JP2003096181A - Method for producing stabilized aromatic polycarbonate, and its composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate having a small haze value after molded and exhibiting a slight increase in the haze value after maintained under a high-temperature and high-humidity condition, and to provide an aromatic polycarbonate hardly suffering from discoloration after stayed in a melt state and exhibiting excellent resistance to hydrolysis, and its composition. SOLUTION: An aromatic dihydroxy compound and a carbonate diester are subjected to polycondensation in the presence of a transesterification catalyst to give an aromatic polycarbonate having an intrinsic viscosity of at least 0.1, and subsequently at least one stabilizer derived from a sulfate is added in an amount of 0.01 ppm to 1 wt.% based on the thus-obtained aromatic polycarbonate to give an aromatic polycarbonate having a desired intrinsic viscosity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention firstly relates to the above formula (1).
The present invention relates to a stabilizer of a transesterified aromatic polycarbonate derived from a sulfate represented by Secondly, it relates to a method for producing an aromatic polycarbonate stabilized by the stabilizer. More specifically, it relates to a method for producing an excellent stabilized aromatic polycarbonate having good transparency and a small haze. Furthermore, the present invention thirdly relates to application of the stabilized aromatic polycarbonate produced by the first method to an optical disc substrate and an optical disc substrate obtained from the aromatic polycarbonate.

The present invention further relates to a composition of a stabilized aromatic polycarbonate produced by the fourth method and a solid inorganic filler, and / or a thermoplastic resin other than the stabilized aromatic polycarbonate. Regarding things.

[0003]

Aromatic polycarbonates are excellent in mechanical properties such as impact resistance, heat resistance and transparency.
It is used for a wide range of purposes. Generally, as a method for producing an aromatic polycarbonate, a method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene which is one of carbonate bond-forming precursors (interfacial polymerization method), or an aromatic dihydroxy compound is used. A method of transesterifying a carbonic acid diester, which is one of the carbonate bond-forming precursors (transesterification method), is known.

A method for producing an aromatic polycarbonate by a transesterification reaction (transesterification method) between an aromatic dihydroxy compound and a carbonic acid diester is more toxic than a method by an interfacial polymerization method, such as toxic phosgene and halogen compounds such as methylene chloride. There is no problem of using as a solvent, there is an advantage that aromatic polycarbonate can be produced at low cost,
Considered to be promising in the future. In the polymerization method by a transesterification reaction, in order to improve the production efficiency, a transesterification catalyst is usually used as described in the literature such as Plastic Material Course 5 Aromatic Polycarbonate; Nikkan Kogyo Shimbun (Showa 44), pages 62-67. .

However, in the transesterification method, since an alkali metal compound, an alkaline earth metal compound or the like is usually used as a transesterification catalyst, the aromatic polycarbonate lacks melt stability due to the remaining catalyst, and when it is melt-molded, it is one of them. The part may be thermally decomposed and the molecular weight may be reduced or it may be colored. In order to suppress these undesirable side reactions, various "sulfonic acid derivative" applications have been investigated as described below.

That is, Japanese Patent Publication No. 54-44303 discloses a composition obtained by blending an aromatic polycarbonate with a sulfonic acid ester represented by methyl benzenesulfonate, and Japanese Patent Laid-Open No. 171024/1993 discloses a phosphonium sulfonate salt. A composition incorporated into an aromatic polycarbonate is disclosed. Further, JP-A 64-14267 discloses a composition in which a phosphite ester is blended in place of the sulfur-containing compound in the above composition.

All of the compositions containing the phosphonium sulfonate are intended to impart a stabilizer and an antistatic property to the aromatic polycarbonate, and the phosphonium sulfonate is used in an amount of 0 parts by weight per 100 parts by weight of the aromatic polycarbonate. Since it is used in a large amount of 1 to 20 parts by weight, hue, transparency, which are important physical properties of the aromatic polycarbonate,
There is an unfavorable effect on hydrolysis resistance.

Further, in JP-A-5-9285, JP-A-5-17564, JP-A-8-59975 and the like, an aromatic compound obtained by melt polycondensation of an aromatic cyhydroxy compound and a carbonic acid diester is disclosed. A method for stabilizing an aromatic polycarbonate by adding a very small amount of a sulfonic acid compound in an amount of 0.05 to 10 ppm to the polycarbonate is disclosed, and a desired effect is given to the stabilization of the aromatic polycarbonate.

However, when such a sulfonic acid derivative is applied to an aromatic polycarbonate, not only a composition containing a relatively large amount of the sulfonic acid derivative for the purpose of a stabilizer and antistatic property but also for the purpose of deactivating a transesterification catalyst. In addition, even in an aromatic polycarbonate to which the sulfonic acid derivative is added in a small amount, the transparency originally possessed by the aromatic polycarbonate is impaired, and haze tends to be high in a molded article. Further, the haze of the aromatic polycarbonate to which a small amount of the sulfonic acid derivative is added tends to be deteriorated by holding the molded product at high temperature and high humidity for a long time.

Although the cause is not clear, it is presumed that the cause may be an increase in water absorption in this region when these sulfonic acid derivatives have a locally high concentration in the aromatic polycarbonate.

Further, in British Patent 808488 and British Patent 808489, dimethyl sulfate as a catalyst neutralizing agent,
Although dibutyl sulfate and the like are exemplified, these sulfuric acid compounds have a problem in safety and it is not considered to use these compounds industrially.

[0012]

DISCLOSURE OF THE INVENTION In the present invention, a sulfate having a specific chemical structure is effective as a stabilizer of a transesterification aromatic polycarbonate, and the stabilizer is added to the transesterification aromatic polycarbonate. , An aromatic polycarbonate having good melt viscosity stability, melt moldability, and hydrolysis resistance can be obtained, and at the same time, the aromatic polycarbonate has excellent transparency, which is an original property of the aromatic polycarbonate, and has a conventional sulfonic acid derivative. Is applied to an aromatic polycarbonate produced by the transesterification method to attain a haze value that cannot be obtained.

[0013]

That is, in the present invention, the first aspect of the present invention is a stabilizer for an aromatic polycarbonate by a transesterification method of a sulfate having a specific chemical structure.
In the second invention, an aromatic dihydroxy compound and a carbonic acid diester are polycondensed in the presence of a transesterification catalyst, and the resulting aromatic polycarbonate has an intrinsic viscosity of at least 0.
After reaching 1, the following formula (1)

[0014]

[Chemical 7]

(In the formula, X and Y each independently represent a proton, 1 equivalent metal cation, an ammonium cation, or a phosphonium cation, provided that both X and Y are not a proton and 1 equivalent metal cation at the same time. ) At least one selected from the group of compounds represented by
A stabilized aromatic polycarbonate, characterized by comprising adding a stabilizer of 0.01 ppm to 1 wt% with respect to the produced aromatic polycarbonate to produce an aromatic polycarbonate having a desired intrinsic viscosity. Regarding the manufacturing method. Furthermore, a third invention relates to a stabilized aromatic polycarbonate produced by the production method of the second invention, further application of the aromatic polycarbonate to an optical disc substrate, and an optical disc substrate obtained from the aromatic polycarbonate. Further, a fourth invention relates to a composition of the stabilized aromatic polycarbonate produced by the production method of the second invention, a solid inorganic filler, and / or a thermoplastic resin other than the aromatic polycarbonate.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION (Stabilizer of the Present Invention) The stabilizer used in the present invention is represented by the following formula (1).

[0017]

[Chemical 8]

(In the formula, X and Y each independently represent a proton, 1 equivalent metal cation, ammonium cation, or phosphonium cation, provided that both X and Y are not proton, 1 equivalent metal cation at the same time. ) Is a stabilizer of a transesterification aromatic polycarbonate obtained by polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a transesterification catalyst. More preferably, in the above formula (1), X and Y are each independently a proton, 1 equivalent metal cation, and the following formula (1)-
a

[0019]

[Chemical 9]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms) or the following formula: (1) -b

[0021]

[Chemical 10]

(In the formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms), which is a phosphonium cation transesterification. It is a stabilizer of aromatic polycarbonate for process.

As one equivalent metal cation, for example, an alkali metal cation such as lithium, sodium or potassium; a divalent alkaline earth metal cation such as calcium or barium, or a divalent metal cation other than the alkaline earth metal cation. / 2 equivalents; or 1/3 equivalent of a trivalent metal cation such as aluminum.

In the present invention, the above formula (1) is preferred.
Wherein X and Y are each independently a proton, 1 equivalent metal cation, and the following formula (1) -a

[0025]

[Chemical 11]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms) or the following formula: (1) -b

[0027]

[Chemical 12]

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms). preferable.

In the above formulas (1) -a and (1) -b,
R ^{1 to} R ⁸ are each independently a hydrogen atom or a carbon number of 1 to 20.
The monovalent hydrocarbon group of is preferable. Carbon number 1
Examples of the monovalent hydrocarbon having 20 have, for example, 1 to 20 carbon atoms.
Are preferred examples of the alkyl group, the cycloalkyl group having 5 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms.

More specifically, examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, iso-propyl group, n-propyl group, n-butyl group, sec-butyl group, tert-butyl group and hexyl group. Group, octyl group, decyl group, hexadecyl group and the like. 5 to 2 carbon atoms
Examples of the cycloalkyl group of 0 include cyclopentyl group, cyclohexyl group, decahydronaphthyl group, 3,5,5-trimethylcyclohexyl group, and the like, and examples of aryl group having 6 to 20 carbon atoms include phenyl group, tolyl group, xylyl group,
a p-tert-butylphenyl group, a naphthyl group, etc., and a benzyl group as an aralkyl group having 7 to 20 carbon atoms,
Examples thereof include a phenethyl group and a cumyl group. Of these, a lower alkyl group such as a methyl group, an ethyl group and an n-butyl group, a phenyl group and the like are exemplified as preferable ones.

More specific sulfates represented by the above formula (1) include (1) diphosphonium sulfate sulfate, (2) phosphonium hydrogen sulfate salt, (3) metal phosphonium sulfate salt,
(4) phosphonium ammonium sulfate, (5) diammonium sulfate, (6) ammonium hydrogensulfate,
(7) Examples include metal ammonium sulfate salts. Specific examples of these compounds include (1) diphosphonium sulfate salts such as bis (tetramethylphosphonium) sulfate, tetramethylphosphonium tetraethylphosphonium sulfate, tetraoctylphosphonium tetrapropylphosphonium sulfate, bis (methyltriethylphosphonium) sulfate , Tetramethylphosphonium sulfate, tetrabutylphosphonium sulfate, bis (tetrabutylphosphonium) sulfate, bis (tetraethylphosphonium) sulfate, bis (diethyldibutylphosphonium) sulfate, bis (tetradecylphosphonium) sulfate, bis (tetraphenylphosphonium) sulfate, bis sulfate (Trimethylphenylphosphonium), bis (tetrabenzylphosphonium) sulfate, bis (triethylbenzylphosphonium) sulfate and the like. (2) Examples of the phosphonium hydrogen sulfate salt include tetramethylphosphonium hydrogen sulfate, tetrabutylphosphonium hydrogen sulfate, tetrapropylphosphonium hydrogen sulfate, tetraoctylphosphonium hydrogen sulfate, tetraphenylphosphonium hydrogen sulfate, ethyltributylphosphonium hydrogen sulfate, and trimethyloctyl hydrogen sulfate. Examples thereof include phosphonium, tetrabenzylphosphonium hydrogen sulfate, diethyldibutylphosphonium hydrogen sulfate, and benzyltrimethylphosphonium hydrogen sulfate. (3) Examples of metal phosphonium sulfate salts include sodium tetrabutylphosphonium sulfate, potassium tetramethylphosphonium sulfate, lithium dimethyldiethylphosphonium sulfate, lithium trimethylbenzylphosphonium sulfate, lithium tripropylbutylphosphonium sulfate, sodium trimethyloctylphosphonium sulfate, and the like. To be (4) Examples of the phosphonium ammonium sulfate salt include tetramethylammonium tetraethylphosphonium sulfate, tetraoctylammonium tetrapropylphosphonium sulfate, tetramethylammonium tetrabutylphosphonium sulfate, and tetraphenylammonium tetraethylphosphonium sulfate. (5) Examples of the diammonium sulfate include bis (tetramethylammonium) sulfate, tetramethylammonium tetraethylammonium sulfate, tetraoctylammonium tetrapropylammonium sulfate, bis (methyltriethylammonium) sulfate, tetramethylammonium tetraethylammonium sulfate, Bis (tetrabutylammonium sulfate), bis (diethyldibutylammonium sulfate), bis (tetradecylammonium) sulfate, bis (tetraphenylammonium sulfate), bis (trimethylphenylammonium sulfate), bis (tetrabenzylammonium sulfate), bisulfate sulfate (Triethylbenzylammonium) and the like. (6) Examples of ammonium hydrogensulfate include tetramethylammonium hydrogensulfate, tetrabutylammonium hydrogensulfate, tetrapropylammonium hydrogensulfate, tetraoctylammonium hydrogensulfate, tetraphenylammonium hydrogensulfate, ethyltributylammonium hydrogensulfate and trimethyl hydrogensulfate. Examples thereof include octyl ammonium, tetrabenzyl ammonium hydrogen sulfate, diethyl dibutyl ammonium hydrogen sulfate, and benzyl trimethyl ammonium hydrogen sulfate. (7) Examples of the ammonium metal sulfate include sodium tetrabutylammonium sulfate, potassium tetramethylammonium sulfate, lithium dimethyldiethylammonium sulfate, lithium trimethylbenzylammonium sulfate, lithium tripropylbutylammonium sulfate, and sodium trimethyloctylammonium sulfate. To be

Among these, diphosphonium sulfate salts,
Phosphonium hydrogensulfate, diammonium sulfate, and the like are preferable because they have a large effect of suppressing the haze of the aromatic polycarbonate molded article which is the object of the present invention. Further, among the stabilizers represented by the above formula (1), the diphosphonium salt type stabilizers are more preferable because they have high thermal stability and are resistant to decomposition during storage and easy to handle.

That is, bis (tetrabutylphosphonium) sulfate, bis (tetraethylphosphonium) sulfate, bis (tetraphenylphosphonium) sulfate, tetraethylphosphonium tetrabutylphosphonium sulfate, tetramethylphosphonium hydrogen sulfate, bis (tetramethylammonium) sulfate, bisulfate sulfate (Tetraethylammonium) and the like are exemplified as the most preferable one in the present invention.

When the stabilizer represented by the above formula (1) is added to the aromatic polycarbonate, the catalyst is promptly detoxified, and the melt viscosity stability, melt moldability and hydrolysis resistance are good. Stable burning is less likely to occur, transparency,
An aromatic polycarbonate having a good haze can be obtained.

In the production method of the present invention, an aromatic polycarbonate having at least one stabilizer selected from the group consisting of the compounds represented by the above formula (1) is added to the aromatic polycarbonate.
It is added at a rate of 01 ppm to 1 wt%. 0.01 to 1000 pp when the main purpose is to detoxify the catalyst.
m, preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm. In such a production method, theoretically, it is sufficient to use 1 equivalent to 1 equivalent of the transesterification catalyst, but generally 0.5 to 100 equivalents, preferably 0.5 to 50 equivalents, More preferably, it is used in a proportion of 0.6 to 30 equivalents, and most preferably 0.6 to 20 equivalents. A more preferred production method is 0.5 to 100 equivalents, preferably 0.5 to 50 equivalents, per 1 equivalent of the alkali metal compound catalyst or alkaline earth metal compound catalyst contained in the aromatic polycarbonate in which the stabilizer is produced. More preferably 0.6-
It is to be used in a ratio of 30 equivalents, most preferably 0.6 to 20 equivalents.

(Aromatic Polycarbonate Used in the Present Invention) The aromatic dihydroxy compound used in producing the aromatic polycarbonate in the present invention has the following formula (2):

[0037]

[Chemical 13]

(In the formula, R ²¹ , R ²² , R ²³ , and R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, and an aralkyl having 7 to 20 carbon atoms. Group, an aralkyloxy group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, W is a single bond, an alkylidene group having 2 to 10 carbon atoms, and a carbon number. 1 to 10 alkylene group, 5 to 5 carbon atoms
20 cycloalkylidene group, C5-20 cycloalkylene group, C6-20 arylene group, C7-20 phenyl group substituted alkylene group, C8-2
0 is an alkylidene-arylene-alkylidene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group. Compounds represented by the formula (1) are preferred.

Specific examples of such an aromatic dihydroxy compound include 4,4'-dihydroxydiphenyl,
Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylethane, 2,2
-Bis (4-hydroxyphenyl) propane (commonly abbreviated as bisphenol A, BPA), 2,2-bis (4
-Hydroxy-3-methylphenyl) propane, 2,2
-Bis (4-hydroxy-3-phenylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-Trimethylcyclohexane, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl)-
p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
-Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether and the like can be mentioned.

Further, aromatic dihydroxy compounds not included in the above formula (2), which are preferably used in the present invention, are 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4). -Hydroxy-3-methylphenyl) fluorene, 2,2
2 ', 2'-Tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobis [1H-indene]-
6,6'-diol, 1,4-dihydroxybenzene,
1,3-dihydroxybenzene etc. are mentioned.

In the present invention, the aromatic dihydroxy compound represented by the above formula (2) and the aromatic dihydroxy compound not included in the above formula (2) may be used alone or in combination of two or more.

Among them, bisphenol A, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
9,9-bis (4-hydroxyphenyl) fluorene,
9,9-bis (4-hydroxy-3-methylphenyl)
Fluorene, 1,1-bis (4-hydroxyphenyl)
At least one selected from the group consisting of cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene. The homopolymers or copolymers obtained by using the bisphenol are preferable, and the homopolymer of bisphenol A and the copolymer mainly containing bisphenol A are preferably used.

In addition, various compounds other than those mentioned above may be incorporated into the aromatic polycarbonate main chain for the desired purpose within the range not deviating from the object of the present invention.

For example, ethylene glycol, 1,4-butanediol, polyethylene glycol, 1,4-cyclohexanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8, Aliphatic and alicyclic diols and polyols such as 10-tetraoxaspiro [5.5] undecane and tricyclodecanedimethanol; 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1 , 2,2-Tetrakis (3-methyl-4-hydroxyphenyl) ethane and other aromatic polyhydroxy compounds; lactic acid, parahydroxybenzoic acid, 6
-Hydroxy-2-naphthoic acid and other aliphatic and aromatic hydroxycarboxylic acids; adipic acid, dodecanedioic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, pyromellitic acid, trimellitic acid and other dicarboxylic acids, poly Examples thereof include carboxylic acids.

The carbonic acid diester used in producing the aromatic polycarbonate may be an optionally substituted aryl group having 6 to 10 carbon atoms or 7 to 10 carbon atoms.
Are preferably carbonic acid diesters such as aralkyl groups, alkyl groups having 1 to 10 carbon atoms, and cycloalkyl groups having 5 to 10 carbon atoms. Specific examples include diphenyl carbonate (hereinafter sometimes abbreviated as DPC), ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, dimethyl carbonate,
Diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. are used. Of these, diphenyl carbonate is preferred in terms of reactivity, purity and cost.

The transesterification catalyst used in the present invention is preferably one which uses the above-mentioned carbonic acid diester and aromatic dihydroxy compound as a starting material and gives a good quality aromatic polycarbonate polymer with less side reactions, less coloring and the like. . Further, it is more preferable that the reaction product of the transesterification catalyst and the stabilizer of the present invention does not cause an undesired side reaction with various additives conventionally blended in the aromatic polycarbonate.

For example, at least one selected from the group consisting of alkali metal compounds or alkaline earth metal compounds, and nitrogen-containing basic compounds or phosphorus-containing basic compounds which are organic basic compounds. A catalyst is preferably used. It may also be advantageous to use other catalysts in combination with these transesterification catalysts.

Examples of the alkali metal compound and the alkaline earth metal compound as the transesterification catalyst include hydroxides, hydrocarbon compounds, carbonates, carboxylates, nitrates,
Examples thereof include nitrite, sulfite, cyanate, thiocyanate, borohydride, phosphoric hydride and aromatic hydroxy compound salt.

Specific examples of the alkali metal compound include lithium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, lithium hydrogen carbonate, potassium hydrogen carbonate,
Rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate,
Lithium acetate, sodium acetate, potassium acetate, rubidium acetate, lithium stearate, rubidium stearate, cesium stearate, lithium benzoate, sodium benzoate, rubidium benzoate, cesium benzoate, cesium nitrate, rubidium nitrite, potassium sulfite, Lithium cyanate, sodium cyanate, rubidium cyanate, cesium cyanate, lithium thiocyanate, potassium thiocyanate, rubidium thiocyanate,
Cesium thiocyanate, lithium borohydride, sodium borohydride, potassium borohydride, potassium tetraphenyl borohydride, dilithium phosphite, potassium hypophosphite,
Dilithium hydrogen phosphate, trilithium phosphate, dilithium salt of bisphenol A, monolithium salt, lithium sodium salt, lithium phenoxide, sodium phenoxide, rubidium phenoxide, cesium phenoxide, lithium 2,6-di-t-butyl-4-methyl Phenoxide, sodium 2,6-di-t-butyl-4-methylphenoxide, rubidium 2,6-di-t-butyl-4-methylphenoxide, cesium 2,6-di-t-
Butyl-4-methylphenoxide and the like can be mentioned.

Specific examples of the alkaline earth metal compound include calcium hydroxide, strontium hydroxide, barium hydrogen carbonate, barium carbonate, magnesium carbonate, barium acetate, magnesium myristate, strontium benzoate, calcium cyanate, barium cyanate, Examples thereof include calcium thiocyanate and barium thiocyanate. Examples include calcium hydroxide, strontium hydroxide, barium hydrogen carbonate, magnesium carbonate, barium acetate, magnesium myristate, and strontium benzoate.

In order to achieve the object of the present invention more preferably, the alkali metal compound which is a transesterification catalyst component is a metal compound selected from lithium, rubidium and cesium (hereinafter abbreviated as a lithium metal compound or the like). It is preferred to use a catalyst containing Among them, it is preferable to use a metal compound selected from rubidium and cesium.

The amount of these polymerization catalysts used in the present invention is 0.01 to 5 as the total amount of the alkali metal and alkaline earth metal compounds per mol of the aromatic dihydroxy compound.
μ stoichiometric equivalent, preferably 0.02 to 3 μ stoichiometric equivalent, and more preferably 0.02 to 2.5 μ stoichiometric equivalent. Of these usage modes, it is possible to use only the lithium metal compound or the like, but the combined use with other alkali metal compounds and alkaline earth metal compounds is also a preferable method. In this case, the amount of the lithium metal compound or the like used is 0.3 or more, preferably 0.4 or less, in a chemical equivalent ratio to the total amount of the alkali metal and alkaline earth metal compounds.
Above, more preferably 0.5, particularly preferably 0.7 or more is selected. By using a catalyst containing a lithium metal compound or the like as a transesterification catalyst component in such an amount ratio, and using it in combination with a stabilizer having a specific chemical structure of the present invention, the aromatic polycarbonate itself or an aromatic amino group, an aliphatic ester With respect to an additive having an unstable functional group such as a group, it has an advantage that various undesirable side reactions such as decomposition and coloring can be more effectively suppressed.

In the present invention, a nitrogen-containing basic compound, which is an organic basic compound, and / or a phosphorus-containing basic compound are used in combination for the purpose of increasing the transesterification rate of the aromatic polycarbonate and improving the production efficiency of the aromatic polycarbonate. Things are preferred.

Specific examples of these nitrogen-containing basic compounds include quaternary ammonium hydroxides having an alkyl, aryl or alkylaryl group such as tetramethylammonium hydroxide and benzyltrimethylammonium hydroxide; tetramethylammonium Alkyl such as acetate, tetraethylammonium phenoxide, tetrabutylammonium carbonate, benzyltrimethylammonium benzoate,
Basic ammonium salts having an aryl or alkylaryl group; tertiary amines such as triethylamine and dimethylbenzylamine; or basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride and tetramethylammonium tetraphenylborate And so on.

Specific examples of the phosphorus-containing basic compound include:
Tetrabutylphosphonium hydroxide, benzyltrimethylphosphonium hydroxide, and other quaternary phosphonium hydroxides having an alkyl, aryl, or alkylaryl group, or tetramethylphosphonium borohydride, tetrabutylphosphonium borohydride, tetramethylphosphonium tetraphenyl Examples thereof include basic salts such as borate and the like.

The above-mentioned nitrogen-containing basic compound and phosphorus-containing basic compound have a basic nitrogen atom or basic phosphorus atom of 10 to 1000 μm per 1 mol of the aromatic dihydroxy compound.
It is preferable to use it in a ratio that provides a chemical equivalent. A more preferable usage ratio is a ratio of 20 to 500 μ chemical equivalent with respect to the same standard. A particularly desirable ratio is 5 based on the same criteria.
It is a ratio of 0 to 500 μ chemical equivalent.

Further, the aromatic polycarbonate of the present invention is preferably produced by a melt polymerization method in which the aromatic dihydroxy compound and the carbonic acid diester are heated and melt-reacted in the presence of an ester exchange catalyst. As the polymerization method in this case, the known method described in JP-A-8-59975 can be used.

By appropriately selecting the above conditions, the repeating unit used in the present invention is represented by the following formula (3).

[0059]

[Chemical 14]

(Where R^{twenty one}, R^{twenty two}, R^{twenty three}, R^{twenty four}Are each
R in the above formula (2)^{twenty one}, R^{twenty two}, R^{twenty three}, R ^{twenty four}Same as the definition of
It An aromatic polycarbonate represented by
Substitution of aromatic polycarbonate represented by the above formula (3)
Group R^{twenty one}, R^{twenty two}, R^{twenty three}, R^{twenty four}Is preferably used in the present invention described above.
Examples of aromatic dihydroxy compounds
Substituents corresponding to the compound are preferred. See also W
Also in the above, the aromatic dihydroxy compounds preferably used in the present invention described above.
The groups corresponding to the compounds exemplified in the explanation of the droxy compound are
It is preferably given.

(End group) The aromatic polycarbonate of the present invention has a main end group structure consisting of an aryloxy group and a phenolic hydroxyl group, and the phenolic hydroxyl group concentration is 5 to 60 mol% based on all the terminal groups. Is preferred. The phenolic hydroxyl group concentration is more preferably 10 to 50 mol%, and further preferably 10 to 40 mol%. Particularly preferably, it is characterized by containing 15 to 30 mol%. The main terminal group structure consisting of an aryloxy group and a phenolic hydroxyl group means that 95 mol% or more of all terminal groups consist of an aryloxy group and a phenolic hydroxyl group. When the aromatic polycarbonate of the present invention is injection-molded, the phenolic hydroxyl group is contained in such an amount ratio, and this has the advantage of better transferring the shape of the mold.

It is considered that by containing the phenolic hydroxyl group in such an amount ratio, the motility of the end of the aromatic polycarbonate molecule is controlled within the range in which the transferability is improved.

Even if the concentration of the phenolic hydroxyl group is reduced to less than 5 mol%, the transferability is not further improved. Further, when the phenolic hydroxyl group concentration exceeds 60%, the composition obtained from the aromatic polycarbonate is burnt in the molded article, which is presumed to be caused by the oxidation reaction, during injection molding, and the object of the present invention is Not good for

The aryloxy group has 1 to 20 carbon atoms.
A phenoxy group in which the hydrocarbon group is substituted or unsubstituted is preferably selected. From the viewpoint of thermal stability, the substituent is preferably a tertiary alkyl group, a tertiary aralkyl group, an aryl group or simply a hydrogen atom. A substance having a hydrogen atom at the benzyl position can be used if it has a desired purpose such as improvement in resistance to actinic radiation, but it is better to avoid it from the viewpoint of stability against heat, heat aging, thermal decomposition and the like.

Specific examples of the aryloxy group preferable from the viewpoint of transferability include phenoxy group, 4-t-butylphenyloxy group, 4-t-amylphenyloxy group, and 4
-Phenylphenyloxy group, 4-cumylphenyloxy group and the like. The position of the substituent of the phenyloxy group is not limited to the 4-position as described above, but the presence of a small amount of those having a substituent at the 2-position may be preferable from the viewpoint of fluidity.

In the interfacial polymerization method, the concentration of the terminal phenolic hydroxyl group is suppressed within the range of 5 to 60 mol% by the molecular weight modifier, but in the melt polymerization method, the terminal phenolic hydroxyl group is 60 mol% in terms of chemical reaction. , Or more, it is necessary to positively decrease the terminal phenolic hydroxyl groups.

That is, the terminal phenolic terminal group concentration can be controlled within the above range by the conventionally known method 1) or 2) described below. 1) Method for controlling molar ratio of charged raw materials for polymerization; this can be achieved by increasing the molar ratio of carbonic acid diester / aromatic dihydroxy compound at the time of charging the polymerization reaction. Although it is necessary to specifically consider the characteristics of the polymerization reactor, the molar ratio is set between 1.03 and 1.10. 2) End capping method: At the time of completion of the polymerization reaction, for example, the terminal phenolic hydroxyl group is capped with the salicylic acid ester compound described in the literature in the above specification according to the method described in US Pat. No. 5,696,222.

When the terminal phenolic hydroxyl group is sealed with a salicylic acid ester compound, the amount of the salicylic acid ester compound used is 0.8 to 10 mol per 1 chemical equivalent of the terminal phenolic hydroxyl group before the sealing reaction. It is preferably in the range of 0.8 to 5 mol, particularly preferably 0.9 to 2 mol. By adding in such an amount ratio, 80 mol% or more of the terminal phenolic hydroxyl group can be suitably sealed. Further, it is preferable to use the catalyst described in the above patent when carrying out the sealing reaction.

The reduction of the terminal phenolic hydroxyl group concentration according to the method 2) is achieved by the formula (1) for detoxifying the polymerization catalyst.
It is preferably carried out before the addition of the stabilizer represented.

The salicylic acid ester compounds include
The salicylic acid ester compounds described in US Pat. No. 5,696,222 can be preferably used, and specifically, 2-
2-Methoxycarbonylphenyl aryl carbonates such as methoxycarbonylphenyl-phenyl carbonate, 2-methoxycarbonylphenyl-alkyl carbonates such as 2-methoxycarbonylphenyl-lauryl carbonate, aromatic carvone such as (2-methoxycarbonylphenyl) benzoate (2'-methoxycarbonylphenyl) ester of acid, (2
And aliphatic carboxylic acid esters such as -methoxycarbonylphenyl) stearate and bis (2-methoxycarbonylphenyl) adipate.

(Various Additives) (Release Agent) In the aromatic polycarbonate of the present invention, in order to improve the releasability of the molded product from the mold at the time of molding, 10 to 10 carbon atoms are added per 100 parts by weight of the aromatic polycarbonate.
It is preferable to contain 5 × 10 ⁻³ to 2 × 10 ⁻¹ parts by weight of a fatty acid ester compound formed from 25 aliphatic monocarboxylic acids and an aliphatic polyhydric alcohol having 2 to 10 carbon atoms as a release agent. By including the release agent in such an amount ratio, for example, when molding an optical disc substrate, it is possible to stably take out the disc substrate from the mold without deforming the grooves, pits, etc. transferred from the stamper to the substrate surface. Can be implemented. In order to achieve the above object, it is preferable that the aliphatic monocarboxylic acid having 10 to 25 carbon atoms and the carbon number of 2 to 1 per 100 parts by weight of the aromatic polycarbonate of the present invention.
The fatty acid ester compound obtained from the aliphatic polyhydric alcohol of 0 is 5 × 10 ⁻³ to 1 × 10 ⁻¹ parts by weight, more preferably 7.5 × 10 ^{−3 to} 7 × 10 ⁻² parts by weight, and further preferably It is preferably added in the range of 1 × 10 ^{−2 to} 5 × 10 ⁻² parts by weight.

The aliphatic monocarboxylic acid having 10 to 25 carbon atoms in the present invention includes an aliphatic linear or branched carboxylic acid and also a saturated or unsaturated carboxylic acid.

Specific examples of the saturated aliphatic monocarboxylic acid include lauric acid, which is a linear carboxylic acid,
Myristic acid, palmitic acid, stearic acid, and branched fatty acids isodecanoic acid, isotridecanoic acid, isomyristic acid [mixture represented by the following formula (4)],

[0074]

[Chemical 15]

Isopalmitic acid [the following formula (5)],

[0076]

[Chemical 16]

Isostearic acid [the following formula (6)],

[0078]

[Chemical 17]

Isoarachidic acid [the following formula (7)],

[0080]

[Chemical 18]

Isohexacoic acid [the following formula (8)],

[0082]

[Chemical 19]

And the like. Other aliphatic unsaturated carboxylic acids, oleic acid, linoleic acid, linolenic acid,
5,8,11,14-eicosatetraenoic acid, 4,7,
Examples include 10,13,16,19-docosahexaenoic acid.

The aliphatic polyhydric alcohol having 2 to 10 carbon atoms of the present invention is specifically ethylene glycol,
Examples include propylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, or 1,4-butenediol, and sorbitol and sorbitan.

Specific examples of the fatty acid ester compound obtained from the aliphatic monocarboxylic acid having 10 to 25 carbon atoms and the aliphatic polyhydric alcohol having 2 to 10 carbon atoms include at least one of the above aliphatic monocarboxylic acids. , A fatty acid ester compound produced from at least one of the above aliphatic polyhydric alcohols.

Of these, among the fatty acid ester compounds obtained from polyhydric alcohols and aliphatic monocarboxylic acids, HL
A fatty acid ester compound having a B value of 3 to 7 is preferable, and a fatty acid ester compound having an HLB value of 3 to 6 is more preferable because the mold releasing property is good and the molding die is less contaminated.

The HLB value is an abbreviation for hydrophile-lipophile balance as described in, for example, [Surfactant; (Kodansha); Fumio Kitahara and 3 others; p24], and represents a hydrophilic / hydrophobic balance. It is a parameter.
Specific examples of the fatty acid ester compound satisfying the parameter range include ethylene glycol monoisopalmitate, propylene glycol dioleate, 1,
4-butanediol diisopalmitate, 1,4-butenediol diisostearate, 1,4-butenediol monostearate, glycerol monolaurate, glycerol monomyristate, glycerol monostearate, glycerol monobehenate, Glycerol monoisomyristate, glycerol monoisostearate, glycerol monooleate, glycerol monolinoleate, glycerol dipalmitate, glycerol distearate, glycerol diisopalmitate, glycerol diisostearate, glycerol dioleate, glycerol stearate Isopalmitate, glycerol trimyristate, glycerol tristearate, glycerol tribehenate, glycerol triisostearate, Trimethylolpropane monostearate, trimethylolpropane monoisopalmitate, trimethylolpropane monooleate, trimethylolpropane dipalmitate, trimethylolpropane diisostearate, trimethylolpropane tristearate, trimethylolpropane triisomyristate , Pentaerythritol monopalmitate, pentaerythritol diisopalmitate, pentaerythritol trioleate, pentaerythritol tetrastearate, pentaerythritol tetraisopalmitate,
Pentaerythritol diolate distearate, sorbitan monostearate, sucrose diisostearate, etc. are exemplified.

Of these, fatty acid ester compounds of glycerol, trimethylolpropane and pentaerythritol are preferably used. In addition, the release agents exemplified below may be used in combination, if desired.

That is, as hydrocarbon releasing agents, natural and synthetic paraffin waxes, polyethylene wax, fluorocarbons and the like; as fatty acid releasing agents, higher fatty acids such as stearic acid and oxyfatty acids such as hydroxystearic acid, etc. However, fatty acid amide-based release agents include fatty acid amides such as ethylenebisstearylamide and alkylene fatty acid amides such as erucic acid amide; alcohol-based release agents include aliphatic alcohols such as stearyl alcohol and cetyl alcohol; Examples of alcohols include polyglycol, polyglycerol, trimethylolpropanes and the like. Other polysiloxanes can also be used. These may be used alone or in combination of two or more.

(Heat Resistance Stabilizer) In the present invention, coloration and molecular weight reduction of the aromatic polycarbonate during the thermoforming process,
In order to suppress the generation of black foreign matter to a low level, a usual heat resistance stabilizer can be added. Specific examples of such stabilizers include conventionally known phosphorus-based stabilizers, phenol-based antioxidants, organic thioether-based stabilizers and hindered amine-based stabilizers.

As the phosphorus-based stabilizer: conventionally known phosphorous acid,
Hypophosphorous acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and ester compounds thereof can be used. As the phosphorus-based stabilizer used in the present invention, for example, those commercially available as stabilizers from commercial manufacturers of stabilizers can be used.

The "phosphorous acid ester-based compound" referred to in the present invention is a trivalent phosphorus compound having at least one hydrocarbon group bonded to a trivalent phosphorus atom via an oxygen atom and having no active hydrogen. Is. Therefore, in addition to the phosphite triester, phosphonous acid diester Note ¹⁾ and phosphinic acid ester Note ¹⁾ are also included in the above-mentioned “phosphorous acid ester compound”. [Note] 1; modern organic synthetic series; 5 organic phosphorus compounds (edited by the Society of Synthetic Organic Chemistry) p78] Specific examples of the “phosphorous acid ester compound” in the present invention include: bis (2,4-dicumyl) Phenyl) pentaerythrityl diphosphite, bis (2,4-di-
t-amylphenyl) pentaerythrityl diphosphite, bis (2,4-di-t-amyl-3-methylphenyl) pentaerythrityl diphosphite, bis (2,4-di-t-butylphenyl) penta Erythrityl diphosphite, bis (2,4-di-t-butyl-
3-Methylphenyl) pentaerythrityl diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) phosphite, bis (2,4-di-t-amylphenyl) octylphosphite, bis (2,4-
Di-cumylphenyl) nonylphosphite, bis (2,4-di-t-butylphenyl) decylphosphite, tetrakis (2,4-di-t-butylphenyl)
Examples thereof include diphenyl-4,4'-diphosphonite and tris (2,4-di-t-butylphenyl) phosphite. Other phosphorous acids and the like can be used, but are not limited thereto. Among these, phosphorous acid, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) diphenyl-4,4'-diphosphonite, bis ( 2,4-di-t-butylphenyl) pentaerythrityl diphosphite and the like are exemplified as preferable ones.

These phosphite compounds are compounds of the present invention.
Phosphorus atom per 100 parts by weight of aromatic polycarbonate
And then 5 × 10^-6~ 5 x 10^-3Parts by weight, preferably 1 ×
10 ^-Five~ 5 x 10^-3Parts by weight, more preferably 2 × 10
^-Five~ 4 x 10^-3It is preferable to add parts by weight.

In the present invention, 5 × 10 ^{−6 to} 5 × 10 ⁻³ parts by weight, preferably 1 × 10 ^{−5 to} 5 × 10 5 parts by weight of the phosphoric acid ester compound as a phosphorus atom per 100 parts by weight of the aromatic polycarbonate. ^-3 parts by weight, more preferably 2
It is preferable to add x10 ^-5 to 4x10 ^-3 parts by weight. The presence of such a quantitative ratio exerts a coexisting action with the "phosphorous acid ester-based compound", and there is little deterioration in color tone during heat molding,
A reduction in molecular weight and an improvement in heat resistance stability with less generation of black foreign matter are realized. A part of the phosphoric acid ester compound and the phosphorous acid ester compound may be bonded to the aromatic aromatic polycarbonate molecular chain.

Specific examples of the phosphoric acid ester compound used in the present invention include bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphate and bis (2,4-di-t-butyl). 3-Methylphenyl) pentaerythrityldiphosphate, 2,2-methylenebis (4,6-di-t-butylphenyl) phosphate, tris (2,4-di-t-butylphenyl) phosphate, tetrakis (2,4) -Di-t-butylphenyl) diphenyl-4,4'-diphosphonate, trimethylphosphate, triphenylphosphate, trimethylphosphate, monooctylphosphate, tributoxyethylphosphate, tricresylphosphate, cresylphenylphosphate, diisopropenylphenylphosphate, Tris (chloroethyl) phosphate, Tris (dichloropro) Pill) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) phosphate and the like. In addition, phosphoric acid, pyrophosphoric acid and the like can be used, but are not limited to these. Among these, phosphoric acid, pyrophosphoric acid, trimethyl phosphate, bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphate and the like are exemplified as preferable ones.

In the present invention, the phenolic antioxidant is used in an amount of 1 × 10 ^-4 to 1 × 10 ^-1 part by weight, preferably 5 × 10 ⁴ per 100 parts by weight of the aromatic polycarbonate of the present invention.
^-4 to 1 x 10 ^-1 part by weight, more preferably 5 x 10 ^-4
It is preferable to add ~ 5 × 10 ^-2 parts by weight. As such a phenolic antioxidant, a compound having a phenolic hydroxyl group, in which at least one of the ortho positions of the phenolic hydroxyl group is substituted with a tertiary carbon atom, is preferable.

Specific examples of these phenolic antioxidants include, for example, n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and tetrakis {methylene-3- ( 3 ', 5'-di-
t-butyl-4-hydroxyphenyl) propionate} methane, triethylene glycol-bis {3- (3
-T-butyl-5-methyl-4-hydroxyphenyl)
Propionate}, 1,6-hexanediol-bis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,4-bis (n-octylthio) -6- (4-hydroxy- 3,5-di-t-butylanilino) -1,3,5-triazine pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate}, 2,2-thiodiethylenebis {3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-t-butylphenol),
N, N′-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris (3,3 5-di-t-butyl-4-hydroxybenzyl) -isocyanurate isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5,7,8-tetramethyl- 2- (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6-ol, N, N′-bis {3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyl hydrazine} and the like.

Examples of the organic thioether stabilizers include dilauryl thiopropionate and dimyristyl-
Examples thereof include 3,3′-thiodipropionate and pentaerythritol-tetrakis- (β-laurylthiopropionate).

Examples of hindered amine stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and 1- [2- {3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy} -2,
2,6,6-tetramethylpiperidine, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-tetramethyl -4-piperidyl) and the like.

These heat resistance stabilizers may be used alone or in combination of two or more. These heat-resistant stabilizers (excluding phosphorus-based stabilizers) are added at 1 × 10 ⁻⁴ to 100 parts by weight of the aromatic polycarbonate component of the present invention.
It can be used in an amount of 5 parts by weight, preferably 5 × 10 ⁻⁴ to 1 part by weight, more preferably 1 × 10 ^{−3 to} 0.5 part by weight.

In the method for producing an aromatic polycarbonate according to the present invention, it is also preferable to add an epoxy compound together with the heat resistance stabilizer. As such an epoxy compound, it is preferable to use a compound containing one or more epoxy groups in the molecule.

Specifically, for example, epoxidized soybean oil, 3,
4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bisphenol A diglycidyl ether, phthalic acid diglycidyl ester, 3-methyl-5-t-butyl −
1,2-epoxycyclohexane etc. can be mentioned. Of these, 3,4-epoxycyclohexylmethyl-
Alicyclic epoxy compounds such as 3 ′, 4′-epoxycyclohexylcarboxylate and cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate can be preferably used. In particular 3,4-epoxycyclohexylmethyl-3 ′,
4'-epoxy cyclohexyl carboxylate can be preferably used. Such an epoxy compound may be used in an amount of 1 × 10 6 with respect to 100 parts by weight of the aromatic polycarbonate of the present invention.
^{-4 to} 0.2 parts by weight, more preferably 1 x 10 ^-4
~ 0.1 parts by weight.

(Light Stabilizer, Ultraviolet Absorber) In addition to the above, the aromatic polycarbonate of the present invention may contain a light stabilizer and an ultraviolet absorber. Specific examples of the light stabilizer and the ultraviolet absorber include 2- (3-t-butyl-2-
Benzotriazole compounds such as hydroxy-5-methylphenyl) -5-chlorobenzotriazole, benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone, 3,5-di-t-butyl-4-hydroxybenzoate, etc. Benzoate compounds, 2-
Examples thereof include cyanoacrylate compounds such as cyano-3,3-diphenylacrylate.

The light stabilizer and the ultraviolet absorber are usually used in an amount of 1 per 100 parts by weight of the aromatic polycarbonate of the present invention.
× 10 ^{−3 to} 5 parts by weight, preferably 1 × 10 ⁻² to 1 important part,
More preferably, it can be used in an amount of 1 × 10 ^{-2 to} 0.5 part by weight. These light stabilizers and ultraviolet absorbers may be used alone or in combination of two or more.

(Other stabilizers) As a heavy metal ion quencher, for example, a nickel-based quencher such as nickel dibutyldithiocarbamate, and as a metal deactivator, for example, N, N '-[3- (3,5-di). -T-butyl-4
-Hydroxyphenyl) propionyl] hydrazine and the like, metal soaps such as calcium stearate and the like, nucleating agents such as methylenebis
Examples thereof include sorbitol-based and phosphate-based compounds such as (2,4-di-t-butylphenyl) monohydrogen phosphate sodium salt. Further, examples of the antistatic agent include (β-lauramidopropionyl) trimethylammonium sulfate, quaternary ammonium salt compounds such as sodium dodecylbenzenesulfonate, sulfonate compound, and alkylphosphate compound.

Further, in the aromatic polycarbonate of the present invention, a coloring agent such as an organic or inorganic dye or pigment can be used if desired. Specific examples of the inorganic colorant include oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as navy blue, chromate salts such as zinc chromate, and barium sulfate. Examples thereof include sulfates, carbonates such as calcium carbonate, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal colorants such as bronze powder and aluminum powder. Specific examples of organic colorants include nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red and chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and indanthrone. Examples include condensed polycyclic colorants such as blue.

These colorants may be used alone or in combination of two or more. These colorants are usually used in an amount of 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ^{−6 to} 3 parts by weight, and more preferably 1 × 10 ⁻⁵ to 1 part by weight per 100 parts by weight of the aromatic polycarbonate component. Can be used.

(Bluish Coloring Agent) In the aromatic polycarbonate composition of the present invention, an organic bluish coloring agent may be used in addition to the above-mentioned coloring agents in order to improve the organoleptic sensitivities of molded articles. The bluish colorant usually has a large tendency to discolor during heat-melt molding. However, it has been found that discoloration can be suppressed by using the stabilizer of the above formula (1) of the present invention. More preferably, a catalyst containing a rubidium metal compound or a cesium metal compound is used as a transesterification catalyst during melt polymerization, and a stabilizer represented by the above formula (1) is used to further enhance the effect of suppressing discoloration. I understood.

Specific examples of the bluish colorant include: Generic name, Solvent Violet 13 [CA. No. (Color index No) 6072
5; Trade name "Macerex Violet B" manufactured by Bayer, "Dialesin Blue G" manufactured by Mitsubishi Chemical Corporation, "Sumiplast Violet B" manufactured by Sumitomo Chemical Co., Ltd., "Plast Violet 8840" manufactured by Arimoto Kagaku] Solvent Violet 31 [CA. No. 68210; Trade name: "Dialesin Violet D" manufactured by Mitsubishi Chemical Corporation] General name: Solvent Violet 33 [CA. No. 609725; Trademark name Mitsubishi Chemical Corporation
"Dialesin Blue J"] General name; Solvent Blue 94 [CA. NO. 61500; Trade name: "Dialesin Blue N" manufactured by Mitsubishi Chemical Corporation] General name: Solvent Violet 36 [CA. NO68210; trademark name "Macrelex Violet 3R" manufactured by Bayer Co., Ltd.] general name; Solvent Blue 97 [trademark name "Macrolex Blue RR"] common name; Solvent Blue 45 [CA. N
O61110; Trade name Sand Company "Tetrazole Blue R
LS ”] Other Ciba Specialty. Examples include Macrolex Violet and Triazole Blue RLS manufactured by Chemicals. Of these, Macrolex Violet and Triazole Blue RLS are preferable. The bluish colorants may be used alone or in combination of two or more. The bluish colorant is aromatic polycarbonate 1
Usually 0.01 × 10 ⁻⁴ to 10 × 10 ⁻⁴ per 100 parts by weight
It can be used in an amount of parts by weight, preferably 0.05 × 10 ^{−4 to} 5 × 10 ⁻⁴ parts by weight, more preferably 0.1 × 10 ^{−4 to} 3 × 10 ⁻⁴ parts by weight.

(Flame Retardant) If desired, the aromatic polycarbonate of the present invention may be used in combination with various conventionally known flame retardants which are exemplified below as the flame retardant. For example, phosphoric acid ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate,
Examples thereof include diisopropenylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate and tris (2,3-dibromopropyl) phosphate. In the present invention, if desired,
As the anti-drip agent, polytetrafluoroethylene (Teflon (registered trademark)) or the like may be blended.

(Solid Filler such as Organic and Inorganic Filler) Further, in order to improve the rigidity, the aromatic polycarbonate of the present invention may be blended with an inorganic or organic solid filler to improve aromaticity. It can also be a polycarbonate composition. Such solid fillers include talc, mica, glass flakes, glass beads, calcium carbonate, titanium oxide and other plate-like or granular inorganic fillers; glass fiber, glass milled fiber, wollastonite, carbon fiber, aramid fiber, metal-based Examples thereof include fibrous fillers such as conductive fibers; organic particle fillers such as crosslinked acrylic particles and crosslinked silicone particles. The blending amount of these inorganic and organic fillers is 1 to 15 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate of the present invention.
0 parts by weight is preferable, and 3 to 100 parts by weight is more preferable.

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 that the decomposition of the aromatic polycarbonate is suppressed.

(Other Thermoplastic Resin) The aromatic polycarbonate of the present invention may be blended with other thermoplastic resin as long as the object of the present invention is not impaired to give an aromatic polycarbonate composition.

Examples of such other thermoplastic resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, Polyester resin such as polybutylene terephthalate, amorphous polyarylate resin, polystyrene resin, acrylonitrile / styrene copolymer resin (AS resin), liquid crystalline polyarylate resin, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), Examples of the resin include polymethacrylate resin, phenol resin, and epoxy resin. The blending amount of these other thermoplastic resins is preferably 10 to 150 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the aromatic polycarbonate of the present invention.

Furthermore, the aromatic polycarbonate 1 of the present invention
1 to 150 parts by weight and 10 parts by weight of another thermoplastic resin are used in an amount of 100 parts by weight to the extent that the object of the present invention is not impaired.
It is also possible to blend up to 150 parts by weight to obtain an aromatic polycarbonate composition.

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

The aromatic polycarbonate and the aromatic polycarbonate composition of the present invention have the durability of the aromatic polycarbonate composition, particularly for a long time under severe temperature and humidity conditions, by appropriately blending the above-mentioned various additives. The effect of maintaining durability and the antistatic property can be obtained. An optical recording medium manufactured by using the aromatic polycarbonate composition, specifically, compact disc (CD), CD-
ROM, CD-R, CD-RW, etc., magnet optical disc (MO), etc., digital versatile disc (DVD-ROM, DVD-Video, DVD-
A high-density optical disc substrate represented by Audio, DVD-R, DVD-RAM, etc.) can provide high reliability for a long period of time. Particularly, it is useful for a high-density optical disc substrate of a digital versatile disc.

The optical recording medium referred to in the present invention is a recording medium for recording, reproducing and / or erasing information by light such as laser light. Specifically, it includes a read-only compact disc, a video disc, a write-once optical disc, a rewritable magneto-optical disc, a phase change disc, and the like. Various types of these discs have been proposed, but the transferability of the resin becomes severe.
mm-thick DVD-RAM, ASMO.90mm 1.
It is particularly preferably used for a 3 GB phase change disk or the like. By forming a recording layer on the optical recording medium substrate of the present invention to construct such an optical recording medium, it is possible to obtain a recording medium having no defective sectors and excellent optical characteristics.

Needless to say, the present invention is applied to optical recording medium substrates including optical disc substrates having a thickness of 1.2 mm, which is the mainstream of the present optical recording media. Furthermore,
For optical recording medium substrates with other thicknesses, especially for substrates for which the mold cavity for molding optical recording medium substrates with a thickness of about 0.6 mm, which has been recently developed, has become more difficult to cool. It can be applied effectively.

The method for producing an optical recording medium substrate and medium from the aromatic polycarbonate and aromatic polycarbonate composition of the present invention is not particularly limited, and general substrate and medium molding techniques can be applied.

Further, the sheet produced from the aromatic polycarbonate and the aromatic polycarbonate composition produced by the present invention is a sheet excellent in flame retardancy, antistatic property, adhesiveness and printability, and its characteristics. It is widely used for electrical parts, building materials, automobile parts, etc., specifically for various window materials such as general houses, gymnasiums, baseball domes, vehicles (construction machinery, automobiles, buses, bullet trains, train cars, etc.) Glazing products for window materials, various side wall plates (skydome, top lights, arcades, condominium waist plates, road side wall plates), window materials for vehicles, OA equipment display, touch panel, membrane switch, photo cover, water tank Aromatic polycarbonate resin laminate, front panel of projection TV and plasma display, Frennel lens, optical card A liquid crystal cell in combination with an optical disc and a polarizing plate is useful to the phase difference correction plate such as an optical application of the. The thickness of the sheet is not particularly limited, but is usually 0.1 to 10 mm, preferably 0.2 to 8 mm, 0.2.
~ 3 mm is particularly preferred. In addition, various processing treatments for adding new functions to the aromatic polycarbonate and the sheet produced from the aromatic polycarbonate composition (various laminating treatments for improving weather resistance, scratch resistance improvement for improving surface hardness). Processing, surface graining, semi- and opaque processing, etc.) may be performed.

Any method may be adopted for blending the above-mentioned additive, solid filler, and other thermoplastic resin with the aromatic polycarbonate of the present invention. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The aromatic polycarbonate and the aromatic polycarbonate composition thus obtained can be used as they are, or once pelletized by a melt extruder, and then formed into a sheet by a melt extrusion method, or a molded product can be produced by an injection molding machine.

[0123]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The various analytical evaluation methods used in the present invention are shown below. a. Analytical Evaluation 1) Intrinsic Viscosity [η] of Aromatic Polycarbonate; The viscosity average molecular weight Mv was calculated from the following equation (9) based on the intrinsic viscosity measured with a Ubbelohde viscometer at 20 ° C. in methylene chloride. [Η] = 1.23 × 10 ⁻⁴ × Mv ^0.83 (9)

2) Terminal phenolic hydroxyl group concentration (mol%); 0.02 g of the sample was dissolved in 0.4 ml of deuterated chloroform and ¹ H-NMR (EX manufactured by JEOL Ltd.) at 20 ° C.
-270), the terminal phenolic hydroxyl group concentration (e
q / ton) was measured. Then, the total number of terminal groups was calculated from the intrinsic viscosity using the following formula (10). The number of terminal phenolic hydroxyl groups corresponding to the terminal phenolic hydroxyl group concentration was subtracted from the total number of terminal groups to obtain the number of terminal aryloxy groups and the terminal aryloxy group concentration (eq / ton). (Total number of end groups) = 56.54 / [η] ^1.4338 (10)

3) Melt viscosity stability: The absolute value of the change in melt viscosity measured at a shear rate of 1 rad / sec and 280 ° C. under a nitrogen stream for 30 minutes using a RAA type flow analysis device manufactured by Rheometrics Co., Ltd. The rate of change per minute was calculated. In order for the aromatic polycarbonate and the aromatic polycarbonate composition to have good short-term and long-term stability, this value should not exceed 0.5%. In particular, when this value exceeds 0.5%, there is a high possibility that the hydrolysis stability of the aromatic polycarbonate and the aromatic polycarbonate composition becomes poor.

4) Hydrolysis resistance (%);
The mixture was treated for 20 hours in a water-sealed autoclave at 0 ° C., and the viscosity average molecular weight before and after the treatment was measured by the method described in 1) to determine the molecular weight reduction rate (%). As the evaluation of the base polymer, the hydrolysis resistance of the aromatic polycarbonate to which only the stabilizer derived from the sulfate of the present invention or the stabilizer of the sulfonic acid derivative of the comparative example is added is the hydrolysis resistance when various additives are added. It is the basis of degradability. When this value was less than 1.0%, it was passed, and when it was more than that, it was rejected.

5) Others: In the evaluation of the optical disk substrate, the stability of quality was the first, and the hydrolysis resistance was less than 1.0% in the state where the additive was added, and the others were rejected. . For general-purpose molded products, the initial molecular weight is large and the influence of the rate of decrease in molecular weight due to hydrolysis is large.
Fail over 5%, pass below 1.5% to over 1.0%,
1.0% or less to over 0.5% was judged to be a good pass, and 0.5% or less was judged to be an excellent pass.

6) Thermal stability during molding; retention stability (optical disk substrate evaluation) The hue (color: L) of the color sample plate molded under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. from an injection molding machine. , a, b) and 380 ° C x 1 in cylinder
The hue (color: L ', a', b ') of the color sample plate obtained by allowing it to stay for 0 minutes and then molding it is measured by a color difference meter (Z-1 manufactured by Nippon Denshoku Co., Ltd.).
001DP color difference meter was used), and retention stability was evaluated by ΔE represented by the following formula (11). While the ΔE value is related to the degree of decrease in molecular weight, it has a great influence on the sensory test of molded articles. ΔE = {(LL ′) ² + (a−a ′) ² + (bb ′) ² } ^0.5 (11) Only the stabilizer of the sulfate salt of the present invention and the stabilizer of the sulfonic acid derivative were added. The base polymer serves as a base for residence baking of the aromatic polycarbonate composition to which various additives are added. If the ΔE value exceeds 1.5, the hue of the molded product to which various additives are added is significantly deteriorated, and there is a high possibility that a molded product having a strong yellow tint can be obtained. The following items were judged to have passed. A) Aromatic polycarbonate composition in which a phosphorous acid ester compound and / or a phosphoric acid ester compound and a fatty acid ester compound are added to an aromatic polycarbonate having a viscosity average molecular weight of 20,000 or less, which is a composition suitable for molding an optical disk substrate. In the case of, a ΔE value of 2.5 or less was determined to be acceptable, and a value exceeding 2.5 was determined to be unacceptable.

(Evaluation of general-purpose molded products other than optical disk substrates) Aromatic polycarbonate having a viscosity-average molecular weight of more than 20,000, which is a composition suitable for producing various general-purpose molded products, is added to a bluish colorant, a phosphite ester compound, and / Or phosphate compounds, phenolic antioxidants,
In addition, in the case of an aromatic polycarbonate composition to which a fatty acid ester compound was added, a ΔE value of 1.0 or less was determined to be acceptable, and a value of more than 1.0 was determined to be unacceptable. Because of the blue colorant △
This is because the E value becomes a small value.

7) Transparency, transparency durability: As an evaluation method for judging whether the transparency of the aromatic polycarbonate and the transparency under severe conditions are maintained, the haze on the color sample plate and the above A durability test was carried out by measuring the haze after holding the color sample plate at 80 ° C. × 85% relative humidity for 500 hours. Measurement conditions: Nippon Denshoku Co., Ltd. automatic digital haze meter UDH-20
Conducted in D. Regarding the base polymer having a viscosity average molecular weight of 20000 or less and the aromatic polycarbonate composition mainly used for optical disk substrates, a haze of 0.5 or less before the durability test and a haze of 0.6 or less after the durability test were judged to be acceptable. When this value was exceeded, it was judged as a failure. For the base polymer having a viscosity average molecular weight of more than 20,000, haze was 1.5 and 1.
A rating of 7 or less was passed, and a rating of more than 7 was determined to be unacceptable. For the aromatic polycarbonate composition having a viscosity average molecular weight of more than 20,000, haze of 0.7 or 0.8 was passed before and after the durability test, and when haze was exceeded, it was determined to be unacceptable.

8) Number of black foreign matter generated (evaluation for general-purpose molded products): A 120 mm × 120 mm × 2 mm flat plate was placed on an injection molding machine at a cylinder temperature of 340 ° C. and a mold temperature of 80 ° C.
Under the conditions of 10000 sheets were molded. Subsequently, the aromatic polycarbonate or the aromatic polycarbonate composition was retained in the cylinder in a molten state for 10 minutes, and then black foreign matters in 10 flat plates formed were visually measured to calculate the average number per flat plate. The number of black foreign matters is an important judgment item that directly affects the quality of the molded product itself. 0-3 (pieces /
The number of sheets was judged to be acceptable, and the case of exceeding 3 (pieces / sheet) was judged to be unacceptable.

9) Polarization abnormality: An injection molding machine (model name) manufactured by Nissei Plastic Industry Co., Ltd. as an evaluation of optical disk substrate applications.
MO40D3H) and a mold and a stamper for a phase-change type optical recording medium substrate with a storage capacity of 2.6 GB (disk diameter 120 mm, thickness 0.6 mm) were used. Molding conditions are: the mold temperature is 123 ° C for the movable part, 128 ° C for the fixed part,
The temperature of the cutter and sprue was 60 ° C. The cylinder temperature is 380 ° C and the injection speed is 250 mm / sec.
Then, the aromatic polycarbonate and the aromatic polycarbonate composition were filled in a mold cavity to mold an optical disk substrate.

The optical disk substrate is set at 80 ° C. × 85% RH ×
After being exposed to the condition of 1000 Hr, the polarization abnormal point of 20 μm or more was measured with a polarization microscope, and the suitability for using the optical disk substrate was judged. An optical recording medium using such an optical disk substrate having many polarization anomalies is likely to cause data anomalies and must be avoided. If the polarization abnormal point exceeds 1.5 (pieces / sheet), it is NG; ×, 1.5 or less to more than 1.0 (pieces)
/ Sheet) is acceptable; ○ ', 1.0 or less to over 0.5 (pieces /
The number of sheets is good: ◯, the number of 0.5 (pieces / sheet) or less is excellent: ◎.

B. Production of Base Polymer [Example 1] (Production of EPC-1) The aromatic polycarbonate of the present invention was produced as follows. 137 parts by weight of purified BPA and 131 parts by weight of purified DPC as raw materials, 4.1 × 10 ⁻⁵ parts by weight of bisphenol A sodium salt as a polymerization catalyst, in a reaction tank equipped with a stirrer, a rectification column and a pressure reducing device. Tetramethylammonium hydroxide (hereinafter sometimes abbreviated as TMAH) 5.5 × 10 ⁻³ parts by weight was charged and melted at 180 ° C. in a nitrogen atmosphere.

With stirring, the inside of the reaction tank was set to 13.33 kPa (1
The pressure was reduced to 00 mmHg), and the reaction was performed for 20 minutes while distilling off the produced phenol. Next, after raising the temperature to 200 ° C., the pressure is gradually reduced to distill off the phenol and 4.
The reaction was performed at 000 kPa (30 mmHg) for 20 minutes.
Gradually raise the temperature to 220 ° C for 20 minutes, 240 ° C
For 20 minutes at 260 ° C for 20 minutes, then 2
The pressure was gradually reduced at 60 ° C and 2.666 kPa (20 m
mHg) for 10 minutes at 1.333 kPa (10 mmH
g), the reaction was continued for 5 minutes, and finally 260 ° C./66.
Intrinsic viscosity [η] of 0.3 at 7 Pa (0.5 mmHg)
7. The reaction was carried out until the viscosity average molecular weight reached 15300. When the viscosity average molecular weight reached 15300, 2-
Add 4.0 parts by weight of methoxycarbonylphenylphenyl carbonate (abbreviated as SAM including tables below) 260
Agitated at 133.3 Pa (1 mmHg) for 10 minutes,
Thereafter, 2.7 × 10 ⁻⁴ parts by weight of bis (tetrabutylphosphonium) sulfate was added to 100 parts by weight of the aromatic polycarbonate, 260 ° C., 66.7 Pa (0.5 mmH
g) was stirred for 10 minutes. The viscosity average molecular weight of the obtained aromatic polycarbonate is 15,300, the terminal phenolic hydroxyl group concentration is 47 (eq / ton-polycarbonate), and the terminal aryloxy group concentration is 192 (eq / to).
n-polycarbonate), melt viscosity stability was 0%.
The physical properties of the obtained aromatic polycarbonate are shown in Tables 1 and 2.

[Examples 2 to 4] (Production of EPC-2 to 4) In the same manner as in Example 1, except that the types and amounts of the catalysts and stabilizers shown in Table 2 were used, the fragrances of the following physical properties were obtained. A group polycarbonate was produced. The physical properties of the obtained aromatic polycarbonate are shown in Tables 1 and 2.

[Comparative Examples 1 and 2] (Production of CPC-1 and 2) Aromatic polycarbonates were produced in the same manner as in Example 1 except that the types and amounts of catalysts and stabilizers shown in Table 2 were used. . Regarding the physical properties of the finally obtained aromatic polycarbonate, the viscosity average molecular weight in Comparative Example 1 was 1530.
0, terminal phenolic hydroxyl group concentration 46 (eq / ton
-Polycarbonate), terminal aryloxy group concentration 1
93 (eq / ton-polycarbonate), melt viscosity stability 0%, viscosity average molecular weight 152 in Comparative Example 2
00, terminal phenolic hydroxyl group concentration 48 (eq / to
n-polycarbonate), the terminal aryloxy group concentration was 191 (eq / ton-polycarbonate), and the melt viscosity stability was 0.2%. The physical properties of the obtained aromatic polycarbonate are shown in Tables 1 and 2.

[Examples 5 to 7] (Production of EPC-5 to 7) In Examples 2, 3 and 4, the polymerization reaction was further promoted and the polymerization was carried out until the viscosity average molecular weight reached about 22,500. The aromatic polycarbonate obtained was then used in Example 1.
The same process was carried out. However, 1.95 parts by weight of SAM was added. The measurement results of the viscosity average molecular weight, the terminal phenolic hydroxyl group concentration, and the melt viscosity stability of the finally obtained aromatic polycarbonate are shown in Tables 1 and 2 for Example 5 and Tables for Examples 6 and 7. It was noted in 1.

[Comparative Examples 3 and 4] (Production of CPC-3 and 4) In Comparative Examples 1 and 2, the polymerization reaction was further promoted and the molecular weight was 2
5000 aromatic polycarbonates were produced. The physical properties of the finally obtained aromatic polycarbonate in Comparative Example 3 are as follows: viscosity average molecular weight 25100, terminal phenolic hydroxyl group concentration 36 (eq / ton-polycarbonate), terminal aryloxy group concentration 114 (eq / ton).
-Polycarbonate), melt viscosity stability 0%, in Comparative Example 4, viscosity average molecular weight 25200, terminal phenolic hydroxyl group concentration 38 (eq / ton-polycarbonate), terminal aryloxy group concentration 112 (eq /
(ton-polycarbonate), melt viscosity stability 0.3%
Met. The evaluation results of these aromatic polycarbonates are shown in Tables 1 and 2. These aromatic polycarbonates were used as base polymers for the evaluation of various molded articles shown below.

[0140]

[Table 1]

[0141]

[Table 2]

C. Production Evaluation of Aromatic Polycarbonate Composition Using EPC-1 to 4 and CPC-1 to 2

[Examples 8 to 14 and Comparative Examples 5 and 6] EPC-produced in Examples 1 to 4 and Comparative Examples 1 and 2 above.
1-4, CPC-1-2 aromatic polycarbonate,
After the components of A) phosphite compound, B) phosphoric acid ester compound, and C) fatty acid ester compound of the types and amounts described in Table 3 are uniformly mixed using a tumbler, a 30 mmφ vent is provided. With a twin-screw extruder (KTX-30 manufactured by Kobe Steel, Ltd.), a cylinder temperature of 26
An aromatic polycarbonate composition having the composition shown in Table 3 was produced while degassing at 0 ° C. and a vacuum degree of 1.33 kPa (10 mmHg). The evaluation results of these aromatic polycarbonate compositions are shown in Table 3.

[0144]

[Table 3]

[Examples 15 to 21 and Comparative Examples 7 and 8]
Then, an injection molding machine (model name: MO40D3H) manufactured by Nissei Plastic Industry Co., Ltd. was used according to the above-mentioned method, and the mold and the stamper were each for a phase-change type optical recording medium substrate (disk diameter 120 mm, thickness of 2.6 GB). A substrate having a thickness of 0.6 mm was formed. The mold temperature is 123
C. and the fixed part was 128.degree. The temperature of the cutter and sprue was 60 ° C. The melting temperature of the aromatic polycarbonate was a cylinder temperature of 380 ° C. Injection speed 250m
The mold cavity was filled with the aromatic polycarbonate composition at m / sec to mold an optical disk substrate. Example 8
-14 and the aromatic polycarbonate compositions of Comparative Examples 5 and 6, optical disk substrates were produced. Examples 15-21
The aromatic polycarbonate composition of No. 2 showed good moldability and transferability. The aromatic polycarbonate compositions of Comparative Examples 7 and 8 were slightly inferior in the transferability of the pit shape.

D. Production Evaluation of Aromatic Polycarbonate Compositions Using PC-7 to 11 [Examples 22 to 24 and Comparative Examples 9 and 10] EPC-5 to 7 produced in Examples 5 to 7 and Comparative Examples 3 and 4 above. CP
Using a tumbler, the components and amounts of A) phosphite compound, B) phosphoric acid ester compound, and C) fatty acid ester compound described in Table 4 were added to the aromatic polycarbonate of C-3,4. And mix evenly, then 30 mm
Twin screw extruder with φ vent (KTX-3 manufactured by Kobe Steel Ltd.)
0), cylinder temperature 260 ° C, 1.33 kPa
The aromatic polycarbonate composition was manufactured by adding the additives shown in Table 4 while degassing at a vacuum degree of (10 mmHg). The evaluation results are shown in Table 4.

[0147]

[Table 4]

E. Evaluation of production of sheet [Example 25] The amount of the aromatic polycarbonate of the above EPC-5 and pentaerythritol tetrastearate (referred to as C in Table 3) 3 as a fatty acid ester compound in an amount of 1000 ppm with respect to the aromatic polycarbonate. After mixing and melting, a fixed amount was supplied by a gear pump and the mixture was sent to a T die of a molding machine. 2mm or 0.2mm thick and 800m wide by sandwiching between mirror cooling roll and mirror surface roll or touching one side
The sheet of m was melt-extruded.

A visible light-curable plastic adhesive [Adele 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. While stacked. After that, it was 5,000mJ by a photo-curing device equipped with a metal halide type for visible light
/ Cm ² of light was irradiated and the adhesive strength of the obtained laminate was measured according to JIS K-6852 (compressive shear adhesive strength test method for adhesives). As a result, the adhesive strength was 10.4.
It was good at MPa (106 Kgf / cm ² ).

On the other hand, the ink [Nazda 70-9132: color
136D smoke] and solvent [isophorone / cyclohexane / isobutanol = 40/40/20 (wt
%)] And mixed to make it uniform, followed by printing with a silk screen printer and drying at 100 ° C. for 60 minutes. There was no transfer failure on the printed ink surface, and the printing was good.

Separately, 30 parts of an aromatic polycarbonate resin (specific viscosity 0.895, Tg 175 ° C.) obtained by subjecting 1,1-bis (4-hydroxyphenyl) cyclohexane and phosgene to an ordinary interfacial polycondensation reaction, a dye As Pl
15 parts of ast Red 8370 (manufactured by Arimoto Chemical Industry),
A sheet (thickness 0.2 mm) printed with a printing ink mixed with 130 parts of dioxane as a solvent was mounted in an injection molding die, and aromatic polycarbonate resin pellets (Panlite L-1225; manufactured by Teijin Chemicals Ltd.) ) Using 31
Insert molding was performed at a molding temperature of 0 ° C. After the insert molding, there was no abnormality such as bleeding or blurring in the printed part pattern of the molded product, and an insert molded product having a good printed part appearance was obtained.

F. Production Evaluation of Polymer Blend Compounds [Examples 26 to 32] EPC-produced in Example 6 above
6, glycerol monostearate, 1000 ppm, plast violet 8840 (manufactured by Arimoto Chemical Co., Ltd.) as a bluish colorant, 0.8 ppm, trimethyl phosphate 0.05 wt%, and Table 5 based on the weight of aromatic polycarbonate. After uniformly mixing the components shown by the symbols in Table 6 using a tumbler, a cylinder temperature of 260 ° C. was obtained by a twin-screw extruder with a 30 mmφ vent (KTX-30 manufactured by Kobe Steel, Ltd.). 33 kPa (10 m
Pelletizing while degassing at a vacuum degree of mHg), drying the obtained pellets at 120 ° C. for 5 hours, and then using an injection molding machine (Sumitomo Heavy Industries, Ltd. SG150U type), cylinder temperature 270 ° C. Tables 5 and 6 show the results of forming molded pieces for measurement under conditions of a mold temperature of 80 ° C. and performing the following evaluations. In addition, each component described in symbols in Tables 5 and 6 is as follows. -1 ABS: Styrene-butadiene-acrylonitrile copolymer; Santak UT-61; Mitsui Chemicals, Inc.
Manufactured-2 AS: Styrene-acrylonitrile copolymer;
Stylak-AS 767 R27; Asahi Kasei Kogyo -3 PET: Polyethylene terephthalate; TR-
8580; Teijin Ltd., intrinsic viscosity 0.8-4 PBT: polybutylene terephthalate; TRB
-H; Teijin Ltd., intrinsic viscosity 1.07-1 MBS: methyl (meth) acrylate-butadiene-styrene copolymer; Kane Ace B-56; Kanegafuchi Chemical Industry Co., Ltd.-2E-1: Butadiene-alkyl acrylate-
Alkyl methacrylate copolymer; Paraloid EXL
-3602; Kureha Chemical Industry Co., Ltd. -3 E-2: A composite rubber in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component have an interpenetrating network structure; Metabrene S-2001;
Mitsubishi Rayon Co., Ltd.-1 T: Talc; HS-T0.8; Hayashi Kasei Co., Ltd.
Made, average particle size 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; Cycatec NN-4;
Manufactured by Tomoe Kogyo Co., Ltd., number average average fiber diameter D = 1.5 μm, average fiber length 17 μm, obtained by electron microscope observation,
Aspect ratio L / D = 20 WAX: Olefin wax by copolymerization of α-olefin and maleic anhydride; Diacarna-P3
0: Mitsubishi Kasei Co., Ltd. (maleic anhydride content = 10w
t%) (A) Flexural modulus The flexural modulus was measured according to ASTM D790. (B) Impact value with notch Using a test piece having a thickness of 3.2 mm according to ASTM D256, the weight was impacted from the notch side to measure the impact value. (C) Fluid cylinder temperature 250 ° C, mold temperature 80 ° C, injection pressure 9
The fluidity was measured by Archimedes-type spiral flow (thickness 2 mm, width 8 mm) at 8.1 MPa. (D) Chemical resistance A tensile test piece used in ASTM D638 was subjected to 1% strain, immersed in Esso-regular gasoline at 30 ° C. for 3 minutes, and the tensile strength was measured to calculate the retention rate.
The retention rate was calculated by the following formula. Retention rate (%) = (strength of treated sample / strength of untreated sample) × 100

[0153]

[Table 5]

[0154]

[Table 6]

[0155]

EFFECTS OF THE INVENTION By controlling the content of the above-mentioned specific impurities in the aromatic polycarbonate to a specific value or less as in the present invention, the durability of the polymer, particularly the long-term durability under severe temperature and humidity conditions. Is significantly improved, and good color tone, transparency, and mechanical strength are retained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI theme code (reference) G11B 7/24 526 G11B 7/24 526G (72) Inventor Yuichi Kageyama 2-1, Hinodemachi, Iwakuni City, Yamaguchi Prefecture Teijin Limited Iwakuni Research Center (72) Inventor Katsushi Sasaki 2-1, Hinodemachi, Iwakuni City, Yamaguchi Prefecture F-term inside Iwakuni Research Center Teijin Limited (reference) 4F071 AA12X AA15 AA20 AA22 AA22X AA33 AA34X AA41 AA42 AA45 AA46 AA48 AA50 AA51 AA53 AA54 AA60 AA62 AA64 AA77X AB03 AB17 AB21 AB26 AB28 AD01 AE17 AH14 4J002 BB03X BB12X BC06X BG05X BN15X CC04X CD00X CF00X CF16X CG00W CH00X CK02X CL00X CM04X CN01X CN03X DE136 DE236 DJ046 DJ056 DL006 FA016 FA046 FA086 4J029 AA09 AB04 AD10 AE05 BB09A BB12A BB13A BB15A BB16A BB18 CD04 CD05 CE04 CF08 DB11 DB13 HC04A HC05A HC05B JC091 JC093 JC31 3 JC631 JC633 JD06 JF051 KB04 KC02 5D029 KA07

Claims (16)

[Claims] 1. The following formula (1): (In the formula, each of X and Y independently represents a proton, 1 equivalent metal cation, ammonium cation, or phosphonium cation, provided that both X and Y simultaneously represent a proton,
It is never a 1 equivalent metal cation. ),
A stabilizer for an aromatic polycarbonate by a transesterification method, which comprises polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a transesterification catalyst. 2. In the above formula (1), X and Y are each independently a proton, 1 equivalent metal cation, and the following formula (1)-
a (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms), or an ammonium cation represented by the following formula (1) -B (Wherein R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms). The stabilizer according to claim 1. 3. An aromatic dihydroxy compound and a carbonic acid diester are polycondensed in the presence of a transesterification catalyst, and after the intrinsic viscosity of the aromatic polycarbonate produced reaches at least 0.1, the following formula (1) 4] (In the formula, each of X and Y independently represents a proton, 1 equivalent metal cation, ammonium cation, or phosphonium cation, provided that both X and Y simultaneously represent a proton,
It is never a 1 equivalent metal cation. ) At least one stabilizer selected from the group of compounds represented by the formula (1) is added in an amount of 0.01 ppm to 1 based on the aromatic polycarbonate produced.
A method for producing a stabilized aromatic polycarbonate, characterized in that the aromatic polycarbonate having a desired intrinsic viscosity is added in an amount of wt% to produce an aromatic polycarbonate. 4. In the above formula (1), X and Y are each independently a proton, 1 equivalent metal cation, and the following formula (1) -a: (Wherein R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms), or an ammonium cation represented by the following formula (1 ) -B (Wherein R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms). The manufacturing method according to claim 3. 5. The transesterification catalyst is at least one of an alkali metal compound or an alkaline earth metal compound,
And the organic basic compound are contained, The manufacturing method of Claim 3 or Claim 4 characterized by the above-mentioned. 6. The method according to claim 5, wherein the alkali metal compound contains a rubidium compound or a cesium compound. 7. The organic basic compound is at least selected from the group consisting of nitrogen-containing basic compounds and phosphorus-containing basic compounds.
The manufacturing method according to claim 5 or 6, wherein one kind is selected. 8. The stabilizer is used in a ratio of 0.5 to 100 equivalents per equivalent of the alkali metal compound catalyst or the alkaline earth metal compound catalyst contained in the produced aromatic polycarbonate. 3 to claim 7
The manufacturing method according to any one of 1. 9. The method according to any one of claims 3 to 8, wherein the stabilizer is added after the intrinsic viscosity of the aromatic polycarbonate reaches at least 0.2. 10. The production method according to claim 3, wherein the stabilizer is added after the intrinsic viscosity of the aromatic polycarbonate reaches at least 0.3. 11. A stabilized aromatic polycarbonate produced by the production method according to any one of claims 3 to 10. 12. Application of the aromatic polycarbonate according to claim 11 to an optical disk substrate. 13. An optical disk substrate molded from the aromatic polycarbonate according to claim 11. 14. An aromatic polycarbonate composition further comprising 1 to 150 parts by weight of a solid filler per 100 parts by weight of the aromatic polycarbonate according to claim 11. 15. An aromatic polycarbonate composition further comprising 10 to 150 parts by weight of a thermoplastic resin different from the aromatic polycarbonate per 100 parts by weight of the aromatic polycarbonate according to claim 11. 16. An aromatic polycarbonate composition further comprising 1 to 150 parts by weight of a solid filler per 100 parts by weight of the aromatic polycarbonate according to claim 11, and 10 to 150 parts by weight of a thermoplastic resin different from the aromatic polycarbonate. object.