JP2006143831A - Polycarbonate resin composition and retardation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in a desired wavelength dispersion characteristics, high transparency and processability, and to provide a retardation film prepared from the composition. <P>SOLUTION: The aromatic polycarbonate resin composition is obtained by mixing (A) 100 pts.wt. of an aromatic polycarbonate copolymer comprising a repeating unit (A1) represented by general formula (1) and a repeating unit (A2) represented by general formula (2) (wherein R<SP>1</SP>-R<SP>4</SP>and R<SP>5</SP>-R<SP>8</SP>each denotes a hydrogen atom, a hydrocarbon group which may contain a 1-9C aromatic group or a halogen atom; and W denotes a single bond, a hydrocarbon group which may contain a 1-20C aromatic group, O, S, SO, SO<SB>2</SB>, CO or COO group), wherein the ratio of the unit (A1) to the unit (A2) is in the range of (A1):(A2)=5:95-95:5 in a molar ratio, with (B) 5-90 pts.wt. of a styrene-based oligomer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to an aromatic polycarbonate resin composition having desired wavelength dispersion characteristics and excellent transparency and processability, and a retardation film comprising the same.
Such a retardation film is suitably used for, for example, a liquid crystal display device, an optical pickup used in a recording device, an optical device such as an optical recording medium, a light emitting element, an optical arithmetic element, an optical communication element, and a touch panel.

In general, a retardation film is used in a display device such as a liquid crystal display device, and has functions such as color compensation, viewing angle expansion, and antireflection. As the material of the retardation film, generally used are polycarbonates obtained by polycondensation of bisphenol A, polyether sulfone, polysulfone, polyvinyl alcohol, and thermoplastic polymers such as norbornene resin.
For example, in a super twist nematic (STN) mode liquid crystal display device, the retardation film is usually used for the purpose of color compensation and widening the viewing angle. The following are known as the retardation film.

  For example, a retardation film made of a resin obtained by mixing a polymer that generates positive birefringence and a polymer that generates negative birefringence has been reported. Specifically, a film formed using a resin in which poly (2,6 dimethyl-1,4 phenylene oxide) and polystyrene or a mixture of polyvinyl chloride and polymethyl methacrylate are uniaxially stretched, and the viewing angle dependency is obtained. It has been reported that a retardation film having a small thickness is obtained. (For example, see Patent Document 1)

  It has also been reported that a polycarbonate resin film having a fluorene structural unit is obtained by a cast film method and has a high refractive index and low birefringence. (For example, see Patent Document 2)

  Such a polycarbonate resin having a fluorene-based bisphenol skeleton has a problem that when it is melt-processed, a gel is easily generated due to decomposition because of its high melting temperature. In addition, since it has a high Tg (glass transition temperature), it requires a high temperature for film stretching and the like, and requires special processing equipment different from the conventional one, so that the workability is not always sufficient. I can't say that.

  In addition, in a reflective liquid crystal display device, particularly a reflective liquid crystal display device using only one polarizing plate, the retardation film is optically designed to exhibit a function of generating circularly polarized light in combination with the polarizing plate. There may be. In such a liquid crystal display device, the optical design of the retardation film is usually performed in order to optimize the optical characteristics of the entire device. However, the wavelength dispersion characteristic of retardation, which is one of optical characteristics, is almost determined by the material constituting the retardation film, so that usable materials are limited. In general, polymers are poorly compatible with each other, and therefore, when they are mixed, they are phase-separated. Therefore, when the obtained mixture is optically observed, the haze is high and is not suitable for a retardation film. Therefore, practical materials are limited, and there are very few combinations of polymers compatible with each other, such as poly (2,6 dimethyl-1,4 phenylene oxide) and polystyrene, or polyvinyl chloride and polymethyl methacrylate. .

  For this reason, it is difficult to perform optical design to match the wavelength dispersion of the retardation of the retardation film with the wavelength dispersion of the retardation of the liquid crystal cell because the types of polymer materials that can be used are limited. In addition, in order to provide various retardation films having the wavelength dispersion characteristics of retardation required by many liquid crystal display device manufacturers, the retardation film manufacturer possesses a very large number of materials and forms films. There was a problem that I had to think about what to do. Further, the above-described compatible polymer combination is a combination of different polymers, but there are problems in terms of thermal durability and productivity.

Moreover, the following technique of laminating two films is known as a retardation film in which the wavelength dispersion of the retardation is controlled.
For example, it has been reported that two or more specific birefringent films having different wavelength differences of retardation are laminated and manufactured at a specific angle. (For example, refer to Patent Document 3) In these cases, since a plurality of retardation films are used, a process of bonding them together or adjusting the bonding angle is necessary, and there is a problem in productivity. In addition, since the entire thickness of the retardation film is increased, there is a problem that the light transmittance is lowered and becomes thicker or darker when incorporated in an apparatus.

The main object of the present invention is to provide an aromatic polycarbonate resin composition that easily and highly controls the wavelength dispersion characteristics of retardation, and has high transparency and excellent processability.
Another object of the present invention is to provide a retardation film formed from the same kind of polymer.
A further object of the present invention is to provide an optical component having excellent optical characteristics.

JP-A-4-194902 JP 2001-253960 A Japanese Patent Laid-Open No. 2-120804

An object of the present invention is to solve these problems.
That is, an object of the present invention is to provide an aromatic polycarbonate resin composition having desired wavelength dispersion characteristics and high transparency and excellent workability, and a retardation film comprising the same.

  As a result of intensive studies, the present inventor has found that excellent transparency, optical characteristics, and processability can be imparted by mixing an appropriate amount of a specific styrene-based oligomer with a special polycarbonate, and has reached the present invention.

［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。］で表される繰り返し単位（Ａ１）及び下記一般式［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。］
で表される繰り返し単位（Ａ２）よりなり、全カーボネート繰り返し単位における単位（Ａ１）と単位（Ａ２）の割合がモル比で（Ａ１）：（Ａ２）＝５：９５〜９５：５の範囲である芳香族ポリカーボネート共重合体１００重量部に対して（Ｂ）スチレン系オリゴマー５〜９０重量部を配合して得られる芳香族ポリカーボネート樹脂組成物及びそれからなる位相差フィルムである。 That is, the present invention provides (A) the following general formula [1]

[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. ] The repeating unit (A1) represented by 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. ]
In the range of (A1) :( A2) = 5: 95 to 95: 5, the ratio of units (A1) to units (A2) in all carbonate repeating units is (A1) :( A2) = 5: 95 to 95: 5. An aromatic polycarbonate resin composition obtained by blending 5 to 90 parts by weight of (B) a styrene-based oligomer with respect to 100 parts by weight of an aromatic polycarbonate copolymer, and a retardation film comprising the same.

In addition, it is preferable that said retardation film satisfies the following formula, when the phase difference in wavelength 450nm and 550nm is set to R (450) and R (550), respectively.
R (450) / R (550) ≦ 1

Hereinafter, the present invention will be described in detail.
[Aromatic polycarbonate copolymer]
In the aromatic polycarbonate copolymer (A) of the present invention, the ratio of the fluorene-based bisphenol represented by the following formula [3] is 5 to 95 mol% of the total aromatic dihydroxy component as the aromatic dihydroxy component constituting the aromatic polycarbonate copolymer (A). , 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 an optical material which is the object of the present invention.

  The fluorene-based bisphenol is preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

［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。］

[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. ]

  The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene has a b value of preferably 6.0 or less, more preferably 5. measured by measuring a solution of 10 g in 50 ml of ethanol at an optical path length of 30 mm. 5 or less, more preferably 5.0 or less. When the b value is within the above range, a molded product formed from the obtained polycarbonate copolymer has a favorable hue and high strength, and a stretched film characteristic is also preferable.

  The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is usually obtained by the reaction of o-cresol and fluorenone. The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene having the specific b value can be obtained by performing a specific treatment to remove impurities. Specifically, after the reaction between o-cresol and fluorenone, unreacted o-cresol is distilled off, and the residue is dissolved in an alcohol, ketone, or benzene derivative solvent, and activated clay or activated carbon is added thereto. In addition, after filtration, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene purified by filtering the product crystallized from the filtrate can be obtained. Examples of impurities to be removed include 2,4′-dihydroxy form, 2,2′-dihydroxy form and impurities whose structure is unknown. The alcohol solvent used for such purification is preferably a lower alcohol such as methanol, ethanol, propanol or butanol, and the ketone solvent is preferably a lower aliphatic ketone such as acetone, methyl ethyl ketone, methyl isopropyl ketone or cyclohexanone and a mixture thereof. As the benzene derivative solvent, toluene, xylene, benzene and a mixture thereof are preferable. The amount of the solvent used is sufficient if the fluorene compound is sufficiently dissolved, and is usually about 2 to 10 times the amount of the fluorene compound. As the activated clay, a commercially available powdery or granular silica-alumina main component is used. Further, as the activated carbon, commercially available powdery or granular materials are used.

  Other dihydroxy components used in the aromatic polycarbonate copolymer of the present invention may be those usually used as a dihydroxy component of an aromatic polycarbonate and are represented by the following formula [4].

［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。］

[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. ]

  For example, hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2- Bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1 -Bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, α, α′-bis (4-hydro Xylphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, and the like. Among them, bisphenol A, bisphenol Z, bisphenol C, bisphenol E, and bisphenol M Bisphenol A is particularly 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 may be used as long as they are used as an end stopper for aromatic polycarbonate resins.

The aromatic polycarbonate copolymer of the present invention has a specific viscosity at 20 ° C. in a solution of the polymer dissolved in methylene chloride as η _sp .
0.18 ≦ η _sp ≦ 0.90
It is preferable that More preferably,
0.20 ≦ η _sp ≦ 0.75
It is.
When η _sp is smaller than 0.18, the resin is brittle and the molded product becomes very easy to break, which is not preferable. When η _sp is larger than 0.90, the melt fluidity of the resin becomes very low and molding becomes difficult, which is not preferable.

[Styrene oligomer]
The styrene oligomer of the present invention is a resin obtained by copolymerization of a styrene monomer with an aliphatic monomer and / or a phenol monomer. This resin may be any of a multi-component copolymer such as a binary copolymer, a ternary copolymer, and a quaternary copolymer by a combination of a styrene monomer and an aliphatic monomer and / or a phenol monomer.

  The styrene monomer is a monomer having a styrene structure, and among them, a monomer having a constituent carbon number of 8 to 30, preferably 8 to 20, and more preferably 8 to 11 is used. Specific examples thereof include styrene, vinyl toluene, α-methyl styrene, isopropenyl toluene and the like. These styrene monomers may be used alone or in combination of two or more.

  An aliphatic monomer is a monomer having a structure in which carbon atoms are connected in a single chain, and among them, a monomer having 2 to 40, preferably 4 to 30, more preferably 5 to 19 carbon atoms is used. . Specific examples thereof include diisobutylene, 5,5-dimethyl-2-hexane, and 2,5,5-trimethyl-2-hexene, and diisobutylene is particularly preferable.

  A phenolic monomer is a monomer having a phenol structure, and among them, a monomer having 8 to 30, preferably 8 to 20, and more preferably 8 to 15 carbon atoms is used. Specific examples thereof include vinylphenol and isopropenylphenol.

  The content ratio of the styrene monomer and the aliphatic monomer and / or phenol monomer is 99.5 / 0.5 to 50/50, preferably 99/1 to 60/40, in molar ratio. is there.

  The weight average molecular weight of the styrenic oligomer of the present invention is preferably from 500 to 6000, more preferably from 500 to 4000. The molecular weight distribution represented by the weight average molecular weight / number average molecular weight of the styrene-based oligomer of the present invention is preferably 4 or less, and more preferably 1.1 to 3. The softening point of the styrenic oligomer of the present invention is preferably in the range of 50 to 170, more preferably in the range of 70 to 150.

The styrene oligomer of the present invention can be produced by copolymerizing the styrene monomer, aliphatic monomer and phenol monomer in the presence of a catalyst.
The catalyst used for the polymerization is generally known as a Friedel-Crafts catalyst, and examples thereof include various complexes of aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride, and boron trifluoride. be able to.
The amount of the catalyst used is preferably in the range of 0.01 to 5.0% by weight, more preferably 0.05 to 3%, based on the total amount of the styrene monomer, the aliphatic monomer and / or the phenol monomer. It is preferably in the range of 0.0% by weight.

  Further, at the time of the polymerization reaction, at least one kind of carbon selected from aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons is used for removing heat of reaction and suppressing increase in viscosity of the reaction mixture. The polymerization reaction is preferably performed in a hydrogen solvent. Preferred hydrocarbon solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, cumene, and cymene, or mixtures thereof, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane and / or cyclopentane. And mixtures with alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. In the polymerization, the amount of the hydrocarbon solvent is preferably adjusted so that the initial concentration of the monomer in the reaction mixture is in the range of 10 to 80%.

The polymerization temperature can be appropriately selected depending on the monomer used and the type and amount of the catalyst, but it is usually preferably in the range of -30 ° C to 50 ° C. The polymerization time is generally about 0.5 to 5 hours, and the polymerization is usually almost completed in 1 to 2 hours.
As the polymerization mode, either a batch system or a continuous system can be adopted. Multistage polymerization can also be performed.

  After completion of the polymerization, the catalyst residue is removed by washing. In general, it is preferable to use an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, or the like is dissolved, or an alcohol such as methanol, and cleaning deashing with methanol is particularly preferable. After completion of washing, unreacted monomers, polymerization solvent and the like are distilled off under reduced pressure to obtain the styrene oligomer of the present invention.

  The blending amount of the styrene oligomer (B) used in the present invention is 5 to 90 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the aromatic polycarbonate copolymer. Part. If the amount is more than 90 parts by weight, the decomposition of the styrene-based oligomer (B) itself is accelerated and film formation is difficult, and if it is 5 parts by weight or less, desired characteristics cannot be obtained.

[Additive]
Various additives can be added to the resin composition of the present invention as long as the object of the present invention is not impaired.
Examples of additives include mold release agents such as montanic acid wax, polyethylene wax, and silicone oil, flame retardants, flame retardant aids, thermal stabilizers, ultraviolet absorbers, pigments, and dyes.

  The heat stabilizer is preferably a phosphorus stabilizer. Examples of such phosphorus stabilizers include phosphite compounds, phosphonite compounds, and phosphate compounds. Examples of the phosphite compound include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, di Decyl 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 diphosphite Sufaito, and bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite and the like.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate , Diisopropyl phosphate and the like.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Examples include phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-biphenylene diphosphonite, and the like. It is done.
Among these, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphate, and trimethyl phosphate are preferable.

These heat stabilizers may be used alone or in combination of two or more. The content (or addition amount) of the heat stabilizer is, for example, in the range of about 0.001 to 0.5% by weight, preferably about 0.005 to 0.3% by weight, based on the entire resin composition. May be.

  Examples of the UV absorber include benzophenone UV absorbers, benzotriazole UV absorbers, triazine UV absorbers, benzoxazine UV absorbers, and salicylic acid phenyl ester UV absorbers.

  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.

  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) benzo Triazole, 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.

  Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-4). -Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2 -Hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1, , 5-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-butoxyethoxy) phenyl] -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy- 4-benzyloxyphenyl) -1,3,5-triazine, 2,4-di (4-methylphenyl) -6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2, 4-di (4-methylphenyl) -6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-di (4-methylphenyl) -6- (2-hydroxy- 4-propoxyphenyl) -1,3,5-triazine, 2,4-di (4-methylphenyl) -6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4 -Di (4-methylphen ) -6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-di (4-methylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-di (4-methylphenyl) -6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-di (4 -Methylphenyl) -6- [2-hydroxy-4- (2-hexyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2 -Hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-butoxyphenyl) -1,3,5- Triazine, 2,4-bis ( 2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy -4- (2-hexyloxyethoxy) phenyl] -1,3,5-triazine and the like, and commercially available products include Tinuvin 400 and Tinuvin 1577 (manufactured by Ciba Specialty Chemicals). Of these, Tinuvin 400 is preferred.

  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 salicylic acid phenyl ester ultraviolet absorber include p-tert-butylphenyl salicylic acid ester and p-octylphenyl salicylic acid ester.

  An ultraviolet absorber may be used independently or may use 2 or more types together. The content (or addition amount) of these ultraviolet absorbers is, for example, 0.01 to 5 wt%, preferably 0.02 to 3 wt%, where the total amount of the polycarbonate resin and the ultraviolet absorber is 100 wt%. About 0.05 to 2% by weight may be particularly preferable. If it is less than 0.01% by weight, the ultraviolet absorption performance may be insufficient. If it exceeds 5% by weight, the hue of the resin may be deteriorated.

  Examples of the release agent include silicone oil, higher fatty acid ester of monohydric or polyhydric alcohol, and the like, a part of monohydric or polyhydric alcohol having 1 to 20 carbon atoms and saturated fatty acid having 10 to 30 carbon atoms. Esters or all esters are preferred. Examples of such release agents include stearic acid monoglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl stearate, palmityl palmitate. Examples thereof include tate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, and stearic acid monoglyceride and pentaerythritol tetrastearate are preferable. The release agents may be used alone or in combination of two or more.

  The compounding amount (addition amount, content) of the release agent is, for example, 0.01 to 2% by weight, preferably 0.015 to 0.5% by weight, more preferably 0.5%, based on the resin composition. It may be about 02 to 0.2% by weight. If the blending amount is within this range, it is preferable because the mold release property is excellent and the mold release agent does not cause mold contamination.

  In addition, other thermoplastic resins such as polyethylene, polypropylene, polystyrene, acrylic resins, fluororesins, polyamides, polyacetals, polysulfones, polyphenylene sulfides; thermosetting resins such as phenol resins and melamine resins are used within the range not impairing the object of the present invention. , Silicone resin, epoxy resin; soft thermoplastic resin such as ethylene / vinyl acetate copolymer, polyester elastomer, epoxy-modified polyolefin, and other fillers such as talc, kaolin, wollastonite, Clay, silica, sericite, titanium oxide, carbon black, graphite, metal powder, glass beads, glass balloons, glass flakes, glass powder, and glass fibers can be added.

[Method for Producing Resin Composition]
The resin composition of the present invention can be obtained by blending the above components (A) and (B) by an arbitrary blending method. The proportion of these components is preferably 5 to 90 parts by weight, more preferably 5 to 70 parts by weight, and most preferably 10 to 50 parts by weight with respect to 100 parts by weight of the component (A). Usually, it is preferable to disperse these blending components more uniformly, and it is preferable to disperse all or part of them simultaneously or separately uniformly.

  In the resin composition of the present invention, it is possible to use a method in which all or a part of the components are simultaneously or separately mixed and homogenized with a mixer such as a blender, kneader, Banbury mixer, roll, or extruder.

Further, it is also possible to use a method in which a pre-dry blended composition is melt-kneaded with a heated extruder, homogenized, extruded into a wire shape, and then cut into a desired length and granulated.
The resin composition of the present invention is suitable as a film or sheet such as a retardation film, a plastic substrate, a protective film for an optical disk, a light guide plate or a diffusion plate.

  Further, since the resin composition of the present invention has high transparency and excellent processability, it is a pickup lens, a camera lens, a microarray lens, a lens such as a projector lens and a Fresnel lens, an optical path conversion component such as a prism and an optical fiber, It is also optimal as an optical component (molded product) such as a reflow soldering component, an optical disc, a plastic mirror, various cases, a tray, or a container.

  According to the aromatic polycarbonate resin composition of the present invention, a retardation film having desired wavelength dispersion characteristics and high transparency and excellent workability is provided.

The following examples illustrate the invention. The raw materials and evaluation methods used in the examples are as follows. The unit in Table 1 with respect to the blending amount is wt%.
1. Resin used The following raw materials were used.
・ Polycarbonate copolymer (PC (1))
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 21540 parts of ion-exchanged water and 4930 parts of a 48% aqueous sodium hydroxide solution. -3-methylphenyl) fluorene (hereinafter abbreviated as “BCF”) 4265 parts, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1325 parts and hydro After dissolving 15 parts of sulfite, 18889 parts of methylene chloride was added, and then 2200 parts of phosgene was blown in at 15 to 25 ° C. with stirring for 60 minutes. After completion of the phosgene blowing, 29 parts of cumylphenol and 705 parts of 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts of triethylamine was added and stirred at 28 to 33 ° C. for 1 hour 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, 5760 parts of a yellowish white polymer having a BCF to BPA molar ratio of 66:34, a specific viscosity of 0.680, and a Tg of 220 ° C. were obtained (yield 95%). Hereinafter, the copolymer obtained here is referred to as “PC (1)” in the table.

・ Polycarbonate copolymer (PC (2))
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts of ion-exchanged water and 4930 parts of a 48% aqueous sodium hydroxide solution were added, and 9,9-bis (4-hydroxy) having an b value of 3.0 in an ethanol solution. -3-methylphenyl) fluorene (hereinafter abbreviated as “BCF”) 3231 parts, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1949 parts and hydro After dissolving 15 parts of sulfite, 14530 parts of methylene chloride was added, and then 2200 parts of phosgene was blown in at a temperature of 15 to 25 ° C. with stirring for 60 minutes. After completion of the phosgene blowing, 163.1 parts of cumylphenol and 705 parts of 48% aqueous sodium hydroxide were added, and after emulsification, 5.9 parts of triethylamine was added and stirred at 28 to 33 ° C. for 1 hour 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, 5350 parts of a yellowish white polymer having a BCF to BPA molar ratio of 50:50, a specific viscosity of 0.297, and a Tg of 197 ° C. were obtained (94% yield). Hereinafter, the copolymer obtained here is referred to as “PC (2)” in the table.

・ Styrene oligomers (PS (1))
FTR2140 manufactured by Mitsui Chemicals, Inc.
(Copolymer of α-methylstyrene and styrene)
Weight average molecular weight 3230, number average molecular weight 1870, Mw / Mn = 1.7
Softening point 137 ° C
・ Styrene oligomers (PS (2))
FTR0120 manufactured by Mitsui Chemicals, Inc.
(Polymer of α-methylstyrene)
Weight average molecular weight 2320, number average molecular weight 1300, Mw / Mn = 1.8
Softening point 120 ° C
・ Styrene oligomers (PS (3))
FTR8120 manufactured by Mitsui Chemicals, Inc.
(Styrene polymer)
Weight average molecular weight 1420, number average molecular weight 920, Mw / Mn = 1.5
Softening point 120 ° C
・ Styrene oligomers (PS (4))
FMR0150 manufactured by Mitsui Chemicals, Inc.
(Copolymer of styrene and phenolic monomer)
Weight average molecular weight 2040, number average molecular weight 1190, Mw / Mn = 1.7
Softening point 145 ° C
・ Polystyrene resin (PS (5))
SO-6 manufactured by Sanyo Chemical Co., Ltd.
Number average molecular weight 30000

2. Haze Measurement A test piece having a length of 50 mm, a width of 50 mm, and a thickness of 180 μm was cut out from the film, and the haze was measured using a Haze Meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.

3. Photoelastic coefficient measurement A test piece having a length of 60 mm, a width of 10 mm, and a thickness of 180 μm was cut out from the film, and the photoelastic coefficient was measured using a Spectroellipsometer M-200 manufactured by JASCO Corporation.

4). Wavelength dispersibility measurement A test piece having a length of 75 mm, a width of 15 mm, and a thickness of 180 μm was cut out from the film, and uniaxially stretched by 1.5 times at a stretching temperature of Tg + 15 ° C., and the resulting film was made by JASCO Corporation The wavelength dispersion was measured using -200.

5. Tg (Glass Transition Temperature) Measurement A 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. was used and measured at a temperature elevation rate of 20 ° C./min.

[Examples 1 to 6 and Comparative Examples 1 to 4]
Various resins were preliminarily dry-blended in the proportions shown in Table 1, and then dissolved in methylene chloride (solution concentration 20 wt%), and cast on a flat glass plate to form a film. Thereafter, the film was cut to a required size and evaluated.

As shown in Table 1, this resin composition exhibited good processability, high transparency, and good optical properties. Moreover, it has confirmed that Examples 1-5 showed reverse dispersibility as shown below with a single film.
(Phase difference at wavelength 450 nm) ÷ (Phase difference at wavelength 550 nm) ≈0.82
(Phase difference at wavelength 650 nm) ÷ (Phase difference at wavelength 550 nm) ≈1.05
It was confirmed that Example 6 was a single film and exhibited flat dispersibility as shown below.
(Phase difference at wavelength 450 nm) ÷ (Phase difference at wavelength 550 nm) ≈0.99
(Phase difference at wavelength 650 nm) ÷ (Phase difference at wavelength 550 nm) ≈1.01
On the other hand, Comparative Examples 1 and 2 have a high photoelastic coefficient and a high Tg with PC alone. Comparative Examples 3 and 4 have no film transparency and are not suitable as optical films.

Claims (8)

(A) The following general formula [1]

[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. ] The repeating unit (A1) represented by 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. ]
In the range of (A1) :( A2) = 5: 95 to 95: 5, the ratio of units (A1) to units (A2) in all carbonate repeating units is (A1) :( A2) = 5: 95 to 95: 5. An aromatic polycarbonate resin composition obtained by blending 5 to 90 parts by weight of (B) styrene-based oligomer with 100 parts by weight of a certain aromatic polycarbonate copolymer. The aromatic polycarbonate resin composition according to claim 1, wherein the repeating unit (A1) is a repeating unit represented by the following formula (3).

The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the repeating unit (A2) is a repeating unit represented by the following formulas (4) to (8).

  The film or sheet which consists of an aromatic polycarbonate resin composition in any one of Claims 1-3.   The film or sheet according to claim 4, wherein the film or sheet is a retardation film, a plastic substrate, a protective film for an optical disk, a light guide plate, or a diffusion plate.   The film or sheet according to claim 4 or 5, wherein the film or sheet is a film or sheet formed by a cast film method.   The molded article which consists of an aromatic polycarbonate resin composition in any one of Claims 1-3.   Molded products are pickup lenses, camera lenses, microarray lenses, projector lenses and Fresnel lenses, optical path conversion parts such as prisms and optical fibers, reflow soldering parts, optical disks, plastic mirrors, various cases, trays or containers. The molded article according to claim 7.