WO2001090215A1 - Aromatic polycarbonate, composition comprising the same and moldings - Google Patents

Abstract

A polycarbonate, characterized in that a solution obtained by dissolving it in methylene chloride contains 50 pieces/kg-polymer or less of fine crystalline particles which are collected by a filter having a nominal pore diameter of 3 νm and have an X-ray refraction pattern; and a composition comprising the carbonate. The polycarbonate has high ductility, retains high transparency due to the decreased number of internal stressed points, and can be controlled to a minimum level with respect to the number of white points produced under a condition of a high temperature and a high humidity.

Description

 Aromatic polycarbonate, its composition and molded article

Technical field

 The present invention relates to aromatic polycarbonates, their compositions and molded articles. More specifically, the present invention relates to an aromatic polyether component suitable for molding a molded product having low molding distortion and excellent durability and stability, and a molded product having the above-mentioned features.

Description Conventional technology Field Moldability on recording media transparent substrates, transparent sheets, lenses, etc. that record and read or reproduce information using laser light such as audio discs, laser discs, optical disc memories, or magneto-optical discs. Polycarbonate resins, which are superior to other resins in terms of mechanical strength, transparency, etc., are used as materials. However, such excellent properties of polycarbonate resin are also based on the non-crystallinity of the polycarbonate, and when polycarbonate crystalline particles are mixed, the mechanical strength represented by the breaking strength and elongation of the molded product is high. Properties such as ductility, which is one of the characteristics of polycarbonate, are reduced, and impact strength is reduced.Internally, distortion occurs due to internal distortion and the external image is distorted. However, it has a disadvantage that it is susceptible to hydrolysis under high temperature and high humidity, and its molecular weight is reduced. Polypropylene resin is produced from an aromatic dihydroxy compound and a precursor capable of forming a polycarbonate bond. The production method is an interface in which phosgene is directly reacted as a precursor capable of forming a carbonate bond. A polycondensation method and a melt polycondensation method in which a transesterification reaction with a carbonic acid diester under heating and reduced pressure is known. Among them, the melt polycondensation method has an advantage that the polycarbonate resin can be produced at a lower cost than the interfacial polycondensation method. However, molded articles, sheets or optical disc substrates using polycarbonate produced by the melt polycondensation method contain crystal particles inside and have low mechanical properties such as elongation at break, which is a characteristic of polycarbonate resin. A certain high However, it tends to be difficult to achieve high ductility, resulting in reduced impact strength, reduced transparency, and reduced molecular weight due to hydrolysis at high temperature and high humidity at the crystal grain interface. Was. Furthermore, a molded article molded from a polycarbonate containing crystal grains, even though apparently not containing crystal grains, tended to have low mechanical properties.

 Foreign matter in polycarbonate is examined in Japanese Patent Application Laid-Open No. 2-135522. In this publication, the amount of a gelled product remaining on a filter when a methylene chloride solution of polycarbonate is filtered through a filter having a size of 21011 is specified. During the thermal decomposition during molding of the polycarbonate obtained by the interfacial polycondensation method, a gelled substance having a length of 1 cm was generated, and when the amount of the gelled substance was large, the polycapsules were formed into sheets. It is described that refraction anomalies at that time increase.

 Compared with the interfacial polycondensation method, it is considered that a large number of types of polycarbonate foreign matters are obtained by the melt polycondensation method, which is subjected to a higher temperature and a longer heat history. However, regarding these various foreign substances, no knowledge has been obtained on the effects of specific foreign substances and their contents on polymer quality.

Polycarbonate resin has an X-ray diffraction pattern, melting point of 310 or more, major axis of 50 m or less (Coarse particles exceeding 50 m are hardly contained, and it is problematic because it is removed with a normal filter. ) May be included. In the melt polycondensation of the transesterification method, the content of the fine crystalline particles is a specific viscosity average molecular weight at the time when the transesterification catalyst has an activity (hereinafter simply referred to as a molecular weight unless otherwise required). ) Tends to increase when the reactant having a temperature below a certain temperature defined by the molecular weight. However, there has been no known technique for reducing the fine crystalline particles to obtain a molded article having good mechanical properties, or for improving the long-term reliability of a transparent resin application, particularly, an optical disc substrate. Was. Disclosure of the invention The present invention has been made in view of the above-mentioned problems, and as a result of intensive studies on the problems, it has been found that a molded article is obtained from a poly-carbonate obtained by melt polycondensation in the presence of a transesterification catalyst. It has been found that the decrease in mechanical properties such as elongation at break is supplemented by a 3 m filter and is caused by a fine crystalline material having an X-ray diffraction pattern. Furthermore, it was clarified that among the fine crystalline particles, those which were insoluble in the methylene chloride solvent and had a melting point of 310 ° C or higher were particularly caused. In the following, the fine crystalline particles having the above X-ray diffraction pattern may be simply described as fine crystals or fine crystalline particles unless it is necessary to particularly explain.

 Since the microcrystalline particles are insoluble in methylene chloride and have a melting point of 310 ° C. or more, the conventional phosgene method which is easily soluble in methylene chloride and has a melting point of at most 240 ° C. It is different from crystalline powder obtained by solid-state polymerization, which has a melting point of at most 285 ° C.

 By setting the content of the fine crystalline particles in the polycarbonate resin to 50 particles / kg or less, the mechanical properties represented by the breaking strength and elongation of a molded article molded from the resin are reduced. The product is surely enhanced to show ductile fracture, and a molded product with high impact strength, which is one of the characteristics of polycarbonate, can be obtained. In addition, the number of strain points contained in substrates, sheets, lenses, etc., which are transparent molded articles, can be greatly reduced, and inferiority such as a decrease in molecular weight in a high-temperature, high-humidity atmosphere can also be controlled very effectively. As a result, it has been clarified that high reliability can be maintained for a long time in optical discs, for example, and that molded products having good transparency and transparency can be obtained in sheets and other optical components.

 Here, the content of fine crystalline particles having a nominal nominal diameter of 3 m and having an X-ray diffraction pattern is set to a class 100 or more in a clean room to eliminate disturbance. It was dissolved in methylene chloride, filtered under pressure through a 3 xm Millipore filter, and the number of fine crystalline particles on the filter was observed and measured with a polarizing microscope at 100 times magnification.

The present invention relates to mechanical properties typified by the elongation at break of a molded article formed from polycarbonate and to transparent sheets, lenses or optical disc substrates which are optical molded articles. Found that the number of internal strains that reduce the transparency and the number of white spots generated under high-temperature and high-humidity conditions are related to the content of fine crystalline particles having an X-ray diffraction pattern contained in the resin. It was achieved by having

 SUMMARY OF THE INVENTION It is an object of the present invention to provide an aromatic polysiloxane having a small content of fine crystalline particles having an X-ray diffraction pattern.

 Another object of the present invention is to increase the mechanical properties of the molded article in the ductile region, reduce the number of strain points on the sheet or the inner surface of the substrate, and prevent a decrease in transparency, and An object of the present invention is to provide an aromatic polycarbonate capable of controlling white spots generated under high temperature and high humidity conditions to a minimum.

 It is still another object of the present invention to provide an aromatic polysiloxane composition containing the aromatic polycarbonate of the present invention together with a solid filler. Still another object of the present invention is to provide a molded article, for example, a transparent sheet or an optical disc substrate, formed from the aromatic polystyrene component or the composition 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 main repeating unit is the following formula (1)

… (

(Wherein R ¹ and R ² are each independently a halogen atom, 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, Represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and m and n are each independently 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 carbon atom having 6 to 4 carbon atoms. A cycloalkylene group having 20 carbon atoms, a cycloalkylidene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylene arylenealkylene group having 6 to 20 carbon atoms. )

Represented by

 (b) produced by subjecting an aromatic dihydroxy compound and a carbonic acid diester to melt polycondensation in the presence of a transesterification catalyst,

 (c) the melt viscosity stability is 0.5% or less,

 (d) having a viscosity average molecular weight of 10,000 to 100,000,

 (e) The terminal group substantially consists of an aryloxy group (A) and a phenolic OH group (B), and the molar ratio (A) / (B) of both is 95/5 to 40Z60. , And

(f) The content of microcrystalline particles which are collected by a filter having a nominal pore size of 3 m when forming a methylene chloride solution and exhibit an X-ray diffraction pattern is 50 or less Zkg polymer,

This is achieved by an aromatic polystyrene resin.

 According to the present invention, the above objects and advantages of the present invention are:

100 to 100 parts by weight of the aromatic polycarbonate of the present invention and 1 to 150 parts by weight of the solid filler and / or 100 to 150 parts by weight of the thermoplastic resin different from the aromatic polyether component of the present invention. This is achieved by an aromatic polycarboxylate composition comprising

 Furthermore, according to the present invention, the above objects and advantages of the present invention are thirdly achieved by a molded article of the aromatic polycarbonate or the composition of the present invention. BRIEF DESCRIPTION OF THE FIGURES

 Figure 1 shows the X-ray diffraction pattern of the fine crystalline particles.

FIG. 2 is a graph showing the relationship between the viscosity average molecular weight Mn of the aromatic poly-carbonate and the minimum temperature (T c) at which fine crystalline particles are not generated. Preferred embodiments of the invention First, the characteristic property (f) of the aromatic polysiloxane of the present invention will be described.

 Polycarbonate resin shows an X-ray diffraction pattern and is trapped in a filter with a nominal pore size of 3 m (hereinafter may be 3 m or more in size) Fine crystalline particles content of 50 If it exceeds / kg, for example, when a molded article is molded from that point of view, the elongation at break of the molded article may be so low as to show brittle fracture, and when a disk substrate is molded, the substrate is used. In the information recording medium described above, the particles and the optical distortion induced by the particles surely cause an error, and reduce the reliability as an optical disk substrate. The fine crystalline particles have a diffraction angle of, for example, (20) 17.2 in the X-ray diffraction pattern. It can be identified as having a main peak at ± 0.3 °. .

 The content of the fine crystalline particles is preferably 50 particles / kg or less, more preferably 30 particles / kg or less, and still more preferably 10 Zkg or less. By reducing the content, the mechanical properties of the molded article can be improved, and the reliability of the optical medium substrate can be increased.

 Also, among these fine crystalline particles, the content of those which are insoluble in a methylene solvent, especially having a melting point of 310 or more, is preferably 40 particles / kg or less, more preferably 30 particles or less. By reducing the value to Zkg or less, particularly preferably to 10 kg or less, the mechanical properties of the molded article can be improved, and the reliability of the optical medium substrate can be raised to a high level.

 In the production of melt-polymerized polycarbonate, it is usually considered effective to remove the organic and inorganic foreign matter, including fine crystalline particles, by using a filter. Also, since the melt viscosity is high, it is necessary to increase the initial pressure during filtration, and it is necessary to gradually increase the filtration pressure as the filtration is continued. If the filtration pressure exceeds, for example, 200 atm, the filter needs to be replaced.

If the operation is interrupted industrially during the operation due to replacement of the filter, etc., there is a large problem such as a difference in the quality of polycarbonate before and after the operation. Also, such fine crystalline grains If a filter with high filtration efficiency is used to remove particles, the flow of the polymer in the filter case will be biased, causing variations in the time of the filter and causing side reactions such as color change and crosslinking.

 In producing a melt-polymerized polycarbonate, the molecular weight of the reaction mixture must be within the specified range during melt polymerization in order to reduce the content of fine crystalline particles having an X-ray diffraction pattern and a melting point of 310 ° C or higher. In the meantime, the temperature of the reaction mixture should not be lowered below the temperature specified by the average molecular weight, and the temperature of the lowest temperature part in the polymerization apparatus where the bulk polycarbonate is in direct contact is specified by the average molecular weight. It is one of the effective methods to keep the temperature below the specified temperature.

 Conventionally, various types of polymerization equipment have been proposed for melt-polymerizing high-melt-viscosity poly-one-ponate.Each of the polymerization equipments focuses on improving the stirring efficiency and increasing the polymerization rate. ing. However, such high-viscosity polymerization equipment often has a temperature difference inside, and it is not unusual that the temperature difference between the low-temperature part and the high-temperature part is 20 ° C to 50 ° C. '

 By maintaining the temperature of the low-temperature portion inside the polymerization apparatus at or above the minimum temperature defined by the average molecular weight of the reaction mixture, the number of fine crystalline particles having the above X-ray diffraction pattern and having a melting point of 310 or more can be reduced. It can be greatly reduced.

 When the viscosity average molecular weight of the reaction mixture is Mn and the minimum temperature is Tc, in the graph where Tc (in) is the ordinate and Mn is the abscissa, in the region where Mn is from 3,000 to 18,000, Point (Tc, Mn) = (220, 4,000), (234, 4, 810), (244, 6, 510), (245, 7, 400), (244, 9, 210), (236 , 12, 050) and (226, 17, 000) can be obtained as shown in the attached graph (Fig. 2).

 In order to reduce the content of fine crystalline particles, it is important that the temperature Tc of the low-temperature part in the reaction system during polymerization does not fall within the range enclosed by the above curve and the horizontal axis. However, it is preferable to keep the minimum temperature in the range of low to medium polymerization above the curve in this range.

As for the upper limit of the minimum temperature during polymerization, a normal polymerization temperature can be appropriately selected. If the polymerization degree is high, monomers and oligomers may volatilize in the low polymerization degree region and the molar balance may be disrupted, and if the polymerization degree is high, side reactions become noticeable. It is preferable that the temperature is 310 ° C for 6,000≤Mn≤10,000 and 330 ° C for Mn> 10,000.

 Once the fine crystalline particles are formed in the viscosity average molecular weight range of 3,000 to 18,000, the fine crystalline particles are heat-treated by the reaction temperature to rapidly raise the melting point. Raise its melting point so that it does not melt.

 The reaction mixture tends to crystallize as the viscosity average molecular weight is lower, but when the viscosity average molecular weight is less than 3,000, the reaction temperature of ordinary melt polymerization is sufficiently higher than the melting point of the fine crystalline particles. The generation of fine crystalline particles by crystallization of the mixture is not a problem.

If the viscosity average molecular weight exceeds 18,000, the polymerization reaction is carried out at 255 ° C or higher to secure the polymerization rate, and at the same time, the crystallization rate of the polycarbonate reaction mixture decreases. The problem of dripping or crystallization of the reaction mixture at low temperatures is reduced. However, fine crystalline particles may be generated even during normal molding. In this case, the generation of fine crystalline particles is promoted by the stagnation of the polymer flow in the processing equipment and the content of bisphenol A in the polycarbonate. In order to suppress the generation of fine crystalline particles during molding, it is effective to control the bisphenol A content to 10 to 50 ppm. The range is more preferably 10 to 40 ppm, particularly preferably 10 to 30 ppm. Even if the bisphenol A content is reduced to less than 10 ppm, the effect of suppressing the generation of fine crystalline particles is small. One of the effective means to achieve such bisphenol A content is to perform high vacuum treatment for a short time in the final stage of the polycondensation reaction, that is, after the melt viscosity stabilizer is added. It is. For example, it is preferable to go through a high vacuum of 13.3 Pa (0. ImmHg) or less for 30 minutes. More preferably, high vacuum treatment of 13.3 Pa to 6.7 Pa (0.1 to 0.05 mmHg) is applied for 1 to 20 minutes. Fine crystalline particles having an X-ray diffraction pattern and a melting point of 310 ° C or higher, produced when the viscosity average molecular weight of the reaction mixture is between 3,000 and 18,000. The particles can be apparently melted and removed by increasing the processing temperature of the polycarbonate to 327 ° C. or more, which is the equilibrium melting point, during molding after polymerization. However, in the case of a molded article obtained by molding the polycrystalline ponate containing fine crystalline particles by such a method, the elongation at break is lower than that of a molded article containing no fine crystalline particles. The problem remains.

 The aromatic polycarbonate of the present invention further comprises (g) a long diameter of 100 m, which is collected by a filter having a nominal diameter of 10 m when it is made into a methylene chloride solution and which emits light when irradiated with ultraviolet light having a wavelength of 380 nm. (It is preferable that the content of particles of 1 m or less is 100 kg or less of polymer.

 If the content of the particles emitting light as described above in the aromatic polycarbonate is less than the above-mentioned value, the mechanical properties such as impact strength and high elongation of the molded product are reduced, and the above-described case where the molded product is exposed to long-term temperature and humidity is obtained. Prevents deterioration of physical properties, abnormal flow orientation in substrates, transparent sheets, lenses, or optical disc substrates, and prevents the occurrence of refractive index differences, as well as hydrolysis generated under high temperature and high humidity conditions, or reduced molecular weight, impact strength Can be minimized.

 If the content of a substance with a major axis of 100 m or less that emits light by irradiation with ultraviolet light with a wavelength of 380 nm in aromatic polycarbonate exceeds 100 pcs / kg, for example, it is obtained from the resin. Mechanical properties such as impact strength and high elongation of molded products are low, and the mechanical properties after long-term exposure to high temperature and high humidity conditions are large, and transparent sheets, lenses or optical disc substrates Anomalies in the flow orientation and differences in the refractive indices will occur.

 The content of the particles is preferably 80 particles / kg or less, more preferably 50 g / kg or less. By reducing this content, the reliability of the optical medium substrate can be further increased.

In producing a melt-polymerized polycarbonate, for example, the following method can be used to reduce the amount of the luminescent particles as described above. i) While lowering the polymerization temperature, and reducing the temperature difference between the temperature of the parc polycarbonate component and the exothermic portion in the polymerization apparatus,

 i i) coating the surface of the poly-polypropylene polymerization device with an inert oxidant layer, as previously suggested by the present inventors,

 iii) One of the effective methods is to reduce the content of metal impurities in polycarbonate by using high-purity raw materials.

 Various types of polymerization apparatuses have been proposed for melt-polymerizing high melt viscosity polycarbonate. In all of the polymerization apparatuses, the main focus is on improving the stirring efficiency and increasing the polymerization rate. However, in such a high-viscosity polymerization apparatus, due to high-efficiency stirring, shear between the stirring blades or between the stirring blade and the polymerization apparatus main body becomes severe, causing shear heat. For this reason, the shear portion may be 100 or more higher than that of the polycarbonate pulp portion in some cases.

 In order to keep the temperature of the shearing part low, it is preferable to keep the pulp temperature of the polycarbonate as low as possible during polymerization. For example, the usual polymerization temperature of 250 to 350 ° C. is changed to 250 to 330 ° C., more preferably to 250 to 300 ° C., particularly preferably to 250 to 230 ° C. Lowering to 80 ° C. It is preferable to reduce the heat generation at the shearing portion after the polymerization temperature is lowered in this way. Reduction of heat generation in the cutting section can be preferably achieved by controlling the stirring speed. During the production of polycarbonate, after the viscosity average molecular weight has reached at least 8,000 and the melt viscosity of the resin has increased, the stirring speed can be controlled while detecting the temperature of the shearing section.

 It is preferred that the polycarbonate avoid contact with hot metal surfaces above 350 ° C. before the transesterification catalyst loses activity due to the melt viscosity stabilizer. More preferably, the temperature should not be raised to 330 ° C. or higher, particularly preferably to 320 ° C. or higher.

In addition, it is preferable to prevent the poly-component from coming into contact with such a high-temperature active metal surface. Metal surfaces are susceptible to decomposition and other side reactions of polycarbonate under high temperature conditions. In order to inactivate the metal active surface, for example, means such as forming an oxide film on the metal active surface is recommended.

 In such a shear heating region, it is assumed that most of the objects emitting light by the 38 O nm light irradiation are generated by the catalytic action of metal ions mixed in the metal surface or polycarbonate. In order to suppress the generation of a luminescent substance by such a reaction mechanism, it is effective to coat the surface of the polymerization apparatus with, for example, an inert oxide layer as described above, or to reduce the content of metal impurities in the polyponate. This is one of the methods. In the present invention, considering the effects on the durability, color tone and transparency of the produced poly-carbonate, Fe, Cr, Mn, Ni, Pb, Cu, P It is recommended that the transition metal element such as d, the metal such as Al and Ti, and the trace metal element content of the amphoteric element be 5 O ppb or less, more preferably 1 O ppb or less.

 In order to obtain more durable aromatic polycarbonates, it is necessary to use an alkaline metal element and / or alkaline earth metal element with a large transesterification capacity contained in aromatic dihydroxy compounds and carbonic acid diesters. The content is preferably from 0 to 60 ppb.

 In addition, in order to obtain an aromatic polycarbonate having better durability, the content of the alkali metal element and / or the alkaline earth metal element in the aromatic dihydroxy compound and the carbonic acid diester should be 80 ppb or less and the transition should be less than 80 ppb. Preferably, the metal element concentration is 10 ppb or less.

 Further, a method characterized in that the concentration of the metal and the amphoteric element contained in the carbonic acid diester and the aromatic dihydroxy compound is not more than 2 Opb is preferable.

 By using as a raw material an aromatic dihydroxy compound and a carbonic acid diester having a lower content of the transition metal element, the metal or the amphoteric element, which are preferably as low as possible, but less than the limit of the conventional technology of 10 ppb, It is possible to obtain aromatic poly-carbonate with excellent durability.

In the present invention, the fragrance having a reduced content of transition metal, metal and amphoteric element impurities is provided. Known purification methods, for example, various purification methods such as distillation, extraction, recrystallization, and sublimation can be used to obtain the aromatic dihydroxy compounds and the carbonic acid diester. Further, it is more preferable to combine the above-mentioned purification methods in various ways.

 Further, in order to obtain a polycarbonate having a small amount of metal impurities in the present invention, in the purification of such a raw material, it is preferable to use a high-purity solvent having an extremely small content of metal impurities, for example, a solvent for the electronics industry can be used. .

 The aromatic polysiloxane of the present invention mainly comprises a 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.

 Examples of the halogen atom include fluorine, chlorine, and bromine.

The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples thereof include methyl, ethyl, propyl, butyl, octyl, decyl and the like. The alkoxy group having 1 to 20 carbon atoms may be linear or branched, and examples thereof include methoxy, ethoxy, propoxy, butoxy, octyloxy, decyloxy and the like. Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl and cyclopentyl. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, 4-t-butylphenyl, and naphthyl. Carbon number? The § La alkyl group of 1-2 0, for example, cumyl _{(P h- C (CH 3)} 2 -) benzyl, may be mentioned Fuene chill like. Examples of the cycloalkoxy group having 6 to 20 carbon atoms include cyclohexyloxy and cyclopentyloxy. Examples of the aryloxy group having 6 to 20 carbon atoms include phenyloxy, triloxy, 41t-butylphenyloxy, naphthyloxy and the like. The definition of X is as described above.

 The alkylene group having 1 to 20 carbon atoms may be linear or branched. Examples thereof include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,10-decylene.

Examples of the alkylidene group having 2 to 20 carbon atoms include ethylidene and 2,2-pro Pyridene, 2,2-butylidene, 3,3-hesilidene and the like can be mentioned. Examples of the cycloalkylene group having 6 to 20 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 include cyclohexylidene and isopropylcyclohexylidene.

 Examples of the arylene group having 6 to 20 carbon atoms include 1,4-phenylene, 4,

4,1-biphenylene, 2-t-butyl-1,4-phenylene and the like can be mentioned.

 Examples of the alkylene-arylene-alkylene group having 6 to 20 carbon atoms include m-diisopropylphenylene group.

 M and n are each independently 0, 1, 2, 3 or 4.

 In the above formula (1), X is preferably an alkylidene group having 2 to 20 carbon atoms, and n and m are preferably both zero. In particular, X is preferably a cyclohexylidene group or a 2,2-propylidene group, and a 2,2-propylidene group is particularly preferred.

 The aromatic polycarbonate preferably occupies at least 85 mol% of the repeating unit represented by the above formula (1) based on the total repeating units.

 The aromatic polycarbonate of the present invention is produced by melt polycondensation of an aromatic dihydroxy compound and a diethyl carbonate in the presence of a transesterification catalyst. As the aromatic dihydroxy compound, the following formula (2)

…)

Where the definitions of R ¹ , R ² , X, n and m are the same as in equation (1),

Is used.

Representative examples of such aromatic dihydroxy compounds include 4, 4'-dihydro Xidiphenyl, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-1,3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis ( 4-Hydroxyphenyl) 1-1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy-13-methylphenyl) propane, 2,2 —Bis (4-hydroxy-1,3,5-dimethylphenyl) propane, 2,2-bis (3,5-dibromo-1-hydroxyphenyl) propane, 2,2-bis (3-isopropyl pill-4 —Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-13-phenylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) 1) -Methylbutane, 2,2-bis (4-hydroxyphenyl) 1,3-Dimethylbutane, 2,4-bis (4-hydroxyphenyl) 1,2-methylbutane, 2,2-bis (4 —Hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -1-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) Phenyl) —3,3,5-trimethylcyclohexane, 2,2,2 ', 2,1-tetrahydro-1,3,3,3', 3,1-tetramethyl-1,1,1-spibis [1H-indene ] —6,6, —diol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-13-methylphenyl) fluorene, hi, —bis (4-hydroxyphenyl) 10-diisopropylbenzene, CK, α'-bis (4-hydroxyphenyl) 1 m-diisopropylbenzene, hi, '-bis (4-hydroxyphenyl) 1 ρ-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) 1,5,7-dimethyladamantane 4,4,1-dihydroxydiphenylsulfone, 4,4, -dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylketone, 4,4'-dihydroxy Examples thereof include diphenyl ether, which can be used alone or in combination of two or more.

Bisphenol II, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bi 2- (4-hydroxyphenyl) -1,3-methylbutane, 2,2-bis (4-hydroxyphenyl) -1,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -1,4-methylpentane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2,2 ', 2, -tetrahydro-1,3,3', 3, -tetramethyl-1,1, Γ Spirobis [1 H-indene] —6,6, —diol and tri-bis (4-hydroxyphenyl) —m-diisopropylpropylbenzenes obtained from at least one bisphenol selected from the group consisting of A copolymer or a copolymer is preferred. Particularly, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) -1,3,3,5-trimethylcyclohexane and bisphenol A, 2,2— Scan {(4-hydroxy-3-methyl) Hue sulfonyl} propane or a, a - bis (4-hydroxyphenyl) - copolymers of m- Jiisopuropiru base benzene are preferably used.

 In the present invention, an aromatic dihydroxy compound other than the above formula (2), specifically, hydroquinone, resorcinol, catechol, or the like may be copolymerized.

 In producing polycarbonate by reacting by the melt polycondensation method, a terminal stopper, an anti-oxidation agent such as sterically hindered phenol, etc. may be used as necessary. Polycarbonate is a branched polycarbonate obtained by copolymerizing a polyfunctional aromatic compound having three or more functional groups, or a polyester carbonate obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid. The mixture may be a mixture of two or more of the obtained polycarbonate.

As the carbonic acid diester, for example, the following formula (3)

Here, A r ¹ and A r ² independently represent an aryl group, an aralkyl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, which may be substituted. Compounds can be mentioned. In formula (3), a carbonate diester in which Ar ¹ and Ar ² are the same group is preferable.

 Examples of the carbonic acid diester include diphenyl carbonyl, ditolyl carbonate, bis (chlorophenyl) carbonyl, m-cresyl carbonate, bis (diphenyl) carbonate, getyl carbonyl, dibutyl carbonate, and the like. Is mentioned. Of these, diphenyl porponate is preferred.

 As the transesterification catalyst, preferably, a) a nitrogen-containing basic compound and / or a phosphorus-containing basic compound (hereinafter abbreviated as NCBA) and a) an alkali metal compound (hereinafter abbreviated as AMC) are used. .

Examples of the nitrogen-containing basic compound include alkyl, aryl, and alkyl such as tetramethylammonium hydroxide (Me ₄ NOH) and benzyltrimethylammonium hydroxide (φ—CH ₂ (Me) ₃ N〇H). Ammonium hydroxides having aryl groups; tetramethylammonium acetate, tetraethylammonium phenoxide, tetrabutylammonium carbonate, benzyltrimethylammonium benzoate, etc. alkyl, Ariru, basic Anmoniumu salts having such Arukirua aryl group; Toryechiruamin tertiary Amin as dimethyl pen Jiruamin or tetramethylammonium Niu beam Polo Hyde chloride, (Me ₄ NBH _4), tetra-Petit Ruan monitor © beam Polo hydride (Bu ₄ NBH _4), tetramethylammonium Niu Mute Rafue two Ruporeto (Me ₄ NBPh ₄₎ may be mentioned basic salts such as.

Examples of the phosphorus-containing basic compound include, for example, alkyl, aryl, and the like such as tetrabutylphosphonium hydroxide (Bu ₄ POH) and benzyltrimethylphosphonium hydroxide (Φ—CH ₂ (Me) ₃ P〇H). phosphonyl © beam hydroxides having an alkyl § aryl group, or tetramethyl phosphonyl © beam Polo Ha Idoraido (Me ₄ PBH _4), tetrabutyl phosphonyl © beam Polo hydride (B u ₄ PBH _4), tetramethyl phosphonyl © beam Basic salts such as tetraphenylporate and (Me ₄ PB P ₄ ) can be mentioned.

The NCBA a basic nitrogen atom or basic phosphorus atom relative to 1 mol of the aromatic dihydroxy shea compounds, used in a proportion to be ^{1 X 10- 5 ~ 1 X 10-} 3 chemical equivalent Is preferred. A more preferred ratio is 2 × 10 ¹⁵ to 5 × 10 ⁴ chemical equivalents based on the same standard. A particularly desirable ratio is in the ratio of the 5 X 10 one ⁵ ~ 5X 10 one ⁴ chemical equivalents based on the same standard.

In particular, at this time, in order to improve the hue of the obtained polycarbonate, the amount of the NCB A compound used should be calculated based on the total amount of iron contained in the starting diester carbonate and the aromatic dihydroxy compound; Fe * (expressed in wt ppb). On the other hand, it has been found that it is effective to use {20X (F e *) +200} × 10 to not exceed ¹⁶ chemical equivalents. Particularly preferably not exceeding {20 X (Fe *) +150 } X 10 _ 6 chemical equivalents.

Further, in the present invention, AMC is used in combination with NCBA as described above in order to realize the effect of reducing impurities in the raw material in the color tone and stability of the polymer. The AMC compound, aromatic dihydroxy compound per mol, and is preferably used in the range of 1 X 10 one ⁸ ~ 5 X 10- ⁶ chemical equivalent to the alkali metal element. By using a catalyst having such a ratio, a branching reaction, a main chain cleavage reaction, and a main chain cleavage reaction that are likely to be generated during the polycondensation reaction without impairing the terminal blocking reaction and the polycondensation reaction rate, and in a device during molding processing. This is preferable because undesirable phenomena such as generation of foreign matter and burning can be effectively suppressed.

 If the ratio is outside the above range, various properties of the obtained polycarbonate are adversely affected, and the transesterification reaction does not sufficiently proceed, and a high-molecular-weight polycarbonate cannot be obtained.

 AMC includes, for example, alkali metal hydroxides, hydrocarbon compounds, carbonates, acetates, carboxylates such as stearates, benzoates, nitrates, nitrites, sulfites, cyanates, thiocyanates Acid salts, borohydride salts, hydrogen phosphates, bisphenols, phenol salts and the like.

Specific examples include sodium hydroxide, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium acetate, rubidium nitrate, lithium nitrate, sodium nitrite, sodium sulfite, sodium cyanate, potassium cyanate, and sodium thiocyanate. , Potassium thiocyanate, cesium thiocyanate, steer Sodium phosphate, sodium borohydride, potassium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, dinadium hydrogen phosphate, dipotassium hydrogen phosphate, disodium salt of bisphenol A, mono Examples include potassium salt, sodium potassium salt, and potassium salt of phenol.

 In addition, if desired, an alkali metal compound may be selected from the group consisting of (a) an alkali metal salt of an art complex of an element belonging to Group 14 of the periodic table described in JP-A-7-26891, and Alkali metal salts of the oxo acids of Table 1 group 4 elements can be used. Here, the elements of the 14th group of the periodic table refer to gay, germanium, and tin. Use of such an alkali metal compound as a catalyst for the polycondensation reaction has an advantage that the polycondensation reaction can be promptly and sufficiently advanced. Further, undesirable side reactions such as a branching reaction that proceeds during the polycondensation reaction can be suppressed to a low level.

 In the polycondensation reaction of the present invention, at least one member selected from the group consisting of oxo acids, oxides and alkoxides of the same element as element 14 of the periodic table, and phenoxide, together with the above catalyst, if necessary Can coexist as a co-catalyst. By using these cocatalysts in a specific ratio, terminal blocking reaction, branching reaction that is easily generated during the polycondensation reaction without impairing the polycondensation reaction rate, main chain cleavage reaction, and the inside of the equipment during molding processing Undesirable phenomena such as generation of foreign matter and burning can be effectively suppressed, which is preferable for the purpose of the present invention. ,

 Examples of the oxo acids of the 14th group of the periodic table include keiic acid, soot, and germanic acid.

 Examples of oxides of Group 14 of the periodic table include silicon dioxide, tin dioxide, germanium dioxide, silicon tetramethoxide, silicon tetraphenoxide, tetraethoxy tin, tetranonyloxy tin, tetraphenoxy tin, and tetrabutoxide. Xigermanium, tetraphenoxygermanium, and condensates thereof can be mentioned.

The co-catalyst is preferably present in a proportion such that the element of Group 14 of the periodic table is 50 mol atoms or less per 1 mol atom of the metal element in the polycondensation reaction catalyst. Same money If the cocatalyst is used in a proportion of more than 50 mole atoms of the group element, the polycondensation reaction rate is undesirably reduced.

 More preferably, the co-catalyst is present in an amount of 0.1 to 30 mol atoms of the group 14 element of the periodic table as a co-catalyst per 1 mol atom of the metal element of the polycondensation reaction catalyst.

The amount of the polymerization catalyst in the present invention, when using the Al force Li metal compounds, 1 X 10- ⁸ ~5X 10 one ^{of six} chemical equivalents to 1 mole of the aromatic dihydroxy compound, preferably 5 X 10 one ⁸ ~ 3X 10- ⁶ chemical equivalents, is particularly preferably selected in the range of ^{7 X 10 "8 ~ 2 X} 10- 6 chemical equivalent.

 In the melt polymerization method, the aromatic dihydroxy compound and the carbonic acid diester are stirred while heating under normal pressure and Z or reduced pressure nitrogen atmosphere in the presence of the transesterification catalyst as described above to form the alcohol or This is carried out by distilling the aromatic monohydroxy compound. The reaction temperature varies depending on the boiling point of the product, etc., but is usually in the range of 120 to 350 ° C in order to remove alcohol or aromatic monohydroxy compounds generated by the reaction.However, the content of fine crystalline particles in polycarbonate It is important that the temperature of the reaction mixture does not fall below Tc from the point when the molecular weight of the reaction mixture exceeds 7,000, and that the reaction mixture does not come into direct contact with the reactor part below Tc in order to reduce the reaction temperature. is there. In addition, it is effective to reduce the content of bisphenol A, which promotes the generation of fine crystalline particles, to 10 to 40 ppm in order to reduce the generation of fine crystalline particles during molding. In the latter stage of the reaction, the pressure of the system is reduced to facilitate the distillation of the alcohol or aromatic monohydroxy compound produced. The internal pressure of the system at the latter stage of the reaction is preferably 133.3 Pa (ImmHg) or less, more preferably 66.7 Pa (0.5 mmHg) or less.

 The aromatic polycarbonate of the present invention has a melt viscosity stability of 0.5% or less.

The melt viscosity stability is evaluated by the absolute value of the change in melt viscosity measured at 300 ° C. for 30 minutes at a shear rate of 1 radZs ec under a nitrogen stream, and is expressed as a rate of change per minute. It is essential that this value be 0.5% or less, and if this value is large, the hydrolysis of the polycarbonate may be degraded, the molecular weight may be reduced, or coloring may be promoted. In fact '' It is sufficient to set this value to 0.5% in order to ensure stable hydrolysis resistance. For this purpose, it is particularly preferable to stabilize the melt viscosity using a melt viscosity stabilizer after the polymerization.

 The melt viscosity stabilizer in the present invention also has a function of deactivating part or all of the activity of the polymerization catalyst used in the production of the polycarbonate.

 As a method of adding the melt viscosity stabilizer, for example, it may be added while the polymer is in a molten state after polymerization, or may be added after re-dissolving after pelletizing polycarbonate once. In the former, the melt viscosity stabilizer may be added while the polycarbonate as a reaction product in the reaction tank or the extruder is in a molten state, or the polycarbonate obtained after polymerization is extruded from the reaction tank. While being pelletized through the machine, a melt viscosity stabilizer can be added and kneaded. Known agents can be used as the melt viscosity stabilizer. Sulfones such as organic sulfonic acid salts, organic sulfonic acid esters, organic sulfonic acid anhydrides, and organic sulfonic acid resins are highly effective in improving the physical properties such as the hue, heat resistance, and boiling water resistance of the resulting polymer. It is preferable to use an acid compound, in particular, a phosphonium salt of sulfonic acid and / or an ammonium salt of sulfonic acid. Among them, particularly preferred are tetrabutylphosphonium dodecylbenzenesulfonate and tetrabutylammonium p-toluenesulfonate.

 The aromatic polystyrene component of the present invention has a viscosity average molecular weight in the range of 100,000 to 100,000. As an injection molded product, for example, as a disk substrate material, the viscosity average molecular weight (Mn) is preferably 100,000 to 22,200, more preferably 12,000 to 200,000. , 13, 00 00 to 18, 00 0 are particularly preferred. Polycarbonate having such a viscosity average molecular weight is preferable because sufficient strength can be obtained as an optical material, and the melt fluidity during molding is good and molding distortion is not generated. In applications such as extruded articles, for example, sheets, the viscosity average molecular weight is preferably 17, 000 to 100, 000, more preferably 20, 000 to 80, 80. 0 is 0.

The aromatic polycarbonate of the present invention further has a terminal group substantially free of aryloxy. It comprises a group (A) and a phenolic hydroxyl group (B), and the molar ratio (A) / (B) of both is 95 Z5 to 40760. Preferably, the phenolic terminal group concentration is at most 40 mol%, more preferably at most 30 mol%. By containing a phenolic terminal group in such a ratio, the object of the present invention can be achieved more suitably, and the moldability of the composition (made of mold soil, mold release; Is also improved.

 On the other hand, even if the phenolic terminal group concentration is reduced to less than 5 mol%, further improvement in the composition of the composition is small, and when the phenolic terminal group concentration is introduced to 60% or more, the object of the present invention is It is obvious from the above discussion that this is not desirable.

 As the aryloxy group, for example, a hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted phenyloxy group is preferably selected. As the substituent, a phenyloxy group having a tertiary alkyl group, a tertiary aralkyl group or an aryl group, or an unsubstituted phenyloxy group is preferable as the substituent from the viewpoint of resin thermal stability. Those having a benzyl-type hydrogen atom can be used if they have a desired purpose such as improvement of actinic radiation, but should be avoided from the viewpoint of stability against heat, heat aging, thermal decomposition, etc. .

 Specific examples of preferred aryloxy groups include phenoxy, 4-t-butylphenyloxy, 4-t-amylphenyloxy, 4-phenylphenyloxy, 4-cumylphenyloxy, and the like. And more preferably a phenoxy group.

 In the interfacial polymerization method, the terminal phenolic terminal group can be suppressed to a low concentration by a molecular weight regulator, but in the melt polymerization method, the phenolic terminal group concentration is 60 mol% or more due to chemical reaction theory. Therefore, it is necessary to actively reduce phenolic end groups.

 That is, the phenolic terminal group concentration within the above range can be advantageously achieved by the method 1) or 2) described below.

1) Controlling the molar ratio of the raw materials for polymerization; increasing the molar ratio of diester carbonate / aromatic dihydroxy compound at the time of charging the polymerization reaction. For example, consider the characteristics of the polymerization reactor Set between 1.03 and 1.10.

 2) Terminal capping method: At the end of the polymerization reaction, for example, according to the method described in US Pat. No. 5,696,222, a terminal hydroxyl group is added by adding a salicylate-based compound described in the above literature. Stop.

 When the terminal hydroxyl group is blocked with a salicylate-based compound, the amount of the salicylate-based compound to be used is 0.8 to 10 mol, more preferably 0.1 to 10 moles per chemical equivalent of the terminal hydroxyl group before the capping reaction. The range is from 8 to 5 mol, particularly preferably from 0.9 to 2 mol. By adding in such an amount ratio, 80% or more of the phenolic terminal groups can be suitably sealed. When the present sealing reaction is performed, it is preferable to use the catalyst described in the above-mentioned U.S. Patent.

 The reduction of the phenolic end group concentration is preferably performed at a stage before deactivating the polymerization catalyst.

 As the salicylic acid ester compound, a salicylic acid ester compound described in US Pat. No. 5,696,222 can be preferably used, and specifically, such as 2-methoxycarbophenyl-phenylcarbonate. 2-methoxycarbonylphenylalkanolate; 2-methoxycarbonylphenyl-lauryl-force-ponate; 2-methoxycarbonylphenylalkylcarbonate; such as 2-ethoxycarbonyl-phenylroofenylcarbonate; 2-ethoxycarbonylphenylalkylcarbonate, such as 2-ethoxycarbonylphenylalkenylcarbonate; aromatic carboxylic acid, such as (2-methoxycarbonylphenyl) benzoate (2, -methoxyca Boerufeniru) ester; and (2 Metokishika Ruponirufue sulfonyl) Suteare Bok, bis (2-methoxycarbonylphenyl) such aliphatic force Rupon esters of § di Bae Ichito the like.

 When the aromatic polycarbonate of the present invention is used to mold various molded articles, conventionally known processing stabilizers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, Flame retardants, release agents, etc. can be added.

For example, the aromatic polycarboxylic acid of the present invention has a reduced molecular weight and deteriorated hue. Heat stabilizers can be included to prevent this. Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and trisnonylphenyl phosphite, tris (2,4-di-tert-butyl phenyl) Le) phosphite, 4,4'-tetrakis (2-, 4-di-tert-butylphenyl) biphenylenediphosphophosphinate, bis (2,4-di-tert-butylphenyl) Phyte, trimethyl phosphate and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more. The amount of the 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 of the present invention. Preferably, the amount is from 0.001 to 0.1 part by weight.

 Further, in order to further improve the releasability from the mold at the time of melt molding, a releasing agent can be added to the aromatic polycarbonate of the present invention as long as the object of the present invention is not impaired. Examples of the release agent include an olefin wax, an olefin wax containing a carboxyl group and Z or a carboxylic anhydride group, silicone oil, an organopolysiloxane, a higher fatty acid ester of a monohydric or polyhydric alcohol. , Paraffin wax, honey 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.

 As the higher fatty acid ester, for example, a partial ester or a whole ester of a monovalent or polyvalent alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. As such a partial ester or a whole ester of a monohydric or polyhydric alcohol and a saturated fatty acid, for example, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used. 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.

Further, the aromatic polycarbonate of the present invention contains a solid filler and Z or the aromatic polycarbonate of the present invention in order to improve the rigidity and the like, as long as the object of the present invention is not impaired. It is possible to blend a thermoplastic resin other than a resin component, thereby providing the aromatic poly component composition of the present invention.

 Such solid 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 fibers, Fibrous fillers such as aramide fibers and metal-based conductive fibers; and organic particles such as crosslinked acrylic particles and crosslinked silicone particles. The compounding amount of these solid fillers is preferably 1 to 150 parts by weight, more preferably 3 to 100 parts by weight, based on 100 parts by weight of the aromatic polysiloxane of the present invention.

 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 the decomposition of the aromatic polyphenol.

 Examples of the thermoplastic resin include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene resins, polyolefin resins such as polypropylene, and polyethylene. Polyester resin such as terephthalate and polybutylene terephthalate, polycarbonate resin, amorphous polyarylate, polystyrene resin, acrylonitrile styrene copolymer (AS tree J3), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethac Examples include shelf resins, phenolic resins, epoxy resins, and the like.

 These thermoplastic resins can be used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the aromatic polycarbonate of the present invention.

The aromatic polycarbonate and the aromatic polycarbonate composition of the present invention are suitably used as a material for a substrate of an optical information recording medium. An optical information recording medium comprising a substrate made of the aromatic polycarbonate and the aromatic polycarbonate composition of the present invention, such as a compact disk (CD), a CD-ROM, a CD-R, a CD-RW, and a magnet. Digital versatile discs (DVD-R （M, DVD-Video, DVD-Audio, DVD- R, D VD—RAM, etc.) have high reliability over a long period of time. It is particularly useful for high-density optical discs such as digital versatile discs.

 Further, the sheet made of the aromatic polycarbonate and the aromatic polycarbonate composition of the present invention is a sheet excellent in adhesiveness and printability, and by taking advantage of its characteristics, is widely used in electric parts, building material parts, automobile parts, and the like. Used. Specifically, glazing products for window materials, such as general houses, gymnasiums, baseball domes, and vehicles (construction machinery, automobiles, buses, Shinkansen, electric vehicles, etc.), and various side walls (Sky Dome, Totobright, arcade, condominium lumbar, road side wall), window materials for vehicles, etc. (4) It is useful for optical applications such as liquid crystal cells and phase difference correction plates in combination with Fresnel lenses, optical power supplies, optical disks and polarizing plates. The thickness of such a sheet is not particularly limited, but is usually 0.1 to: L Omm, preferably 0.2 to 8 mm, and particularly preferably 0.2 to 3 mm. In addition, various processings that add new functions to such sheets (various laminations to improve weather resistance, abrasion resistance improvement to improve surface hardness, surface graining, semi-transparent Process).

 In order to mix the above-mentioned components with the aromatic polycarbonate of the present invention, an arbitrary method is adopted. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a NOWA mixer, a Banbury mixer, a kneading roll, an extruder, or the like is appropriately used. The aromatic polycarbonate resin composition thus obtained can be formed into a sheet by a melt extrusion method as it is or after being once formed into a pellet by a melt extruder.

After the polycarbonate of the present invention is produced by a melt polymerization method, in an extrusion step (pelletizing step) for obtaining pellets for injection molding (a pelletizing step), when it is in a molten state, it is passed through a sintered metal filter having a filtration accuracy of 10 m. It is preferable to remove the foreign matter. If necessary, it is also preferable to add an additive such as a phosphorus-based antioxidant. In any case, it is necessary for the raw material resin before injection molding to keep the content of foreign matter, impurities, solvents and the like as low as possible.

 When an optical disc substrate is produced from the aromatic polycarbonate and aromatic polycarbonate composition of the present invention, an injection molding machine (including an injection compression molding machine) is used. This injection molding machine may be a commonly used one, but from the viewpoint of suppressing the generation of carbides and increasing the reliability of the disc substrate, the cylinder has a low adhesion to resin as a screw and has low corrosion resistance. However, it is preferable to use a material made of a material exhibiting wear resistance. Injection molding conditions are preferably a cylinder temperature of 300 to 400 ° C. and a mold temperature of 50 to 140, whereby an optically excellent optical disc substrate can be obtained. The environment in the molding process is preferably as clean as possible from the viewpoint of the present invention. It is also important to sufficiently dry the material to be molded to remove moisture and to prevent stagnation that may cause decomposition of the molten resin.

 The aromatic polycarbonate and the aromatic polyponate of the present invention may be used for any purpose, and various molded articles such as electronic and communication equipment, OA equipment, lenses, prisms, optical disk substrates, optical fibers, and the like. Parts; Electronics such as home appliances, lighting components, heavy electrical components, etc.Electrical components; Vehicle interior / exterior, precision machinery, mechanical components such as insulating materials; medical materials, security and protection materials, sports and leisure goods, household goods, and other miscellaneous goods Components: Can be used for containers 'packaging materials, display' decoration materials, etc. Further, it can be suitably used as a composite material with another resin or an organic / inorganic material. Example

 Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.

 Analytical method

 The test method of the aromatic polysiloxane produced in the examples and comparative examples was as follows.

1) Viscosity average molecular weight (Mn): Ubbelohde at 20 ° C as methylene chloride solution From the intrinsic viscosity ([77]) measured with a viscometer, it was determined by the following equation.

[??] = 1. 23X 10 one ^{4 ΧΜη 0} · ⁸³

 2) Determination of metal impurity content

Equipment: Seiko Electronics Co., Ltd. ICP-MS, SPQ9000

Sample concentration: Sample (0.5 g) was used for isopropyl alcohol for electronics industry (polymerization material: used for quantification of bisphenol A and diphenyl carbonyl) or N-methylpyrrolidone (NMP) (used for quantification of polyphenol) It was dissolved in 25 g and quantified by the standard sample calibration curve.

 3) measurement of the number of microcrystalline particles;

 Dissolve 1 kg of polycarbonate resin in 20 L of methylene chloride in a clean room of class 1000 or more, filter under pressure through a 3 m millipore filter, and reduce the number of crystalline fine particles on the filter to 100 times magnification with a polarizing microscope. Observed and measured.

 4) Measurement of X-ray diffraction pattern; Equipment; Rigaku Corporation RAD-rB

Measurement conditions: Cu K ALPHA1 / 50 kV / 20 OmA

Counter; Yuichi Scintillation Counsel

Divergent slit; 0.5 °

Scattering slit; 0.5 °

Receiving slit: 0.6 mm

Scan mode; continuous

Scan speed; 4 ° / min

Scan step; 0.02 °

Scanning range; 5-50 °

 5) Melt viscosity stability

The melt viscosity was measured at 300 ° C for 30 minutes at a shear rate of 1 radZs ec at 300 ° C using a rheometrics RAA type flow analyzer, and the absolute value of the change in viscosity was divided by the melt viscosity. The rate of change was determined, and this value was taken as the melt viscosity stability. In order for the long-term stability of aromatic polycarbonate to be good, this value should be 0.5%. Do not exceed it.

 6) Hue measurement;

The hue (color L, a, b) of the swatches obtained by molding with an injection molding machine at a cylinder temperature of 300 ° C and a mold temperature of 80 ° C was measured with a color difference meter and evaluated. The instrument used was a Z-1001DP color difference meter manufactured by Nihon Denshoku Co., Ltd.

 7) Determination of phenolic terminal group concentration and aryloxy terminal number

A polymer sample 0.028 was dissolved in 0.4 ml of deuterated chloroform, and the phenolic terminal group concentration was measured at 20 ° C. using ¹ H-NMR (EX-270 manufactured by JEOL Ltd.).

 The number of aryloxy end groups was calculated as the difference between the total number of end groups and the number of phenolic end groups determined by the following equation from the intrinsic viscosity [77].

Total number of terminal groups = 56. 54 / [7?] ⁴³³⁸

 8) Measurement of the number of white spots after high temperature and high humidity treatment;

 In order to reproduce the increase in white spots when left in a harsh atmosphere for a long time, the disc was kept in a thermo-hygrostat controlled at a temperature of 80 ° C and a relative humidity of 85% for 1,000 hours. The number of white spots greater than 20 tm was counted using a polarizing microscope. This was performed on 25 optical disc substrates (120 mm in diameter), and the average value was obtained, which was used as the number of white spots. If this was 1 or less Z sheets, it was judged as passing.

 9) Strain point detection

Strain point-1: 25 disk substrates were observed with a polarizing microscope, the number of refractive index abnormal points was counted, and this was set as the strain point-1, and the average value per sheet was determined. If this is one or less, it was judged as a pass.

Strain point-2; Extruded sheet with thickness of 2mm, 50cm x 50cm, 10 sheets are observed with a polarizing microscope, the number of refractive index abnormal points is counted, and this is set as the strain point, and the average value per sheet is calculated. Was. If the number was 3 or less, it was determined to be acceptable.

 10) Impact resistance

The Izod impact strength was evaluated according to ASTM D-256 (notched). After drying the polymer under high vacuum at 120 ° C for 12 hours, it An extruded test piece was prepared and the Izod impact strength was measured.

 11) measurement of the number of luminescent substances;

 Dissolve 1 kg of polycarbonate resin in a clean room of class 1000 or more in 20 L of methylene chloride, filter through a 1 Om filter at normal temperature and normal pressure, dry the residue on the filter, and wavelength 380 nm The number of substances that emit light by the irradiation of light was observed and measured with an optical microscope.

 Raw material purification example

 1) Bisphenol A:

 Commercially available bisphenol A (hereinafter abbreviated as BP A) is dissolved in 5 times the amount of phenol, and adduct crystals of BP A and phenol are prepared with 4 O. The resulting adduct crystals are obtained at 5.33 kPa (40 Torr). The phenol was removed at 180 ° C until the phenol concentration in the BPA became 3%, and then the phenol was removed by steam stripping. Then, the above-mentioned BP A was charged into a vessel equipped with a decompression device and a cooling device, and purified by sublimation under a nitrogen atmosphere at a pressure of 13.3 Pa (0.3 rr) at a temperature of 139. Sublimation purification was repeated twice to obtain purified BPA.

 2) Diphenyl carbonate

 The raw material diphenyl alcohol (hereinafter abbreviated as DPC) is referred to as “Plastic Materials Course 17 Poly-Poly-Ionate” Author Toshihisa Tachikawa et al. (Nikkan Kogyo Shimbun) According to the method described on page 45, washing with hot water (50 ° C) Repeated three times, dried, vacuum distilled, and a fraction of /2.000 kPa (15 mmHg) was collected at 167 to 168, and further subjected to the same sublimation purification as above to obtain a purified DPC. .

Table 1 below shows the metal contents in the BPA and DPC prepared as described above. BPA / DPC metal impurity amount; ppb

 Na Fe Cr Mn Ni Pb Cu Zn Pd In Si Al Ti Commercial BPA 86 60 5 4 8 5 1 * 11 1 * 7 25 22 1 * Purified BPA 6 8 1 * 1 * 1 * 1 * 1 * 1 * 1 * 1 * 1 1 1 * Raw material DPC 96 40 15 5 5 1 1 * 11 1 * 15 15 42 3 Purified DPC 10 9 1 * .1 * 1 * 1 * 1 * 1 * 1 * 1 * 2 1 1 * l *: Represents lppb or less.

Example 1 (manufacture of PC-1)

The production of the polycarbonate according to the fine crystalline particles was performed as follows. In a reaction vessel equipped with a stirrer, rectification column and decompression device, 137 parts by weight of the purified BPA and 135 parts by weight of the purified DPC as raw materials, and disodium salt of bisphenol A as a polymerization catalyst 4.1 X 10_ ⁵ parts by weight and 5.5 × 10 ³ parts by weight of tetramethylammonium hydroxide were charged and melted at 180 ° C. under a nitrogen atmosphere.

 The pressure inside the reaction vessel was reduced to 13.3 kPa (l O OmmHg) while stirring at a rotation speed of 40 rpm, and the reaction was carried out for 20 minutes while distilling off the phenol produced.

 Next, the temperature was raised to 200, and the pressure was gradually reduced. The reaction was carried out at 4.0 kPa (3 OmmHg) for 20 minutes while distilling off phenol.

Further, the temperature was gradually raised, and the reaction was performed at 220 for 20 minutes. At this point, the viscosity average molecular weight was 3,200 and Tc was 180 ° C. Next, the reaction mixture was sent to a second polymerization tank heated to 240 by a polymerization tank heating jacket so that the temperature of the reaction mixture did not become Tc or lower, and 4. The reaction was carried out at OkPa (30 mmHg) for 20 minutes. At this time, the viscosity average molecular weight was 4,800 and Tc was 233 ° C. Next, the temperature of the reaction mixture was rapidly raised to 250 ° C. and reacted for 20 minutes. At this point, the reaction mixture had a viscosity average molecular weight of 7,000 and a Tc of 245 ° C. Then, at 250 ° C, change the stirring speed to 30 rpm and gradually increase the degree of decompression.

0 ° C, degree of vacuum, 2.67 kPa (2 OmmHg) for 10 minutes, 1.33 kPa

(1 OmmHg) for 5 minutes to maintain the temperature of the shear zone between the agitating blade and the reactor where the temperature rises most in the polymerization reactor at 320 ° C or less. When the viscosity average molecular weight became 8,000, the rotation speed was reduced to 20 rpm.

 Thereafter, the reaction temperature was further increased and the reaction was carried out at 260 ° C for 20 minutes.The temperature was raised to 270 ° C, the degree of vacuum was gradually increased, and finally the viscosity average molecular weight was 15 ° C at 270 ° C and 66.7 Pa (0.5 mmHg). , Until 300.

Thereafter, dodecylbenzenesulfonic acid tetrabutylphosphonium phosphonyl © unsalted 3. 6X 10- ⁴ parts by weight was added to each and stirred 27 O / 66. In 7 P a (0. 5mmHg) 10 min. Finally, the obtained poly-polyponate has a viscosity average molecular weight of 15,300, a phenolic end group concentration of 85 (eq / t on-PC), a phenoxy end group concentration of 154 (eq / t on-PC), The melt viscosity stability was 0%. The content of fine crystalline particles was 0 particles / kg-PC.

Comparative Example 1 (manufacture of PC-2)

Stirrer, the reaction vessel equipped with a rectifying column and decompressor, 135 parts by weight of 137 parts by weight of purified DP C Purified BP A as a raw material, disodium salt of bisphenol A as polymerization catalyst 4. 1X 10- ⁵ parts, was melted in a nitrogen atmosphere at 18 Ot charged with tetramethylammonium Niu arm hydro Kishido 5. 5X 10 one ³ parts by weight.

 The pressure in the reactor was reduced to 13.33 kPa '(10 OmmHg) while stirring at a rotation speed of 40 rpm, and the reaction was carried out for 20 minutes while distilling off the phenol produced. Next, after the temperature was raised to 200 ° C., the pressure was gradually reduced, and the reaction was carried out for 20 minutes at 4. OkPa (3 OmmHg) while distilling off phenol.

Further, the temperature was gradually raised and the reaction was carried out at 220 ° C for 20 minutes. At this time, the viscosity average molecular weight was 3,200 and Tc was 180 ° C. Next, the reaction mixture was fed to a second polymerization tank heated to 230 ° C. by a polymerization tank heating jacket, and reacted for 30 minutes. At this point, the viscosity average molecular weight was 4,800, and Tc was 233 ° C. During this time, polymerization tank disruption It is estimated that a part of the stirring shaft became Tc or less. Then, the temperature of the reaction mixture was gradually raised to 250 ° C. over 20 minutes, and the reaction was further performed at the same temperature and reduced pressure for 20 minutes. At this time, the viscosity average molecular weight is 7,000 and Tc is 245. C. Then, change the rotation speed to 30 rpm at 250 ° C, gradually increase the degree of vacuum, continue the reaction at 2.67 kPa (2 OmmHg) for 10 minutes, and 1.3 kPa (1 OmmHg) for 5 minutes. When the viscosity average molecular weight reached 8,000, the rotation speed was reduced to 20 rpm.

 Thereafter, the reaction temperature was further increased, the reaction was carried out at 260 ° C for 20 minutes, the temperature was increased to 270, the degree of decompression was gradually increased, and finally the viscosity-average molecular weight was increased at 270 at /66.7 Pa (0.5 mmHg). It was reacted until it reached 15,300.

Thereafter, dodecylbenzenesulfonic acid tetrabutylphosphonium phosphonyl © unsalted 3. 6X 10- ⁴ parts by weight was added to each, and stirred 270 ° C / 66. 10 min 7Pa (0. 5mmHg). Finally, the viscosity average molecular weight was 15,300, the phenolic terminal group concentration was 87 (eq / ton-PC), the phenoxy terminal group concentration was 152 (ea / ton-PC), and the melt viscosity stability was 0%. . The content of fine crystalline particles was 200 Zkg-PC. The melting point of the fine crystalline particles was 320.

Example 2, Comparative Example 2 (manufacture of PC-3, PC-4)

In Example 1 and Comparative Example 1, when the polymerization was continued until the viscosity-average molecular weight reached 22,500, 2.1 parts by weight of the end capping agent 2-methoxycarbonylphenylphenolate (SAM) was added. 265 ° C, 133. 3 stirred P a (lmm Hg) for 10 minutes, then as melt viscosity stabilizers, dodecylbenzene sulfonic acid tetrabutyl phosphonyl © unsalted 6. 9 X 10_ ⁴ parts by weight was added, 265 The mixture was stirred at /<6.7 Pa (0.5 mmHg) for 10 minutes.

Finally, viscosity average molecular weight 22,500, phenolic terminal OH concentration 30 (eq / t on-PC), 32 (eq / t on-PC), phenoxy terminal group concentration 120 (eq / t on-PC)ゝ 118 (eq / ton on PC), Aromatic polycarbonate with a melt viscosity stability of 0% was obtained (PC-3 and PC-4, respectively). The content of microcrystalline particles was 0 and 203 Zkg-PC, respectively. Table 2 below shows the physical properties of the aromatic polycarbonates obtained by the production methods of Examples 1 and 2 and Comparative Examples 1 and 2.

Example 3 and Comparative Example 3

 Tris (2,4-di-tert-butylphenyl) phosphite was added to the aromatic poly-polyponate of Example 1 and Comparative Example 1 in an amount of 0.01% by weight and monoglyceride stearate in an amount of 0.08% by weight. Next, this composition was melt-kneaded with a vent-type twin-screw extruder (KTX-46, manufactured by Kobe Steel Ltd.) while degassing at a cylinder temperature of 240 ° C. to obtain pellets. A DVD (DVD-Video) disk substrate was formed using the pellets, and subjected to a heat and humidity deterioration test.

Disc substrate molding ·

Attach a special DVD mold to the DISK 3 MIII injection molding machine manufactured by Sumitomo Heavy Industries, and attach a nickel DVD stamper containing information such as address signals to this mold to automatically transport the pellets. Into the hopper of the molding machine, with a cylinder temperature of 380 ° C, a mold temperature of 115, an injection speed of 20 Omm / sec, a holding pressure of 3, 432 kPa (35 kg f / cm ² ), and a diameter of 120 mm. A DVD disc substrate having a thickness of 0.6 mm was formed.

To test the reliability of an optical disk under severe temperature and humidity conditions for a long period of time, an aromatic polystyrene optical disk substrate was heated at a temperature of 80 and a relative humidity of 85% for 1.0%. After holding for 00 hours, the substrate was evaluated by the following measurements.

 The number of strain points for each (in the case of a disk substrate; observation with a polarizing microscope, observation of 25 disk substrates after molding, counting the number of abnormal refractive index points, and calculating the average value), the number of white spots generated (Observation of the optical disc substrate after the heat and humidity deterioration test using a polarizing microscope was performed, and the number of white spots of 2 O ^ m or more was counted. This was measured for 25 optical disc substrates (diameter of 120 mm). The average value was calculated and the average value was calculated) is shown in Table 3 below.

 Table 3

Example 4 and Comparative Example 4

After the aromatic polycarbonates of Example 2 and Comparative Example 2 were melted, a fixed amount was supplied by a gear pump and sent to a T-die of a molding machine. 0.03% by weight of tris nonylphenyl phosphite was added from just before the gear pump, and sandwiched between mirror cooling rolls and mirror rolls, or into a sheet with a thickness of 2 mm or 0.2 mm and a width of 800 mm with a single-sided sunset. Melt extruded. For a 2 mm thick sample, the number of strain points-1 (obtained thickness of 2 mm, 50 cm x 50 cm poly-force sheet, 10 sheets observed with a polarizing microscope, number of abnormal refractive index points) And the average value per sheet was determined.) And the breaking strength and elongation were measured in accordance with JIS, K6735. The results are shown in Table 4 below. Table 4

Example 5

A visible light-curable plastic adhesive [Adel BEN EF IX PC Co., Ltd.] was applied to one side of an aromatic polycarbonate sheet (2 mm thick) obtained from the polycarbonate of Example 2, and air bubbles entered the same sheet. after lamination with the pushed out to the one as no visible only metal eight ride five types by photocuring device equipped with, 00 OmJZcm the adhesive strength of the laminate obtained by irradiating a ^second light JIS K-6852 (Measurement method for compressive shear bond strength of adhesive). As a result, the adhesive strength was 10.4 MPa (106 kgf / cm ² ).

Example 6

 On a 0.2 mm thick aromatic polycarbonate sheet obtained from the polycarbonate of Example 2, ink [Natsuda 70-9132: color 136D smoke] and solvent [isophorone / cyclohexane / isobutanol = 40 / 40/20 (wt%)], and the mixture was printed with a silk screen printing machine and dried at 100 ° C. for 60 minutes. There was no transfer failure on the printed ink surface, and good printing was obtained.

Example 7

30 parts of polycarbonate resin (specific viscosity 0.895, Tg 175 ° C) obtained by the usual interfacial polycondensation reaction of 1,1-bis (4-hydroxyphenyl) cyclohexane and phosgene, as a dye Plast Red 8370 (A printing ink obtained by mixing 15 parts of Arimoto Chemical Industry and 130 parts of dioxane as a solvent was obtained. A sheet (0.2 mm thick) obtained from the polycarbonate of Example 4 printed with the printing ink was mounted in an injection mold, and polycarbonate resin pellets (Panlite L-1225, Teijin Chemicals Ltd.) The insert molding was performed at a molding temperature of 310 ° C by using the method of the present invention. An insert molded product having a good appearance of the printed portion without abnormalities such as blurring or blurring in the printed portion pattern of the molded product after the insert molding was obtained. Example 8

 90 parts by weight of the polycarbonate of Example 2 and 10 parts by weight of Panlite L-1250 manufactured by Teijin Chemicals were melt-kneaded using a vented twin-screw extruder (KTX-46 manufactured by Kobe Steel) while devolatilizing at a cylinder temperature of 240 ° C. A pellet was obtained. Using this pellet, a sheet was prepared in the same manner as in Example 4. Table 4 shows the physical properties of this sheet.

 Example 9

The production of polycarbonate relating to the luminescent fine particles was performed as follows. In a reaction vessel equipped with a stirrer, rectification tower and decompression device, 137 parts by weight of the purified BPA and 135 parts by weight of the purified DPC as raw materials, and disodium salt of bisphenol A as a polymerization catalyst 4.1 × 10— ⁵ parts by weight and 5.5 × 10 ³ parts by weight of tetramethylammonium hydroxide were charged and melted at 180 ° C. under a nitrogen atmosphere.

 The pressure inside the reaction vessel was reduced to 13.33 kPa (10 OmmHg) while stirring at a rotation speed of 40 rpm, and the reaction was carried out for 20 minutes while distilling off the phenol produced. Next, after the temperature was raised to 200 ° C., the pressure was gradually reduced, and the reaction was carried out at 4.0 kPa (3 OmmH) for 20 minutes while distilling off phenol.

Further, the temperature was gradually raised and the reaction was carried out at 220 ° C for 20 minutes. At this point, the viscosity average molecular weight was 3,200 and Tc was 180 ° C. Next, the temperature of the reaction mixture was kept at T c or lower, and the polymerization jacket heating jacket was sent to a second polymerization vessel heated to 240 ° C., where the reaction was carried out for 20 minutes. At this time, the viscosity average molecular weight was 4,800 and Tc was 233 ° C. Then, the temperature of the reaction mixture was rapidly raised to 250 ° C. over a period of 20 minutes so that the temperature did not exceed the set temperature. At this time, the viscosity average molecular weight was 7,000 and c was 245. Then, while stirring at a rotation speed of 30 rpm at 250 ^, The pressure was gradually reduced, and the reaction was continued at 2.666 kPa (2 OmmHg) for 10 minutes and 1.333 kPa (1 OmmHg) for 5 minutes. When the viscosity average molecular weight reached 8,000, the reaction The rotation speed was changed to 2 O pm so that the temperature of the shear heating section did not exceed 330 ° C, and finally the viscosity average molecular weight became 15,300 at 260 ° O 66.7 Pa (0.5 mmHg). Reacted.

Thereafter, dodecylbenzenesulfonic acid tetrabutylphosphonium phosphonyl © unsalted 3. 6X 10- ⁴ parts by weight was added to each, and stirred 260 ° CZ66. In 7 P a (0. 5mmHg) 10 min. Finally, the viscosity average molecular weight was 15,300, the phenolic terminal group concentration was 85 (eq / ton-PC), the phenoxy terminal group concentration was 154 (eq / ton-PC), and the melt viscosity stability was 0%. .

Comparative Example 5

The production of the aromatic polycarbonate was performed as follows. In a reaction vessel equipped with a stirrer, rectification column and depressurizer, 137 parts by weight of purified BP A and 135 parts by weight of purified DPC as raw materials, disodium salt of bisphenol A as a polymerization catalyst 4.1 X 10 - ⁵ parts by weight, was melted at tetramethylammonium Niu arm hydroxide 5. 5X 10- ³ by weight parts of the charged under a nitrogen atmosphere 180 in ° C.

 The pressure in the reaction vessel was reduced to 13.3 kPa (100 mmHg) while stirring at a rotation speed of 40 rpm, and the reaction was carried out for 20 minutes while distilling off the phenol produced. Next, after the temperature was raised to 200 ° C., the reaction was carried out at 4.0 kPa (3 OmmHg) for 20 minutes while gradually reducing the pressure and distilling off phenol.

The temperature is then gradually increased, 220 for 20 minutes, 240 ° C for 20 minutes, 260. (: 20 minutes, then stir at 270 ° C with the stirring speed kept at 4 O pm, gradually reduce the pressure, 2.666 kPa (2 OmmHg) for 10 minutes, 1.333 The reaction was continued at 5 kPa (1 OmmHg) for 5 minutes, and then the pressure was reduced to 66.7 Pa (0.5 mmHg). The temperature of the shearing part with the reaction tank may be 350, and even when the viscosity average molecular weight reaches 10,000, the stirring is continued at 40 rpm due to the relationship between the rotational power and the viscosity average molecular weight. 270V / 6 The reaction was performed at 6.7 Pa (0.5 mmHg) until the viscosity average molecular weight reached 15,300.

Thereafter, dodecylbenzenesulfonic acid tetrabutylphosphonium phosphonyl © unsalted 3. 6X 10- ⁴ parts by weight was added to each, and stirred 270 ° C // 66. In 7 P a (0. 5mmHg) 10 min. The finally obtained polycarbonate has a viscosity average molecular weight of 15300, a phenolic terminal group concentration of 86 (eqZton-PC), a phenoxy terminal group concentration of 153 (eq / ton-PC), and a melt viscosity stability of 0. %Met.

Example 10

 In Example 8, when the rotation speed was changed to 20 rpm at 260, I RGANOX HP 2215 / FF manufactured by Chino Specialty Chemicals Co., Ltd .; 0.03 parts by weight (200 ppm) was added. The pressure was gradually reduced with further stirring, and the reaction was continued until the viscosity-average molecular weight reached 15,300 at 66.7 Pa (0.5 mmHg) at 260.

Thereafter, dodecylbenzenesulfonic acid tetrabutylphosphonium phosphonyl © unsalted 3. 6X 10- ⁴ parts by weight was added to each and stirred for 10 min at 66. 7 P a (0. 5mmHg) at 260. Finally, the viscosity average molecular weight was 15,300, the phenolic terminal group concentration was 85 (eq / ton-PC), the phenoxy terminal group concentration was 154 (eq / ton-PC), and the melt viscosity stability was 0%. Was.

Examples 11 to 12 and Comparative Example 6

In Examples 9 and 10 and Comparative Example 5, polymerization was continued until the viscosity-average molecular weight reached 22,500. At this time, the end capping agent 2-methoxycarbonylphenylphenylcaponate (SAM) was 2.1 wt. Parts added, 265. C, 133. 3 stirred P a (1 mmH g) for 10 minutes, then as melt viscosity stabilizers, and dodecyl benzene sulfonate tetrabutyl phosphonyl © unsalted 6. 9 X 10- ⁴ parts by pressurizing example, 265 The mixture was stirred for 10 minutes at ° 0 66.7 Pa (0.5 mmHg). Finally, viscosity average molecular weight 15, 300, phenolic terminal concentration 30 (eq / t on-PC), 29 (e QZt on-PC), 31 (eq / t on-PC), phenolic terminal group concentration respectively Are 120 (eq / t on-PC) and 121 (eq / t on-P C), 119 (eq / ton on-PC) An aromatic polyphenol having a melt viscosity stability of 0% was obtained.

 When the X-ray diffraction pattern of the fine crystalline particles of the aromatic polycarbonate obtained in Examples 9 to 12 was measured, as shown in FIG. 1, the diffraction angle (20) showed a main peak at 17.180 °. showed that.

 Table 5 below shows the physical properties of the aromatic polycarbonate obtained by the production methods of Examples 9 to 12, Comparative Example 5 and Comparative Example 6. Table 5

Examples 13 to 19 and Comparative Examples 7 to 13

Aromatic polycarbonate pellets obtained by adding 0.003% by weight of trisnonylphenyl phosphite and 0.055% by weight of trimethyl phosphate to the aromatic polycarbonate of Example 2 and mixing uniformly. I got After uniformly mixing the pellets and the components indicated by the following symbols in Tables 6 and 7 using a tumbler, a twin-screw extruder equipped with a 30 mm φ vent (KT X- made by Kobe Steel Co., Ltd.) According to 30), the cylinder temperature was 260 ° C, the pellet was formed while degassing at a vacuum of 1.33 kPa (1 OmmHg), and the obtained pellet was dried at 120 ° C for 5 hours. Using heavy machinery (SG150U type) Molded pieces for measurement were prepared under the conditions of a soldering temperature of 270 ° C and a mold temperature of 80 ° C, and the results were shown in Examples 12 to 18. The following evaluation was performed. The results are shown in Tables 6 and 7. Similarly, the same operation was performed using the aromatic polycarbonate of Comparative Example 2 to obtain Comparative Examples 7 to 13. ,

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

 (1) 1 2 AS: Styrene-acrylonitrile copolymer; Stylac-1 AS 767 R27; manufactured by Asahi Kasei Corporation

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

 ①-4 PBT: Polybutylene terephthalate; TRB-H; Teijin Limited, intrinsic viscosity 1. 07

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

② 1 E-1: Butadiene monoalkyl acrylate-alkyl methacrylate copolymer; Paraloid EXL-2602; manufactured by Kureha Chemical Industry Co., Ltd.

 (1) 3E-2: Composite rubber in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component have an interpenetrating network structure; MEBUREN S-2001; manufactured by Mitsubishi Rayon Co., Ltd.

③ ー 1 T: talc; HS—T 0.8; average particle diameter L = 5 m, L / D = 8, measured by laser diffraction method, manufactured by Hayashi Kasei Co., Ltd.

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

 (3) 1 W: Wollastonite; Saiteck NN-4; Tomoe Kogyo Co., Ltd., number-average average fiber diameter D = l. 5; ^ m, average fiber length determined by electron microscopy, 17 urn , 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 D-790.

 (B) Notched impact value

 According to ASTM D-256, a 3.2 mm thick specimen was used to impact the weight from the notch side, and the impact value was measured.

 (C) Fluidity-Fluidity was measured with an Archimedes-type spiral flute (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

 A 1% strain was applied to the tensile test piece used in ASTM D-638, and the test piece was immersed in 3 O ETSO regular gasoline for 3 minutes, the tensile strength was measured, and the retention was calculated. The retention was calculated by the following equation.

Retention (%) = (strength of treated sample / strength of untreated sample) XI 00

Table 6 Example 13 Comparative Example 7 Example 14 Comparative Example 8 Example 15 Comparative Example 9 Example 16 Comparative Example 10 e. Recall, Nate type PC-3PC-4PC-3PC-4PC-3PC-4PC-3PC-4 Liquorho, 60 60 60 60 60 60 60 60

ABS 40 40 40 40 40 40

 AS 30 30

MBS 10 10 Composition

 π 100 100 100 100 100 100 100 100

G 15 15 15 15

W 15 15

 T 15 15

 WAX 1 1 1. 1

Flexural modulus MPa 3,465 3,445 3,234 3,211 2,925 2,907 3,322 3,314 Characteristics Flowability cm 33 31 28 27 29 29 36 34 Notched impact value / m 76 55 72 58 52 37 87 65

Table 7

Claims

The scope of the claims

1. (a) The main repeating unit is the following formula (1)

. (1)

(Wherein R ¹ and R ² are each independently a halogen atom, 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, Represents an aryl group having 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and m and ぴ n each independently represent a number from 0 to 4. 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, a cycloalkylidene group having 6 to 20 carbon atoms Represents an arylene group having 6 to 20 carbon atoms or an alkylene arylene alkylene group having 6 to 20 carbon atoms.)

Represented by

 (b) produced by subjecting an aromatic dihydroxy compound and a carbonic acid diester to melt polycondensation in the presence of a transesterification catalyst,

 (c) the melt viscosity stability is 0.5% or less,

 (d) a viscosity average molecular weight of 10,000 to 100,000;

 (e) the terminal group consists essentially of an aryloxy group (A) and a phenolic OH group (B), the molar ratio of both (A) / (B) being 955-40 / 60, and

(f) the content of fine crystalline particles which are collected by a filter having a nominal pore size of 3 m when forming a methylene chloride solution and show an X-ray diffraction pattern is not more than 50 particles /: kg polymer;

Aromatic polycarbonate, characterized in that:

2. (g) When the methylene chloride solution is used, the content of particles with a major diameter of 100 m or less that is collected by a filter with a nominal pore size of 10 / zm and emits when irradiated with ultraviolet light having a wavelength of 380 nm is emitted. Less than 100 pcs / kg polymer,

The aromatic polycarboxylic acid of claim 1 further specified by:

3. The aromatic polycarbonate according to claim 1, wherein the main repeating unit represented by the above formula (1) accounts for at least 85 mol% of all repeating units.

4. The aromatic polycarbonate according to claim 1, wherein in the formula (1), X is an alkylidene group having 2 to 20 carbon atoms, and n and m are both zero.

5. The aromatic polycarbonate according to claim 1, wherein the aryloxy group as a terminal group is a phenoxy group. -

6. The aromatic polycarbonate according to claim 1, wherein the fine crystalline particles have a main peak at a diffraction angle (20) 17.2 ° soil 0.3 ° in an X-ray diffraction pattern.

7. 100 parts by weight of the aromatic polycarbonate according to claim 1 and 1 to 150 parts by weight of the solid filler and / or a thermoplastic resin different from the aromatic poly-polyponate according to claim 1 An aromatic polycarbonate composition containing 150 parts by weight.

8. A molded article comprising the aromatic polycarbonate according to claim 1.

9. A molded article comprising the aromatic polycarbonate composition according to claim 7.

10. A substrate for an optical information recording medium comprising the aromatic polycarbonate according to claim 1.

11. A substrate for an optical information recording medium comprising the aromatic polycarbonate composition according to claim 7.

1 2. A sheet comprising the aromatic poly-polypropylene according to claim 1.

1 3. A sheet comprising the aromatic polycarboxylic acid composition of claim 7.

1 4. Use of the aromatic polystyrene component according to claim 1 as a substrate material of an optical information recording medium.

1 5. Use of the aromatic polycarboxylic acid composition according to claim 7 as a material for a substrate of an optical information recording medium.

1 6. Use of the aromatic polyadiponate according to claim 1 as a sheet material.

1 7. Use of the aromatic polycarbonate composition according to claim 7 as a sheet material.