WO2002031024A1 - Polycarbonate and substrates for optical discs - Google Patents

Abstract

A polycarbonate which little contains impurities, is excellent in close adhesion to a recording film, and exhibits excellent performance when used as the substrate for an optical or magnetic disc. This polycarbonate is characterized by extractability of less than 1 wt% by 2-ethoxyethyl acetate, that of less than 2 wt% by acetone, and an acetone extract containing aromatic dihydroxyl compounds and carbonic diesters in amounts of 5 to 40 ppm and 50 to 200 ppm by weight respectively based on the polycarbonate.

Description

 Description Polycarbonate and optical disc substrates Technical field

 The present invention relates to polycarbonate and optical disc substrates. More specifically, the present invention relates to a polypropylene having a low content of impurities and suitably used as a material for an optical disk substrate, and an optical disk substrate using the same. Conventional technology

 Polycarbonate is used as a material for disk substrates such as optical disks and magnetic disks.

 Examples of the method for producing such a polycarbonate include a method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene (interfacial method), or a method in which an aromatic dihydroxy compound such as bisphenol A is mixed with diphenyl compound. A method of performing a melt polycondensation reaction (ester exchange reaction) with a carbonic acid diester such as luka-ponate (a melt polycondensation method) and the like are known.

 Of these, the interfacial method using phosgene is currently widely practiced. However, the polycarbonate obtained by the phosgene method contains unreacted raw materials, used solvents or low-molecular-weight components as impurities, and such impurities were used for molding this polycarbonate as a disk substrate. Sometimes, ① the adhesion between the substrate and the recording film is insufficient, ② the metals such as iron, gallium and terbium existing in the recording film are gradually corroded, ③ the mold is corroded during molding. As a result, the life of the stamper was shortened, causing a problem.

In Japanese Patent Application Laid-Open No. H10-241149, therefore, impurities are removed from a polyponate obtained by the phosgene method so that the content of the impurities exceeds 2% by weight of the low molecular weight component and 3% by weight. %, Less than 20 ppm of unreacted bisphenols and less than 20 ppm of methylene chloride. Japanese Patent Application Laid-Open No. 2000-222774 also discloses that polypolyponate similarly obtained by the phosgene method has an impurity content of less than 2% by weight in a low molecular weight component extracted from acetone solvent by Soxhlet, and unreacted bisphenols of 20 p. A polyponate for a disc substrate that is less than 20 pm and less than 20 ppm of methylene chloride is disclosed. On the other hand, the melt polycondensation method has the advantage that polycarbonate can be produced at lower cost than the interface method, and furthermore does not use toxic substances such as phosgene. Have been.

 Also, unlike the interfacial method, the poly-polypropylene obtained by the melt polycondensation method does not contain a solvent such as methylene chloride, so that metals such as iron, gallium, and terbium existing in the recording film gradually disappear. Since the mold is corroded during molding or the mold is corroded during molding, the problem of shortening the life of the stamper can be avoided.

 However, the poly-polyponate obtained by the melt polycondensation method still has a problem in that when used as a disk substrate, the adhesion between the substrate and the recording film is insufficient. It is thought to be due to impurities different from the obtained polycarbonate.

Japanese Patent Application Laid-Open No. 9-110978 discloses that the polycarbonate obtained by melt polycondensation contains, as trace components, (a) an alkali metal or Z and an alkaline earth metal content of 800 ppb or less, and (b) The content of the aromatic monohydroxy compound is less than 20 Oppm, (c) The content of the oligomer component having a molecular weight of less than 1,000 and the content of the residual monomer is less than T ₂ % by weight, (伹, T ₂ = l, 520, 00 OX (weight average molecular weight of the poly force one Poneto) - polycarbonate composition is shown open in the range of ¹ - ^44). This polycarbonate composition has the characteristics of low craze generation under moist heat conditions and less defects such as black dust (carbonized deterioration), color unevenness and burns that occur at the start of remolding after continuous molding is interrupted. Have. Disclosure of the invention

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyponate having a low impurity content. Another object of the present invention is to provide excellent adhesion between a recording layer and an optical disc substrate. An object of the present invention is to provide a polycarbonate exhibiting properties.

 Still another object of the present invention is to provide the above-mentioned poly-polycarbonate wherein the impurity content of the poly-polycarbonate exhibiting excellent adhesiveness as described above is specified by an extraction amount with respect to a specific organic solvent. It is in.

 Still another object of the present invention is to provide a substrate for an optical disk made of the polycarbonate of the present invention.

 Still other objects and advantages of the present invention will become apparent from the following description. According to the present invention, the above objects and advantages of the present invention are:

 (A) The following formula (1)

…)

-, Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, and a 6 to 20 carbon atoms. An aryl group, a cycloalkyloxy group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms,

 X is a single bond, an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, and a carbon atom having 6 to 20 carbon atoms. A cycloalkylidene group, an arylene group having 6 to 20 carbon atoms or an alkylene-arylene-alkylene group having 6 to 20 carbon atoms,

m and n are each independently an integer from 0 to 4,

Consisting essentially of a repeating unit represented by

 (B) the amount of extraction with 2-ethoxycetyl acetate is 2% by weight or less,

 (C) the amount of extraction with acetone is 2% by weight or less, and

(D) aromatic dihydroxy compound in acetone extract and Carbonic diesters are contained at 5 to 5 parts per million by weight, respectively, of the polycarbonate: LOO ppm and 100 to 200 ppm.

This is achieved by a polycarbonate characterized in that:

 Further, according to the present invention, the above object and advantages of the present invention are, secondly, to use an optical disk substrate comprising the polycarbonate of the present invention or the polycarbonate of the present invention for an optical disk substrate. Preferred embodiments of the invention

The polycarbonate of the present invention is substantially composed of the repeating unit represented by the above formula (1). In the above formula (1), the definitions of R ¹ and R ² are as described above. The alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, may be linear or branched. Examples include methyl, ethyl, propyl, butyl, octyl, decyl and the like.

 The alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, may be linear or branched. Examples thereof include methoxy, ethoxy, propoxy, butoxy, octoxy, decyloxy and the like.

 Examples of the cycloalkyl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms include cyclohexyl and 3,3,5-trimethylcyclohexyl. Examples of the cycloalkyloxy group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, include cyclohexyloxy, 3,3,5-trimethylcyclohexyloxy and the like.

 Examples of the aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms include phenyl, tolyl, and naphthyl.

 The aryloxy group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, includes, for example, phenyloxy, tolyloxy, naphthyloxy and the like.

 The definition of X is as described above.

The alkylene group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, may be linear or branched. Examples thereof include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene and the like.

 Examples of the alkylidene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, include ethylidene, 2,2-propylidene, 2,2-butylidene, 3,3-hexylidene, and the like.

 Examples of the cycloalkylene group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms include 1,4-cyclohexylene, 2-isopropyl-1,4-cyclohexylene and the like.

 Examples of the cycloalkylidene group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, include, for example, cyclohexylidene, isopropylcyclohexylidene and the like.

 Examples of the alkylene arylene-alkylene group having 6 to 20 carbon atoms, preferably 8 to 15 carbon atoms include m-diisopropyl phenylene group.

In the above formula (1), it is preferable that X is an alkylidene group having 2 to 10 carbon atoms, and R ¹ and R ² are both hydrogen atoms. In particular, X is preferably a cyclohexylidene group or a 2,2-propylidene group, and particularly preferably a 2,2-propylidene group.

 The production of this polycarbonate is carried out in such a manner that 10 to 100/2 stoichiometric amounts of the nitrogen-containing basic compound and / or the phosphorus-containing basic compound per mole of the aromatic dihydroxy compound, and 0.1 to 0.1 mole per mole of the aromatic dihydroxy compound. 0 to 5 It is preferable to use a melt polycondensation method in which an aromatic dihydroxy compound and a carbonic acid diester are polycondensed in the presence of a catalyst containing 5 to 5 chemical equivalents of an alkali metal compound and Z or an alkaline earth metal compound. .

As the aromatic dihydroxy compound used in the present invention, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (2-hydroxyphenylyl) methane, 1,1-bis ( 4-Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) ) Propane, 2,2_bis (4-hydroxy-1,3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-13-methylphenyl) propane, 2,2-bis (4— Hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 , 5-Trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-13-methylphenyl) fluorene, hi, '-bis (4-hydroxyphenyl) _m —Diisopropylbenzene, 2,2,2 ', 2, -tetrahydro-3,3,3', 3, -tetramethyl_1,1,1-spirobis [1H-indene] -6,6'-diol, Bis (4-hydroxyphenyl) sulfur , Bis (4-hydroxyphenyl) sulfone and the aromatic ring, for example, alkyl groups include those Ariru group is substituted, especially preferably Bisufue Nord A from among them cost. These may be used alone or in combination of two or more. Examples of the carbonic acid diester include diphenylcapone, dinaphthylcaponate, bis (diphenyl) capillonate, dimethylcaponate, and dibutylcapone. Of these, diphenyl carbonate is preferred from the viewpoint of cost.

 Trace metal elements contained as impurities in the aromatic dihydroxy compound and the carbonic acid diester are preferably controlled because they adversely affect the durability, color tone, and transparency of the produced polycarbonate.

 The melt polycondensation method is carried out by stirring an aromatic dihydric oxyxyl compound and a carbonic acid diester while heating under normal pressure and under a Z or reduced pressure nitrogen atmosphere to distill off the produced alcohol or phenol. The reaction temperature varies depending on the boiling point of the product, etc., but is preferably in the range of 120 to 350 in order to remove alcohol or phenol formed by the reaction, and more preferably, it is preferable to obtain good hue and thermal stability. The range is 180-28.

In the late stage of the reaction, the pressure of the system is reduced to facilitate the distillation of the alcohol or phenol formed. The internal pressure in the latter half of the reaction is preferably 133.3 Pa (ImmHg) or less. And more preferably 66.7 Pa (0.5 mmHg) or less.

 Specific examples of nitrogen-containing basic compounds, phosphorus-containing basic compounds (hereinafter abbreviated as NCBA), alkali metal compounds, and alkaline earth metal compounds (hereinafter abbreviated as AMC) used as catalysts in the above polycondensation reaction The following compounds can be mentioned as examples.

 Specific examples of NCBA include, for example, a nitrogen-containing basic catalyst having an alkyl, aryl, alkylaryl group such as tetramethylammonium hydroxide and benzyltrimethylammonium hydroxide. Ammonium hydroxides, tetramethylammonium acetate, tetraethylammonium enoxide, tetrabutylammonium carbonate, benzyltrimethylammonium benzoate, etc. Tertiary amines such as basic ammonium salts, triethylamine, dimethylpenzylamine, etc., or tetramethylammonium borohydride, tetrabutylammonium borohydride, tetramethylammonium tetraphenylporate, etc. And the like.

 Specific examples of the phosphorus-containing basic compound include, for example, phosphonium hydroxides having an alkyl, aryl, alkylaryl group such as tetrabutylphosphonium hydroxide and benzyltrimethylphosphonium hydroxide, and the like. Examples thereof include basic salts such as tetramethylphosphoniumporohydride, tetrabutylphosphoniumpomide hydride, and tetramethylphosphoniumtetraphenylporate.

 The above-mentioned NCBA is used in such a ratio that a basic nitrogen atom or a basic phosphorus atom becomes 10 to 1000 chemical equivalents to 1 mole of the aromatic dihydroxy compound. If the amount is less than 100 chemical equivalents, the reaction becomes slow, which is not preferable. A more preferred range of use is a ratio that gives 20 to 500 chemical equivalents based on the same standard. A particularly desirable ratio is a ratio that results in 50 to 500 chemical equivalents with respect to the same standard.

Further, in the present invention, in order to realize the effect of reducing trace metal elements as impurities in the raw material to improve the stability of the polymer color tone, AM It is preferred to use As AMC, a compound containing an alkali metal is preferably used.

 The AMC used in the present invention includes, for example, hydroxides of alkali metals and alkaline earth metals, hydrocarbon compounds, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearins Acid salts, borohydride salts, benzoates, hydrogen phosphate compounds, bisphenols, phenol salts and the like.

 Specific examples include sodium hydroxide, cesium hydroxide, rubidium hydroxide, furansium hydroxide, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium acetate, sodium nitrite, sodium sulfite, sodium cyanate. , Potassium cyanate, sodium thiocyanate, potassium thiocyanate, cesium thiocyanate, sodium stearate, sodium borohydride, potassium borohydride, lithium borohydride, sodium tetraphenylborate, sodium benzoate, dihydrogen phosphate Sodium, dipotassium hydrogen phosphate, disodium salt of bisphenol A, monopotassium salt, sodium potassium salt, potassium salt of phenol, dicesium salt of bisphenol A, monocesium salt, phenol Cesium salt and the like.

 Such AMC is used in the range of 0.05 to 5/2 chemical equivalent as the alkali metal element and Z or the alkaline earth metal element per mole of the aromatic dihydroxy compound. By using a catalyst with a large volume ratio, a branching reaction, a main chain cleavage reaction, and the generation of foreign matter in an apparatus during molding, which are easily generated during the polycondensation reaction without impairing the polycondensation reaction rate, Unwanted phenomena such as burns can be effectively suppressed.

 If the ratio is out of the above range, there may be problems such as easily adversely affecting the physical properties of the obtained polycarbonate, difficulty in transesterification reaction sufficiently progressing, and difficulty in obtaining a high-molecular-weight polycarbonate. Not preferred.

In the polycarbonate of the present invention, a sulfonic acid compound can be used as a melt viscosity stabilizer. By using the sulfonic acid compound, deterioration of the polycarbonate during molding is suppressed. Examples of such a sulfonic acid compound include sulfonic acid salts such as phosphonium salt and ammonium salt of sulfonic acid, sulfonic acid, and sulfonic acid lower ester. These sulfonic acid compounds can be used alone or in combination.

 Specific examples of the above sulfonate include, for example, tetrabutyl phosphonium octylsulfonate, tetrabutyl phosphonium decylsulfonate, tetramethylphosphonium benzenesulfonate, tetrabutyl phosphonium benzenesulfonate , Tetradecylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetramethylammonium decylsulfonate, tetrabenzenesulfonate Ethyl ammonium salt and dodecylbenzene sulfonic acid tetrabutylammonium salt.

 Specific examples of the above sulfonic acid and sulfonic acid lower ester include aromatic sulfonic acid such as benzenesulfonic acid, p-toluenesulfonic acid, dodecylsulfonic acid, hexadecylsulfonic acid, nonylsulfonic acid, and the like. Aliphatic sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p-toluene Examples thereof include butyl sulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, methyl dodecylsulfonate, ethyl hexadecylsulfonate, propyl nonylsulfonate, and butyl decylsulfonate.

 Preferably, a sulfonic acid lower ester compound is used.

 As a method for adding the sulfonic acid compound, for example, it may be added while the reaction product, polycarbonate, is in a molten state, or the polycarbonate obtained after polymerization may be passed through an extruder from a reaction tank. During the pelletization, a sulfonic acid compound can be added and kneaded.

Such a sulfonic acid compound is preferably used in an amount of 0.7 to 100 chemical equivalents per 1 chemical equivalent of the total amount of the alkaline metal element and the alkaline metal element of AMC. Good.

 If it is less than 0.7 chemical equivalent, the effect of suppressing inferiority during molding tends to be insufficient. If it exceeds 100 chemical equivalents, metals such as iron, gallium, and terbium existing in the recording film are gradually corroded, or the mold is corroded during molding. There is a risk that problems may occur. The amount of the sulfonic acid compound to be used is preferably 0.8 to 30 chemical equivalents, more preferably 0.8 to 30 chemical equivalents per 1 chemical equivalent of the total amount of the metallic alkali element and the alkaline earth metal element. 9 to 20 chemical equivalents.

The above-mentioned pellet-like polycarbonate is not limited to a pellet-like polycarbonate in a strict sense, but also includes a flake-like polycarbonate and the like. In other words, it is obtained by cooling and solidifying the molten polycarbonate obtained by the melt polycondensation method, and includes all small lumps. The size of the pellets is usually a 4 to 2 O mm ^3.

 The pellet-like polycarbonate obtained by the above-mentioned melt polycondensation method usually contains 3 to 5% by weight of low molecular weight components such as oligomers of polycarbonate and 50 to 50% of unreacted aromatic dihydroxy compounds such as bisphenol A as impurities. It often contains about 300 to 500 ppm of an unreacted carbonic acid diester compound such as diphenyl carbonate.

 The polycarbonate of the present invention is substantially composed of the repeating unit represented by the above formula (1).

 (B) the amount of extraction with 2-ethoxycetyl acetate is 2% by weight or less,

 (C) the amount of extraction with acetone is 2% by weight or less, and

 (D) The aromatic dihydroxy compound and the carbonic acid diester are contained in the acetone extract at 5 to 100 ppm and 10 to 200 ppm by weight, respectively, based on the polycarbonate.

The inventors of the present invention have confirmed that the above-mentioned characteristics (B), (C) and (D) make it possible to secure a poly-polypropylene component capable of achieving excellent adhesion to a recording layer when used as an optical disk substrate. It was revealed for the first time. The amount of extraction with 2-ethoxyxetil acetate is preferably 2% by weight or less, more preferably 1% by weight or less. The amount of extraction with acetone is preferably 2% by weight or less, more preferably less than 1.8% by weight. Further, the content of each of the aromatic dihydroxy compound and the carbonate in the acetone extract is from 5 to: L 0 ppm, preferably from 5 to 40 ppm, more preferably from 5 to 40 ppm by weight, based on the weight of the polypropionate. Is 5 to 20 ppm, more preferably 5 to 10 ppm, and 10 to 200 ppm, preferably 50 to 200 ppm, more preferably 50 to: L 50 ppm, and still more preferably Is 70 to 150 ppm.

 The polycarbonate of the present invention can be obtained, for example, by subjecting the pellet-like polycarbonate obtained by the melt polycondensation method to an extraction treatment with an organic solvent, particularly, a solvent containing 2-ethoxyethyl acetate.

 The organic solvent means a solvent containing an organic solvent, and includes not only 2-ethoxyxetyl acetate alone but also a mixture of an organic solvent and a mixture of an organic solvent and water. In the extraction treatment, the above organic solvent is used in the range of 0.5 to 20 times the weight of the pellet-like polycarbonate, and the temperature is set to a range of 40 ° C or higher and the boiling point of the organic solvent to be used or lower. Is preferred.

 This extraction process is usually performed under normal pressure, but can be performed under pressure. Further, as the organic solvent used for the extraction treatment, a solvent containing 70% by weight or more of 2-ethoxyxyl acetate is particularly preferable.

 As described above, the polyacrylonitrile of the present invention is excellent in the adhesive force and the adhesive force typified by the adhesion between the substrate and the recording film. Therefore, the polycarbonate of the present invention is useful not only for disk substrates but also for other applications in which the demands for adhesion and adhesion are strict.

 The polycarbonate composition of the present invention may further contain, if necessary, conventionally known heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, release agents, and the like.

Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Such heat stabilizers include, for example, Lisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, 4,4'-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), trimethyl phosphate And dimethyl benzenephosphonate. These heat stabilizers may be used alone or in combination of two or more. The blending amount of such a heat stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, based on 100 parts by weight of the aromatic polycarbonate obtained by the present invention. Is more preferable, and 0.001 to 0.1 part by weight is even more preferable.

 Further, it is preferable that a mold release agent is added to the polycarbonate resin composition of the present invention within a range that does not impair the object of the present invention. Examples of the release agent include an olefin wax, an olefin wax containing a carboxylic acid group and a Z or carboxylic acid anhydride group, silicone oil, an organopolysiloxane, a higher fatty acid ester of a monohydric or polyhydric alcohol, Examples thereof include paraffin wax and honey, of which fatty acid esters are preferable, and higher fatty acid esters of polyhydric alcohols are particularly preferable.

 The higher fatty acid ester of a polyhydric alcohol is an ester of a higher fatty acid having 8 to 30 carbon atoms in which at least one hydroxyl group of a polyhydric alcohol having 2 to 20 carbon atoms and having 2 or more hydroxyl groups is used. What is forming is mentioned. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, neopentylene glycol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentylerythritol.

 Specific examples of the higher fatty acids having 8 or more carbon atoms include, for example, stearic acid, valeric acid, cabronic acid, acetic acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, serotinic acid, melicic acid, and tetracarboxylic acid. Examples thereof include triacontanic acid, daltaric acid, adipic acid, and azelaic acid.

Specific examples of higher fatty acid esters of polyhydric alcohols include, for example, ethylene daryl glycol monostearate, glycerin monostearate, trimethylolpropane monostearate, and pentaerythr! ^ One Lumonostearate, Eri Eri Suri Tall monolaurate, Penyu erythritol distearate, glycerin dilaureate, glycerin tristearate, trimethylolpropane distearate, glycerin distearate, glycerin tristearate, Penpo erythritol tristearate And trimethylolpropane triforce plate, trimethylolpropanediolate, pentaerythritol tetrastearate and the like.

 The amount of the release agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate of the present invention.

 In addition, the following release agents may be used in combination, if desired. That is, hydrocarbon-based release agents include natural and synthetic paraffin waxes, polyethylene wax, fluorocarbons, and the like; fatty acid-based release agents include higher fatty acids such as stearic acid and oxy fatty acids such as hydroxystearic acid. But fatty acid amide release agents include fatty acid amides such as ethylenebisstearylamide, and alkylene fatty acid amides such as erlic acid amide; and alcohol release agents include aliphatic alcohols such as stearyl alcohol and cetyl alcohol. Examples of the polyhydric alcohol include polyglycol, polyglycerol, and trimethylolpropane. Other polysiloxanes can also be used. These may be used alone or as a mixture of two or more.

Further, various conventionally known additives can be used. For example, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -1-5-benzobenzotriazole as a light stabilizer, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) Benzotriazole, 2- {2-hydroxy-13- (3,4,5,6-tetrahydrophthalimidomethyl) phenyl} benzotriazole based compounds such as benzotriazole, 2-hydroxy-14-octylo Benzophenone compounds such as xybenzophenone, benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-cyano 3,3-diphenylacrylate, etc. And cyanoacrylate-based light stabilizers, quaternary ammonium salt-based, and alkyl phosphate-based antistatic agents. These light stabilizers and ultraviolet absorbers are usually used in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the resin component. Can be used in an amount of 5 parts by weight. These agents may be used alone or as a mixture.

 In the resin of the present invention, if necessary, an organic or inorganic coloring agent such as a dye or a pigment can be used. Specific examples of the inorganic colorant include: oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfate, pherocyanides such as navy blue, chromates such as zinc chromate, and the like. Examples include sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal coloring agents such as bronze powder and aluminum powder. .

 Organic colorants include nitroso-based dyes such as Naphthol Green B, nitro-based dyes such as Naphthol Yellow S, and Naf! Examples include azo-based, chromophtalyl yellow-based azo-based, phthalocyanine-based such as phthalocyanine blue and fast sky blue, and condensed polycyclic-based coloring agents such as indian blue.

These colorants may be used alone or as a mixture. These colorants are usually per 1 0 0 parts by weight of the resin component 1 X 1 0 one ^6-5 parts by weight, preferably rather the 1 X 1 0 one ^6-3 parts by weight, more preferably 1 X 1 0 one ⁵ Can be used in amounts of up to 1 part by weight.

Furthermore, inorganic and organic fillers can be blended with the aromatic polycarbonate of the present invention in order to improve rigidity and the like, as long as the object of the present invention is not impaired. Such inorganic fillers include, for example, plate-like or granular inorganic fillers such as talc, my strength, glass flakes, glass beads, calcium carbonate, and titanium oxide; glass fibers, glass milled fibers, wollastonite, carbon Examples include fibrous fillers such as fibers, aramide fibers, and metallic conductive fibers, and organic particles such as crosslinked acrylic particles and crosslinked silicone particles. The amounts of these inorganic and organic fillers are based on 100 parts by weight of the aromatic polyether-ponate; It is preferably from 150 to 150 parts by weight, more preferably from 3 to 100 parts by weight. The inorganic filler usable in the present invention may be surface-treated with a silane coupling agent or the like. By this surface treatment, good results are obtained, such as suppression of decomposition of the aromatic polycarbonate.

 Other resins can be blended with the aromatic polysiloxane of the present invention as long as the object of the present invention is not impaired.

 Examples of such other if-fats include polyamide resins, polyimide resins, polyesterimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, and the like. Polyester resin such as polybutylene terephthalate, amorphous polyarylate resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, Examples include phenolic resins and epoxy resins. The amount of these other purposes is preferably 10 to 150 parts by weight based on 100 parts by weight of the aromatic polycarbonate.

 The aromatic polycarbonate of the present invention is excellent in durability, in particular, the effect of maintaining long-term durability under severe temperature and humidity conditions. Therefore, compact discs (CD), CD-ROM, CD-R, CD-RW, magnetic optical disc (MO), digital versatile disc (DV D-ROM, Substrates for high-density optical discs represented by DVD-Video, DVD-Audio, DVD-R, DVD-RAM, etc. have high reliability over a long period of time. In particular, it is useful for a high-density optical disk such as a digital versatile disk. There is no particular limitation on the thickness of such an aromatic poly-polypropylene disc, but usually 0.7 mm or less is particularly preferred. Example

 Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these.

“Parts” means “parts by weight” unless otherwise specified. The analysis method used is as follows.

Viscosity-average molecular weight of poly-polypropylene

 It was measured in methylene chloride at 20 ° C with an Ubbelohde viscosity tube. The viscosity average molecular weight was calculated from the intrinsic viscosity by the following formula.

. [77] ^{= 1 23 X 10 "4 XMW} ° - 83

 Analysis of the components of 2-ethoxyxetil acetate:

 To 100 g of pelletized polycarbonate (diameter: 2.0 to 3.0 Omm, length: 2.5 to 3.5 mm), add 200 g of ethoxyethoxyl acetate and stir at 40 ° C for 1 hour to perform extraction. went. Thereafter, the solid content was filtered off, the residue after evaporating 2-ethoxyethyl acetate from the filtrate was weighed, and this was used as the 2-ethoxyxetil acetate-extracted component and its amount.

 Analysis of low molecular weight components:

 It is a component obtained by Soxhlet extraction using acetone as a solvent. That is, 15 g of a sample, polycarbonate, which had been ground and passed through a 100-mesh wire mesh, was collected on a cylindrical filter paper No. 84 (28 x 100 mm), and this was collected using a 300-ml acetone to obtain 3-4 The mixture was refluxed once a minute (20 mlZ times) for 8 hours to extract. Thereafter, the residue after evaporating 300 ml of acetone was weighed, and this was defined as a low molecular weight component and its amount.

 Unreacted bisphenol A and unreacted diphenyl alcohol: The above low molecular weight components were subjected to Soxhlet extraction using acetone as a solvent, and then quantified by liquid chromatography from the acetone.

 Adhesion test:

 After leaving the optical disk for 90 hours in an atmosphere at a temperature of 90 ° C and a relative humidity of 90%, a pinhole test was performed using 180 ° peeling of cellophane tape, and the area of the remaining area where the magneto-optical film on the surface remained without peeling was measured. The ratio to the area used for the test was expressed as adhesiveness based on the following formula.

Adhesiveness = [(area of remaining portion) / (test area)] XI 00 (%) Example 1 228 parts by weight of bisphenol A, 223 parts by weight of diphenylcaponate, 0.009 parts by weight of tetramethylammonium hydroxide and 0.00014 parts by weight of disodium salt of bisphenol A were stirred with a stirrer, a decompression device, a distillation column, etc. The mixture was charged into the equipped reaction apparatus, and stirred and dissolved in a nitrogen atmosphere at 180 ° C. for 25 minutes. Next, the reaction was carried out at the same temperature under reduced pressure of 100 mmHg for 30 minutes while distilling off phenol.

 The pressure was further reduced to 3 OmmHg while increasing the temperature to 220 ° C, and the reaction was carried out at the same temperature and pressure for 30 minutes.

 Further, the temperature of the reaction system was gradually increased and reduced to 270 and 0.5 mmHg, and the reaction was carried out for 1 hour to obtain a polyphenol resin.

 To 100 parts by weight of the obtained resin, 0.0012 parts by weight of tetradecylphosphonium dodecylbenzenesulfonate was added and mixed for 20 minutes. The viscosity average molecular weight of the obtained resin was 15,300.

 Acetic acid 2 was added to 100 parts of the thus obtained pellet-like polyphenol containing 4% by weight of the low molecular weight component, 80 ppm of unreacted bisphenol A and 32 Oppm of unreacted diphenyl alcohol. —200 parts of ethoxyl was added, and the mixture was stirred at 40 for 1 hour to perform a contact treatment (extraction treatment).

 Thereafter, the 2-ethoxyethoxyl acetate was removed, and washed with 500 parts of water. This was dried at 120 ° C. under a reduced pressure of 30 to 1 mmHg for 20 hours. The impurity content in the obtained pellet-shaped polycarbonate was as shown in Table 1.

Next, after adding 0.002 parts of tris (2,4-di-tert-butylphenyl) phosphite and 0.02 parts of glycerin monostearate to 100 parts of the pellet-shaped polycarbonate, the mixture was pelletized by an extruder and injection-molded. A disc substrate having a diameter of 13 cm was formed by a machine. Thickness 80 OA of silicon oxide (S i O _x) layer / thickness of 1, 000A of the metal (Tb, F e, C o ) layer Z thickness 800 A silicon oxide (S i O _x) layer trilayer A magneto-optical film having a structure was formed on the disk substrate by a sputtering method.

The obtained optical disk is evaluated by an adhesion test (adhesion between the magneto-optical film and the substrate) did. Table 1 shows the results.

 Example 2

 In Example I, the same operation as in Example 1 was performed except that the extraction treatment with 2-ethoxyxyl acetate was performed at 50 ° C. Table 1 shows the results.

 Example 3

 The same operation as in Example 1 was performed, except that a mixture of 2-ethoxyxetyl acetate and acetone (90% by weight of 2-ethoxyxyl acetate) was used in place of 2-ethoxyxetyl acetate in Example 1. Table 1 shows the results.

 Example 4

 The same operation as in Example 1 was performed, except that a mixture of 2-ethoxyxetyl acetate and water (90% by weight of 2-ethoxyxetyl acetate) was used in place of 2-ethoxyxetyl acetate in Example 1. Table 1 shows the results.

 Comparative Example 1

 The same operation as in Example 1 was performed except that the extraction treatment with 2-ethoxyxyl acetate was not performed. Table 1 shows the results.

 Comparative Example 2

 The same operation as in Example 1 was performed, except that water was used instead of 2-ethoxyxetyl acetate. Table 1 shows the results.

 Example 5

 Pellets containing 4% by weight of low molecular weight component, 120 ppm of bisphenol A, and 220 ppm of diphenylcaponate in the same manner as in Example 1 except that diphenylcapone was used in 2 parts by weight. A polycarbonate was obtained. Hereinafter, the same operation as in Example 1 was performed. Table 1 shows the results.

 Example 6

 The same operation as in Example 3 was performed, except that the extraction treatment with a mixture of 2-ethoxyxetyl acetate and acetone (90% by weight of 2-ethoxyxethyl acetate) was performed at 20 ° C. for 1 hour. Table 1 shows the results.

Comparative Example 3 The same operation as in Example 1 was performed, except that was used instead of 2-ethoxyxetyl acetate. Table 1 shows the results. table 1

実施例 7〜1 3

Examples 7 to 13

 Stirring 228 parts by weight of bisphenol A, 223 parts by weight of diphenylcaponate, 0.09 parts by weight of tetramethylammonium hydroxide and 0.014 parts by weight of disodium salt of bisphenol A It was charged into a reactor equipped with an apparatus, a decompression device, a distillation column, and the like, and was stirred and dissolved under a nitrogen atmosphere at 180 ° C for 30 minutes.

 Then, the reaction was carried out at the same temperature under reduced pressure of 10 O mmHg for 30 minutes while distilling off phenol.

 The pressure was further reduced to 30 mmHg while the temperature was raised to 230 ° C, and the reaction was carried out at the same temperature and pressure for 60 minutes.

 Further, the temperature of the reaction system was gradually increased and reduced, and finally, the temperature was adjusted to 290 ° C. and 0.5 mmHg, and the reaction was performed for 1 hour to obtain a polycarbonate resin.

100 parts by weight of the obtained resin was added to tetrabutyl dodecylbenzenesulfonate. 0.0012 parts by weight of ruphosphonium salt was added and mixed for 20 minutes. The viscosity average molecular weight of the obtained resin was 22,500.

 To 100 parts of a pellet-like polycarbonate containing 3% by weight of low molecular weight component, 80 ppm of unreacted bisphenol A and 280 ppm of unreacted diphenyl carbonate, 200 parts of 2-ethoxyxetyl acetate was added. The mixture was stirred for 1 hour to perform the contact treatment (extraction treatment).

 Thereafter, 2-ethoxyhexyl acetate was removed and washed with 500 parts of water. This was dried at 120 ° C. under a reduced pressure of 30 to 1 mmHg for 20 hours. The extract of 2-ethoxyxetyl acetate in the obtained pellet-like polycarbonate was 0.4 wt%, the low molecular weight component was 1.3 wt%, and the contents of bisphenol A and diphenyl carbonate were 10 ppm and 80 ppm, respectively. Met.

 To 100 parts of the aromatic polycarbonate of Example 1, 0.003 part of tris (2,4-t_butylphenyl) phosphite and 0.05 part of trimethyl phosphate were added, and mixed uniformly. This mixture and the components shown in Tables 2 and 3 (each component indicated by the symbol shown below) were uniformly mixed using a tumbler, and then a twin-screw extruder with a 30 mm φ vent (Kobe Steel ( KTX-30) (made by K.K. Co., Ltd.), degassed at a cylinder temperature of 270 ° C and a vacuum of 1.33 kPa (l OmmHg) and dried the obtained pellets at 120 ° C for 5 hours. Using an injection molding machine (SG150U type, manufactured by Sumitomo Heavy Industries, Ltd.), a molded piece for measurement was prepared under the conditions of a cylinder temperature of 270 ° C and a mold temperature of 80 ° C, and the following evaluation was performed. . The results are shown in Tables 2 and 3.

 ①-1 ABS: Styrene-butadiene-acrylonitrile copolymer; Santaku UT-61 manufactured by Mitsui Chemicals, Inc.

①—2 AS Styrene-acrylonitrile copolymer; Styrac-AS7 67 R27 manufactured by Asahi Kasei Corporation

 ① 1 3 PET: polyethylene terephthalate; TR-8580; Teijin Limited, intrinsic viscosity 0.8

(1) PBT: polybutylene terephthalate; TRB-H; manufactured by Teijin Limited Viscous 1.07

 © — 1 MBS: Methyl (meth) acrylate-butadiene-styrene copolymer; Kaneace B-56; manufactured by Kanegafuchi Chemical Industry Co., Ltd.

 ②—2E—1: butadiene-alkyl acrylate-alkyl methacrylate copolymer; paraloid EXL-2602; manufactured by Kureha Chemical Industry Co., Ltd.

 ②-3 E-2: Composite rubber in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component have an interpenetrating network structure; Metaprene S-2001; manufactured by Mitsubishi Rayon Co., Ltd.

 ③— 1 T: talc; HS—TO. 8; average particle diameter measured by laser diffraction method, manufactured by Hayashi Kasei Co., Ltd. L = 5 m, L / D = 8

 ③— 2 G: Glass fiber; chopped strand EC S-03T—511; Nippon Electric Glass Co., Ltd., urethane focusing treatment, fiber diameter 13 m

 ③ ー 3 W: Wollastonite; Psychatec NN-4; Tomoe Kogyo Co., Ltd., number-average average fiber diameter determined by electron microscopy 1) = 1.5 m, average fiber length 17 m, Aspect ratio LZD = 20

 ④ WAX: olefin-based copolymer obtained by copolymerization of α-olefin and maleic anhydride ヮ x; Diacarna 30 ； manufactured by Mitsubishi Kasei Corporation (maleic anhydride content = 1 Owt%)

 (A) Flexural modulus

 The flexural modulus was measured according to ASTM D790.

 (B) Notched impact value

 According to ASTM D256, a 3.2 mm thick specimen was used to impact the weight from the notch side, and the impact value was measured.

 (C) Liquidity

 The fluidity was measured using an Archimedes-type spiral lip (thickness 2 mm, width 8 mm) at a cylinder temperature of 250 ° C, a mold temperature of 80 ° C, and an injection pressure of 98. IMP a.

(D) Chemical resistance

Apply 1% strain to the tensile test piece used in ASTM D638 and -After immersion in Yular gasoline for 3 minutes, the tensile strength was measured to calculate the retention. The retention was calculated by the following equation.

Retention rate (%) = (Strength of treated Sankare z Strength of untreated sample) X 100

Table 2

Table 3

 Example 11 Example 12 Example 13 The phosphoric acid phosphate of Example 1 70 70 70

 PBT 30 5

 PET 30 25

 Π B 1 100 100 100 pairs E— 1 part by weight 5 5

 E-2 5

 G20

 W 10

 T 10

 WAX 1 1

 Special bending elasticity rate MPa 5,230 3,360 3,220

 Chemical resistance% 91 84 85

 Notch impact value J / m 204 530 507

Claims

The scope of the claims 1. (A) The following equation (1)

Here, R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, and a 6 to 2 carbon atoms. An aryl group having 0, a cycloalkyloxy group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms,  X is a single bond, an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms. An alkylidene group, an arylene group having 6 to 20 carbon atoms or an alkylene-arylene-alkylene group having 6 to 20 carbon atoms, m and n are each independently an integer from 0 to 4, Consisting essentially of a repeating unit represented by  (B) the amount of extraction with 2-ethoxycetyl acetate is 2% by weight or less,  (C) the amount of extraction with acetone is 2% by weight or less, and  (D) an aromatic dihydroxy compound and Carbonic acid diesters are contained at a weight of 5 to 100 ppm and 10 to 200 ppm, respectively, for the polyponate; A polycarbonate characterized by the above. 2. (B) less than 1% by weight of 2-ethoxyethoxyl acetate, (C) less than 2% by weight of acetone, and (D) less extractables in acetone extract. The polycarbonate according to claim 1, wherein the aromatic dihydroxy compound and the carbonic acid diester are contained in the polycarbonate at 5 to 40 ppm and 50 to 200 ppm, respectively, by weight. 3. The polycarbonate according to claim 1, which is a product of a polycondensation reaction between an aromatic dihydroxy compound and a carbonic acid diester. 4. The polycarbonate according to claim 3, wherein the aromatic dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane and the carbonic acid diester is diphenylcapone. 5. A polycarbonate composition comprising 100 parts by weight of the polycarbonate according to claim 1 and 1 to 150 parts by weight of a solid filler. 6. A polyolefin composition comprising 100 parts by weight of the polycarbonate according to claim 1 and 10 to 150 parts by weight of a thermoplastic resin different from the polycarbonate. 7. An optical disc substrate comprising the polycarbonate according to any one of claims 1 to 4. 8. The optical disk substrate according to claim 7, wherein the thickness is 0.7 mm or less. 9. Use of the polycarbonate according to any one of claims 1 to 4 for producing an optical disc substrate.