JP4369208B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the light resistance is improved suitable for applications such as lighting covers and globes, optical lenses, LED lenses, optical waveguides, retardation films for liquid crystal display elements, films such as plastic substrate substrates that require heat resistance, and sheets. The present invention relates to an aromatic polycarbonate resin composition.

  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. Especially because of its excellent transparency, it has many uses as an optical material. Lighting covers and gloves that require heat resistance in recent years, electronic component materials, LED lenses, prisms, hard disk carriers, films for liquid crystal substrates for liquid crystal displays and retardation It is also being studied for applications that require heat resistance, such as film applications. In these cases, in the case of a normal polycarbonate resin from bisphenol A, for example, in the case of a film used for a liquid crystal display, a high temperature treatment of 180 ° C. or more is required in an alignment film forming process or an electrode forming process, and the heat resistance is insufficient. There is. In addition, when used for lighting covers and gloves, the amount of heat generated has increased in recent years due to an increase in light emission luminance, and conventional polycarbonate resins have had problems with heat resistance.

  In order to improve the heat resistance of the polycarbonate resin, there is generally a method using bisphenols having a bulky structure that hardly moves, and various polycarbonates have been proposed. Among them, a polycarbonate resin having a specific fluorene structure has been proposed. (For example, see Patent Documents 1, 2, 3, and 4) However, although the polycarbonate resin having a fluorene structure is excellent in heat resistance, the molded product is very easily deteriorated by ultraviolet irradiation and easily yellows. It was difficult to use as a part.

  On the other hand, some have improved the thermal stability and light resistance of a polycarbonate resin composition having a specific composition. (For example, see Patent Document 5) However, it is extremely difficult and insufficient to improve the light resistance of a polycarbonate resin having such a specific composition by adding a small amount of a general benzotriazole-based or benzophenone-based UV absorber. When a large amount of these ultraviolet absorbers is added to compensate for the light resistance, there is a drawback that the molded product is poorly molded or colored, or the heat resistance inherent in the polycarbonate resin is impaired.

  Also, benzoxazin-one UV absorbers different from general benzotriazole and benzophenone UV absorbers have been reported. (For example, see Patent Document 6) However, since the ultraviolet absorber has a low ultraviolet absorption ability near 290 to 310 nm, which is most likely to cause light degradation in the conventional bisphenol A type polycarbonate, it is generally not effective as a polycarbonate. Has not been used.

JP-A-6-25401 JP-A-7-52271 JP-A-11-174424 Japanese Patent Laid-Open No. 11-306823 JP 11-35815 A JP 62-11744 A

  An object of the present invention is to provide a polycarbonate resin composition having better heat resistance and birefringence as compared with an aromatic polycarbonate made of ordinary bisphenol A and having excellent light resistance. As a result of intensive studies to achieve this object, the present inventor has blended a specific ultraviolet absorber into an aromatic polycarbonate resin composition obtained by using a specific bisphenol, whereby The inventors have found that the object is achieved, and have reached the present invention.

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

［式中、Ｒ¹〜Ｒ⁴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、またはハロゲン原子である。］
９５〜５モル％が下記一般式［２］

[Wherein, R ^{1 to} R ⁴ each independently represents a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ]
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。］
で表される芳香族ジヒドロキシ成分からなるポリカーボネート共重合体（Ａ）に、塩化メチレン中に１０ｍｇ／Ｌの濃度で溶解した際の光路長１ｃｍで測定した３６０ｎｍにおける吸光度（Ａ_{３６０ｎｍ}）が０．５以上であり且つ４００ｎｍにおける吸光度（Ａ_{４００ｎｍ}）が０．０１以下である下記一般式［３］で表されるベンゾオキサジン−オン構造を含有する紫外線吸収剤（Ｂ）０．０１〜５重量％を含有せしめてなる芳香族ポリカーボネート樹脂組成物から構成される。

［式中、Ｒ ^９ 〜Ｒ ^１１ 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、またはハロゲン原子である。］

[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. ]
In in the aromatic polycarbonate copolymer composed of dihydroxy component represented (A), the absorbance at 360nm measured with an optical path length 1cm when dissolved at a concentration of 10 mg / L in methylene chloride _{(A 360nm)} of 0.5 The ultraviolet absorber (B) having a benzoxazin-one structure represented by the following general formula [3] having an absorbance at 400 nm (A _{400 nm} ) of 0.01 or less is 0.01 to 5% by weight. It is comprised from the aromatic polycarbonate resin composition made to contain.

[Wherein, R ^{9 to} R ¹¹ each independently represent a hydrogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ]

  In the aromatic polycarbonate copolymer of the present invention, 9,9-bis (4-hydroxyphenyl) fluorene represented by the above formula (1) is 5 of the wholly aromatic dihydroxy component as the aromatic dihydroxy component constituting the aromatic polycarbonate copolymer. It is -95 mol%, Preferably it is 10-90 mol%, More preferably, it is 15-80 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.

  Examples of 9,9-bis (4-hydroxyphenyl) fluorenes include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, -Bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, etc., among which 9,9-bis (4-hydroxy-3-methylphenyl) ) Fluorene is preferred.

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, 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-hydroxyphenyl -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 which bisphenol A, bisphenol C, bisphenol Z and bisphenol M are preferable, and bisphenol is particularly preferable. A is preferred.

  In the aromatic polycarbonate copolymer, the specific viscosity at 20 ° C. in a solution of the polymer 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, The range of 0.27 to 0.80 is more preferable. If the specific viscosity is within the above range, the strength of the molded product or film 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 in which an aromatic dihydroxy component is reacted 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 ¹² , —CO—O—R ¹³ or R ¹⁴ , wherein R ¹² , R ¹³ and R ¹⁴ 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.
I 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, 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.

  Moreover, in the aromatic polycarbonate copolymer of the present invention, when 9,9-bis (4-hydroxyphenyl) 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 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 point of preferably 150 ° C. or higher, more preferably 160 ° C. or higher, and further preferably 165 ° C. or higher.

The ultraviolet absorber used in the present invention is preferably one having an absorbance at _{360 nm} (A _{360 nm} ) of 0.5 or more measured at an optical path length of 1 cm when dissolved in methylene chloride at a concentration of 10 mg / L. It is more preferable that the absorbance is 0.6 or more.

Further, the ultraviolet absorber used in the present invention preferably has an absorbance at _{400 nm} (A _{400 nm} ) of 0.01 or less measured at an optical path length of 1 cm when dissolved in the methylene chloride at a concentration of 10 mg / L. . When _{A400 nm} is larger than 0.01, the hue of the resin itself is affected, and the molded product is colored. As the hue, the yellowness (YI) of a molded sample plate having a thickness of 2 mm is preferably 10 or less, and particularly preferably 5 or less.

In the present invention, the glass transition temperature of the aromatic polycarbonate resin composition in which 2 parts by weight of the ultraviolet absorber (B) is added to 100 parts by weight of the aromatic polycarbonate copolymer (A) is Tg ′, and the ultraviolet absorber is added. When the glass transition temperature of the aromatic polycarbonate resin that is not used is Tg,
Tg−Tg ′ ≦ 5 ° C.
It is preferable that Low molecular weight or liquid UV absorbers are not preferred because Tg is greatly reduced and heat resistance is greatly impaired.

As such an ultraviolet absorber, the ultraviolet absorber containing the benzoxazin-one structure represented by the following general formula [3] is mentioned, for example.

  In the present invention, examples of the ultraviolet absorber containing a benzoxazin-one structure include 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1-benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzo Oxazin-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 ' -(4,4'-diphenylene) bis ( , 1-benzoxazin-4-one), 2,2 ′-(2,6 or 1,5-naphthalene) bis (3,1-benzoxazin-4-one), 1,3,5-tri (3 , 1-Benzoxazin-4-one-2-yl) benzene, 2,8-dimethyl-4H, 6H-benzo [1,2-d; 5,4-d ′] bis- [1,3] -oxazine -4,6-dione, 6,6'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one) and the like, among which 2,2'-p-phenylenebis (3 , 1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) Bis (3,1-benzoxazin-4-one) is preferred, especially the following general formula 2,2'-p-phenylene bis represented by 4] (3,1-benzoxazin-4-one) is preferred.

These ultraviolet absorbers may be used alone or in combination of two or more.
The content of these ultraviolet absorbers is 0.01 to 5% by weight, preferably 0.02 to 3% by weight, and more preferably 0.05 to 2% by weight, based on 100% by weight of the aromatic polycarbonate resin. 5% 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.

  As the stabilizer used in the present invention, a benzofuranone-based stabilizer is preferably used. Examples of the benzofuranone-based stabilizer include 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofurano-2-one, 5,7-di-t-butyl-3- ( 2,3-dimethylphenyl) -3H-benzofurano-2-one. These stabilizers may be used alone or in combination of two or more.

  These stabilizers are 0.01 to 5% by weight, preferably 0.01 to 0.1% by weight, particularly preferably 0, based on 100% by weight of the total amount of the polycarbonate resin and other additives. 0.01 to 0.05% by weight. If it is less than 0.01% by weight, the performance is insufficient, and if it exceeds 5% by weight, the performance 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 into the aromatic polycarbonate resin at a concentration of 0.1 to 3 ppm, more preferably 0.3 to 2.5 ppm, and most preferably 0.5 to 2.2 ppm.

  In the present invention, the aromatic polycarbonate copolymer contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, and esters thereof. On the other hand, it can be blended at a ratio of 0.0001 to 0.05% by weight. 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, and preferably the following general formulas [5] to [8] ] At least one phosphorus compound selected from the group consisting of:

Here, R ^{15 to} R ²⁶ are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, It 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. When two alkyl groups are present in one compound, the two alkyl groups may be bonded to each other to form a ring.

  Examples of the phosphorus compound represented by the above formula (5) 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) pentaerythritol Examples include tall diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like. Examples of the phosphorus compound represented by the above formula (6) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. Examples of the phosphorus compound represented by the formula (7) include tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, and the formula (8) above. The compounds, dimethylbenzene phosphonate, benzene phosphonic acid diethyl, and the like dipropyl benzene phosphonate. Of these, distearyl pentaerythritol diphosphite, triethyl phosphate, dimethyl benzenephosphonate, and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferably used.

  The amount of the phosphorus compound is 0.0001 to 0.05% by weight, preferably 0.0005 to 0.02% by weight, and preferably 0.001 to 0.01% by weight based on the aromatic polycarbonate copolymer. % Is particularly preferred. If the blending amount is less than 0.0001% by weight, it is difficult to obtain the above effect. If the blending amount exceeds 0.05% by weight, the thermal stability of the aromatic polycarbonate copolymer is adversely affected, and hydrolysis resistance is also reduced. Since it falls, it is not preferable.

  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 colorants, antistatic agents, lubricants, diffusing agents, fillers, other polycarbonate resins, and other thermoplastic resins do not impair the purpose of the present invention. A small proportion can be added within the range.

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

The aromatic polycarbonate resin composition of the present invention has a yellowness after irradiation of a mercury lamp with an irradiation intensity of 15 mW / cm ² at 300 to 400 nm for 7 days on a 2 mm-thick molded plate made of polycarbonate resin without containing an ultraviolet absorber. The amount of change in (YI) is ΔYI ₀ , and mercury having an irradiation intensity of 15 mW / cm ² at 300 to 400 nm is formed on a 2 mm thick molded plate made of a polycarbonate resin composition when a predetermined amount of the ultraviolet absorber used in the present invention is added. The change in yellowness after irradiating the lamp for 7 days is defined as ΔYI _1, and the degree of light resistance improvement effect by the ultraviolet absorber (R _YI ) is R _YI = (1−ΔYI ₁ / ΔYI ₀ ) × 100 (%)
When
R _YI ≧ 50%
The effect of the ultraviolet absorber in this composition is great, and the polycarbonate resin composition exhibits good light resistance.

  Molded articles produced by such a method are used in various applications requiring heat resistance, such as glazing applications, automobile lamp lenses, lamp covers, optical lenses, prisms, OHP sheets, name plates, display lamps, optical waveguides, and the like. Moreover, the film manufactured by this method is suitably used as a placel substrate or a retardation film for flat panel display substrate applications. The placel substrate is used unstretched, but in order to use it as a retardation film, it is stretched and oriented in at least a uniaxial direction so as to have an optimal birefringence characteristic to form a retardation film.

Since the aromatic polycarbonate resin composition of the present invention has good heat resistance and excellent light resistance, the illumination cover and globe, optical lens, LED lens, optical waveguide, retardation film for liquid crystal display element, It is particularly suitably used for forming films, sheets and the like such as a plastic substrate that require heat resistance and light resistance.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to this. In the examples, “parts” means “parts by weight”. The evaluation was performed by the following method.

(I) Evaluation Items (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 point (Tg)
A 2910 type DSC manufactured by TS Instruments Japan Co., Ltd. was used, and the temperature was increased at a rate of 20 ° C./min.
(3) Sample plate hue The yellowness (YI) of the molded sample plate having a thickness of 2 mm was measured using a spectrocolorimeter SE-2000 (light source: C / 2) manufactured by Nippon Denshoku Co., Ltd.
(4) Light resistance A 400 W transparent mercury lamp is used as the light source without changing the irradiation surface of the molded sample plate having a thickness of 2 mm, the UV irradiation intensity of 300 to 400 nm is 15 mW / cm ² , and the test temperature is 7 ° C. UV irradiation was performed for a day, and the test piece was taken out and the yellowness (YI) change before and after the test was evaluated using a spectrocolorimeter SE-2000 (light source: C / 2) manufactured by Nippon Denshoku Co., Ltd.

Here, ΔYI _{0 is} a test result using a molded sample plate made of an aromatic polycarbonate resin to which no UV absorber is added, and a molded sample plate made of an aromatic polycarbonate resin composition to which a specified amount of UV absorber is added. The test result used is ΔYI ₁ and the degree of light fastness improvement effect (R _YI ) is R _YI = (1−ΔYI ₁ / ΔYI ₀ ) × 100 (%)
As shown.

(II) Synthesis of each component in the composition (a) Polycarbonate resin (PC resin)
◎ Production of polycarbonate copolymer of the present invention-Part 1
In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 19580 parts of ion-exchanged water and 3845 parts of 48% sodium hydroxide aqueous solution were added, and 2835 parts of bisphenol A, 1175 parts of biscresol fluorene and 8.4 parts of hydrosulfite were dissolved. After adding 13209 parts of methylene chloride, 2000 parts of phosgene was blown in at 60 to 20 ° C. for 60 minutes while stirring. After completion of the phosgene blowing, 93.2 parts of p-tert-butylphenol and 641 parts of 48% aqueous sodium hydroxide solution were added, and 2.0 parts of triethylamine was further added, followed by stirring at 20 to 27 ° C. for 40 minutes to complete the reaction. . 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, 4250 parts of light yellow polymer (abbreviated as “EX-PC1”) having a molar ratio of bisphenol A and biscresol fluorene of 80:20, a specific viscosity of 0.370, and a Tg of 172 ° C. were obtained. Rate 95%).

◎ Production of polycarbonate copolymer of the present invention-2
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts of ion-exchanged water and 4230 parts of a 48% aqueous sodium hydroxide solution were added, and 1949 parts of bisphenol A, 3231 parts of biscresol fluorene and 10.9 parts of hydrosulfite were dissolved. After adding 14530 parts of methylene chloride, 2200 parts of phosgene was blown in at a temperature of 16 to 20 ° C. with stirring for 60 minutes. After completion of the phosgene blowing, 115.4 parts of p-tert-butylphenol and 705 parts of a 48% aqueous sodium hydroxide solution were added, and 2.6 parts of triethylamine was further added, followed by stirring at 20 to 27 ° C. for 40 minutes to complete the reaction. . 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, A light yellow polymer (abbreviated as “EX-PC2”) having a molar ratio of bisphenol A and biscresol fluorene of 50:50, a specific viscosity of 0.280, and a Tg of 198 ° C. was obtained. Rate 95%).

Production of Aromatic Polycarbonate Resin for Comparison In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 19760 parts of ion exchange water and 4240 parts of 48% aqueous sodium hydroxide solution are added, 5010 parts of bisphenol A, and 10 parts of hydrosulfite. After dissolving 0 parts and adding 12510 parts of methylene chloride, 2500 parts of phosgene was blown in for 60 minutes at 18 to 20 ° C. with stirring. After completion of the phosgene blowing, 148.2 parts of p-tert-butylphenol and 650 parts of 48% aqueous sodium hydroxide solution were added, and 5.5 parts of triethylamine was further added, followed by stirring at 20 to 27 ° C. for 40 minutes to complete the reaction. . 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, 5380 parts of white bisphenol A homopolymer (abbreviated as “CEX-PC1”) having a specific viscosity of 0.368 and a Tg of 145 ° C. were obtained (yield 94%).

(B) Ultraviolet absorber (UVA)
◎ 2,2′-p-phenylenebis (3,1-benzoxazin-4-one): CEi-P (abbreviated as “EX-UVA1”) manufactured by Takemoto Yushi Co., Ltd.
2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one): synthesized and used. (Abbreviated as “EX-UVA2”)
◎ 1,4-bis (4-benzoyl-3-hydroxyphenoxy) butane: Seesorb 151 (abbreviated as “CEX-UVA1”) manufactured by Cypro Kasei Co., Ltd.
◎ 2- [5-Chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol: Tinuvin 326 ("CEX-UVA2" manufactured by Ciba Specialty Chemicals Co., Ltd.) (Omitted)

Absorbance at _{360 nm} (A _{360 nm} ) and absorbance at _{400 nm} (A _{400 nm} ) measured at an optical path length of 1 cm when each ultraviolet absorber was dissolved in methylene chloride at a concentration of 10 mg / L, and no ultraviolet absorber was added. Glass transition temperature (Tg) of EX-PC1 and EX-PC2, and glass transition temperature of aromatic polycarbonate resin composition in which 2 parts by weight of each ultraviolet absorber is added to 100 parts by weight of EX-PC1 and EX-PC2 ( Tg ′) is shown in Table 1.

[Examples 1 to 4, Comparative Examples 1 to 5]
EX-PC1 and EX-PC2 obtained above were mixed with 0.007% 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofurano-2-one, bis (2, 4-Dicumylphenyl) pentaerythritol diphosphite 0.050%, pentaerythritol tetrastearate 0.050%, and each UV absorber listed in Table 2 was mixed uniformly using a tumbler, and then 30 mmφ Using a twin screw extruder with a vent (KTX-30 manufactured by Kobe Steel Co., Ltd.), the pellet was pelletized while degassing at a cylinder temperature of 300 ° C. and a vacuum of 10 mmHg, and the resulting pellet was dried at 120 ° C. for 5 hours and then injected. Using a molding machine (SG150U model manufactured by Sumitomo Heavy Industries, Ltd.), a test with a thickness of 2 mm under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 100 ° C. We have created a sample plate. Each evaluation result is shown in Table 2.

  As is apparent from each comparison, the aromatic polycarbonate resin composition comprising the polycarbonate copolymer of the present invention and a specific ultraviolet absorber is found to have excellent light resistance.

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. ]
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. ]
The absorbance at _{360 nm} (A _{360 nm} ) measured at an optical path length of 1 cm when dissolved in methylene chloride at a concentration of 10 mg / L in a polycarbonate copolymer (A) composed of an aromatic dihydroxy component represented by The ultraviolet absorber (B) having a benzoxazin-one structure represented by the following general formula [3] having an absorbance at 400 nm (A _{400 nm} ) of 0.01 or less is 0.01 to 5% by weight. An aromatic polycarbonate resin composition to be contained.

[Wherein, R ^{9 to} R ¹¹ each independently represent a hydrogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ]   The aromatic polycarbonate according to claim 1, wherein 15 to 85 mol% of the wholly aromatic dihydroxy component is an aromatic dihydroxy component represented by the general formula [1] and 85 to 15 mol% of the general formula [2]. Resin composition. The amount of change in yellowing degree (YI) after 7 days of irradiation with a mercury lamp with an irradiation intensity of 15 mW / cm ² at 300 to 400 nm on a 2 mm thick molded plate made of polycarbonate resin of (A) is expressed as ΔYI ₀ , (A) and The change in yellowing degree after irradiating a mercury lamp of 300 to 400 nm with a 15 mW / cm ² irradiation intensity for 7 days on a 2 mm thick molded plate made of the polycarbonate resin composition consisting of (B) is ΔYI ₁ and is light resistant by an ultraviolet absorber. The degree (R _Y1 ) of the effect of improving the property is R _YI = (1−ΔYI ₁ / ΔYI ₀ ) × 100 (%)
When R _Y1 ≧ 50%
The aromatic polycarbonate resin composition according to claim 1, wherein The glass transition temperature of the aromatic polycarbonate resin composition in which 2 parts by weight of the ultraviolet absorber (B) is added to 100 parts by weight of the aromatic polycarbonate copolymer (A) is Tg ′, and the fragrance to which no ultraviolet absorber is added. Tg is 150 ° C. or higher and Tg−Tg ′ ≦ 5 ° C. when the glass transition temperature of the group polycarbonate resin is Tg.
The aromatic polycarbonate resin composition according to claim 1, wherein The aromatic polycarbonate resin according to claim 1, wherein the ultraviolet absorber (B) is 2,2'-p-phenylenebis (3,1-benzoxazin-4-one) represented by the following general formula [4]. Composition.

  The aromatic polycarbonate resin composition according to claim 1, wherein the general formula [1] is 9,9-bis (4-hydroxyphenyl) fluorene or 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.   The compound represented by the general formula [2] is 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, α, α′-bis (4 The aromatic polycarbonate resin composition according to claim 1, which is at least one selected from the group consisting of -hydroxyphenyl) -m-diisopropylbenzene and 1,1-bis (4-hydroxyphenyl) cyclohexane.