JP2010044841A - Aromatic polycarbonate resin composition for optical information recording medium, and optical information recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition that is colored like expensive glass in appearance and used for an optical recording medium which retains recorded information for a long time even when used under a harsh environment. <P>SOLUTION: This aromatic polycarbonate resin composition for optical information recording medium, has an average viscosity molecular weight of 1.0×10<SP>4</SP>-2.0×10<SP>4</SP>, Cl content of 100 ppm or less and contains 0.01-5 ppm of anthraquinone-based dyestuff having no OH functional group in bone skeleton in an aromatic polycarbonate resin whose OH end group content is 0.1-30 eq/ton. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition for an optical information recording medium and an optical information recording medium.

  Aromatic polycarbonate resins are optical discs such as compact discs, laser discs, magneto-optical discs, digital video discs, etc., and near-field recording information media characterized by reading and writing signals from the information surface or their substrates. Widely used as a raw material for information recording media.

  These optical information recording media are manufactured by a method in which molten aromatic polycarbonate resin is injected into a mold cavity exposing a stamper on which information signals of pits and grooves are imprinted, and information signals are transferred. Yes.

  The reason why aromatic polycarbonate resin is used in the production of this optical information recording medium is that this resin is excellent in transparency, optical properties, strength, heat resistance, dimensional stability, impact resistance, and moldability. It is because it is also excellent. In particular, when a substrate of an optical information recording medium is manufactured by an injection molding method, a fine concavo-convex pattern (information signal) engraved on a stamper is accurately transferred to the surface of the substrate, and is excellent in warpage and flatness of the substrate. This is because a high-quality optical information recording medium can be obtained, and further, by using an injection compression molding method, it is possible to improve the quality of warp and the like.

  In recent years, in order to obtain a high-quality optical information recording medium, it has been desired to color the polycarbonate resin in a glass-like appearance. However, the molding processing temperature tends to be very high due to the thinning of the optical information recording medium, and discoloration during molding is a problem.

  In addition, the usage environment of optical information recording media has become harsh, such as use and storage in vehicles such as passenger cars, trains and airplanes, and in hot and humid places such as bathrooms and saunas, long-distance transportation in the hold, In addition, there are increasing opportunities for portable devices to be used outdoors in hot weather, and there is an increasing need to keep information recorded for a long time even in harsh environments. However, when the polycarbonate resin is colored by a conventional coloring method, there is a problem that information recorded on an optical information recording medium molded at a high temperature cannot withstand long-time holding. .

Patent Document 1 discloses an optical information recording medium colored with a colorant that defines an alkali metal content and a toluene insoluble content. However, the optical information recording medium in this document not only has a high-quality glass-like appearance, but also cannot withstand the retention of recorded information for a long time.
JP 2001-348494 A

  An object of the present invention is to provide an aromatic polycarbonate resin composition for an optical information recording medium that is colored in a high-quality glass-like appearance and can retain recorded information for a long time even under a severe use environment. It is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have identified a colorant having a specific structure in an aromatic polycarbonate resin in a specific molecular weight range in which the Cl content and the OH end group amount are adjusted. Provided is an optical information recording medium in which an aromatic polycarbonate resin composition blended in a quantity is colored in a high-quality glass-like appearance and can retain recorded information for a long time even under severe use environment. And reached the present invention.

That is, according to the present invention,
1. In contrast to an aromatic polycarbonate resin having a viscosity average molecular weight of 1.0 × 10 ^{4 to} 2.0 × 10 ⁴ , a Cl content of 100 ppm or less, and an OH end group amount of 0.1 to 30 eq / ton, An aromatic polycarbonate resin composition for optical information recording media, containing 0.01 to 5 ppm of an anthraquinone dye having no functional group,
2. The aromatic polycarbonate resin composition for an optical information recording medium according to item 1, which contains 100 to 3000 ppm of a glycerin monoester type release agent with respect to the aromatic polycarbonate resin;
3. 3. The aromatic polycarbonate resin composition for optical information recording media according to item 2, wherein the main component of the glycerin monoester type release agent is a monoester of behenic acid,
4). 2. The aromatic polycarbonate resin composition for optical information recording media according to item 1 above, wherein the aromatic polycarbonate resin has a viscosity average molecular weight of 1.5 × 10 ^{4 to} 1.8 × 10 ⁴ .
5). 2. The aromatic polycarbonate resin composition for optical information recording media according to item 1 above, wherein the hue of the pellets obtained from the aromatic polycarbonate resin composition is in the following range, and L value = 65.0 to 70.0
a value = −0.5 to −5.0
b value = -0.5 to -10.0
6). An optical information recording medium formed by injection compression molding from the resin composition according to item 1;
Is provided.

Hereinafter, the present invention will be described in detail.
An aromatic polycarbonate resin (hereinafter sometimes simply referred to as “polycarbonate”) is obtained by reacting a dihydric phenol and a carbonate precursor. The reaction may be performed by an interfacial polycondensation method, a melt transesterification method, or the like. And a solid phase transesterification method of a carbonate prepolymer and a ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “bisphenol”). A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, particularly bisphenol A (hereinafter sometimes abbreviated as “BPA”) is preferable, and the ratio thereof is preferably 50 to 100 mol% in the dihydric phenol component.

In the present invention, in addition to the bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe.

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.

  The polycarbonate is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid, a copolymer polycarbonate obtained by copolymerizing a bifunctional alcohol (including alicyclic), and the like. The polyester carbonate which copolymerized both bifunctional carboxylic acid and bifunctional alcohol may be sufficient. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

  In the polycarbonate polymerization reaction, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is preferably used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are preferably used. In order to accelerate the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can also be used. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As monofunctional phenols, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used.

  The organic solvent solution of the polycarbonate resin obtained by the interfacial polycondensation method is usually washed with water. This washing step is preferably performed with water having an electric conductivity of 10 μS / cm or less, such as ion-exchanged water, and more preferably 1 μS / cm or less. The organic solvent solution and water are mixed and stirred, and then allowed to stand. Alternatively, the organic solvent solution phase and the aqueous phase are separated using a centrifuge or the like, and the organic solvent solution phase is removed repeatedly to remove water-soluble impurities. By washing with high-purity water, water-soluble impurities are efficiently removed, and the resulting polycarbonate resin has a good hue.

The organic solvent solution of the polycarbonate resin described above is preferably subjected to acid cleaning or alkali cleaning in order to remove impurities such as a catalyst.
The organic solvent solution is preferably removed from foreign substances that are insoluble impurities. As a method for removing the foreign matter, a method of filtering or a method of treating with a centrifuge is preferably employed.

The organic solvent solution that has been washed with water is then subjected to an operation of removing the solvent to obtain a polycarbonate resin powder.
As a method (granulation process) for obtaining a polycarbonate resin granule, since operation and post-treatment are simple, stirring is performed in a granulation apparatus in which polycarbonate granule and hot water (about 65 to 90 ° C.) are present. However, a method of producing a slurry by continuously supplying an organic solvent solution of polycarbonate and evaporating the solvent is used. As the granulator, a mixer such as a stirring tank or a kneader is used. The produced slurry is continuously discharged from the upper or lower part of the granulator.

  The discharged slurry can then be subjected to hot water treatment. In the hydrothermal treatment step, the slurry is supplied to a hydrothermal treatment container containing hot water at 90 to 100 ° C., or after being supplied, the water temperature is changed to 90 to 100 ° C. by blowing steam or the like. The organic solvent contained is removed.

  The slurry discharged in the granulation step or the slurry after the hot water treatment is preferably filtered, centrifuged, etc. to remove water and organic solvent, and then dried to give polycarbonate resin granules (powder or flakes) Can be obtained.

  The dryer may be a conduction heating method or a hot air heating method, and the polycarbonate resin particles may be allowed to stand, be transferred, or stirred. Among these, a grooved or cylindrical dryer in which the polycarbonate resin particles are stirred by a conductive heating method is preferable, and a grooved dryer is particularly preferable. The drying temperature is preferably in the range of 130 ° C to 150 ° C.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases it is in the range of 120 to 350 ° C. In the latter stage of the reaction, the pressure of the reaction system is reduced to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.
The molten polycarbonate resin obtained by the melt transesterification method can be pelletized by a melt extruder. This pellet is used for molding.

When the viscosity average molecular weight of the polycarbonate resin of the present invention is less than 1.0 × 10 ⁴ , strength and the like are lowered, and when it exceeds 2.0 × 10 ⁴ , molding properties are lowered. The range of 0 × 10 ^{4 to} 2.0 × 10 ⁴ is preferable, the range of 1.3 × 10 ^{4 to} 1.9 × 10 ⁴ is more preferable, and the range of 1.5 × 10 ^{4 to} 1.8 × 10 ⁴ is preferable. Is more preferable.

The viscosity-average molecular weight in the present invention, first, determined using an Ostwald viscometer specific viscosity is calculated by the following equation (eta _SP) from a solution prepared by dissolving polycarbonate resin 0.7g methylene chloride 100ml at 20 ° C.,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

In addition, when measuring the viscosity average molecular weight of the polycarbonate resin of this invention, it can carry out in the following way. That is, the polycarbonate resin is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble component is collected by celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. A specific viscosity (η _SP ) at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.

  In the present invention, the Cl content in the aromatic polycarbonate resin can be adjusted by the following method. In the case of the interfacial polycondensation method described above, the Cl content can be effectively reduced by drying strengthening in the granulation step. It is also effective to replace the solvent itself with a solvent containing no Cl such as heptane in the granulation step. Further, a method of strengthening the vacuum vent in the step of melting and pelletizing is also effective. Furthermore, it is possible to reduce the Cl content by injecting a poor solvent of polycarbonate resin such as water or heptane at the time of melt extrusion and azeotropically using a vacuum vent. On the other hand, aromatic polycarbonate resin polymerized by the melt transesterification method is useful because it hardly contains Cl in the first place.

  The Cl content in the aromatic polycarbonate resin is 100 ppm or less, preferably 0.1 to 100 ppm, more preferably 0.1 to 70 ppm, and further preferably 0.1 to 50 ppm.

  The Cl content in the aromatic polycarbonate resin is measured by a combustion method. After the sample is weighed, it is burned in a mixed gas stream of argon and oxygen, and determined by the amount of electrification and movement of the silver electrode. The measurement was performed with Mitsubishi Chemical Corporation TOX-2100H.

  In the present invention, the amount of OH terminal groups of the aromatic polycarbonate resin can be adjusted by the following method. In the case of the interfacial polycondensation method, the amount of OH end groups can be adjusted by the use of a catalyst, the addition amount of an end terminator, and the addition time. Further, performing the polymerization reaction in a stationary state is also effective in reducing the amount of OH end groups. In the melt transesterification method, the amount of OH end groups can be reduced by making the abundance ratio of dihydric phenol and carbonate ester more than equimolar carbonate ester.

  The amount of OH terminal groups of the aromatic polycarbonate resin group is 0.1 to 30 eq / ton, preferably 0.1 to 25 eq / ton, and more preferably 0.1 to 20 eq / ton. In addition, the amount of OH end groups of the aromatic polycarbonate resin is measured by an NMR method.

  In the present invention, the anthraquinone dye having no OH functional group in the skeleton used as the dye includes those generally used as a bluing agent by those skilled in the art, but is not limited to blue. Many types such as red, orange, green, yellow and purple can be used, and high-quality glass-like coloring can be achieved by a combination of one or more dyes.

  Specific examples of anthraquinone dyes having no OH functional group in the skeleton include PLAST Blue 8520, PLAST Violet 8855, PLAST Red 8350, PLAST Red 8340, PLAST Red 8320, OIL Green 5602, manufactured by Bayer, manufactured by Arimoto Chemical Industry Co., Ltd. MACROLEX Blue RR, Mitsubishi Chemical Corporation DIARESIN Blue N, Sumitomo Chemical Co., Ltd. SUMIPLAST Violet RR, etc. are mentioned.

  The amount of the anthraquinone dye is 0.01 to 5 ppm, preferably 0.05 to 3 ppm, more preferably 0.1 to 1.5 ppm, and still more preferably 0 with respect to the aromatic polycarbonate resin. .1 to 1.0 ppm.

  Dyes other than anthraquinone can be used in combination, but 50% or more of the dye is preferably an anthraquinone dye that does not have an OH functional group in the skeleton. The added amount is 0.01 to 5 ppm with respect to the aromatic polycarbonate resin.

  In the present invention, the glycerin monoester preferably used as a release agent in the present invention is mainly composed of a monoester of glycerin and a fatty acid, and suitable fatty acids include stearic acid, palmitic acid, behenic acid, arachidic acid, and montanic acid. And saturated fatty acids such as lauric acid and unsaturated fatty acids such as oleic acid, linoleic acid and sorbic acid, stearic acid, behenic acid and palmitic acid are particularly preferred, and behenic acid is particularly preferred. Those synthesized from natural fatty acids are preferred, most of which are mixtures.

  The content of glycerin monoester with respect to the aromatic polycarbonate resin is preferably 100 to 3000 ppm, more preferably 200 to 2000 ppm, still more preferably 250 to 1500 ppm. When the content is too small, good releasability cannot be obtained, and when the content is too large, discoloration of the molded product is deteriorated.

  The mold release agent can be used in combination with other mold release agents known to those skilled in the art, but even when used in combination, the content of glycerin monoester is 100 to 3000 ppm and is preferably the main component of the mold release agent. .

  The aromatic polycarbonate resin of the present invention includes a heat stabilizer, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a heat ray shielding agent, a fluorescent dye (fluorescent whitening agent) as long as the object of the present invention is not impaired. Including), pigments, light diffusing agents, reinforcing fillers, other resins, elastomers, and the like.

Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer.
Examples of the phosphorous heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( 2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite Phyto, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erisrito Diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di Phosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, Dipropyl benzenephosphonate, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite Tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3′-biphenylenediphosphonite, bis ( 2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite.

Among them, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3 '-Biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite And particularly preferably tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite is used. The
As content of the phosphorus-type heat stabilizer in aromatic polycarbonate resin, 0.001-0.2 weight part is preferable with respect to 100 weight part of aromatic polycarbonate resin.

As the sulfur-based heat stabilizer, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), Examples include dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thiodipropionate, distearyl-3, 3′-thiodipropionate, and pentaerythritol-tetrakis (3- Lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), dilauryl-3, 3'-thiodipropionate, dimyristyl-3, 3'-thiodipropionate. Particularly preferred is pentaerythritol-tetrakis (3-laurylthiopropionate). The thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name), Sumilizer TPM (trade name), and the like, and can be easily used.
As content of the sulfur type heat stabilizer in aromatic polycarbonate resin, 0.001-0.2 weight part is preferable with respect to 100 weight part of aromatic polycarbonate resin.

  Examples of the hindered phenol heat stabilizer include 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-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1- And dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane. Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferably used.

  As content of the hindered phenol type heat stabilizer in aromatic polycarbonate resin, 0.001-0.1 weight part is preferable with respect to 100 weight part of aromatic polycarbonate resin.

  As the UV absorber, at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylates Is preferred.

  Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy- 3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1 , 3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy 3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3- Benzoxazin-4-one), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and these may be used alone or in combination of two or more. Can be used in a mixture.

  Preferably, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumyl) Phenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole And more preferably 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2,2 ′ Methylenebis [4- (1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) phenol].

  Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2- Methoxyphenyl) meta , 2-hydroxy -4-n-dodecyloxy benzoin phenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone.

  Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-bis ( And 2.4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol.

  Examples of cyclic imino ester UV absorbers include 2,2′-bis (3,1-benzoxazin-4-one) and 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-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) bis (3,1-benzoxazin-4-one) ), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-nitro-p-phenylene) bis (3,1- Benzoxazin-4-one) and 2,2 ′-(2-chloro-p-ph) Ylene) bis (3,1-benzoxazin-4-one) is illustrated. Among them, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) And 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) are preferred, especially 2,2′-p-phenylenebis (3,1-benzoxazine-4 -On) is preferred. Such a compound is commercially available from Takemoto Yushi Co., Ltd. as CEi-P (trade name) and can be easily used.

  As the cyanoacrylate ultraviolet absorber, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenyl) Examples include acryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, further preferably 100 parts by weight of the aromatic polycarbonate resin. Is 0.05 to 0.8 part by weight. If it is the range of this compounding quantity, it is possible to provide sufficient weather resistance to a polycarbonate resin molded product according to a use.

  The resin composition of the present invention was obtained by placing the molded pellets in a cell with a thickness of 5 cm and measuring the L value, a value, and b value measured by the C light source reflection method within a specific range. It is preferable because the appearance of the medium is glass-like and excellent in luxury. The L value is preferably 65.0 to 70.0, more preferably 67.0 to 70.0, and the a value is preferably -0.5 to -5.0, more preferably -1.0 to In the range of -3.0, the b value is preferably -0.5 to -10.0, more preferably -1.0 to -8.0.

  As an optical information recording medium comprising the aromatic polycarbonate resin composition of the present invention, a digital versatile disk (DVD) represented by a digital video disk, DVD-ROM, DVD-Audio, DVD-R, DVD-RAM, etc. Optical disc substrate, support substrate, reflective layer formed on the substrate, and light-transmitting polycarbonate film cover layer formed on the reflective layer, and laser light is incident from the cover layer side Thus, there can be mentioned substrates for recording and / or reproducing optical disks, for example, substrates for high-density optical disks represented by Blu-ray Disc (BD) and hologram disks. In the case of a Blu-ray Disc (recording type), it is created by forming a light reflecting layer, a recording layer comprising a recording film and a recording film protective film, and a light transmissive cover layer on a 1.1 mm thick substrate. Is done. A plurality of these layers may be formed.

  When these optical information recording media are manufactured, an injection molding machine, more preferably an injection compression molding machine is used. This injection molding machine and injection compression molding machine may be those generally used, but from the viewpoint of suppressing the generation of carbides and increasing the reliability of the disk substrate, the adhesion to the resin as a cylinder or screw is low, In addition, it is preferable to use a material made of a material exhibiting corrosion resistance and wear resistance.

  As conditions for injection molding or injection compression molding, the cylinder temperature is preferably 260 to 450 ° C, more preferably 280 to 380 ° C, and the mold temperature is preferably 50 to 180 ° C, more preferably 70 to 135 ° C, Thus, an optically excellent optical disk substrate can be obtained.

  The environment in the molding process is preferably as clean as possible in view of the object of the present invention. It is also important to take into consideration that the material used for molding is sufficiently dried to remove moisture, and that no retention that causes decomposition of the molten resin occurs.

  In the optical information recording medium of the present invention, it is necessary to form a reflective layer and / or a recording layer on one side. As a method for producing the inorganic thin films of the recording layer and the reflective layer, various thin film forming methods such as a known vacuum deposition method, PVD method such as sputtering method, or CVD method can be applied. However, it is preferable that the optical disk medium is manufactured under conditions where adhesion to the polymer substrate is particularly high in order not to cause peeling that occurs in a high temperature and high humidity environmental resistance test. For this purpose, sputtering is preferred.

  For example, in the case of a DVD or HD DVD, an adhesive and a light-transmitting second substrate having the same thickness as the first substrate are sequentially formed on a first substrate having a thickness of 0.6 mm, and the first substrate A reflective layer and / or a recording layer are formed on the first substrate side of the second substrate, and information is recorded / reproduced by irradiating laser light from the second substrate side. The second substrate preferably has a transmittance of 80% or more with respect to the wavelength of the laser light, and preferably 90% or more.

  Alternatively, an adhesive and a light-transmitting second substrate having the same thickness as the first substrate are sequentially formed on the first substrate, and the first and second substrates are respectively opposite to each other. The optical disc is formed with a first and second reflective layers and / or first and second recording layers, and records and reproduces information by irradiating a laser beam from the second substrate side. The second substrate preferably has a transmittance of 80% or more with respect to the wavelength of the laser light, and preferably 90% or more.

  For example, in the case of BD, an optical disk substrate needs to have a reflective layer and / or a recording layer formed on one side. As a method for producing the inorganic thin films of the recording layer and the reflective layer, various thin film forming methods such as a known vacuum deposition method, PVD method such as sputtering method, or CVD method can be applied. However, it is preferable that the optical disk medium is manufactured under conditions where adhesion to the polymer substrate is particularly high in order not to cause peeling that occurs in a high temperature and high humidity environmental resistance test. For this purpose, sputtering is preferred.

  Further, a light transmissive cover layer is formed on the reflective layer and / or the recording layer. The light-transmitting cover layer is made of a material that transmits laser light. As such a material, a polycarbonate resin is preferably used. For example, a polycarbonate sheet formed by a melt extrusion method or a polycarbonate formed by a solution casting method. A casting film is mentioned. As a means for forming the light-transmitting cover layer, for example, a method of bonding a transparent plate such as a sheet or film made of polycarbonate on the recording layer with an adhesive or the like can be mentioned. Furthermore, this light-transmitting cover layer is limited to a thickness of 3 to 200 μm in order to keep coma aberration considerably small.

  For the adhesive used when forming the cover film, an ultraviolet curable polymer material may be used as a main component. In this case, the ultraviolet curable polymer material is preferably an acrylate copolymer having an ultraviolet curable group in a side chain, the ultraviolet curable group is an unsaturated group, and the acrylic acid The weight average molecular weight of the ester copolymer is preferably 100,000 or more. For example, a mixture of an acrylate copolymer having an ultraviolet curable group in the side chain and an ultraviolet curable polyfunctional monomer and / or oligomer is used as the ultraviolet curable polymer material. Alternatively, it may be a mixture of an acrylic ester copolymer having no ultraviolet curable group and an ultraviolet curable polyfunctional monomer and / or oligomer. In addition, the adhesive may be mainly composed of a mixture of a polymer component having no ultraviolet curable property and an ultraviolet curable polyfunctional monomer and / or oligomer. In any case, it is preferable that the material exhibits tackiness before curing and has strong adhesiveness and appropriate hardness after curing.

  In the case of a write-once optical disk, the recording film is a recording film on which a irreversible optical characteristic is changed or a concavo-convex shape is formed by irradiation with laser light. A cyanine-based, phthalocyanine-based, azo-based organic dye or the like that changes the optical constant and causes deformation of the substrate due to a volume change is used.

  In the case of a rewritable optical disc, the recording film is a material (phase change recording type) in which a reversible phase structure change between the amorphous state and the crystalline state of the substance caused by laser light irradiation, or perpendicular to the film surface This is a magnetic thin film (magneto-optical recording type) having a magneto-optic effect that has an easy magnetization direction in any direction and can record, reproduce, and erase information by creating an arbitrary inversion magnetic domain. Examples of the phase change recording film include GeSbTe, InSbTe, InSe, InTe, AsTeGe, TeOx-GeSn, TeSeSn, FeTe, SbSeBi, and BiSeGe that are chalcogenide materials. Although it is used, a film made of GeSbTe is preferable because of its stable operation during repeated recording / erasing. Examples of magneto-optical recording films include amorphous alloy thin films of rare earth elements and transition metal elements such as TbFe, TbFeCo, GdTbFe, NdDyFeCo, NdDyTbFeCo, NdFe, PrFe, and CeFe, and those utilizing exchange coupling. A two-layer film, an artificial lattice multilayer film such as Co / Pt or Co / Pd, or a CoPt alloy can be used.

In addition, it is preferable to use a dielectric material as the recording film protective film for sandwiching the recording film. Thereby, the difference in reflectance between the crystalline phase and the amorphous phase as a medium, and the magneto-optical effect can be enhanced. In this case, the dielectric material is preferably a material having a high refractive index n, that is, a material satisfying n ≧ 1.6, more preferably a material satisfying n ≧ 1.8. Eg, SiO-based, _{SiON-based, Ta 2 O 3, TiO 2} , Al 2 O 3, Y 2 O 3, CeO, La 2 O 3, In 2 O 3, GeO, GeO 2, PbO, SnO, SnO 2, _{Bi 2 O 3, TeO 2 WO} 2, WO 3, Sc 2 O 3, ZrO 2 oxide such, TaN, AlN, SiN-based, nitride AlSiN system or the _{like, ZnS, Sb 2 S 3,} CdS, in 2 It is preferable to use a sulfide such as S ₃ , Ga ₂ S ₃ , GeS, SnS ₂ , PbS, Bi ₂ S ₃ , a mixed material thereof, a laminate thereof, or the like as the protective film.

  The light reflecting layer is preferably a material having higher reflectivity than the recording layer with respect to the laser beam of the drive head used for evaluation. Specifically, it is preferable to select a material in which the refractive index n and the extinction coefficient k, which are optical constants at the used laser light wavelength, satisfy n ≦ 3.5 and k ≧ 3.5. More preferably, n ≦ 2.5 and 4.5 ≦ k ≦ 8.5. With a medium manufactured under these conditions, the reproduction signal characteristics can be further improved.

  On the other hand, when recording a signal by heating with laser light, if the thermal conductivity of the light reflecting layer is too high, thermal diffusion is large and a strong laser power is required. For this reason, in order to enable signal recording with a semiconductor laser having a power of 15 mW or less, the thermal conductivity of the material used for the light reflection layer is 100 [W / (m · K)] or less. It is more preferable that it is 80 [W / (m · K)] or less.

As a material satisfying such conditions, one or more elements such as Au, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Ru, Os, Ir, etc. as Al or Ag An alloy to which is added. In these alloys, if the amount of the additive element is less than 0.5 atomic%, the effect of the above-described decrease in heat conduction is small. This is disadvantageous. Therefore, the content of the additive element is preferably within the range of 0.5 to 20 atomic%. In particular, Ti, Zr, Hf, Ta, Cr, and Re are preferable in the specific element group in terms of enhancing durability of the metal reflective film itself. The film thickness range of these reflective layers is 10 to 500 nm, but preferably 30 to 200 nm, particularly in order to suppress the deterioration of the reproduction signal characteristics due to the decrease in reflectance and to enable recording at a laser power of 15 mW. Preferably it is 40-100 nm.
In the case of a read-only optical disc medium, only the light reflecting layer described above is formed on the substrate, but the same materials can be used.

  The resin composition of the present invention is excellent in retaining recorded information even after being used for a long time without causing discoloration even when colored in a high-quality glass-like appearance. The effect is exceptional.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. In addition, the measurement of the various characteristics in an Example was based on the following method.

(1) Cl content in aromatic polycarbonate resin Aromatic polycarbonate resin pellets and powder were weighed, burned in a mixed gas stream of argon and oxygen, and titrated with the amount of electrification and movement of the silver electrode. The measurement was performed with Mitsubishi Chemical Corporation TOX-2100H.

(2) Amount of OH terminal group of aromatic polycarbonate resin 40 mg each of aromatic polycarbonate resin pellets and powder are dissolved in 1 ml of deuterated chloroform, and charged to an NMR sample tube with an inner diameter of 5 mm so that the liquid level is 40 mm. The sample for NMR measurement was prepared. This was measured by non-decoupling and 512 integrations using 1H-NMR using FT-NMR AL-400 manufactured by JEOL Ltd. The integrated values of peaks at chemical shifts of 6.66 to 6.73 ppm and 6.93 to 7.00 ppm were obtained from the obtained NMR spectrum chart, and the OH end group amount (eq / ton) was calculated from the following formula. In addition, the chart used for the measurement and each peak are shown in FIG.
OH end group amount (eq / ton) = (A / 2) / (B / (C × 2/100)) × (1000000 / D)
A: integrated value of peak of 6.66 to 6.73 ppm B: integrated value of peak of 6.93 to 7.00 ppm C: abundance of carbon isotope 13C (1.18%)
D: Mass number per unit of PC (bisphenol A polycarbonate: 254)

(3) Viscosity-average molecular weight ratio calculated viscosity (eta _SP) by using an Ostwald viscometer polycarbonate resin 0.7g at 20 ° C. from the solution in methylene chloride 100 ml, the viscosity by the following equation from the specific viscosity (eta _SP) The average molecular weight M was calculated.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(4) Evaluation of hue (color difference ΔE) A pellet placed in a cell with a thickness of 5 cm was measured by a C light source reflection method using a color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. The value was determined.

(5) Long-term storage of recorded information Using pellets, an injection molding machine [M-35B-D-DM, manufactured by Meiki Seisakusho Co., Ltd.] has a cylinder temperature of 380 ° C. and a mold temperature of 120 ° C. and a diameter of 120 mmφ. An optical disk substrate having a thickness of 0.6 mm was injection molded. A reflective film was sputter-deposited on the signal surface side of the obtained optical disk substrate having a thickness of 0.6 mm, and two DVDs were bonded using a DVD Bonding Machine FA-YG23 manufactured by Matsushita Electric Industrial Co., Ltd. 100 sheets of each were obtained.
After confirming the reproducible number of DVD-ROMs obtained with a commercially available DVD player, only reproducible discs were processed for 2000 hours under conditions of 80 ° C. and 85% RH, and the reproducible number after processing was confirmed.

[Examples 1-4, Comparative Examples 1-4]
A polycarbonate resin composition obtained by blending the components shown in Table 1 was extruded at 300 ° C. with TEX-30α manufactured by Nippon Steel Works, and the strands were cut to obtain pellets. The obtained pellets were dried at 120 ° C. for 4 hours. Various evaluation was performed using the obtained pellet. The results are shown in Table 1.

In addition, each component in a table | surface is as follows.
PC1: aromatic polycarbonate resin powder CM-1000 (viscosity average molecular weight 16,000) manufactured by Teijin Chemicals Ltd.
PC2: Teijin Chemicals Co., Ltd. aromatic polycarbonate resin powder L-1225WL (viscosity average molecular weight 18,500)
PC3: Teijin Chemicals Co., Ltd. aromatic polycarbonate resin powder L-1225WP (viscosity average molecular weight 22,500)
L1: Riken vitamin internal mold release agent S-100A (main component glycerin monostearate)
L2: Riken vitamin internal mold release agent B-100A (main component glycerin monobehenate)
A1: Phosphorus stabilizer P-EPQ manufactured by Clariant Japan
(Anthraquinone dyes that do not have OH functional groups in the skeleton)
H1: Arimoto Chemical Industry PLAST Blue 8520
H2: Bayer MACROLEX Blue RR
(Anthraquinone dye having OH functional group in the skeleton)
H3: Bayer MACROLEX Violet B

It is the figure which showed the 1H-NMR spectrum chart of the aromatic polycarbonate resin pellet.

Claims (6)

In contrast to an aromatic polycarbonate resin having a viscosity average molecular weight of 1.0 × 10 ^{4 to} 2.0 × 10 ⁴ , a Cl content of 100 ppm or less, and an OH end group amount of 0.1 to 30 eq / ton, An aromatic polycarbonate resin composition for optical information recording media, containing 0.01 to 5 ppm of an anthraquinone dye having no functional group.   2. The aromatic polycarbonate resin composition for an optical information recording medium according to claim 1, comprising 100 to 3000 ppm of a glycerin monoester type release agent with respect to the aromatic polycarbonate resin.   The aromatic polycarbonate resin composition for an optical information recording medium according to claim 2, wherein the main component of the release agent of the glycerin monoester type is a monoester of behenic acid. The aromatic polycarbonate resin composition for an optical information recording medium according to claim 1, wherein the aromatic polycarbonate resin has a viscosity average molecular weight of 1.5 × 10 ^{4 to} 1.8 × 10 ⁴ . The aromatic polycarbonate resin composition for an optical information recording medium according to claim 1, wherein the hue of the pellet obtained from the aromatic polycarbonate resin composition is in the following range.
L value = 65.0-70.0
a value = −0.5 to −5.0
b value = -0.5 to -10.0   An optical information recording medium formed by injection compression molding from the resin composition according to claim 1.

Images