JP5112980B2 - Aromatic polycarbonate resin composition for optical information recording medium and optical information recording medium - Google Patents

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 an optical information recording medium substrate is manufactured by an injection molding method, a fine concavo-convex pattern (information signal) engraved on a stamper is accurately transferred to the substrate surface, resulting in excellent 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.

  On the other hand, optical information recording media in recent years have been different from the original shape of a single CD substrate. For example, in DVD, two substrates having a thickness of 0.6 mm are bonded together using an ultraviolet curable resin. A Blu-ray disc (abbreviated as BD) has a shape in which a cover layer made of an ultraviolet curable resin is formed on the surface of a substrate made of polycarbonate resin, or a shape in which a cover film is bonded to the substrate.

  However, the ultraviolet light for curing the ultraviolet curable resin is irradiated from the signal reading surface side, and when excessive irradiation is performed, the aromatic polycarbonate resin or the like deteriorates and the molecular weight of the resin decreases. Etc. may be caused.

  In addition, the introduction of video equipment such as car navigation has become widespread in automobiles, and it has become possible to easily watch movies and the like in the car. In particular, the interior of a vehicle in midsummer tends to be in a high temperature and high humidity state, and if the optical information recording medium is left in the vehicle for a long time, the resin used for the substrate deteriorates. Then, there is a problem that the optical information recording medium is easily broken by an impact such as dropping.

  In order to solve this problem, basically, it is effective to increase the molecular weight of the aromatic polycarbonate resin. However, an aromatic polycarbonate resin having a high molecular weight cannot be used as an optical information recording medium because the melt viscosity is lowered and the birefringence of the substrate is increased. A manufacturing method in which an optical information recording medium is molded by using a molding machine having a high cylinder temperature can be considered. However, the cooling time becomes long and the substrate productivity deteriorates.

  In addition, in the production of conventional optical information recording medium substrates, the cylinder temperature is set to a lower temperature and the cooling time is shortened to produce more optical information recording media in a shorter time and improve productivity. Is common. In order to achieve this, even if the cylinder temperature is lowered, the molecular weight of the resin is generally lowered so that the aromatic polycarbonate resin has a sufficient melt viscosity. However, when the molecular weight is set low, the amount of low molecular weight substances such as monomers and oligomers in the resin increases, resulting in a problem that the mold becomes dirty at the time of molding and the productivity is remarkably lowered.

  As an invention of an optical disk substrate using a polycarbonate resin having an adjusted molecular weight, there is an optical disk substrate made of a polycarbonate resin having a viscosity average molecular weight of 14,000 to 15000 containing 0.06-0.09% stearic acid monoglyceride. However, this patent specifies the content of the release agent and describes the effect of suppressing deformation at the time of molding, but there is no description of the strength of the optical disk substrate, and there remains a problem (Patent Document 1).

  Further, there is an optical disk substrate made of a polycarbonate resin having a viscosity average molecular weight of 10,000 to 17000 and a weight average molecular weight / number average molecular weight of 2.3 or more. However, although it is described that there are few cracks at the time of shaping | molding, the generation | occurrence | production cause and the crack of the board | substrate after long-term use are not clear (patent document 2).

  As another attempt, it has been proposed to use a branched polycarbonate resin as a material for optical moldings such as optical disks, which prevents stringing during molding and improves birefringence, strength, and continuous moldability. However, it is necessary to use a special branched polycarbonate resin (Patent Document 3 and Patent Document 4).

  Furthermore, there is a proposal of a method of mixing an ultrahigh molecular weight polycarbonate resin. However, the polycarbonate resin generally used for optical discs has a large molecular weight difference from the ultra-high molecular weight polycarbonate resin to be mixed. Therefore, when ultra-high molecular weight polycarbonate is mixed, it becomes optically non-uniform and minute white streaks and molding At times, silver and delamination phenomena occur and mechanical strength is uneven, which is unsuitable for optical applications (Patent Document 5).

  Further, an optical disk substrate made of a polycarbonate resin having a metal content or a chlorinated solvent equal to or less than a specific amount is disclosed (Patent Document 6). However, although it is described that the optical long-term reliability is effective, there is no description about the strength of the disc after long-term use. Similarly, an optical disk substrate made of a polycarbonate resin in which the amount of terminal hydroxyl groups and metal sodium is not more than a specific amount is disclosed (Patent Document 7). However, although it is described that the optical long-term reliability is effective, there is no description about the strength of the disc after long-term use.

  Furthermore, a high fluidity polycarbonate resin in which a low molecular weight carbonate compound having a molecular weight of 1,000 or less contained in the polycarbonate resin is less than 1% by weight is known (Patent Document 8). However, although it is described that the resin is excellent in fluidity at the time of melting, transferability, and high cycle moldability, there is no description about the strength of the disk after long-term use.

  Further, there is known a polycarbonate for optical recording media in which the total nitrogen amount contained in the polycarbonate resin is 10 ppm or less (Patent Document 9). However, although it is described that the disk substrate obtained from the resin has high reliability in the long-term reliability test, there is no description about the strength of the disk after long-term use.

Japanese Patent Laid-Open No. 04-168151 JP 2003-162841 A JP 2006-348132 A Japanese Patent Laid-Open No. 60-215019 Japanese Patent Laid-Open No. 04-342760 Japanese Patent Laid-Open No. 02-276037 Japanese Patent Laid-Open No. 03-1001001 JP 09-208684 A JP 09-165442 A

  The object of the present invention is to solve the problem of mold contamination while achieving fluidity that can maintain high productivity even when molded at a low cylinder temperature, and the long-term optical information recording medium after molding. It is to provide an aromatic polycarbonate resin composition that maintains a sufficient strength and can withstand ultraviolet irradiation.

  As a result of intensive studies to achieve the above object, the present inventors have found that even if the molecular weight of the aromatic polycarbonate resin can achieve high fluidity and can maintain high productivity, the amount of OH end groups of the polycarbonate resin, Cl By adjusting the content, low molecular weight components, and total nitrogen content to the prescribed amount, the problem of mold fouling can be solved, withstands ultraviolet irradiation, has good thermal stability, and can maintain long-term strength The present inventors have found that an optical information recording medium can be obtained and have reached the present invention.

That is, according to the present invention,
1. Viscosity average molecular weight is 1.0 × 10 ^{4 to} 2.0 × 10 ⁴ , low molecular weight component content with a molecular weight of 1000 or less is 1.5 wt% or less, total nitrogen content is 15 ppm or less, Cl content is 100 ppm or less, For optical information recording medium containing 0.01 to 0.3 parts by weight of glycerin monoester type release agent with respect to 100 parts by weight of aromatic polycarbonate resin having an OH end group amount of 0.1 to 30 eq / ton Aromatic polycarbonate resin composition,
2. 2. The aromatic polycarbonate resin composition for optical information recording media according to item 1, wherein the main component of the glycerin monoester type release agent is a monoester of behenic acid;
3. 2. The aromatic polycarbonate resin composition for optical information recording media according to item 1 above, wherein the viscosity average molecular weight of the aromatic polycarbonate resin composition is 1.3 × 10 ^{4 to} 1.75 × 10 ⁴ .
4). 2. The aromatic polycarbonate resin composition for optical information recording media according to item 1 above, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin that is polymerized by a non-catalytic interfacial polycondensation method and subjected to low molecular weight component extraction treatment with acetone after polymerization. And 5. 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 interfacial polycondensation, melt transesterification, or the like. Method, solid phase transesterification method of carbonate prepolymer, ring-opening polymerization method of cyclic carbonate compound and the like, but the most preferable one in the present invention is the interfacial polycondensation method.

  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 an optical disc information recording medium in which change and shape stability requirements 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 promote the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can be used. In the present invention, it is premised that a trace amount of nitrogen is not increased by using a catalyst. Therefore, a polymerization reaction by a non-catalytic method is preferable. 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.
In addition, the organic solvent solution of the polycarbonate resin described above is preferably subjected to acid cleaning or alkali cleaning in order to remove impurities.

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 polycarbonate resin granules obtained as described above usually contain impurities such as oligomers and monomers. In the present invention, the content of low molecular weight components having a molecular weight of 1000 or less is 1.5% by weight or less, preferably 1.3% by weight or less, and most preferably 1.1% by weight or less.

  As a method for removing the low molecular weight component, acetone treatment may be mentioned. The method described in JP-A-4-306227 is preferably used, and this method is a method for removing low molecular weight components easily and inexpensively.

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 1.0 × 10 ^{4 to} 1.75 × 10 ⁴ is more preferable, and the range of 1.3 × 10 ^{4 to} 1.75 × 10 ⁴ is preferable. Is more preferable.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., with a specific viscosity (η _SP ) calculated by the following formula:
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.

  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, the aromatic polycarbonate resin polymerized by the melt transesterification method is useful because it does not contain 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.

  The amount of OH end 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 is adjusted depending on the use of the catalyst, the amount of the end terminator added, and the addition time. It is also effective to perform the polymerization reaction in a stationary state. 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 to carbonate ester.

  The amount of OH end groups of the aromatic polycarbonate resin 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.

  The total amount of nitrogen in the aromatic polycarbonate resin can be adjusted by the presence or absence of a catalyst during polymerization and the amount used. In the present invention, an aromatic polycarbonate resin is preferably polymerized by an interfacial polycondensation method without a catalyst.

  The total nitrogen content in the aromatic polycarbonate resin is 15 ppm or less, preferably 0.1 to 15 ppm, more preferably 0.1 to 13 ppm, and still more preferably 0.1 to 10 ppm. The total nitrogen content in the aromatic polycarbonate resin is measured by a chemiluminescence method.

  The glycerin monoester 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, montanic acid, lauric acid and the like. Examples include saturated fatty acids, unsaturated fatty acids such as oleic acid, linoleic acid, and sorbic acid, stearic acid, behenic acid, and palmitic acid are particularly preferable, and behenic acid is particularly preferable. Those synthesized from natural fatty acids are preferred, most of which are mixtures.

  The content of glycerin monoester is 0.01 to 0.3 parts by weight, preferably 0.02 to 0.2 parts by weight, more preferably 0.025 to 0 parts per 100 parts by weight of the aromatic polycarbonate resin. 15 parts by weight. 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 glycerin monoester content is 0.01 to 0.3 parts by weight. Preferably it is a component.

  The 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, and a fluorescent dye (including a fluorescent whitening agent) as long as the object of the present invention is not impaired. , Pigments, light diffusing agents, reinforcing fillers, other resins, elastomers, and the like can be blended.

  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'-biphenylenediphosphonai Tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3′-biphenylenediphosphonite, bis And (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. It is.

  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.

Examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer and polysynthremble-RLS manufactured by Clariant. The bluing agent is effective for eliminating the yellow color of the polycarbonate resin particles.
The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm with respect to the polycarbonate resin.

  The optical information recording medium comprising the aromatic polycarbonate resin composition of the present invention is a digital versatile disk (DVD) represented by a digital video disk, DVD-ROM, DVD-Audio, DVD-R, DVD-RAM, or the like. An optical disk substrate or a Blu-ray Disc (BD) substrate.

  When manufacturing this optical information recording medium, 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.

  The optical information recording medium of the present invention comprises a support substrate, a reflective layer formed on the substrate, and a light transmission layer formed on the reflection layer, and laser light is incident from the light transmission layer side. Therefore, it is also suitably used as a large capacity disk substrate typified by an optical disk of a recording and / or reproducing type, for example, BD, HD DVD, and hologram disk.

  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.

  The optical information recording medium of the present invention has a support substrate, a reflective layer formed on the substrate, and a cover layer of a light-transmitting polycarbonate film formed on the reflective layer. It is also suitably used as a substrate for high-density optical discs typified by optical discs that record and / or reproduce by entering light, such as Blu-ray Disc (BD) and hologram discs. In particular, in the case of Blu-ray Disc (recording type), it is created by forming a light reflecting layer, a recording layer consisting of 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.

  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. For example, the recording film is decomposed by heating by laser light irradiation, 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 type recording film include a chalcogenide-based material such as GeSbTe, InSbTe, InSe, InTe, AsTeGe, TeOx-GeSn, TeSeSn, FeTe, SbSeBi, and BiSeGe. 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 and} other oxides, nitrides such as TaN, AlN, SiN and AlSiN, ZnS, Sb ₂ S ₃ , CdS and 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.

(Bendability)
The optical information recording medium of the present invention has bendability after long-term use. This is an optical information recording medium that not only has excellent bendability at the time of molding, but also has excellent bendability even after long-term use.
This measurement method is determined by setting an optical disk substrate vertically on a jig, compressing at a distance of 120 mm to 20 mm at 50 mm / min, and applying a pressure of 1 MPa (FIG. 2).
Further, the optical disk substrate is placed in an environment of temperature 80 degrees and humidity 85% RH for 96 hours, and then allowed to stand at room temperature and humidity of temperature 23 ° C. and humidity 50% RH for 24 hours, and then the above test is performed.

  The aromatic polycarbonate resin composition for optical information recording medium of the present invention has good thermal stability when molded into an optical information recording medium, and the obtained optical information recording medium is excellent in strength after long-term use. The industrial effects that it plays are 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) Measurement of low molecular weight component content It calculated | required by the area ratio (%) in the GPC analysis using the column which arranged TOHSOHXL-2000 and HXL-3000 in series.

(4) Measurement of total nitrogen content Using a trace total nitrogen analyzer TN-110 manufactured by Mitsubishi Chemical Corporation, the total nitrogen content in 20 mg was measured.

(5) Evaluation of Hue (Color Difference ΔE) A 2 mm thick square plate was molded from the pellets by using a Japanese-made Tsunasho injection molding machine J85-ELIII at a cylinder temperature of 370 ° C., a mold temperature of 80 ° C., and a 1-minute cycle. After 20 shots were continuously formed, the resin was allowed to stay in the cylinder of the injection molding machine for 10 minutes to form a 2 mm thick square plate after the stay. The hue (L, a, b) of the flat plate before and after the residence was measured by a C light source reflection method using a color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the color difference ΔE was determined by the following formula.
ΔE = {(L−L ′) ² + (aa ′) ² + (b−b ′) ² } ^1/2
Hue of “measurement flat plate before residence”: L, a, b
Hue of “plate for measurement after residence”: L ′, a ′, b ′

(6) Manufacture of optical disk substrate and bending test The obtained pellets were dried at 120 ° C. for 5 hours, and then injection compression molding machine [SD-40E, manufactured by Sumitomo Heavy Industries, Ltd.] was used. An optical disk substrate was injection compression molded.
The optical disk substrate was set vertically on a jig as shown in FIG. 2 and compressed at a distance of 120 mm to 20 mm at 50 mm / min. The thing which the board | substrate broke in the process bent from 120 mm to 20 mm was set to x, and the thing which was not cracked was set to (circle).
On the other hand, the optical disk substrate was placed in an environment of temperature 80 degrees and humidity 85% RH for 96 hours, and then allowed to stand at room temperature and humidity of temperature 23 ° C. and humidity 50% RH for 24 hours, and then a bending test was performed. The thing which the board | substrate broke was set to x, and the thing which was not broken was set to (circle).

[Synthesis Example 1]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 219.4 parts of ion-exchanged water and 40.2 parts of a 48% aqueous sodium hydroxide solution, and 2,2-bis (4-hydroxyphenyl) propane 57. After 5 parts and 0.12 part of hydrosulfite were added and dissolved in 25 minutes, 181 parts of methylene chloride was added over 5 minutes, and 27.8 parts of phosgene was blown in at a temperature of 15 to 25 ° C. for 40 minutes. It is. After completion of phosgene blowing, 2,2-bis (4-hydroxyphenyl) propane was added to 7.2 parts of 48% aqueous sodium hydroxide and 2.04 parts of p-tert-butylphenol and 1 part of 7.4% aqueous sodium hydroxide. 0.65 part of a solution in which 0.20 part was dissolved was added, and after emulsification with a homomixer, stirring was stopped and the reaction was terminated by allowing to stand at 28 to 33 ° C. for 2.5 hours. After completion of the reaction, 200 parts of methylene chloride was added to and mixed with the product, the stirring was stopped, and the aqueous phase and the organic phase were separated to obtain an organic solvent solution having a polycarbonate resin concentration of 15% by weight. After adding 200 parts of ion-exchanged water to this organic solvent solution and stirring and mixing, stirring was stopped and the aqueous phase and the organic phase were separated. This operation was repeated (four times) until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water. The obtained purified polycarbonate resin solution was filtered with a 1 μm filter made of SUS304.

  Next, 100 L of ion-exchanged water is introduced into a 1000 L kneader made of SUS316L, and the methylene chloride is evaporated at a water temperature of 42 ° C. The powder and the mixture of the powder and water were put into a hot water treatment tank of a hot water treatment process having a hot water treatment tank with a stirrer controlled at a water temperature of 95 ° C., and 25 parts of powder and water The mixture was stirred for 30 minutes at a mixing ratio of 75 parts. This mixture of powder and water was separated by a centrifugal separator to obtain a powder containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, this granular material was continuously supplied at 50 kg / Hr (in terms of polycarbonate resin) to a SUS316L conductive heat receiving groove type biaxial stirring continuous dryer controlled at 140 ° C., and the condition of an average drying time of 6 hours And dried to obtain a powder particle having a viscosity average molecular weight of 15000 and a Cl content of 50 ppm. The obtained granular material was put into acetone, and after stirring for 30 minutes, the granular material slurry solution was taken out. After solid-liquid separation, it was dried in a nitrogen atmosphere at 140 ° C. for 4 hours, and extracted with acetone. Viscosity average molecular weight 15600, Cl A granular material (powder) having a content of 2.2 ppm was obtained.

[Synthesis Example 2]
Synthesis was performed in the same manner as in Synthesis Example 1 except that p-tert-butylphenol was changed to 3.10 parts, and viscosity average molecular weight 12500 extracted from acetone from a granular material having a viscosity average molecular weight of 11800 and a Cl content of 38 ppm, A granular material (powder) having a Cl content of 1.3 ppm was obtained.

[Synthesis Example 3]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 219.4 parts of ion-exchanged water and 40.2 parts of a 48% aqueous sodium hydroxide solution, and 2,2-bis (4-hydroxyphenyl) propane 57. After 5 parts and 0.12 part of hydrosulfite were added and dissolved in 25 minutes, 181 parts of methylene chloride was added over 5 minutes, and 27.8 parts of phosgene was blown in at a temperature of 15 to 25 ° C. for 40 minutes. It is. After completion of the phosgene blowing, 2,2-bis (4-hydroxyphenyl) propane was added to 7.2 parts of 48% aqueous sodium hydroxide and 2.14 parts of p-tert-butylphenol and 1 part of 7.4% aqueous sodium hydroxide. 0.65 part of a solution in which 0.20 part was dissolved was added, and after emulsification with a homomixer, stirring was stopped. After 10 minutes after the stirring was stopped, the mixture was again stirred and emulsified, and then 0.06 part of triethylamine was added thereto, and the reaction was completed in 30 minutes at 28 to 33 ° C. After completion of the reaction, 200 parts of methylene chloride was added to and mixed with the product, the stirring was stopped, and the aqueous phase and the organic phase were separated to obtain an organic solvent solution having a polycarbonate resin concentration of 15% by weight. After adding 200 parts of ion-exchanged water to this organic solvent solution and stirring and mixing, stirring was stopped and the aqueous phase and the organic phase were separated. This operation was repeated (four times) until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water. The obtained purified polycarbonate resin solution was filtered with a 1 μm filter made of SUS304.

  Next, 100 L of ion-exchanged water is introduced into a 1000 L kneader made of SUS316L, and the methylene chloride is evaporated at a water temperature of 42 ° C. The powder and the mixture of the powder and water were put into a hot water treatment tank of a hot water treatment process having a hot water treatment tank with a stirrer controlled at a water temperature of 95 ° C., and 25 parts of powder and water The mixture was stirred for 30 minutes at a mixing ratio of 75 parts. This mixture of powder and water was separated by a centrifugal separator to obtain a powder containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, this granular material was continuously supplied at 50 kg / Hr (in terms of polycarbonate resin) to a SUS316L conductive heat receiving groove type biaxial stirring continuous dryer controlled at 140 ° C., and the condition of an average drying time of 6 hours Was dried to obtain a powder (powder) having a viscosity average molecular weight of 15000 and a Cl content of 52 ppm.

[Synthesis Example 4]
Synthesis was performed in the same manner as in Synthesis Example 3 except that p-tert-butylphenol was changed to 3.25 parts, and a powder (viscosity) having a viscosity average molecular weight of 11800 and a Cl content of 37 ppm was obtained.
Table 1 shows the characteristics of the aromatic polycarbonate resin granules PC-1 to PC-4 synthesized in Synthesis Examples 1 to 4 and the following PC-5.

[Examples 1-4, Comparative Examples 1-4]
The polycarbonate resin composition blended with each component shown in Table 2 was extruded at 300 ° C. with TEX-30α manufactured by Nippon Steel Works, and the strand was cut to obtain pellets. The obtained pellets were dried at 120 ° C. for 4 hours. The above various evaluations were performed using the obtained pellets. The results are shown in Table 2.
In addition, each component in Table 1 and Table 2 is as follows.

PC-1: Aromatic polycarbonate resin granules (powder) synthesized in Synthesis Example 1
PC-2: Aromatic polycarbonate resin granules (powder) synthesized in Synthesis Example 2
PC-3: Aromatic polycarbonate resin granules (powder) synthesized in Synthesis Example 3
PC-4: Aromatic polycarbonate resin granules (powder) synthesized in Synthesis Example 4
PC-5: Aromatic polycarbonate resin granules (Teijin Chemicals Panlite L-1225)
L1: Release agent; Riken vitamin S-100A (main component glycerin monostearate)
L2: Mold release agent; Riken vitamin B-100A (main component glycerin monobehenate)
A1: Phosphorus stabilizer; P-EPQ manufactured by Clariant Japan
H1: Brewing agent; Macrolex Violet B from Bayer
H2: Brewing agent; Bayer Macrolex Blue RR

It is the figure which showed the 1H-NMR spectrum chart of the aromatic polycarbonate resin pellet. It is the schematic which shows the bending test which sets an optical disk board | substrate to a jig and applies a pressure.

Explanation of symbols

1. Jig 2. 2. Optical disk substrate Width between jigs (120mm)
4). Width between jigs (20mm)

Claims (5)

Viscosity average molecular weight is 1.0 × 10 ^{4 to} 2.0 × 10 ⁴ , low molecular weight component content with a molecular weight of 1000 or less is 1.5 wt% or less, total nitrogen content is 15 ppm or less, Cl content is 100 ppm or less, For optical information recording medium containing 0.01 to 0.3 parts by weight of glycerin monoester type release agent with respect to 100 parts by weight of aromatic polycarbonate resin having an OH end group amount of 0.1 to 30 eq / ton Aromatic polycarbonate resin composition.   2. The aromatic polycarbonate resin composition for an optical information recording medium according to claim 1, wherein the main component of the glycerin monoester type release agent 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 composition has a viscosity average molecular weight of 1.3 × 10 ^{4 to} 1.75 × 10 ⁴ .   2. The aromatic polycarbonate resin composition for an optical information recording medium according to claim 1, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin that is polymerized by a non-catalytic interfacial polycondensation method and is subjected to low molecular weight component extraction treatment with acetone after polymerization. object.   An optical information recording medium formed by injection compression molding from the resin composition according to claim 1.

Images