JP2004176052A - Aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition having good heat resistance and excellent light resistance. <P>SOLUTION: The aromatic polycarbonate resin composition comprises incorporating 0.01-5 wt.% of an ultraviolet absorbent (B) which an absorbance (A<SB>360nm</SB>) in 360nm measured by 1 cm of an optical path when the absorbent is dissolved at a concentration of 10 mg/L in methylene chloride is ≥0.3, and an absorbance (A<SB>400nm</SB>) in 400nm is ≤0.01, in a polycarbonate copolymer (A) comprising an aromatic dihydroxy component of 5-95 mol% of the whole aromatic dihydroxy component, which is represented by formula (1) (wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>are each independently a hydrogen atom, a 1-9C hydrocarbon group which may contain an aromatic group, or a halogen atom), and of 95-5 mol% of the whole dihydroxy component, which is represented by formula (2) (wherein R<SP>5</SP>, R<SP>6</SP>, R<SP>7</SP>, and R<SP>8</SP>are each independently a hydrogen atom, a 1-9C hydrocarbon group which may contain an aromatic group or a halogen atom; W is a single bond, a 1-20C hydrocarbon group which may contain an aromatic group, O, S, SO, SO<SB>2</SB>, CO or a COO group). <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, improved light resistance suitable for applications such as lighting covers and gloves, optical lenses, LED lenses, optical waveguides, retardation films for liquid crystal display elements, films such as placell substrates and the like requiring heat resistance, sheets, etc. 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. In particular, it has many uses as an optical material because of its excellent transparency. Lighting covers and gloves that require heat resistance in recent years, materials for electronic components, LED lenses, prisms, hard disk carriers, films for liquid crystal substrates of liquid crystal displays, and retardation It is also being studied for applications requiring heat resistance, such as film applications. In these cases, the usual polycarbonate resin from bisphenol A requires a high-temperature treatment of 180 ° C. or more in a film used for a liquid crystal display, for example, 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 recently increased due to an increase in the emission luminance of lighting, and the conventional polycarbonate resin has a problem in heat resistance.

  In order to improve the heat resistance of the polycarbonate resin, there is generally a method using a bisphenol having a bulky and hard-moving structure, 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, 2, 3, and 4.) However, these polycarbonate resins having a fluorene structure are excellent in heat resistance, but molded articles are easily deteriorated by ultraviolet irradiation and are easily yellowed. It was difficult to use as a part.

  On the other hand, there is also a method in which the heat stability and light resistance of a polycarbonate resin composition having a specific composition are improved. (See, for example, 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 ultraviolet absorber. When these ultraviolet absorbers are added in a large amount in order to compensate for the light resistance described above, there are drawbacks in that molded articles may have poor molding or coloring, or may impair the heat resistance originally possessed by the polycarbonate resin.

  Also, benzoxazin-one-based UV absorbers different from general benzotriazole and benzophenone-based UV absorbers have been reported. However, since the ultraviolet absorber has a low ultraviolet absorption capacity at around 290 to 310 nm, which is most liable to cause photodegradation in a conventional bisphenol A type polycarbonate, and has a low effect as a light stabilizer, it is generally used for polycarbonate. Has not been used.

JP-A-6-25401 JP-A-7-52271 JP-A-11-174424 JP-A-11-306823 JP-A-11-35815 JP-A-62-11744

  An object of the present invention is to provide a polycarbonate resin composition which has better heat resistance and birefringence than a normal aromatic polycarbonate comprising bisphenol A, and is excellent in light resistance. The present inventors have conducted intensive studies to achieve this object, and as a result, by blending a specific ultraviolet absorber into an aromatic polycarbonate resin composition obtained by using a specific bisphenol, The inventors have found that the object is achieved, and have reached the present invention.

  That is, according to the present invention, the present polycarbonate resin composition has 5 to 95 mol% of the total 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 are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ]
95 to 5 mol% of the following general formula [2]

［式中、Ｒ⁵〜Ｒ⁸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０．３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。

[Wherein, R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom, and W is a single bond, 1 to 9 carbon atoms. A hydrocarbon group, which may contain 20 aromatic groups, an O, S, SO, SO ₂ , CO or COO group. ]
When dissolved in methylene chloride at a concentration of 10 mg / L in a polycarbonate copolymer (A) comprising an aromatic dihydroxy component represented by the formula, the absorbance at _{360 nm} (A _{360 nm} ) measured at an optical path length of 1 cm is 0.3. It is composed of an aromatic polycarbonate resin composition containing 0.01 to 5% by weight of an ultraviolet absorber (B) having an absorbance at 400 nm of _{400 nm} or less (A _{400 nm} ) or less.

  In the aromatic polycarbonate copolymer of the present invention, 9,9-bis (4-hydroxyphenyl) fluorene represented by the above formula (1) is used as an aromatic dihydroxy component constituting the aromatic dihydroxy component. -95 mol%, preferably 10-90 mol%, more preferably 15-80 mol%. If the amount is less than 5 mol%, unsatisfactory properties as a heat-resistant material, which is the object of the present invention, are not preferred.

  As the 9,9-bis (4-hydroxyphenyl) fluorene, for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene and the like, 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 usually used as a dihydroxy component of an aromatic polycarbonate, such as hydroquinone and 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, etc., of which bisphenol A, bisphenol C, bisphenol Z and bisphenol M are preferable, and bisphenol M is particularly preferable. A is preferred.

  The aromatic polycarbonate copolymer has a specific viscosity at 20 ° C. in a solution of the polymer dissolved in methylene chloride in a range of preferably 0.2 to 1.2, more preferably 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 article or film is sufficiently strong, the melt viscosity and the solution viscosity are appropriate, and the handling is easy, which is 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 a carbonate precursor such as phosgene or a carbonic acid diester with an aromatic dihydroxy component. . Next, basic means of 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. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

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

  Further, a catalyst usually used in a transesterification reaction for promoting the reaction can also be used. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.

  In the aromatic polycarbonate copolymer of the present invention, monofunctional phenols that are generally used as a terminal stopper in the polymerization reaction can be used. Particularly in the case of the reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminating agent for controlling the molecular weight, and the obtained aromatic polycarbonate copolymer has a monofunctional terminal. Since it is blocked by a group based on phenols, it has better heat stability than that which is not.

  The monofunctional phenol may be any one used as a terminal terminator of an aromatic polycarbonate resin, and is generally a phenol or a lower alkyl-substituted phenol, and is a monofunctional phenol represented by the following general formula. Can be shown.

［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。］

[In the formula, A is a hydrogen atom, a linear or branched alkyl group or an arylalkyl group having 1 to 9 carbon atoms, 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 aliphatic ester group as a substituent, or long-chain alkyl carboxylic acid chlorides can be used. When these compounds are used to block the ends of the aromatic polycarbonate copolymer, they not only function as a terminal terminator or a molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding and processing. Also, the physical properties are improved. Particularly, it has an effect of lowering the water absorption of the resin, and is preferably used. These are represented by the following general formulas [Ia] to [Ih].

[In the above general formulas [Ia] to [Ih], X is -RO-, -R-CO-O- or -RO-CO-, wherein R is a single bond or Represents 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, preferably 1 to 5 carbon atoms, p represents an integer of 0 to 4, and Y represents 1 to 10 carbon atoms, preferably 1 to 5 represents a divalent aliphatic hydrocarbon group, wherein 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 C 1-10, preferably C 1-5 monovalent aliphatic hydrocarbon group, C 4-8, preferably C 5-6 monovalent alicyclic hydrocarbon group or C 6-15, It preferably represents 6 to 12 monovalent aromatic hydrocarbon groups.
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, It preferably represents a divalent aliphatic hydrocarbon group of 1 to 5, W ² represents a hydrogen atom, a carbon atom of 1 to 10, preferably a monovalent aliphatic hydrocarbon group of 1 to 5, a carbon number of 4 to 8, It preferably 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, preferred are the substituted phenols [Ia] and [Ib]. As the substituted phenols of [Ia], those having n of 10 to 30, especially 10 to 26 are preferable, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, 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 are preferable. Suitable and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and tricontyl hydroxybenzoate.

  In the substituted phenols or substituted benzoyl chlorides represented by the 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 at least 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained aromatic polycarbonate copolymer, and the monofunctional phenols are used alone. Alternatively, two or more kinds may be used in combination.

  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 reduced. Therefore, it is preferable to use substituted phenols or substituted benzoic acid chlorides represented by the general formulas [Ia] to [Ig] as a terminal stopper.

  The aromatic polycarbonate copolymer of the present invention may be a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the spirit of the present invention is not impaired. . Alternatively, a branched polycarbonate obtained by copolymerizing a small amount of a trifunctional compound may be used.

  The glass transition point of the aromatic polycarbonate copolymer of the present invention is preferably 150 ° C. or higher, more preferably 160 ° C. or higher, even more preferably 165 ° C. or higher.

As the ultraviolet absorber used in the present invention, those having an absorbance at _{360 nm} ( _A360nm ) 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 are preferable. It is more preferable that the absorbance is 0.6 or more.

The ultraviolet absorber used in the present invention preferably has an absorbance at _{400 nm} ( _A400nm ) of 0.01 or less measured at an optical path length of 1 cm when dissolved in methylene chloride at a concentration of 10 mg / L. . When A _{400 nm} is larger than 0.01, the hue of the resin itself is affected, and the molded product is undesirably colored. As the hue, the yellowness (YI) of the 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 obtained by adding 2 parts by weight of the ultraviolet absorber (B) 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 an unreacted aromatic polycarbonate resin is Tg,
Tg−Tg ′ ≦ 5 ° C.
It is preferable that A low molecular weight or liquid ultraviolet absorber is not preferable because Tg is greatly reduced and heat resistance is greatly impaired.

  Such an ultraviolet absorber may be any as long as it satisfies the above characteristics. For example, an ultraviolet absorber having a benzoxazin-one structure represented by the following general formula [3], benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, cyanoacrylate UV absorbers, coumarin UV absorbers, etc., among which UV absorbers having a benzoxazin-one structure are particularly preferred.

  In the present invention, examples of the ultraviolet absorber having 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 them, 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 preferable, and particularly, the following general formula: 2,2'-p-phenylene bis represented by 4] (3,1-benzoxazin-4-one) is preferred.

These UV 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, particularly preferably 0.05 to 2% by weight of the aromatic polycarbonate resin as 100% by weight. 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 deteriorate, which is not preferable.

  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 and 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 used in an amount of 0.01 to 5% by weight, preferably 0.01 to 0.1% by weight, particularly preferably 0 to 0.1% by weight, based on the total amount of the polycarbonate resin and other additives as 100% by weight. 0.01 to 0.05% by weight. If the amount is less than 0.01% by weight, the performance is insufficient. If the amount exceeds 5% by weight, the performance of the resin may be deteriorated, which is not preferable.

  In the present invention, a bluing agent may be used. Examples of the bluing agent include Macrolex Violet manufactured by Bayer Corp., Diaresin Violet manufactured by Mitsubishi Chemical Corporation, Diaresin Blue, and Sandoz Co., Ltd. And terazole blue, and Macrox Violet as the most preferable one. 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 2.5 ppm, and most preferably 0.5 to 2.2 ppm.

  In the present invention, the aromatic polycarbonate copolymer has at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof, in the copolymer. 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 such an 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 is preferably represented by 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) pentaerythri Tall diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and the like. Examples of the phosphorus compound represented by the formula (6) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate. Examples of the phosphorus compound represented by the formula (7) include tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite and the like. The compounds, dimethylbenzene phosphonate, benzene phosphonic acid diethyl, and the like dipropyl benzene phosphonate. Among them, distearyl pentaerythritol diphosphite, triethyl phosphate, dimethyl benzenephosphonate, and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferably used.

  The compounding amount of the phosphorus compound is 0.0001 to 0.05% by weight, preferably 0.0005 to 0.02% by weight, and more preferably 0.001 to 0.01% by weight based on the aromatic polycarbonate copolymer. % Is particularly preferred. If the amount is less than 0.0001% by weight, it is difficult to obtain the above effects. If the amount exceeds 0.05% by weight, the thermal stability of the aromatic polycarbonate copolymer is adversely affected, and the hydrolysis resistance is also lowered. It is not preferable because it lowers.

  An antioxidant generally known for the purpose of preventing oxidation can be added to the polycarbonate copolymer of the present invention. Examples thereof include phenolic antioxidants, and 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-h) Roxy-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 and the like. The preferable range of the addition amount of these antioxidants is 0.0001 to 0.05% by weight based on the polycarbonate copolymer.

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

  The higher fatty acid ester is preferably a partial ester or a whole ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of the partial or total ester of a monohydric or polyhydric alcohol with a saturated fatty acid include monoglyceride stearate, monosorbitate stearate, monoglyceride behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, and propylene glycol. Monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, and the like, among which stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used .

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

  In the aromatic polycarbonate copolymer of the present invention, further additives such as a coloring agent, an antistatic agent, a lubricant, a diffusing agent, a filler and other polycarbonate resins, other thermoplastic resins do not impair the object of the present invention. A small proportion can be added within the range.

  As a method for obtaining a molded article 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 excellent in uniformity and free from optical defects such as gel, buttocks, fish eyes, and scratches is preferable, and examples thereof include a solvent casting method, a melt extrusion method, and a calendering method.

The aromatic polycarbonate resin composition of the present invention has a yellowness after irradiating a 2 mm-thick molded plate of a polycarbonate resin containing no ultraviolet absorber with a mercury lamp having an irradiation intensity of 15 mW / cm ² at 300 to 400 nm for 7 days. 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 applied to 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. lamps yellowness changes after irradiation for 7 days and .DELTA.YI _1, the degree of light resistance improving effect by the ultraviolet absorber _{(R YI)} of _{R YI = (1-ΔYI 1} / ΔYI 0) × 100 (%)
And when
R _YI ≧ 50%
In this composition, the effect of the ultraviolet absorber is large, and the polycarbonate resin composition shows good light resistance.

  Molded articles produced by such a method are used for various applications requiring heat resistance, for example, glazing applications, automotive lamp lenses, lamp covers, optical lenses, prisms, OHP sheets, nameplates, indicating lamps, optical waveguides, and the like. Further, the film produced by such a method is suitably used as a placell substrate or a retardation film for flat panel display substrates. Although the placell substrate is used in an unstretched state, in order to use it as a retardation film, it is stretched and oriented in at least one axial direction so as to have optimal birefringence characteristics, thereby forming a retardation film.

The aromatic polycarbonate resin composition of the present invention has good heat resistance and excellent light resistance, so that a lighting cover and a globe, an optical lens, an LED lens, an optical waveguide, a retardation film for a liquid crystal display element, It is particularly suitable for use in molding films and sheets, such as placell boards, which require heat resistance and light resistance.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. 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 a polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.
(2) Glass transition point (Tg)
The measurement was performed at a heating rate of 20 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan Co., Ltd.
(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 manufactured by Nippon Denshoku Co., Ltd. (light source: C / 2).
(4) Light resistance A molded 2 mm thick sample plate was used without changing the irradiation surface, using a 400 W transparent mercury lamp as a light source, 300-400 nm UV irradiation intensity 15 mW / cm ² , test temperature 80 ° C. 7 UV irradiation was performed for one day, the test piece was taken out, and the change in yellowness (YI) before and after the test was evaluated using a spectrocolorimeter SE-2000 manufactured by Nippon Denshoku Co., Ltd. (light source: C / 2).

Here, ΔYI ₀ , a test result using a molded sample plate made of an aromatic polycarbonate resin to which no ultraviolet absorber was added, a molded sample plate made of an aromatic polycarbonate resin composition to which a specified amount of an ultraviolet absorber was added, the test results using a .DELTA.YI _1, the degree of light resistance improving effect _{(R YI)} of _{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 the 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 a 48% aqueous sodium hydroxide 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 18 to 20 ° C for 60 minutes while stirring. After phosgene blowing was completed, 93.2 parts of p-tert-butylphenol and 641 parts of a 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 the completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water.When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated by a kneader. 4250 parts of a pale yellow polymer (abbreviated as “EX-PC1”) having a specific viscosity of 0.370 and a Tg of 172 ° C. in a molar ratio of bisphenol A to biscresol fluorene of 80:20 were obtained (collected). 95%).

Production of the polycarbonate copolymer of the present invention-Part 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 16 to 20 ° C for 60 minutes while stirring. After phosgene blowing was completed, 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 terminate the reaction. . After the completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water.When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated by a kneader. 5500 parts of a pale yellow polymer (abbreviated as “EX-PC2”) having a specific viscosity of 0.280 and a Tg of 198 ° C. in a molar ratio of bisphenol A to biscresol fluorene of 50:50 were obtained. 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-exchanged water and 4240 parts of a 48% aqueous sodium hydroxide solution were put, 5010 parts of bisphenol A, and 10 parts of hydrosulfite. After dissolving 0 parts, 12510 parts of methylene chloride was added, and 2500 parts of phosgene was blown in at 60 ° C for 20 minutes while stirring. After phosgene blowing was completed, 148.2 parts of p-tert-butylphenol and 650 parts of a 48% aqueous sodium hydroxide solution were added, and further 5.5 parts of triethylamine was added, followed by stirring at 20 to 27 ° C for 40 minutes to complete the reaction. . After the completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water.When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated by a kneader. 5,380 parts of a white bisphenol A homopolymer (abbreviated as “CEX-PC1”) having a specific viscosity of 0.368 and a Tg of 145 ° C. were obtained (94% yield).

(B) UV absorber (UVA)
◎ 2,2′-p-phenylenebis (3,1-benzoxazin-4-one): CEi-P manufactured by Takemoto Yushi Co., Ltd. (abbreviated as “EX-UVA1”)
* 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 manufactured by Cipro Kasei Co., Ltd. (abbreviated as “CEX-UVA1”)
-2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol: Tinuvin 326 ("CEX-UVA2" manufactured by Ciba Specialty Chemicals Co., Ltd.) Abbreviated)

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 The glass transition temperature (Tg) of EX-PC1 and EX-PC2, and the glass transition temperature (Tg) of the aromatic polycarbonate resin composition obtained by adding 2 parts by weight of each ultraviolet absorber 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]
To EX-PC1 and EX-PC2 obtained above, 0.0050% of 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofurano-2-one, bis (2, After adding 0.050% of 4-dicumylphenyl) pentaerythritol diphosphite and 0.050% of pentaerythritol tetrastearate, and further uniformly mixing each of the ultraviolet absorbers shown in Table 2 using a tumbler, 30 mmφ was obtained. Using a vented twin-screw extruder (KTX-30 manufactured by Kobe Steel Co., Ltd.), the mixture was pelletized while degassing at a cylinder temperature of 300 ° C. and a vacuum of 10 mmHg. The obtained pellets were dried at 120 ° C. for 5 hours and then injected. Using a molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.), a test of a thickness of 2 mm at a cylinder temperature of 320 ° C. and a mold temperature of 100 ° C. We have created a sample plate. Table 2 shows the evaluation results.

  As is clear from the respective comparisons, it is understood that the aromatic polycarbonate resin composition comprising the polycarbonate copolymer of the present invention and the specific ultraviolet absorber has excellent light resistance.

Claims (8)

5-95 mol% of the wholly aromatic dihydroxy component has the following general formula [1],

[Wherein, R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ]
95 to 5 mol% of the following general formula [2]

[Wherein, R ^{5 to} R ⁸ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom, and W is a single bond, 1 to 9 carbon atoms. A hydrocarbon group, which may contain 20 aromatic groups, an O, S, SO, SO ₂ , CO or COO group. ]
When dissolved in methylene chloride at a concentration of 10 mg / L in a polycarbonate copolymer (A) comprising an aromatic dihydroxy component represented by the following formula, the absorbance at _{360 nm} (A _{360 nm} ) measured at an optical path length of 1 cm is 0.5. An aromatic polycarbonate resin composition containing the above ultraviolet absorber (B) having an absorbance at 400 nm ( _A400nm ) of 0.01 or less and 0.01 to 5% by weight.   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% is a general formula [2]. Resin composition. The amount of change in yellowness (YI) after irradiating a 2 mm thick molded plate made of the polycarbonate resin of (A) with a 300-400 nm irradiation intensity of 15 mW / cm ² for 7 days is represented by ΔYI ₀ , (A) and (A). yellowness change after molding plate irradiated with a mercury lamp irradiation intensity 15 mW / cm ² of 300 to 400 nm 7 days of thickness 2mm made of polycarbonate resin composition comprising B) a .DELTA.YI _1, the light resistance improvement by ultraviolet absorber The degree of effect (R _YI ) is _calculated as R _YI = (1−ΔYI ₁ / ΔYI ₀ ) × 100 (%)
And when
R _YI ≧ 50%
The aromatic polycarbonate resin composition according to claim 1, wherein The glass transition temperature of the aromatic polycarbonate resin composition obtained by adding 2 parts by weight of the ultraviolet absorber (B) to 100 parts by weight of the aromatic polycarbonate copolymer (A) is Tg ′, and the fragrance not containing the ultraviolet absorber is added. When the glass transition temperature of the aromatic polycarbonate resin is Tg, Tg is 150 ° C. or more and Tg−Tg ′ ≦ 5 ° C.
The aromatic polycarbonate resin composition according to claim 1, which satisfies the following. The aromatic polycarbonate resin composition according to claim 1, wherein the ultraviolet absorbent (B) contains a benzoxazin-one structure represented by the following general formula [3].

[Wherein, R ^{9 to} R ¹¹ are each independently a hydrogen atom, a hydrocarbon group which may contain an aromatic group having 1 to 9 carbon atoms, or a halogen atom. ] The aromatic polycarbonate 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]. Resin 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 member selected from the group consisting of -hydroxyphenyl) -m-diisopropylbenzene and 1,1-bis (4-hydroxyphenyl) cyclohexane.