1 and wet heat treatment was performed in the same manner, Mv decreased by 300 to 12,900. In addition, no change was observed in the lens appearance. The results are shown in Table 1.

[Example 4]
When the Fresnel lens, the microarray lens, and the prism were manufactured by a known method using the pellet prepared in Example 1, and the wet heat treatment was performed in the same manner, no change was observed in the appearance.

[Comparative Example 1]
In Example 1, after completion of the reaction, the product was diluted with methylene chloride, washed with water, and not acidified with hydrochloric acid. Table 1 shows the results of producing lenses using the obtained pellets in the same manner as in Example 1 and evaluating in the same manner.

[Comparative Example 2]
In Example 2, after washing with water, the methylene chloride phase was concentrated and not washed again with water. Table 1 shows the results of manufacturing lenses using the obtained pellets in the same manner as in Example 2 and evaluating in the same manner.

[Comparative Example 3]
In Example 3, no centrifugation operation was performed. Table 1 shows the results of producing lenses using the obtained pellets in the same manner as in Example 3 and evaluating the lenses in the same manner.

Claims (5)

It is an optical member made of a transparent resin such that the incident light beam and the outgoing light beam from the incident light beam are changed in the optical path.
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. 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. ]
An optical member comprising an aromatic polycarbonate resin comprising a dihydroxy component represented by the formula (1), wherein the content of the alkali metal compound is 10 ppm or less as an alkali metal atom.   2. The optical member according to claim 1, wherein the optical member is a pickup lens, a camera lens, a microarray lens, a lens such as a projector lens or a Fresnel lens, an optical path conversion component such as a prism and an optical fiber, a reflow soldering component, or a plastic mirror.   The optical member according to claim 1 or 2, wherein the fluorene-based bisphenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.   2. 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 optical member in any one of -3. 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. 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. ]
An aromatic polycarbonate resin comprising a dihydroxy component represented by the formula (1), wherein the content of the alkali metal compound is 10 ppm or less as an alkali metal atom.