JP2001342248A - Method for producing aromatic polycarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate obtained by polycondensing an aromatic dihydroxy compound with a diester of carbonic acid, having high durability and excellent in color, transparency and mechanical strength. SOLUTION: An aromatic dihydroxy compound having a spherical shape with a specified particle diameter distribution, a specific surface area and a pore volume not larger than a specific value, and preferably having specified color is used as the aromatic dihydroxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of an aromatic polycarbonate from an aromatic dihydroxy compound and a carbonic acid diester in the presence of a catalyst. About the law. More specifically, an aromatic dihydroxy compound having a spherical shape with a specific particle size distribution, a specific surface area, and a pore volume of a specific value or less, more preferably an aromatic polycarbonate by using an aromatic dihydroxy compound having a specific color tone A method for producing the same. Furthermore, the present invention relates to an aromatic polycarbonate obtained by the production method and having good color tone, and a molded article having good durability and stability therefrom, particularly an optical disk substrate.

[0002]

2. Description of the Related Art Aromatic polycarbonate is an engineering plastic excellent in hue, transparency, dimensional stability and impact resistance. In recent years, its use has been diversified and the environmental conditions in which it is used are also wide, so that the hue and transparency are further improved, and the above characteristics are maintained even when used for a long time under high temperature and high humidity conditions. Durability and stability are required.

[0003] In particular, hue and transparency are important quality items for use in an optical disk substrate. That is, there is a demand for strict control of the hue and transparency variations in addition to the hue and transparency levels, which have not been a problem with molded articles obtained from conventional aromatic polycarbonates.

[0004] Further, with the recent increase in density and capacity,
Environments such as temperature and humidity and time for use are becoming severe, and a highly stable substrate material that can obtain sufficient reliability is required.

However, in a molded article obtained from a conventional aromatic polycarbonate, there are variations in hue and transparency, a decrease in molecular weight and deterioration of hue in long-term use under high temperature and high humidity conditions, and variations in hue and transparency. It is pointed out that deterioration such as whitening occurs and there is a problem in durability and stability.

[0006] A decrease in the molecular weight of the polymer lowers the mechanical properties such as impact resistance of the molded product, and a variation in hue and transparency reduces the advantage of using the aromatic polycarbonate. In particular, fluctuations in hue and transparency particularly pose a problem to the reliability of recording and reproduction.

Deterioration of the molecular weight of the aromatic polycarbonate due to temperature and humidity, deterioration of the hue, and whitening are feared to be affected by trace impurities, especially metal elements, mixed into the molded product from the raw material. Consideration has been given to the content of.

Conventionally, in producing aromatic polycarbonates by reacting 2,2-bis (4-hydroxyphenyl) propane as an aromatic dihydroxy compound and diphenyl carbonate as a carbonic acid diester, those raw materials are purified and subjected to weather resistance. Several purification methods and production methods have been proposed for obtaining aromatic polycarbonates having good properties.

For example, a method of crystallizing and reprecipitating an aromatic dihydroxy compound (Japanese Patent Publication No. 41-17478),
Extraction and purification by contact with a solvent (JP-B-49-396)
No. 69, JP-B-47-10384), a method of separation and purification by distillation (JP-B-63-39611), and the like.

Conventionally, stability has been improved by focusing on the content of trace metals in aromatic polycarbonate. However, it is pointed out that any of these methods cannot provide sufficient stability and durability under moist heat conditions. Further, the number of metal element species referred to as impurities in the raw material was small, and only some of the metal elements that could adversely affect durability were found.

For example, Japanese Patent Application Laid-Open No. Hei 5-148355 discloses the effect of reducing the metal content on the heat stability of an aromatic polycarbonate, particularly on the improvement of the coloring property, but only metals of interest are iron and sodium. And their content is 5 ppm or less for the former and 1 p for the latter.
pm or less, the content was high. Also, Japanese Unexamined Patent Publication No.
No. 885 discloses a polycarbonate having good color tone and transparency having a total content of iron, chromium, and molybdenum of 10 ppm or less, and a total content of nickel and copper of 50 ppm or less. In the embodiment where the optimum condition is realized,
1 ppm of nickel and 1 pp of copper contained in the polymer
m and the content were high.

Japanese Patent Application Laid-Open No. 9-183895 discloses a polycarbonate made from an aromatic dihydroxy compound having a content of iron, chromium and nickel of 0 to 50 ppb. No mention is made of the relationship between the amount of catalyst and the amount of impurities.

On the other hand, Japanese Patent Application Laid-Open No. H11-310630 discloses an improvement in the color tone, heat resistance and gel of an aromatic polycarbonate produced by reducing the iron content of metal impurities to 10 ppb and chroman impurities to 40 ppm. We have achieved some results.

[0014] However, even when such a purified raw material is used, the produced aromatic polycarbonate may have a variation in color tone and transparency, which remains as a problem to be solved.

[0015]

The present invention provides an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polymerization catalyst.
In the method for producing an aromatic polycarbonate by melt polycondensation, as an aromatic dihydroxy compound as a raw material, it is necessary to define structural characteristics, that is, to have a spherical shape with a specific particle size distribution, a specific surface area, a specific value of pore volume. By using the following, the color tone of the aromatic polycarbonate,
The purpose is to obtain a molded product having good durability and stability, particularly an optical disk substrate, by controlling the variation in transparency.

[0016]

Means for Solving the Problems The inventors of the present invention have conducted a melt polycondensation reaction between an aromatic dihydroxy compound and a carbonic acid diester in the presence of a polymerization catalyst to produce an aromatic polycarbonate. By determining the particle size distribution, specific surface area, and pore volume of, the hue and transparency level can be improved, and the hue and transparency under high-temperature and high-humidity conditions can be controlled. Was.

That is, the present invention relates to a) a nitrogen-containing basic compound and / or a phosphorus-containing basic compound in an amount of 10 to 1000 .mu.m. Chemical equivalent / 1 mol of an aromatic dihydroxy compound, and a) an alkali metal compound and / or an alkaline earth metal compound. In a method for producing an aromatic polycarbonate in which an aromatic dihydroxy compound and a carbonic acid diester are polycondensed in the presence of a catalyst containing 0.05 to 5 µ chemical equivalent / one mole of an aromatic dihydroxy compound, the aromatic dihydroxy compound is used as an aromatic dihydroxy compound. Spherical prill and diameter 0.1-3
mm prill distribution ratio is 70 wt% or more, specific surface area ≦
A polycarbonate production method characterized by using a material having a pore volume of 0.2 m ² / g and a pore volume of ≦ 0.1 ml / g.

Hereinafter, the present invention will be described in detail. The aromatic polycarbonate in the present invention has a main repeating structure obtained by polycondensation of an aromatic dihydroxy compound and a carbonic acid diester, having the following formula (1):

[0019]

Embedded image

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
0, an alkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, m, n Is an integer of 1 to 4. X is a single bond, oxygen atom, carbonyl group, alkylene group having 1 to 20 carbon atoms, alkylidene group, cycloalkylene group having 6 to 20 carbon atoms, cycloalkylidene group or 6 to 2 carbon atoms
Represents an arylene group of 0. ), Molecular weight 1
0000 to 35000 aromatic polycarbonates.

The aromatic dihydroxy compound used in the present invention is represented by the following formula (2).

[0022]

Embedded image

(Wherein R ₁ , R ₂ , m, n, and X are the same as those in the above formula (1).) The aromatic dihydroxy compound is, for example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter, referred to as a compound) BPA), bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, 1,1-bis (4
-Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane , 2,2-
Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4 -Hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl)
Examples thereof include sulfide, bis (4-hydroxyphenyl) sulfone and the like in which an aromatic ring is substituted with, for example, an alkyl group or an aryl group.
PA is particularly preferred. These may be used alone or in combination of two or more.

Examples of the carbonic acid diester include diphenyl carbonate (hereinafter abbreviated as DPC), dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, dibutyl carbonate and the like.
Among them, DPC is preferable from the viewpoint of cost.

When such an aromatic dihydroxy compound and a carbonic acid diester are used as raw materials for an aromatic polycarbonate, the trace metal element contained as an impurity is produced, although the clear chemical structure and the type of contribution of the species present are unknown. It is preferable to control the aromatic polycarbonate so as to adversely affect the durability, color tone, and transparency of the aromatic polycarbonate.

In the present invention, when an aromatic dihydroxy compound and a carbonic diester are subjected to polycondensation under heat and melting to produce an aromatic polycarbonate, a) a nitrogen-containing basic compound and / or a phosphorus-containing basic compound are mixed with 10 In the presence of a catalyst containing 0.05 to 5 μchemical equivalents / mol of aromatic dihydroxy compound, and b) an alkali metal compound and / or an alkaline earth metal compound. In the method for producing a polycarbonate by polycondensation, an aromatic dihydroxy compound having a diameter of 0.1.
The distribution ratio of spherical particles of 1 to 3 mm is 70 wt% or more, specific surface area ≦ 0.2 m ² / g, pore volume ≦ 0.1 m
1 / g is used.

The shape of the aromatic dihydroxy compound is a spherical shape called prill in the art, and a particle size distribution of 0.1 to 2 mm is 70% by weight or more, preferably 80% or more, particularly preferably 90% or more. % Or more is preferable for hue stability. More preferably, the diameter is 0.
The distribution of those having a diameter of 1 mm or less is 10 wt% or less, more preferably 5 wt% or less, and particularly preferably 3 wt% or less.

BE of aromatic dihydroxy compound prill
Regarding the specific surface area (m ² / g) measured by the T method,
The specific surface area is preferably 0.2 m ² / g or less, more preferably 0.1 m ² / g or less.

The pore volume of the aromatic dihydroxy compound prill has a radius of 100 nm to 6 μm measured by a mercury intrusion method.
This is a value obtained by determining the peak of m as the particle pore distribution and calculating the pore volume from this.

This value is preferably not more than 0.1 ml / g, more preferably not more than 0.06 ml / g, still more preferably not more than 0.04 ml / g, particularly preferably not more than 0.03 ml / g. is there.

When these values are in the above ranges, the color tone and the transparency level of the aromatic polycarbonate are good, and the fluctuation of the color tone and the transparency level is small.

In the case of using a solid-state raw material for the diester carbonate, which is another aromatic polycarbonate raw material, the smaller the specific surface area and the smaller the pore volume are, the more preferable the same as for the aromatic dihydroxy compound prill. In this case, the stability is better than that of the aromatic dihydroxy compound, and thus the necessity of strict control like the aromatic dihydroxy compound is small. In addition, since the raw material is often supplied as a melt, it is naturally less necessary to consider the specific surface area and the pore volume in this case.

It is not clear why the above-mentioned effect is exhibited by the aromatic dihydroxy compound prill, but it is assumed that the factor deteriorating the quality of the aromatic dihydroxy compound is taken into the surface of the agent, especially inside the pores, thereby deteriorating the quality of the aromatic dihydroxy compound. Presumed.

In a further preferred embodiment, the color L value is 80 with respect to the hue of the aromatic dihydroxy compound.
As described above, the color b value is preferably 2 or less. More preferably, the color L value is 83 or more, and the color b value is 1.5.
Hereinafter, the color L value is more preferably 85 or more, and the color b value is 1 or less. Particularly preferably, the color L value is in the range of 85 or more and the color b value is in the range of 0.5 or less. By being in such a range, the variation range becomes good along with the hue level.

In the present invention, considering the effects on durability, color tone and transparency of the produced polycarbonate, Fe, Cr, Mn, Ni, P contained as impurities in the raw material are considered.
Transition metal elements such as b, Cu, Pd, etc. Metals such as Si, Al, Ti, etc.
In the following, it is more preferable that the content be 10 ppb or less.

In order to obtain an aromatic polycarbonate having more excellent durability, the content of the alkali metal element and / or alkaline earth metal element having a large transesterification ability contained in the aromatic dihydroxy compound and the carbonic acid diester is 0%. Preferably it is 60 ppb.

Further, 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 is not more than 80 ppb and the transition metal element concentration. Is preferably 10 ppb or less.

Further, a method characterized in that the concentration of the above-mentioned metal and semi-metal elements contained in the carbonic acid diester and the aromatic dihydroxy compound is 20 ppb or less.

As the raw material, an aromatic dihydroxy compound and a carbonic acid diester having a lower content of 10 ppb or less, which is the limit of the prior art, are preferably used as the content of such a transition metal element, metal or semi-metal group element is lower. Thus, an aromatic polycarbonate having excellent durability can be obtained. You.

In the present invention, in order to obtain an aromatic dihydroxy compound and a carbonic acid diester having reduced contents of transition metals, metals and semi-metal elements, known purification methods, for example, distillation, extraction, and recrystallization And various purification methods such as sublimation. In particular, it is preferable to purify the raw material by slowly sublimating it near the sublimation temperature, and it is more preferable to further combine the above-mentioned purification methods in addition to sublimation. According to these methods, the metal impurity content can be reduced to the ppb level which is 1/1000 or less of the metal impurity content which was conventionally at the ppm level.

In order to satisfy the above-mentioned particle size distribution and structural characteristics of the aromatic dihydroxy compound, for example, a molten aromatic dihydroxy compound is dropped from a nozzle to form droplets, quenched in a countercurrent cooling inert gas, and cooled to 100 ° C. / After cooling and solidifying at a cooling rate of not less than sec, a method of sieving is easy.

The polycarbonate resin disclosed in the present invention is produced by a melting method (transesterification reaction). The melting method is carried out by heating and stirring an aromatic dihydroxy compound and a carbonic acid diester under a normal pressure and / or a reduced pressure nitrogen atmosphere to distill off the produced alcohol or phenol. The reaction temperature varies depending on the boiling point of the product and the like, but is usually in the range of 120 to 350 ° C. in order to remove alcohol or phenol generated by the reaction, and is preferably 180 to 350 ° C. because good hue and thermal stability can be obtained. 280 ° C. range.

In the latter half of the reaction, the pressure of the system is reduced to facilitate the distillation of the alcohol or phenol formed. The internal pressure of the system at the latter stage of the reaction is preferably 133.3 Pa (1 mmH
g) or less, and more preferably 66.7 Pa (0.5
mmHg) or less.

In the present invention, a specific type of catalyst is used. That is, a) a nitrogen-containing basic compound and / or a phosphorus-containing basic compound, and b) an alkali metal compound and / or an alkaline earth metal compound.

Specific examples of the nitrogen-containing basic compound and / or the phosphorus-containing basic compound as these catalysts include, for example, nitrogen-containing basic compounds such as tetramethylammonium hydroxide (Me ₄ NOH) and benzyltrimethylammonium hydroxide. (Φ-CH ₂ (Me) ₃ N
OH), such as ammonium hydroxides having alkyl, aryl, alkylaryl groups, etc., tetramethylammonium acetate, tetraethylammonium phenoxide, tetrabutylammonium carbonate, benzyltrimethylammonium benzoate, etc., alkyl, aryl, alkylaryl Or a tertiary amine such as triethylamine or dimethylbenzylamine, or tetramethylammonium borohydride (Me ₄ NBH ₄ ) or tetrabutylammonium borohydride (Bu ₄ NB)
H ₄ ) and basic salts such as tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ).

Specific examples of the phosphorus-containing basic compound include, for example, tetrabutylphosphonium hydroxide (Bu
Alkyl such as ₄ POH), benzyltrimethylphosphonium hydroxide (φ-CH ₂ (Me) ₃ POH),
Aryl, phosphonium hydroxides having an alkyl aryl group or tetramethyl phosphonium borohydride (Me ₄ PBH _4),, tetrabutylphosphonium borohydride (Bu ₄ PBH _4), tetramethyl phosphonium tetraphenylborate, (Me ₄ P
And basic salts such as BPh ₄ ).

The above-mentioned nitrogen-containing basic compound and / or phosphorus-containing basic compound have a basic nitrogen atom or a basic phosphorus atom in an aromatic dihydroxy compound, and are preferably used in an amount of 1 to 1 mol.
It is preferable to use it at a ratio of 0 to 1000 µ chemical equivalent. A more preferable usage ratio is 20 to 50 with respect to the same standard.
It is a ratio that becomes 0 μ chemical equivalent. A particularly desirable ratio is a ratio that results in a chemical equivalent of 50 to 500 μ with respect to the same standard.

In particular, at this time, in order to improve the hue of the obtained polycarbonate, the amount of the nitrogen-containing basic compound and / or the phosphorus-containing basic compound used is contained in the starting carbonic acid diesters and the aromatic dihydroxy compounds. Total iron content; 20 ^{* for} Fe ^* (expressed in wtppb)
It is preferable to use it so as not to exceed (Fe ^* ) + 200 μ chemical equivalent. Particularly preferably, 20 × (Fe ^* )
The range does not exceed +150.

The reason for this is not clear, but the iron contained in the starting carbonic acid diester and the aromatic dihydroxy compound interacts with the nitrogen-containing basic compound and / or the phosphorus-containing basic compound to deteriorate the color tone of the polycarbonate. It is presumed that. In this sense, it is preferable to reduce the contents of various metal impurities as much as possible.

Further, in the present invention, an alkali metal and / or a phosphorus-containing basic compound are added together with the above-mentioned nitrogen-containing basic compound and / or phosphorus-containing basic compound in order to realize the effect of reducing impurities in the raw material in the color tone and stability of the polymer. An alkaline earth metal compound is used in combination, but the alkali metal and / or
Alternatively, as the alkaline earth metal compound, a compound containing an alkali metal compound is preferably used. Such alkali metal compounds include aromatic dihydroxy compounds,
5 × 10 ^{−8 to} 5 as an alkali metal element per 1 mol
It is used in the range of × 10 ^-6 chemical equivalent. By using a catalyst having such a quantitative ratio, a terminal blocking reaction that continues below, a branching reaction that is likely to be generated during the polycondensation reaction without impairing the polycondensation reaction rate, a main chain cleavage reaction, or an internal reaction 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.

If the ratio is outside the above range, there are problems such as adverse effects on various physical properties of the obtained polycarbonate, and insufficient transesterification reaction so that a high molecular weight polycarbonate cannot be obtained.

The nitrogen-containing basic compound and / or the phosphorus-containing basic compound used in the present invention as a catalyst include, for example, hydroxides of alkali metals and alkaline earth metals, hydrocarbon compounds, carbonates, acetates and nitrates. , Nitrite, sulfite, cyanate, thiocyanate, stearate, borohydride, benzoate, hydride phosphate, bisphenol, phenol salts and the like.

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

In the present invention, if desired, the alkali metal compound used as a catalyst may be (a) an alkali metal salt of an ate complex of an element of group 14 of the periodic table or (a) an oxo acid of an element of group 14 of the periodic table. Alkali metal salts can be used. Here, the elements of Group 14 of the periodic table refer to silicon, germanium, and tin.

The use of such an alkali metal compound as a catalyst for the polycondensation reaction has the advantage that the polycondensation reaction can be rapidly and sufficiently advanced. Also, undesirable side reactions such as a branching reaction that proceeds during the polycondensation reaction can be suppressed to a low level.

The alkali metal salt of the ate complex of the element belonging to Group 14 of the Periodic Table (A) is described in JP-A-7-2680.
No. 91, specifically, NaGe
(OMe) ₅ , NaGe (OPh) ₅ , LiGe (OB
u) ₅ , NaSn (OEt) ₂ (OMe), NaSn (O
Ph) _{5 and the} like.

Preferred examples of the alkali metal salt of oxo acid of Group 14 element of the periodic table include, for example, alkali metal salts of silicic acid, stannic acid, germanium (II) acid, and germanium (IV) acid. be able to.

Specific examples thereof include tetrasodium orthosilicate, disodium monostannate, monosodium germanate (II) (NaHGeO ₂ ), disodium orthogermanate (IV), tetrasodium orthogermanate (IV), Germanium (I
V) disodium acid and (Na ₂ Ge ₂ O ₅ ).

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

The oxo acids of Group 14 of the periodic table include, for example, silicic acid, stannic acid and germanic acid.

The oxides of Group 14 of the periodic table include silicon dioxide, tin dioxide, germanium dioxide, silicon tetramethoxide, silicon tetraphenoxide, tetraethoxytin, tetranonyloxytin, tetraphenoxytin, tetrabutoxygermanium, Examples include tetraphenoxygermanium, and condensates thereof.

The co-catalyst contains 50 elements of group 14 of the periodic table per mole atom of the alkali metal element in the polycondensation reaction catalyst.
It is preferable that the compound be present in a ratio of not more than a molar atom.
Use of a co-catalyst in a proportion of more than 50 mole atoms of the same metal element is not preferred because the rate of the polycondensation reaction is reduced.

It is more preferable that the cocatalyst be present in an amount such that the element of Group 14 of the periodic table as the cocatalyst is 0.1 to 30 mol atoms per 1 mol atom of the alkali metal element of the polycondensation reaction catalyst. No.

The sodium compound has less influence on the durability of the produced aromatic polycarbonate than the compound of an alkali metal or alkaline earth metal other than sodium. In order to obtain polycarbonate, it is preferable to use a sodium compound as a catalyst.

The amount of these polymerization catalysts used in the present invention is 0.05 to 5 μm equivalent, preferably 0 to 5 mol per mol of aromatic dihydroxy compound when an alkali metal compound and an alkaline earth metal compound are used. .07-
It is selected in the range of 3 µ chemical equivalent, particularly preferably 0.07 to 2 µ chemical equivalent.

In the present invention, in order to obtain an aromatic polycarbonate having good stability, which is unlikely to cause a decrease in molecular weight or coloring, in order to improve the stability of the polymer after polymerization under various conditions, Attention should be paid to the melt viscosity stability of the molten polymer, and it is essential that this value be 0.5% or less. Therefore, it is particularly preferable to use a melt viscosity stabilizer after polymerization. In addition, the melt viscosity stability is evaluated by an absolute value of a change in melt viscosity measured at 300 ° C. for 30 minutes at a shear rate of 1 rad / sec under a nitrogen stream, and is expressed as a rate of change per minute.

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

As a method for adding a melt viscosity stabilizer, for example, the aromatic polycarbonate which is a reaction product may be added while it is in a molten state, or the aromatic polycarbonate may be pelletized once and then re-dissolved. May be added. In the former, the aromatic polycarbonate which is a reaction product in the reaction vessel or the extruder may be added while it is in a molten state, or the aromatic polycarbonate obtained after the polymerization may pass through the extruder from the reaction vessel. During the pelletization, a melt viscosity stabilizer can be added and kneaded.

As the melt viscosity stabilizer, any known agents can be used. However, salts of organic sulfonic acids, salts of organic sulfonic acids, and the like have great effects on improving the physical properties such as hue, heat resistance and boiling water resistance of the obtained polymer. Organic sulfonic acid esters,
It is preferred to use sulfonic acid compounds such as organic sulfonic anhydrides and organic sulfonic acid betaines. Among them, it is preferable to use a sulfonic acid phosphonium salt and / or a sulfonic acid ammonium salt. Among them, particularly preferred are tetradecylphosphonium dodecylbenzenesulfonate and tetrabutylammonium p-toluenesulfonate.

The polymer having excellent durability and stability of the present invention can be obtained by the above-mentioned method. In the case of molding various molded articles using the polymer, conventionally known processing stabilizers and
Heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents,
You may add a flame retardant, a release agent, etc.

Further, a heat stabilizer can be blended in order to prevent a decrease in the molecular weight of the aromatic polycarbonate of the present invention and a deterioration in hue. Examples of such a heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite , 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 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 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, more preferably 0.001 to 0.5 part by weight, per 100 parts by weight of the aromatic polycarbonate of the present invention. One part by weight is more preferred.

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. is there. Examples of the release agent include olefin wax, olefin wax containing a carboxyl group and / or a carboxylic anhydride group, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax. And the like. The amount of the release agent is 0.01 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate of the present invention.
Parts by weight are preferred.

The higher fatty acid esters include monohydric or polyhydric alcohols having 1 to 20 carbon atoms and 10 to 10 carbon atoms.
It is preferably a partial ester or a total ester with 30 saturated fatty acids. As such a partial ester or a whole ester of a monohydric or polyhydric alcohol and a saturated fatty acid, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used. The amount of the release agent is 0.01 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate of the present invention.
Parts by weight are preferred.

Further, inorganic and organic fillers can be added to the aromatic polycarbonate of the present invention in order to improve rigidity and the like within a range not to impair the object of the present invention. Such inorganic fillers include plate-like or granular inorganic fillers such as talc, mica, glass flakes, glass beads, calcium carbonate, and titanium oxide, glass fibers, glass milled fibers, wollastonite, carbon fibers, aramid fibers, and metals. Examples include fibrous fillers such as system conductive fibers, and organic particles such as crosslinked acrylic particles and crosslinked silicone particles. The compounding amount of these inorganic and organic fillers is preferably from 1 to 150 parts by weight, more preferably from 3 to 100 parts by weight, based on 100 parts by weight of the aromatic polycarbonate 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 such as suppression of decomposition of the aromatic polycarbonate can be obtained.

Other resins 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 such other resins include polyamide resins, polyimide resins, polyetherimide resins,
Polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, amorphous polyarylate resin, polystyrene resin, acrylonitrile / styrene copolymer ( AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin,
Resins such as phenolic resins and epoxy resins are exemplified.

A molded article having good durability and stability can be obtained from the polycarbonate produced by the present invention by an injection molding method or the like.

The aromatic polycarbonate of the present invention has an effect of maintaining the durability of the polymer, particularly the long-term durability under severe temperature and humidity conditions, by suppressing the above-mentioned specific impurities to a specific value or less. Compact disk (CD), CD-ROM, CD-ROM obtained using the polymer
Digital versatile discs (DVD-R, CD-RW, etc.), magnet optical discs (MO), etc.
ROM, DVD-Video, DVD-Audio, D
A substrate for a high-density optical disk typified by VD-R, DVD-RAM, etc. can provide high reliability over a long period of time.
In particular, it is useful for a high-density optical disk such as a digital versatile disk.

The sheet made of the aromatic polycarbonate resin produced in the present invention is an aromatic polycarbonate sheet having excellent adhesiveness and printability, and is widely used for electric parts, building material parts, automobile parts, etc. by utilizing its properties. More specifically, glazing products for window materials such as various types of window materials, such as general houses, gymnasiums, baseball domes, vehicles (construction machines, automobiles, buses, bullet trains, train cars, etc.), and various side walls (sky dome, top) Lights, arcades, apartment lumbar boards,
Roadside walls), window materials for vehicles, etc., displays and touch panels for OA equipment, membrane switches, photo covers, polycarbonate resin laminates for water tanks, front panels for projection televisions and plasma displays, Fresnel lenses, optical cards, optical disks, etc. It is useful for optical applications such as a liquid crystal cell and a phase difference correction plate in combination with a polarizing plate. The thickness of the aromatic polycarbonate sheet is not particularly limited, but is usually 0.1 to 10 mm, preferably 0.2 to 8 mm, and particularly preferably 0.2 to 3 mm. In addition, various processings (various lamination processing for improving weather resistance, abrasion resistance improvement processing for improving surface hardness, surface graining, semi- and opaque processing) for adding new functions to the aromatic polycarbonate sheet. Processing).

For blending each of the above 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 Nauta mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The aromatic polycarbonate resin composition thus obtained is pelletized as it is or by a melt extruder, and then formed into a sheet by a melt extrusion method.

Even when an aromatic polycarbonate is produced by a so-called interfacial polymerization method using a high-purity aromatic dihydroxy compound which suppresses the particle size distribution and structural characteristics, more preferably the hue and metal impurities described in the present invention, Hue,
It goes without saying that an aromatic polycarbonate having good quality such as stability is produced.

A molded article having good durability and stability can be obtained from the aromatic polycarbonate produced by the present invention by an injection molding method or the like.

The aromatic polycarbonate produced by the present invention may be used for any purpose, and is particularly preferably used as an optical disk substrate material.

In addition, the aromatic polycarbonate of the present invention or the aromatic polycarbonate produced from the aromatic dihydroxy compound having a regulated amount of impurities according to the present invention is suitably used for transparent resin applications such as sheets and lenses. .

[0086]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In addition, the test method of bisphenol A, diphenyl carbonate, and polycarbonate was based on the following method.

1) Viscosity average molecular weight (Mw): The viscosity average molecular weight (Mw) was determined from the intrinsic viscosity ([η]) measured with an Ubbelohde viscometer at 20 ° C. in methylene chloride by the following equation. [Η] = 1.23 × 10 ⁻⁴ Mw ^0.83

2) BET Specific Surface Area Measuring Method Apparatus; High-precision fully automatic gas adsorption apparatus “B” manufactured by Nippon Bell Co., Ltd.
ELSORP 36 "adsorption gas; Kr dead volume; He adsorption temperature: liquid nitrogen temperature (77K) Pre-measurement treatment: 50 ° C, devolatilization under reduced pressure (attained vacuum degree to 1 Pa) Measurement mode: adsorption at isothermal measurement range: relative pressure ( P / P ₀ ) = 0.01-0.4 Equilibrium time = 180 sec for each equilibrium relative pressure Measurement method: 0.2-0.5 g of sample is precisely weighed and sealed in a sample tube, BET theory is applied, the same theory Is satisfied, and the relative pressure (P / P ₀ ) range from 0.05 to ₀ .
The range of 30 was analyzed to determine the specific surface area.

3) Measurement of pore volume Apparatus: Pore Sizer 932 manufactured by Micromeritex
0 Measurement pressure range: about 0.37 kPa to 207 Mpa (pore diameter: 7 nm to 400 μm) Measurement mode: pressure increase process in the above pressure range Cell volume: 5 cm ³ Measurement n number: 1 and 2 Measurement: sample 0.2 to 1.2 g Was precisely weighed and placed in a cell, mercury was injected under reduced pressure, the pore volume was determined per radius of 100 nm to 6 μm in consideration of deformation of sample particles and particle gap.

4) Method for Quantifying Metal Impurity Content Apparatus: ICP-MS, SPQ manufactured by Seiko Electronics Industry Co., Ltd.
9000 Sample concentration: A sample (0.5 g) is dissolved in isopropyl alcohol (25 g) for electronic industry, and quantified by a standard sample calibration curve.

5) Polycarbonate Wet Heat Deterioration Test In order to test the long-term durability of the polycarbonate under severe temperature and humidity conditions, the polycarbonate was kept in an autoclave at a temperature of 80 ° C. and a relative humidity of 85% for 1000 hours. The polymer was evaluated by measuring. It should be noted that although a method for evaluating deterioration of hue due to deterioration due to temperature and humidity is not usually performed, it can be said that it is a proper evaluation method for deterioration under severe temperature and humidity conditions.

5) -1 Hue deterioration: The hue of the polymer chip was measured with a Z-1001DP color difference meter manufactured by Nippon Denshoku Co., Ltd. Ten samples were prepared, and L value and b value were calculated as the average value of the samples. The higher the L value, the higher the brightness, and the lower the b value, the less yellow coloring is preferable, and usually 1 or less indicates good quality. b value increase (△ b value in the table) If the variation of the b value increase (△ bMax-Min (note) in the table) is 0 to 1.0, it can be used for a long time under severe temperature and humidity conditions. It was evaluated that the desired hue stability was maintained. Note: Difference between the maximum value and the minimum value of the Δb value of 10 samples

5) -2 Transparency; 50 × 50 × 5 mm flat plate was molded at a cylinder temperature of 280 ° C. using a Neomat N150 / 75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.
Molding was performed in 5 seconds, and the total light transmittance of the flat plate was measured by NDH- # 80 manufactured by Nippon Denshoku Co., Ltd. The higher the total light transmittance, the better the transparency. When the total light transmittance was 90% or more, it was evaluated that the desired transparency was maintained even after long-time use under severe temperature and humidity conditions.

5) -3 Wet heat stability of impact resistance: Evaluated by Izod impact strength ASTM D-256 (notched). Polymer at 120 ° C. under high vacuum
After drying for an hour, a 3.2 mm injection molded test piece was prepared using a mold. After the wet heat deterioration test, the retention of the Izod impact strength for 1000 hours was determined. When the retention was 90% or more, it was determined that the desired strength was maintained under long-term wet heat conditions.

6) Prill hue: Measured with a Z-1001DP colorimeter manufactured by Nippon Denshoku Co., Ltd., following the hue of a polymer chip. The higher the L value, the higher the lightness, and the lower the b value, the less yellow coloration, which is preferable.

[Preparation of bisphenol A and diphenyl carbonate] 1) Purification of bisphenol A: Dissolve commercially available bisphenol A in 5 times the amount of phenol,
An adduct crystal of phenol and phenol was prepared. The obtained adduct crystal was removed at 5.33 kPa (40 Torr) at 180 ° C. until the phenol concentration in bisphenol became 3%, and then the phenol was removed by steam stripping. . Next, the above-mentioned bisphenol A was charged into a vessel equipped with a decompression device and a cooling device, and a pressure of 13.3 Pa (0.1 Torr) and a temperature of 13 in a nitrogen atmosphere.
Purification was performed by sublimation at 9 ° C. Sublimation purification was repeated twice to obtain purified bisphenol A. Table 1 below shows the amounts of metal impurities in commercially available bisphenol A and purified bisphenol A.

[0097]

[Table 1]

2) Bisphenol A: Prill- (a) The above purified bisphenol A was heated and melted at 170 ° C.
Drop it under pressure from a 0.3 mm diameter nozzle to create a droplet,
Countercurrent contact with 77K cooling nitrogen gas, cooling rate 100 ° C /
After cooling for at least sec, those having a size of 0.2 mm or less and 3 mm or more were sieved and removed to obtain prill having an average particle size of 1.5 mm.

3) Bisphenol A: Prill- (b) The melt of the above purified bisphenol A was dropped by pressure from a nozzle having a diameter of 0.5 mm to form droplets, which were brought into countercurrent contact with a 77K cooling nitrogen gas, and a cooling rate. After cooling at 100 ° C./sec or more, those having a diameter of 0.2 mm or less and 3 mm or more were sieved and removed to obtain prill having an average particle size of 2.2 mm.

4) Bisphenol A: Prill- (c) A melt of purified bisphenol A was dropped under pressure from a nozzle having a diameter of 0.5 mm to form droplets, which were brought into countercurrent contact with a cooling nitrogen gas at 0 ° C. and cooled. It was slowly cooled at a rate of 100 ° C./sec or less, and sieved to remove those having a diameter of 0.2 mm or less and 3 mm or more to obtain prills having an average particle diameter of 2.3 mm.

Table 2 below shows the physical properties of prills (a), (b) and (c) of the above-mentioned raw material bisphenol A and purified bisphenol A.

[0102]

[Table 2]

5) Purification of diphenyl carbonate (a) Diphenyl carbonate (before purification) was charged into a vessel equipped with a decompression device and a cooling device, and the pressure was set to 13.3 under a nitrogen atmosphere.
Sublimation was performed at Pa (0.1 Torr) and a temperature of 74 ° C. to obtain a purified product (a) of diphenyl carbonate.

6) Purification of diphenyl carbonate (b) The raw material diphenyl carbonate was prepared using the method described in "Plastic Materials Course 17 Polycarbonate Author Toshihisa Tachikawa et al. (Nikkan Kogyo Shimbun)"
℃) Washing was repeated 3 times, dried and distilled under reduced pressure to obtain 16
A fraction at 7-168 ° C./2.000 kPa (15 mmHg) was collected, and further subjected to the same sublimation purification treatment as in the above 5) to obtain a purified product (b) of diphenyl carbonate.

The metal impurities contained in the diphenyl carbonate produced and purified as described above were measured by the above-mentioned method. The results are shown in Table 3.

[0106]

[Table 3]

[Examples 1 and 2, Comparative Example 1] An aromatic polycarbonate was produced as follows. Purified bisphenol A-prill (a) (Example 1), purified bisphenol A-prill (b) (Example 2), purified bisphenol A- 137 parts by weight of prill (c) (Comparative Example 1) and 13 parts of purified diphenyl carbonate- (b)
5 parts by weight, 8.2 × 10 ⁻⁵ parts by weight of bisphenol A disodium salt as a polymerization catalyst, and 5.5 × 10 ⁻³ parts by weight of tetramethylammonium hydroxide were melted at 180 ° C. under a nitrogen atmosphere. 13. With stirring, the inside of the reaction vessel is 13.
The pressure was reduced to 33 kPa (100 mmHg), and the reaction was carried out for 20 minutes while distilling off the generated phenol. Then 200
After the temperature was raised to ° C., the pressure was gradually reduced, and the reaction was carried out at 4.000 kPa (30 mmHg) for 20 minutes while distilling off phenol. Then gradually raise the temperature to 220 ° C for 20 minutes for 24 minutes.
The reaction was carried out at 0 ° C. for 20 minutes and at 265 ° C. for 20 minutes, and then the pressure was gradually reduced at 265 ° C. to 2.666 kPa (20 m
(mHg) for 10 minutes and 1.333 kPa (10 mmH
g) for 5 minutes, and finally at 265 ° C./66.
The viscosity average molecular weight is 1530 at 7 Pa (0.5 mmHg).
The reaction was continued until it reached zero. At this time, the terminal blocking agent 2
1.70 parts by weight of -methoxycarbonylphenylphenyl carbonate (SAM) was added at 265 ° C.
The mixture was stirred at 3 Pa (1 mmHg) for 10 minutes, and then 6.9 × 10 ^-4 parts by weight of tetrabutylphosphonium dodecylbenzenesulfonate was added as a melt viscosity stabilizer.
The mixture was stirred at 65 ° C / 66.7 Pa (0.5 mmHg) for 10 minutes. Finally viscosity average molecular weight 15300, terminal OH
Concentration 60, phenoxy end group concentration 179 (eq / ton
-PC) An aromatic polycarbonate having a melt viscosity stability of 0 was obtained.

Reference Examples 1 and 2: Production of Polymer A 5 l capacity equipped with a phosgene blowing tube, a thermometer and a stirrer.
In the reaction vessel of No. 502, 8 g (2.21 mol) of a raw material bisphenol A (Reference Example 1) or bisphenol A-prill (a) (Reference Example 2) as a raw material, a 7.2% aqueous sodium hydroxide solution, 2.21 l (4.19 mol of sodium hydroxide) and 0.98 g (0.0056 mol) of sodium hydrosulfite were charged and dissolved, and methylene chloride, 1.27 l and 48.5 were stirred under stirring.
80.70 g (sodium hydroxide, 0.98 mol) of phosgene, 25%
0.80 g (0.253 mol) was added at 25 ° C. over 180 minutes to carry out a phosgenation reaction.

After completion of the phosgenation, p-tert-butylphenol, 17.51 g (0.117 mol), and 4
8.5% sodium hydroxide aqueous solution, 80.40 g
(0.97 mol) and triethylamine as catalyst,
1.81 ml (0.013 mol) was added, the mixture was kept at 33 ° C., and stirred for 2 hours to terminate the reaction. The methylene chloride layer was separated from the reaction mixture, and washed repeatedly with water five times to obtain a polycarbonate resin having a viscosity average molecular weight of 15,300. 0.01% by weight of tris (2,4-di-tert-butylphenyl) phosphite and 0.08% by weight of monoglyceride stearate were added to the obtained aromatic polycarbonate, and the mixture was kneaded and pelletized by a twin-screw extruder. The polymer hue in Reference Example 2 was as good as 0.7, compared to the color b value of 1.1 in Reference Example 1. The evaluation results of the obtained polycarbonate resin are summarized in Table 4 below.

[Examples 3 and 4, Comparative Example 2] Examples 1 and 2
In each of Comparative Example 1 and Comparative Example 1, the viscosity average molecular weight was 225.
The polymerization was continued until the temperature reached 00, at which point the terminal blocking agent 2-
Methoxycarbonylphenyl phenyl carbonate (S
AM), 265 ° C, 133.3 Pa
(1 mmHg) for 10 minutes, and then 6.9 × 10 ^-4 parts by weight of tetrabutylphosphonium dodecylbenzenesulfonate as a melt viscosity stabilizer was added, and 265 ° C.
The mixture was stirred at /66.7 Pa (0.5 mmHg) for 10 minutes. Finally, the viscosity average molecular weight is 15,300, the terminal OH concentration is 30, and the phenoxy terminal group concentration is 120 (eq / ton-P
C) An aromatic polycarbonate having a melt viscosity stability of 0 was obtained.

The above polycarbonate resin (5)
Table 1 below summarizes the evaluation results of -1 to 5) -3.

[0112]

[Table 4]

Example 5, Comparative Example 3 Tris (2, 4) was added to the aromatic polycarbonate of Example 1 and Comparative Example 1.
-Di-tert-butylphenyl) phosphite to 0.1.
01% by weight and 0.08% by weight of stearic acid monoglyceride were added. 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. DVD (DVD-Video)
o) A disk substrate temperature / humidity deterioration test was performed.

Injection molding machine, DISK3 manufactured by Sumitomo Heavy Industries, Ltd.
A mold dedicated to DVD is attached to M III, and a nickel DV containing information such as address signals is attached to the mold.
A stamper for D was mounted, and the pellets were put into a hopper of a molding machine by automatic conveyance. The conditions were as follows: cylinder temperature: 380 ° C., mold temperature: 115 ° C., injection speed: 200 mm / sec, holding pressure: 3432 kPa (35 kgf / cm ² ). To form a DVD disk substrate having a diameter of 120 mm and a thickness of 0.6 mm.

In order to test the reliability of the optical disk under severe temperature and humidity conditions for a long time, an aromatic polycarbonate optical disk substrate was heated at a temperature of 80 ° C. and a relative humidity of 85%.
After holding for 000 hours, the substrate was evaluated by the following measurements.

Number of white spots: The number of white spots of 20 μm or more was counted by observing the optical disk substrate after the heat and humidity deterioration test using a polarizing microscope. This is performed for 25 optical disc substrates (120 mm in diameter), and the average value is obtained.
This was defined as the number of white spots.

As a result, the number of white spots in Example 5 and Comparative Example 3 was 0.1 and 2.2, respectively.

Example 6 The aromatic polycarbonate of Example 3 was supplied in a fixed amount by a gear pump while maintaining the molten state, and sent to a T-die of a molding machine. 0.003% by weight of trisnonylphenyl phosphite before the gear pump
In addition, it was melt-extruded into a sheet having a thickness of 2 mm or 0.2 mm and a width of 800 mm by pinching or one-sided touch between the mirror-surface cooling roll and the mirror-surface roll.

A visible light-curable plastic adhesive [Adel BENEFIX PC Co., Ltd.] was applied to one side of the obtained aromatic polycarbonate sheet (2 mm thick), and the same sheet was extruded to one side so that air bubbles did not enter. After laminating, 5,000 mJ / cm ² by a light curing device equipped with a metal halide type dedicated to visible light.
JIS K
As a result of measuring in accordance with-6852 (test method for compressive shear bond strength of adhesive), the bond strength was 9.91 MPa (1
01Kgf / cm ² ).

On the other hand, an ink [Natsuda 70-9132: color] was coated on an aromatic polycarbonate sheet having a thickness of 0.2 mm.
136D smoke] and a solvent [isophorone / cyclohexane / isobutanol = 40/40/20 (wt.
%)], Mixed and printed with a silk screen printer, and dried at 100 ° C. for 60 minutes. There was no transfer failure on the printed ink surface, and printing was good.

Separately, a polycarbonate resin obtained by subjecting 1,1-bis (4-hydroxyphenyl) cyclohexane and phosgene to an ordinary interfacial polycondensation reaction (having a specific viscosity of 0.1%).
895, Tg 175 ° C) 30 parts, Plast as a dye
A sheet (0.2 mm thick) printed with a printing ink obtained by mixing 15 parts of Red 8370 (manufactured by Arimoto Chemical Industries) and 130 parts of dioxane as a solvent was mounted in an injection molding die, and polycarbonate resin pellets (panlite) were mounted. L-
Insert molding was performed at a molding temperature of 310 ° C. using a 1225 Teijin Chemicals Ltd.). An insert molded product having a good printed portion appearance was obtained without any abnormality such as bleeding or blurring in the printed portion pattern of the molded product after the insert molding.

[Examples 7 to 13] The aromatic polycarbonate of Example 3 was fed to an extruder by a gear pump while maintaining the molten state. In the middle of the extruder, 0.003% by weight of trisnonylphenyl phosphite and 0.05% by weight of trimethyl phosphate were added to obtain an aromatic polycarbonate pellet. After uniformly mixing the pellets and the components indicated by the following symbols in Tables 5 and 6 using a tumbler, a twin-screw extruder with a 30 mmφ vent (KTX-30 manufactured by Kobe Steel Ltd.) was used. Cylinder temperature 260 ° C., 1.33 kPa (10 m
The resulting pellets were dried at 120 ° C. for 5 hours, and the cylinder temperature was 270 ° C. using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.). A molded piece for measurement was prepared under the conditions of a mold temperature of 80 ° C., and the following evaluation was performed. The results are shown in Tables 5 and 6 below.

-1 ABS: styrene-butadiene-
Acrylonitrile copolymer; Santac UT-61; manufactured by Mitsui Chemicals, Inc.-2 AS: styrene-acrylonitrile copolymer;
Styrac-AS 767 R27; manufactured by Asahi Kasei Corporation-3 PET: polyethylene terephthalate; TR-
8580; Teijin Limited, intrinsic viscosity 0.8-4 PBT: polybutylene terephthalate; TRB
-H: Teijin Limited, intrinsic viscosity 1.07 -1 MBS: Methyl (meth) acrylate-butadiene-styrene copolymer; Kaneace B-56; Kanebuchi Chemical Industry Co., Ltd. -2E-1: Butadiene-alkyl acrylate-
Alkyl methacrylate copolymer; Paraloid EXL
-3E-2: Composite rubber having a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component having an interpenetrating network structure; Metablen S-2001;
Mitsubishi Rayon Co., Ltd. -1 T: Talc; HS-T0.8; Hayashi Kasei Co., Ltd.
, Average particle diameter L = 5 measured by laser diffraction method
μm, L / D = 8 −2 G: glass fiber; chopped strand ECS
-03T-511; manufactured by Nippon Electric Glass Co., Ltd., urethane focusing treatment, fiber diameter 13 μm −3 W: wollastonite; Psycatek NN-4;
Tomoe Kogyo Co., Ltd., number-average average fiber diameter D = 1.5 μm, average fiber length 17 μm determined by electron microscope observation,
Aspect ratio L / D = 20 WAX: Olefin wax obtained by copolymerization of α-olefin and maleic anhydride; DIAKARNA-P3
0; manufactured by Mitsubishi Kasei Corporation (maleic anhydride content = 10w)
t%)

(A) Flexural modulus The flexural modulus was measured according to ASTM D790. (B) Notched Impact Value According to ASTM D256, a 3.2 mm thick test piece was used to impact a weight from the notch side, and the impact value was measured. (C) Fluidity Cylinder temperature 250 ° C, mold temperature 80 ° C, injection pressure 9
The fluidity was measured at 8.1 MPa by Archimedes-type spiral flow (thickness 2 mm, width 8 mm). (D) Chemical Resistance A 1% strain was applied to a tensile test piece used according to ASTM D638, and the test piece was immersed in Esso regular gasoline at 30 ° C. for 3 minutes, and then the tensile strength was measured to calculate the retention.
The retention was calculated by the following equation. Retention (%) = (strength of treated sample / strength of untreated sample) × 100

[0125]

[Table 5]

[0126]

[Table 6]

[0127]

As described in the present invention, an aromatic dihydroxy compound having a spherical shape with a specific particle size distribution, a specific surface area and a pore volume of a specific value or less, and more preferably a specific color tone, is obtained by preparing an aromatic polycarbonate. By using it as a raw material,
An aromatic polycarbonate having high durability and excellent color tone, transparency and mechanical strength can be produced. The molded product obtained from the aromatic polycarbonate produced by the present invention is excellent in color tone and transparency, and in particular, the disk substrate molded using the polycarbonate produced by the present invention can be used for a long time under severe temperature and humidity conditions. Even in use, good stability can be maintained, and higher reliability can be obtained as compared with a disk substrate obtained from a conventional aromatic polycarbonate.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuichi Kageyama 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. Inside the Iwakuni Research Center (72) Inventor Katsuji Sasaki 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Shares F-term in the Iwakuni Research Center (reference) 4F071 AA50 AF29 AH12 AH19 BB05 BC07 4J029 AA09 AB04 AB07 AC01 AE01 AE05 BB12A BB13A BB13B BD09A BG08X BH02 DB07 DB13 HC03 HC04A HC05A JA091 J121 J051J01J01J01J051 JF031 JF041 JF051 JF581 KA02 KB05 KE05 5D029 KA08

Claims (5)

[Claims] 1. A) a nitrogen-containing basic compound and / or a phosphorus-containing basic compound in an amount of 10 to 1000 .mu.m equivalents / 1 mol of aromatic dihydroxy compounds, and a) an alkali metal compound and / or an alkaline earth metal compound 0.05. ~
In a method for producing an aromatic polycarbonate, in which an aromatic dihydroxy compound and a carbonic acid diester are polycondensed in the presence of a catalyst containing 5 µ chemical equivalents / one mole of an aromatic dihydroxy compound, the aromatic dihydroxy compound has spherical prill and diameter A method for producing a polycarbonate, characterized by using a prill having a distribution ratio of 0.1 to 3 mm of 70 wt% or more, a specific surface area of ≦ 0.2 m ² / g and a pore volume of ≦ 0.1 ml / g. 2. The method according to claim 1, wherein said aromatic dihydroxy compound has a prill hue; color L value ≧ 80 and color b value ≦ 2. 3. The distribution ratio of spherical prill as an aromatic dihydroxy compound having a diameter of 0.1 to 3 mm is 7%.
An aromatic polycarbonate obtained by polycondensing an aromatic dihydroxy compound having a specific surface area of ≦ 0.2 m ² / g and a pore volume of ≦ 0.1 ml / g with carbonic acid diesters in an amount of 0 wt% or more. 4. A molded article of the aromatic polycarbonate according to claim 3. 5. The molded product according to claim 4, wherein the molded product is an optical disk substrate.