JP3144831B2 - Copolycarbonate and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymerized polycarbonate and a method for producing the same, and more particularly to a copolymerized polycarbonate which does not impair the inherent heat resistance and good hue of the polycarbonate and which has improved fluidity during melt molding. The present invention relates to a polycarbonate and a method for producing a copolymerized polycarbonate capable of producing such a copolymerized polycarbonate.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate has excellent mechanical properties such as impact resistance, and also has excellent heat resistance and transparency, and is widely used in various mechanical parts, optical discs, automobile parts, and the like. ing.

Conventional polycarbonates having the above-mentioned properties are usually produced by an interfacial polymerization method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene.

When such a polycarbonate is molded into, for example, an optical disk, it is melted at a high temperature in order to increase the fluidity. In general, polymers are more susceptible to molded articles, such as the longer the melting time at high temperatures, the lower the transparency or hue.
For this reason, if the fluidity of the copolymerized polycarbonate can be improved, a molded article less affected by heat during molding will be obtained, and the molding cycle will be faster, and the moldability will be improved, such as increasing the production yield. Become like

[0005] For this reason, there has been a demand for the emergence of a copolymerized polycarbonate which does not impair the excellent heat resistance and good hue inherently possessed by polycarbonate, and which has improved fluidity and moldability.

The present inventors have studied to obtain such a copolycarbonate, and as a result, a novel copolycarbonate obtained by melt copolycondensation of a specific aromatic dihydroxy compound with diester carbonate together with bisphenol A is described above. The inventors have found that such requirements are satisfied, and have completed the present invention.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has improved the fluidity during melt molding without impairing the heat resistance and favorable hue inherent to polycarbonate. It is an object of the present invention to provide a copolymerized polycarbonate and a method for producing a copolymerized polycarbonate capable of producing such a copolymerized polycarbonate.

[0008]

SUMMARY OF THE INVENTION A copolymer polycarbonate according to the present invention comprises a repeating structural unit represented by the following general formula [I]:
A repeating structural unit represented by the following general formula [II]
It is characterized in that it is contained in a molar ratio of 9: 1 to 10:90.

[0009]

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(In the formula, R ¹ represents hydrogen or a methyl group.) Further, in the copolymerized polycarbonate according to the present invention, a repeating structural unit represented by the above general formula [I];
The repeating structural unit represented by the general formula [II] is represented by 9
It contains a repeating structural unit represented by the following general formula [III] in a molar ratio of 9: 1 to 10:90 and a compound represented by the formula [I
It may be contained in an amount of 80 mol or less based on 100 mol of the total amount of the repeating structural unit represented by I] and the repeating structural unit represented by the formula [III].

[0011]

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(In the formula, R ² represents hydrogen or a methyl group.) A method for producing a copolymerized polycarbonate according to the present invention comprises an aromatic dihydroxy compound represented by the following general formula [IV]: An aromatic dihydroxy compound represented by the formula [V] in a molar ratio of 99: 1 to 10:90, and a carbonic acid diester:
It is characterized by performing melt copolycondensation in the presence of an alkaline compound catalyst.

[0013]

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(In the formula, R ¹ represents hydrogen or a methyl group.) Further, in the method for producing a copolymerized polycarbonate according to the present invention, the aromatic dihydroxy compound is an aromatic dihydroxy compound represented by the above general formula [IV]. Along with the dihydroxy compound and the aromatic dihydroxy compound represented by the general formula [V], an aromatic dihydroxy compound represented by the following general formula [VI] is combined with a compound represented by the formula [VI] and a compound represented by the formula [V]. It may be used in an amount of 80 mol or less based on 100 mol in total with the compound represented.

[0015]

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(In the formula, R ² represents hydrogen or a methyl group.) Further, in the method for producing a copolymerized polycarbonate according to the present invention, [A] a copolymerized polycarbonate which is a reaction product, The sulfonic acid compound represented by the formula [VII] is added to the copolymerized polycarbonate in an amount of 0.0
Preferably, it is added in an amount of 5 to 10 ppm.

[0017]

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Wherein R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms (hydrogen may be substituted by halogen);
⁸ is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms (hydrogen may be substituted by halogen), and n is an integer of 0 to 3. In the method for producing a copolymerized polycarbonate according to the present invention, the reaction product [A] copolymerized polycarbonate is added to the above-mentioned [B] sulfonic acid compound,
[C] The epoxy compound is added in an amount of 1 to 2000 ppm based on the copolymerized polycarbonate, and the [D] phosphorus compound is further added in an amount of 10 to 1000 ppm based on the copolymerized polycarbonate.
Preferably, it is added in the amount of ppm.

In the method for producing a copolymerized polycarbonate according to the present invention, (a) a nitrogen-containing basic compound is used as an alkaline compound catalyst in an amount of 5 × 10 ^{−5 to} 7.5 × per mole of an aromatic dihydroxy compound. It is preferred to use an amount of 10 ^-4 mol and / or (b) an alkali metal compound and / or an alkaline earth metal compound in an amount of 5 x 10 ^-8 to 8 x 10 ^-7 mol.

The copolymerized polycarbonate according to the present invention comprises:
It is a novel compound containing a specific amount of a structural unit derived from a specific aromatic dihydroxy compound. Such a copolymerized polycarbonate is excellent in fluidity at the time of melt molding without impairing the heat resistance and good hue inherent to the polycarbonate.

In the process for producing a copolycarbonate according to the present invention, the copolycondensation is carried out in the presence of an alkaline compound catalyst, and a [B] sulfonic acid specific to the reaction product [A] copolycarbonate is preferably used. Compound,
By adding the [C] epoxy compound and the [D] phosphorus compound, the above-mentioned copolymerized polycarbonate can be produced.

[0022]

DETAILED DESCRIPTION OF THE INVENTION First, the copolymerized polycarbonate according to the present invention will be described. The copolymerized polycarbonate according to the present invention is composed of a repeating structural unit represented by the following general formula [I] and a repeating structural unit represented by the following general formula [II].

[0023]

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In the above formula [I], R ¹ represents hydrogen or a methyl group. In the copolymerized polycarbonate according to the present invention, the repeating structural unit represented by the general formula [I] and the repeating structural unit represented by the general formula [II] are used in a ratio of 99: 1.
-10: 90, preferably 97: 3-20: 80.

Further, the copolymerized polycarbonate according to the present invention may contain a repeating structural unit represented by the following general formula [III].

[0026]

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In the above formula [III], R ² represents hydrogen or a methyl group. When the copolymerized polycarbonate according to the present invention contains such a repeating structural unit represented by the formula [III], the structural unit [III] is replaced with the repeating structural unit represented by the formula [III]. And the formula [II]
May be contained in an amount of 80 mol or less, preferably 70 to 2 mol, based on 100 mol of the total amount of the repeating structural unit represented by the formula (1).

The copolymerized polycarbonate according to the present invention comprises:
A novel copolymeric polycarbonate containing a repeating structural unit represented by the general formula [II] and, if necessary, a repeating structural unit represented by the general formula [III], wherein the heat resistance inherent to the polycarbonate is: It does not impair good hue and has excellent fluidity during melt molding. As described above, the copolymerized polycarbonate according to the present invention, which has excellent fluidity, hardly undergoes thermal decomposition at the time of melt molding, and therefore has a low molecular weight and is hardly colored. Such a copolymerized polycarbonate has excellent hue stability over a long period of time and can form a molded article having excellent transparency.

Hereinafter, a method for producing such a copolymerized polycarbonate will be specifically described. In the present invention, first, an aromatic dihydroxy compound and a carbonic acid diester are melt-copolycondensed in the presence of an alkaline compound catalyst to produce a copolymerized polycarbonate.

In the present invention, a compound represented by the following formula [IV] (bisphenol A) and a compound represented by the following formula [V] are used as the aromatic dihydroxy compound.

[0031]

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In the formula [V], R ¹ represents hydrogen or a methyl group. Specific examples of the compound represented by the formula [V] include 2,4′-dihydroxydiphenylmethane and 2,4′-dihydroxydiphenyl-1,1-ethane.

These can be used alone or in combination. In the present invention, the aromatic dihydroxy compound represented by [IV] and [V] is used in a molar ratio of 99: 1 to 10:90, preferably 97: 3 to 2 in a molar ratio.
Used at a ratio of 0:80.

Further, in the present invention, together with the aromatic dihydroxy compounds represented by the above [IV] and [V],
If necessary, an aromatic dihydroxy compound represented by the following general formula [VI] can be used.

[0035]

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In the formula [VI], R ² represents hydrogen or a methyl group. Specific examples of such a compound represented by the formula [VI] include 4,4′-dihydroxydiphenylmethane and 4,4′-dihydroxydiphenyl-1,1-ethane.

These can be used alone or in combination. When such a compound represented by the formula [VI] is used, the compound represented by the formula [VI] is replaced with a compound represented by the formula [V] and a compound represented by the formula [VI]. It is usually used in an amount of 80 mol or less, preferably 70 to 2 mol, based on the total amount of 100 mol.

As the carbonic acid diester used in the present invention,
Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate,
Dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like can be mentioned.

Of these, diphenyl carbonate is particularly preferably used. These carbonic acid diesters can be used alone or in combination.

The above-mentioned carbonate diester may contain a dicarboxylic acid or a dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

Such dicarboxylic acids or dicarboxylic esters include terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as diphenyl terephthalate and diphenyl isophthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, spearic acid, azelaic acid, sebacic acid, decandioic acid, dodecandioic acid, diphenyl sebacate, and decandioic acid Diphenyl, aliphatic dicarboxylic acids such as diphenyl dodecane diacid, cyclopropane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,
3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diphenylcyclopropanedicarboxylate, diphenyl 1,2-cyclobutanedicarboxylate, 1,3- Diphenyl cyclobutane dicarboxylate, diphenyl 1,2-cyclopentane dicarboxylate, diphenyl 1,3-cyclopentane dicarboxylate, diphenyl 1,2-cyclohexane dicarboxylate, diphenyl 1,3-cyclohexane dicarboxylate, 1,4-cyclohexane dicarboxylic acid Alicyclic dicarboxylic acids such as diphenyl can be exemplified.

Such a dicarboxylic acid or dicarboxylic acid ester may be contained alone or in combination. The carbonic acid diester as described above is usually used for 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferably used in an amount of 1.0 to 1.30 mol, preferably 1.01 to 1.20 mol.

In the present invention, when producing the copolymerized polycarbonate, a polyfunctional compound having three or more functional groups in one molecule can be used together with the aromatic dihydroxy compound and the carbonic acid diester. .

As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferable, and a compound having three phenolic hydroxyl groups is particularly preferable. Specifically, for example, 1,1,1-tris (4-
(Hydroxyphenyl) ethane, 2,2 ', 2 "-tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-
α, α ', α'-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α, α', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin , 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2,1,3,5-tri (4-hydroxyphenyl)
Benzene, 2,2-bis- [4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid,
Examples include 3,5-benzenetricarboxylic acid and pyromellitic acid.

Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are preferred. Used.

When a polyfunctional compound is used, the polyfunctional compound is usually used in an amount of usually not more than 0.03 mol, preferably 0.001 mol, per 1 mol of the total amount of the aromatic dihydroxy compound.
To 0.02 mol, more preferably 0.001 to 0.01 mol.
It is used in molar amounts.

In the present invention, the aromatic dihydroxy compound and the carbonic acid diester are melt-copolycondensed in the presence of an alkaline compound catalyst. As such an alkaline compound catalyst, (a) a nitrogen-containing basic compound and / or
Or (b) an alkali metal compound and an alkali metal compound can be used.

The (a) nitrogen-containing basic compound includes, for example, a nitrogen-containing basic compound which is easily decomposable or volatile at a high temperature, and specific examples include the following compounds. Can be.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (C ₆ H ₅ —CH ₂ (Me ) ₃ NOH), such as ammonium hydroxides having an alkyl group, an aryl group, an araryl group, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, and triphenylamine, R ₂ NH (where R is methyl, Secondary amines represented by alkyl such as ethyl, aryl groups such as phenyl and toluyl), primary amines represented by RNH ₂ (where R is the same as described above), and further 2-methylimidazole; Imidazoles such as 2-phenylimidazole, ammonia, tetra Methyl ammonium borohydride (Me ₄ NBH ₄ ), tetrabutyl ammonium borohydride (Bu ₄ NBH ₄ ), tetrabutyl ammonium tetraphenyl borate (Bu ₄ NBPh ₄ ), tetramethyl ammonium tetraphenyl borate (Me ₄ NBPh ₄ ), etc. Basic salts.

These compounds can be used alone or in combination. Of these, alkylammonium hydroxides are preferred, and tetramethylammonium hydroxide or tetra-n-butylammonium hydroxide is more preferably used.

The (a) nitrogen-containing basic compound used in the present invention preferably has a chlorine content of 10 ppm or less and a sodium content of 20 ppb or less. Specifically, as the nitrogen-containing basic compound having a low content of sodium impurities, in particular, tetraalkylammonium hydroxides, those commercially available as brands used for electronic applications can be used.

These (a) nitrogen-containing basic compounds can be used as an aqueous solution or a phenol solution.
In the present invention, the nitrogen-containing basic compound (a) is 5 × 1 with respect to a total of 1 mole of the aromatic dihydroxy compound.
It is preferably used in an amount of 0 ^{-5 to} 7.5 × 10 ^-4 mol.

Further, in the present invention, in the copolycondensation reaction carried out in a multi-stage process described below, the above-mentioned amount of (a) the nitrogen-containing basic compound may be added all at once in the initial stage. If necessary, the used amount may be divided into two or more, and these may be added in different copolycondensation stages.

When the (a) nitrogen-containing basic compound as a catalyst is added to the copolycondensation system in the amount described above and the aromatic dihydroxy compound and the carbonic acid diester are melt-copolycondensed, immediately after the copolycondensation, In addition, it is possible to produce a copolymerized polycarbonate that is less colored, has excellent retention stability during melt molding, and has excellent water resistance.

The alkali metal compound and alkaline earth metal compound (b) used in the present invention include, specifically, organic acid salts of alkali metals and alkaline earth metals,
Preferred examples include inorganic acid salts, oxides, hydroxides, hydrides, and alcoholates.

More specifically, examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, and sodium acetate. , Potassium acetate, lithium acetate,
Sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate , Dilithium hydrogen phosphate, disodium salt of bisphenol A,
Examples thereof include dipotassium salts, dilithium salts, phenol sodium salts, potassium salts, and lithium salts.

Specific examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, and carbon dioxide. Calcium, barium carbonate,
Examples thereof include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

These compounds may be used alone or in combination.
It can be used together. Such (b) alkali gold
Genus compounds and / or alkaline earth metal compounds are
5 moles per mole of the aromatic dihydroxy compound
× 10^-8~ 8 × 10 ^-7Mol, preferably 1 × 10^-7~ 7
× 10^-7Mol, more preferably 1 × 10^-7~ 6 × 10
^-7It is used in a molar amount.

Such an alkali metal compound or alkaline earth metal compound (b) may be used at 240 ° C., preferably at 18 ° C.
It is desirable to add it to the copolycondensation reaction carried out at a temperature of 0 ° C., more preferably 140 ° C. or less. It is preferable to add the metal compound (b) under such conditions, since a copolymerized polycarbonate having a high molecular weight, little coloring and excellent water resistance can be obtained.

In the method for producing a copolymerized polycarbonate according to the present invention, it is preferable to use (c) a borate ester. Such a boric acid compound (c) can be used as a catalyst in the melt copolycondensation, or can be added to the reaction product (A) copolymerized polycarbonate after the melt copolycondensation, Also, it can be added to both. In the present invention, it is preferable to add as a catalyst at the time of melt copolycondensation.

Examples of the boric acid compound (c) include boric acid and boric acid esters.
Examples of the borate ester include a borate ester represented by the following general formula.

B (OR) _n (OH) _{3-n wherein} R is alkyl such as methyl and ethyl, aryl such as phenyl, and n is 1, 2 or 3.

Specific examples of such borate esters include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Is mentioned.

In the present invention, when (c) boric acid or boric acid ester is used, it is used in an amount of 1 × 10 ^-6 to 1 × 10 ^-4 mol per 1 mol of the aromatic dihydroxy compound.

In the present invention, (a) a nitrogen-containing basic compound and (b) an alkali metal compound and / or an alkaline earth metal compound are combined as a catalyst, and (b) a nitrogen-containing basic compound; It is preferable to use a combination of b) an alkali metal compound and / or an alkaline earth metal compound, and (c) boric acid or a borate ester.

In the above-mentioned amount used, the catalyst comprising a combination of (a) a nitrogen-containing basic compound and (b) an alkali metal compound and / or an alkaline earth metal compound can be used at a sufficient rate for the copolycondensation reaction. And high molecular weight copolymerized polycarbonate can be produced with high polymerization activity.

(C) using a boric acid compound as a catalyst and / or
Alternatively, by adding to the reaction product [A] copolymerized polycarbonate after the melt copolycondensation, the heat resistance stability is finally improved, and a copolymerized polycarbonate having a reduced molecular weight during molding can be obtained. Become.

In the presence of such a catalyst, the copolycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester can be carried out under the same conditions as conventionally known copolycondensation reaction conditions.

Specifically, in the first stage, 80 to 2
At a temperature of 40C, preferably 100-230C, more preferably 120-220C, for 0.1-5 hours, preferably 0.2-4 hours, more preferably 0.25-3 hours, under normal pressure, The aromatic dihydroxy compound is reacted with the carbonic acid diester.

Next, the second-stage reaction was carried out at 140 to 30.
At a temperature of 0C, preferably 160-290C, more preferably 180-280C, for 0.1-5 hours, preferably 0.2-4 hours, more preferably 0.25-3 hours,
It is performed under a reduced pressure of 200 mmHg.

Next, the reaction temperature was raised while the pressure in the reaction system was reduced, and finally the pressure was reduced to 0.05 to 5 mmHg.
A copolycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is performed at 40 to 320 ° C.

The copolycondensation reaction as described above may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The reaction product [A] copolymerized polycarbonate obtained as described above usually has an intrinsic viscosity of 0.25 to 1.0 dl measured in methylene chloride at 20 ° C.
/ G, preferably 0.30 to 0.65 dl / g.

As described above, the production method according to the present invention does not use phosgene or methylene chloride which are toxic substances at the time of copolycondensation, and is therefore preferable from the viewpoint of environmental health. In the present invention, it is preferable to add [B] a sulfonic acid compound represented by the following general formula [VII] to the reaction product [A] copolymerized polycarbonate as described above.

[0075]

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In the formula, R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms (hydrogen may be substituted by halogen);
⁸ is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms (hydrogen may be substituted by halogen), and n is an integer of 0 to 3, preferably 0 or 1.

Specific examples of the sulfonic acid compound represented by the general formula [VII] [B] include sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, methyl benzenesulfonate, and benzene. Ethyl sulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, p-toluene Sulfonate such as phenyl sulfonate can be mentioned.

Further, trifluoromethanesulfonic acid,
Sulfonic acid compounds such as naphthalenesulfonic acid, sulfonated polystyrene, and methyl acrylate-sulfonated styrene copolymer may be used.

These compounds can be used alone or in combination. In the present invention, the above [B] sulfonic acid compound represented by the above general formula [VII] is usually added to the above [A] copolymerized polycarbonate at 0.05 to 10 pmm, preferably 0.1 to 10 pmm. It is preferably added in an amount of from 5 to 5 ppm, particularly preferably from 0.2 to 2 ppm.

By adding the specific [B] sulfonic acid compound in such an amount to the reaction product [A] copolymerized polycarbonate, the alkaline metal compound remaining in the [A] copolymerized polycarbonate is reduced. It is possible to obtain a copolymerized polycarbonate which has been added or weakened and finally has further improved retention stability and water resistance.

In the method for producing a copolymerized polycarbonate according to the present invention, it is preferable to add an epoxy compound [C] together with the sulfonic acid compound [B]. As such an epoxy compound [C], a compound having one or more epoxy groups in one molecule is used. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 3 , 4-Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4 '
-Epoxycyclohexylcarboxylate, 4- (3,4-
Epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl
3,4-epoxycyclohexyl carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6′-methylsilohexyl carboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, Diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3 1,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl- 3,4-epoxy B hexyl carboxylate, N- butyl-2,2-dimethyl-3,4
Epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-
3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-
3 ', 4'-epoxycyclohexylcarboxylate, 4,5-
Epoxy tetrahydrophthalic anhydride, 3-t-butyl-4,5-
Epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di
-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate.

Of these, alicyclic epoxy compounds are preferably used, and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (the following general formula [VIII]) is particularly preferably used.

[0083]

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These may be used alone or as a mixture of two or more. In the present invention, the epoxy compound [C] is used in an amount of 1 to 2000 ppm, preferably 10 to 100 ppm, based on the copolymer [A].
It is desirable to add it in an amount of 0 ppm.

As described above, when the epoxy compound [C] is added in the above amount, even if the above [B] sulfonic acid compound remains excessively in the [A] copolymerized polycarbonate, it reacts with the [C] epoxy compound. To obtain a copolymerized polycarbonate which is neutralized and has particularly improved water resistance.

In the method for producing a copolymerized polycarbonate according to the present invention, a phosphorus compound [D] may be added together with a sulfonic acid compound [B]. As such a [D] phosphorus compound, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphite ester can be used.

Specific examples of such phosphate esters include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2 -Chloroethyl) phosphate, trialkyl phosphates such as tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethyl Triaryl phosphates such as phenyldiphenyl phosphate can be exemplified.

The phosphites include compounds represented by the following general formula. P (OR) ₃ (wherein, R represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, which may be the same or different). As the compound represented by, for example, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tris (2-ethylhexyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, Tristearyl phosphite, tris (2-chloroethyl) phosphite,
Trialkyl phosphites such as tris (2,3-dichloropropyl) phosphite, tricycloalkyl phosphites such as tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-
Triarylphosphites such as butylphenyl) phosphite, tris (nonylphenyl) phosphite and tris (hydroxyphenyl) phosphite, phenyldidecylphosphite, diphenyldecylphosphite,
Examples include arylalkyl phosphites such as diphenylisooctyl phosphite, phenylisooctyl phosphite, and 2-ethylhexyl diphenyl phosphite.

Further, phosphites such as distearyl pentaerythrityl diphosphite and bis (2,4-di
-t-butylphenyl) pentaerythrityl diphosphite and the like.

These compounds can be used alone or in combination. Of these, as the [D] phosphorus compound, a phosphite represented by the above general formula is preferable, and an aromatic phosphite is more preferable, and tris (2,4-di-t-butylphenyl) phospho is particularly preferable. Fight is preferably used.

These may be added separately or simultaneously. In the present invention, the above [D] phosphorus compound is added to the [A] copolymerized polycarbonate in an amount of 10 to 1000 ppm, preferably 50 to 500 ppm.
It is desirable to add in the amount of ppm.

In the present invention, when the above-mentioned [B] sulfonic acid compound, [C] epoxy compound and [D] phosphorus compound are added to the reaction product [A] copolymerized polycarbonate, These may be added while the product [A] copolymerized polycarbonate is in a molten state, or may be added after the [A] copolymerized polycarbonate has been pelletized and then remelted. In the former, these are added while [A] copolymerized polycarbonate, which is a reaction product in a melted reactor or extruder obtained after completion of the copolycondensation reaction, is in a molten state.

Specifically, for example, a copolymer [B] and a compound [C] and [D] are added to the copolymer [A] obtained by the copolycondensation reaction in the reactor to prepare the copolymer polycarbonate. May be pelletized through an extruder, or [B] while the [A] copolymerized polycarbonate obtained in the copolycondensation reaction is pelletized from the reactor through the extruder, [C],
By adding the compound [D] and kneading them, a copolymerized polycarbonate can be obtained.

At this time, these compounds may be added simultaneously or separately. The order in which these compounds are added does not matter. In the present invention, to the copolymerized polycarbonate obtained as described above, as long as the object of the present invention is not impaired, ordinary heat stabilizers, ultraviolet absorbers, release agents, coloring agents, and antistatic agents as shown below. Agents, slip agents, anti-blocking agents, lubricants, anti-fogging agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like may be added. Such additives are
The compounds [B], [C] and [D] may be added simultaneously or separately.

Specific examples of such heat-resistant stabilizers include phenol-based stabilizers, organic thioether-based stabilizers, and hindered amine-based stabilizers.

Examples of the phenolic stabilizer include, for example,
n-octadecyl-3- (4-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, tetrakis [methylene-3-
(3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, distearyl ( 4-hydroxy-3-methyl-5-t-butyl) benzylmalonate,
Examples thereof include 4-hydroxymethyl-2,6-di-t-butylphenol, and these may be used alone or as a mixture of two or more.

Examples of the thioether-based stabilizer include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, and ditridecyl-3,3'-thiodipropionate. , Pentaerythritol-tetrakis- (β-lauryl-
Thiopropionate).

These may be used alone or as a mixture of two or more. Examples of the hindered amine stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-).
Piperidyl) sebacate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxy ピ -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl
-1,2,3-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2- (3,5-di-t-butyl -4-hydroxybenzyl) -2
bis (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butylmalonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4- Butane tetracarboxylate and the like can be mentioned.

These may be used alone or as a mixture of two or more. These heat stabilizers are used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the copolymerized polycarbonate. Preferably, it is used in an amount.

Such a heat stabilizer may be added in a solid state or a liquid state. It is preferable to add such a heat stabilizer while the [A] copolymerized polycarbonate is in a molten state while being cooled and pelletized from the final polymerization vessel. The number is small. Also, when heat treatment such as extrusion or pelletizing again, since the copolymerized polycarbonate contains a heat stabilizer,
Thermal decomposition can be suppressed.

The ultraviolet absorber may be a general ultraviolet absorber, and is not particularly limited. Examples thereof include a salicylic acid ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a cyanoacrylate ultraviolet absorber. Agents and the like.

Specific examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate. Benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2′-dihydroxy
-4-methoxybenzophenone, 2,2'-dihydroxy-4,4 '
-Dimethoxybenzophenone, 2-hydroxy-4-methoxy
-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4 -Dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-
Methoxybenzophenone-5-sulfonic acid and the like.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butyl). Phenyl) benzotriazole, 2- (2'-hydroxy-3'-t
-Butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl-phenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy
-5'-t-octylphenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5 ' -Methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like. .

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate and the like. Even if these are used alone,
You may mix and use 2 or more types.

These ultraviolet absorbents are usually used in an amount of 0.001 to 100 parts by weight of the copolymer (A).
To 5 parts by weight, preferably 0.005 to 1.0 parts by weight, more preferably 0.01 to 0.5 parts by weight.

The release agent may be a general release agent and is not particularly limited. For example, examples of the hydrocarbon release agent include natural and synthetic paraffins, polyethylene waxes, and fluorocarbons.

Examples of the fatty acid-based release agent include stearic acid,
Higher fatty acids such as hydroxystearic acid, oxy fatty acids and the like can be mentioned. Examples of the fatty acid amide release agent include fatty acid amides such as stearic acid amide and ethylenebisstearamide, and alkylenebisfatty acid amides.

Examples of the alcohol release agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols and polyglycerols.

Examples of the fatty acid ester release agent include lower alcohol esters of aliphatic acids such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters.

Examples of the silicone release agent include silicone oils. These may be used alone or in combination of two or more.

These release agents are usually used in an amount of 0.001 to 5 based on 100 parts by weight of the copolymer (A).
It can be used in an amount of from 0.005 to 1 part by weight, more preferably from 0.01 to 0.5 part by weight.

Further, the colorant may be a pigment or a dye. Coloring agents include inorganic and organic coloring agents, either of which may be used.
They may be used in combination.

Specific examples of the inorganic colorant include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as navy blue, and zinc chromate. , Chromates such as molybdenum red, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine blue,
Phosphates such as manganese violet; carbon such as carbon black; and metallic powder coloring agents such as bronze powder and aluminum powder.

Specific examples of the organic colorant include nitroso-based dyes such as naphthol green B, nitro-based dyes such as naphthol yellow-S, lithol red and Bordeaux 10
B, phthalocyanine such as naphthol red and chromophtal yellow, phthalocyanine such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue, quinacridone violet, and dioxazine violet.

These coloring agents may be used alone or in combination. These colorants are usually used in an amount of 1 × 10
^{-6 to} 5 parts by weight, preferably 1 × 10 ^{-5 to} 3 parts by weight, more preferably 1 × 10 ^-5 to 1 part by weight.

In the present invention, it is preferable to subject the copolymerized polycarbonate obtained as described above to a reduced pressure treatment. When performing such a decompression treatment, the treatment apparatus is not particularly limited. For example, a reactor with a decompression device may be used, or an extruder with a decompression device may be used.

When a reactor is used, either a vertical tank reactor or a horizontal tank reactor may be used, and a horizontal tank reactor is preferably used. When performing the decompression treatment in the reactor as described above, the pressure is 0.05 to 750 mm.
Hg, preferably under the condition of 0.05 to 5 mmHg.

It is preferable that such a decompression treatment is carried out for about 10 seconds to 15 minutes when using an extruder, and about 5 minutes to 3 hours when using a reactor. Further, the decompression treatment is preferably performed at a temperature of about 240 to 350 ° C.

When the depressurizing treatment is performed in the extruder, either a single-screw extruder with a vent or a twin-screw extruder may be used, and the pelletizing may be performed while the depressurizing treatment is performed by the extruder.

When the decompression treatment is performed in an extruder,
The reduced pressure treatment is performed at a pressure of 1 to 750 mmHg, preferably 5 to 70 mmHg.
It is performed under the condition of 0 mmHg. In this way, the copolymerized polycarbonate as a reaction product is preferably added to [B] a sulfonic acid compound, [C] an epoxy compound,
[D] After the phosphorus compound is added, a reduced pressure treatment is performed.
It is possible to obtain a copolymerized polycarbonate in which residual monomers and oligomers are reduced. Such a copolymerized polycarbonate is less likely to cause mold contamination during molding, can form a molded article having excellent molding quality, and can reduce the frequency of mold replacement.

In the method for producing a copolymerized polycarbonate according to the present invention, as described above, an aromatic dihydroxy compound containing a specific dihydroxy compound and a carbonic acid diester are melt-copolycondensed. Furthermore, a specific sulfonic acid compound, an epoxy compound and a phosphorus compound are further added to the copolymerized polycarbonate obtained preferably after the copolycondensation.

The copolymerized polycarbonate thus obtained has excellent hue stability over a long period of time and can form a molded article having excellent transparency.
It can be widely and preferably used for optical applications such as compact discs, transparent components such as automobiles used outdoors, and housings for various devices.

[0123]

As described above, the copolymerized polycarbonate according to the present invention has a specific aromatic dihydroxy compound (2,4'-dihydroxydiphenylmethane and / or 2,4'-dihydroxydiphenyl-1,1-ethane). Is a novel compound containing a structural unit derived from

In such a copolymerized polycarbonate,
The fluidity during melt molding is improved while maintaining the heat resistance and good hue inherent to polycarbonate. In the method for producing a copolymerized polycarbonate according to the present invention, the aromatic dihydroxy compound containing the specific dihydroxy compound and a carbonic acid diester are melt-copolycondensed.

According to such a method for producing a copolymerized polycarbonate according to the present invention, while maintaining the heat resistance and good hue inherent to polycarbonate as described above,
Copolymerized polycarbonate with improved fluidity and moldability during melt molding can be easily produced.

Furthermore, a specific sulfonic acid compound, and further an epoxy compound and a phosphorus compound are added to the copolymerized polycarbonate obtained after the copolycondensation, whereby the water resistance and hue stability are further improved. A copolymerized polycarbonate can be obtained.

The copolymerized polycarbonate thus obtained has excellent hue stability over a long period of time and can form a molded article having excellent transparency.
It can be widely and preferably used for optical applications such as compact discs, transparent components such as automobiles used outdoors, and housings for various devices.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0129]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

In the present specification, the intrinsic viscosity [IV], MFR, yellowness [YI], light transmittance, haze, retention stability and water resistance of a polycarbonate are measured as follows.

[Intrinsic viscosity [IV]] Methylene chloride (0.1%)
5 dl / g) at 20 ° C. using an Ubbelohde viscometer.

[MFR (g / 10 min)] JIS K-7
The measurement was performed at a temperature of 300 ° C. and a load of 1.2 kg according to the method of Example 210.

[Yellowness (YI)] A 3 mm-thick injection molded plate was subjected to a cylinder temperature of 320 ° C., an injection pressure of 1000 kg / cm,
One cycle 45 seconds, molding at a mold temperature of 90 ° C, X, Y,
Use Z value for Colorand Color Deffer manufactured by Nippon Denshoku Industries Co., Ltd.
The yellowness [YI] was measured by a transmission method using ence Meter ND-1001 DP.

YI = (100 / Y) × (1.277X-1.060Z) [Light Transmittance] An injection molded plate having a thickness of 3 mm was measured using NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd.

[Haze] The haze was measured on an injection molded plate having a thickness of 3 mm using NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd.

[Water resistance] An injection molded plate having a thickness of 3 mm was immersed in water in an autoclave and placed in an oven at 125 ° C for 5 minutes.
Hold for days. The haze was measured using this test piece.

[Retention stability] After maintaining in a cylinder of an injection molding machine at a temperature of 320 ° C. for 15 minutes, injection molding was performed at that temperature, and the MFR and YI of the obtained molded plate were measured.

[0138]

Example 1 396 mol of bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) and 17.6 mol of 4,4'-
Dihydroxydiphenyl-1,1-ethane and 26.4 moles of 2,4′-dihydroxydiphenyl-1,1-ethane and 460 moles of diphenyl carbonate were charged into a 250-liter stirred tank, and after purging with nitrogen, Melted at 140 ° C.

Using this as a catalyst, 110 mmol of tetramethylammonium hydroxide (2.5 × 10 ⁻⁴ mol / mol-aromatic dihydroxy compound) and 0.176 mmol of sodium hydroxide (4 × 10 ⁻⁷ mol / mol) −
An aromatic dihydroxy compound) was added, and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage reaction.

Next, after the temperature was raised to 210 ° C., the pressure was gradually reduced to 200 mmHg, and the mixture was stirred for 30 minutes to carry out the second-stage reaction. Next, the temperature was raised to 240 ° C., gradually reduced to 15 mmHg, and the mixture was stirred for 1 hour to perform a third-stage reaction.

The pressure of the obtained reaction product was increased by a gear pump and sent to a centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively.

Next, a 29
Biaxial horizontal stirring polymerization tank controlled at 0 ° C. and 0.2 mmHg (L / D = 3, stirring blade rotation diameter 220 mm, internal volume 8
0 liters) at a rate of 40 kg / hr and a residence time of 30
In minutes.

The obtained polymer was kept in a molten state.
This polymer was twin-screw extruded (L / D = 1) using a gear pump.
7.5, barrel temperature 285 ° C.), and 0.7 ppm of butyl p-toluenesulfonate, tris (2,4-di-t-butylphenyl) phosphite (mark 21) with respect to the resin.
12: 300 ppm of Adeka Argus Co., Ltd.) and 300 ppm of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (Celoxide 2021P: Daicel Chemical Co., Ltd.), kneaded into a strand through a die, and cut with a cutter. Pellets were used.

Incidentally, tetramethylammonium hydroxide is commercially available 20% as a grade for electronic use.
An aqueous solution was used. Na content in aqueous solution is 9 ppb, C
The l content was 3 ppm.

Table 1 shows the obtained results.

[0146]

EXAMPLE 2 308 moles of bisphenol A, 66 moles of 4,4'-dihydroxydiphenyl-1,1-ethane and 66 moles of 2,4'-dihydroxydiphenyl-1,1-ethane were combined with diphenyl carbonate 460. And a 250-liter stirred tank, and after purging with nitrogen, 14
Melted at 0 ° C.

Using this as a catalyst, 110 mmol of tetramethylammonium hydroxide (2.5 × 10 ⁻⁴ mol / mol-aromatic dihydroxy compound) and 0.22 mmol of sodium hydroxide (5 × 10 ⁻⁷ mol / mol) -Aromatic dihydroxy compound), and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage reaction.

After the second stage reaction, the reaction was carried out in the same manner as in Example 1 except that butyl p-toluenesulfonate was not used. Table 1 shows the obtained results.

[0149]

Example 3 220 moles of bisphenol A and 132
Moles of 4,4'-dihydroxydiphenylmethane and 88
A mole of 2,4'-dihydroxydiphenylmethane and 460 moles of diphenyl carbonate were charged into a 250-liter stirred tank, purged with nitrogen, and then melted at 140 ° C.

Using this as a catalyst, 110 mmol of tetramethylammonium hydroxide (2.5 × 10 ^-4 mol / mol-aromatic dihydroxy compound) and 0.22 mmol of sodium hydroxide (5 × 10 ^-7 mol / mol) (Aromatic dihydroxy compound) and 11 mmol (2.5 × 10 ⁻⁵ mol / mol-aromatic dihydroxy compound) of boric acid were added, and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage reaction.

After the second stage reaction, the reaction was carried out in the same manner as in Example 2. Table 1 shows the obtained results.

[0152]

Example 4 88 mol of bisphenol A, 264 mol of 4,4'-dihydroxydiphenylmethane and 88 mol of 2,4'-dihydroxydiphenylmethane were charged into 460 mol of diphenyl carbonate and a 250-liter stirred tank. After the replacement with nitrogen, the mixture was melted at 140 ° C.

Using this as a catalyst, 110 mmol (2.5 × 10 ^-4 mol / mol-aromatic dihydroxy compound) of tetramethylammonium hydroxide and 0.22 mmol (5 × 10 ^-7 mol / mol of sodium hydroxide) of sodium hydroxide were used. (Aromatic dihydroxy compound) and 11 mmol (2.5 × 10 ⁻⁵ mol / mol-aromatic dihydroxy compound) of boric acid were added, and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage reaction.

After the second stage reaction, the reaction was carried out in the same manner as in Example 2. Table 1 shows the obtained results.

[0155]

Example 5 396 moles of bisphenol A and 44 moles of 2,4'-dihydroxydiphenyl-1,1-ethane were charged into 460 moles of diphenyl carbonate in a 250-liter stirred tank, followed by purging with nitrogen. At 140 ° C.

Using this as a catalyst, 110 mmol of tetramethylammonium hydroxide (2.5 × 10 ⁻⁴ mol / mol-aromatic dihydroxy compound) and 0.176 mmol of sodium hydroxide (4 × 10 ⁻⁷ mol / mol) −
An aromatic dihydroxy compound) was added, and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage reaction.

After the second stage reaction, the reaction was carried out in the same manner as in Example 2. Table 1 shows the obtained results.

[0158]

Example 6 352 moles of bisphenol A, 44 moles of 4,4'-dihydroxydiphenylmethane and 44 moles of 2,4'-dihydroxydiphenyl-1,1-ethane
460 mol of diphenyl carbonate and 250 liter tank type stirring tank were charged and purged with nitrogen, and then melted at 140 ° C.

Using this as a catalyst, 110 mmol (2.5 × 10 ⁻⁴ mol / mol-aromatic dihydroxy compound) of tetramethylammonium hydroxide and 0.176 mmol (4 × 10 ⁻⁷ mol / mol of sodium hydroxide) of sodium hydroxide were used. (Aromatic dihydroxy compound) and 11 mmol (2.5 × 10 ⁻⁵ mol / mol-aromatic dihydroxy compound) of boric acid were added, and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage reaction.

After the second-stage reaction, the same procedure as in Example 2 was carried out. Table 1 shows the obtained results.

[0161]

Example 7 Example 1 was repeated except that tris (2,4-di-t-butylphenyl) phosphite was not used.
Performed in the same manner as in Example 1.

Table 1 shows the obtained results.

[0163]

Example 8 396 moles of bisphenol A and 17.
6 moles of 4,4'-dihydroxydiphenyl-1,1-ethane and 26.4 moles of 2,4'-dihydroxydiphenyl-1,1
-Ethane is combined with 460 moles of diphenyl carbonate and 2
After charging into a 50-liter stirred tank and purging with nitrogen, the mixture was melted at 140 ° C.

Using this as a catalyst, 110 mmol of tetramethylammonium hydroxide (2.5 × 10 ⁻⁴ mol / mol-aromatic dihydroxy compound) and 0.176 mmol of sodium hydroxide (4 × 10 ⁻⁷ mol / mol) were used. (Aromatic dihydroxy compound) and 11 mmol (2.5 × 10 ⁻⁵ mol / mol-aromatic dihydroxy compound) of boric acid were added, and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage reaction.

After the second stage reaction, butyl p-toluenesulfonate, 3,4-epoxycyclohexylmethyl-3,4-
The procedure was performed in the same manner as in Example 1 except that epoxycyclohexylcarboxylate and tris (2,4-di-t-butylphenyl) phosphite were not used.

Table 1 shows the obtained results.

[0167]

Example 9 In Example 2, boric acid was not used during the polymerization, and 0.7 ppm of butyl p-toluenesulfonate was added after the polymerization.
The procedure was performed in the same manner as in Example 1 except that the addition was performed.

Table 1 shows the obtained results.

[0169]

Comparative Example 1 In Example 1, bisphenol A was added
Using 40 mol, 4,4'-dihydroxydiphenyl-1,1-
Example 1 was repeated except that ethane and 2,4'-dihydroxydiphenyl-1,1-ethane were not used.

Table 1 shows the obtained results.

[0171]

Comparative Example 2 Example 2 was repeated except that 132 mol of 4,4′-dihydroxydiphenyl-1,1-ethane was used and that 2,4′-dihydroxydiphenyl-1,1-ethane was not used. Performed as in Example 2.

Table 1 shows the obtained results.

[0173]

Comparative Example 3 The procedure of Example 3 was repeated, except that 2,4′-dihydroxydiphenyl-1,1-ethane was used in an amount of 220 mol and 2,4′-dihydroxydiphenyl-1,1-ethane was not used. Performed as in Example 3.

Table 1 shows the obtained results.

[0175]

[Table 1]

[0176]

[Table 2]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-243115 (JP, A) JP-A-59-166528 (JP, A) JP-A-59-131623 (JP, A) International publication 86/80 (WO, A2) European Patent Application Publication 435124 (EP, A2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 C08L 69/00 CA (STN)

Claims (12)

(57) [Claims] Claims: 1. A repeating structural unit represented by the following general formula [I] and a repeating structural unit represented by the following general formula [II] are contained in a molar ratio of 99: 1 to 10:90. A copolymerized polycarbonate characterized by the following. Embedded image (In the formula [I], R ¹ represents hydrogen or a methyl group.) 2. A composition comprising the repeating structural unit represented by the general formula [I] and the repeating structural unit represented by the general formula [II] in a molar ratio of 99: 1 to 10:90. The repeating structural unit represented by the following general formula [III] is used in an amount of 80 mol per 100 mol of the total amount of the repeating structural unit represented by the formula [II] and the repeating structural unit represented by the formula [III]. Copolycarbonate characterized by being contained in an amount of not more than mol. Embedded image (In the formula, R ² represents hydrogen or a methyl group.) 3. An aromatic dihydroxy compound represented by the following general formula [IV] and an aromatic dihydroxy compound represented by the following general formula [V] in a molar ratio of 99: 1 to 10:90. A method for producing a copolymerized polycarbonate, comprising subjecting an aromatic dihydroxy compound and a carbonic acid diester to melt copolycondensation in the presence of an alkaline compound catalyst. Embedded image (In the formula [IV], R ¹ represents hydrogen or a methyl group.) 4. An aromatic dihydroxy compound represented by the above general formula [IV] and an aromatic dihydroxy compound represented by the above general formula [V] in a molar ratio of 99: 1 to 10:90. An aromatic dihydroxy compound represented by the following general formula [VI] is used in an amount of 80 mol or less based on 100 mol of the total amount of the compound represented by the formula [V] and the compound represented by the formula [VI]. 1. A method for producing a copolymerized polycarbonate, comprising subjecting an aromatic dihydroxy compound and a carbonic acid diester to be contained in an amount in an amount by melt copolycondensation in the presence of an alkaline compound catalyst. Embedded image (In the formula, R ² represents hydrogen or a methyl group.) 5. An aromatic dihydroxy compound represented by the general formula [IV] and an aromatic dihydroxy compound represented by the general formula [V] in a molar ratio of 99: 1 to 10:90. and aromatic dihydroxy compounds, and carbonic acid diester, mixture was allowed to melt co polycondensation in the presence of an alkaline compound catalyst, [B] a sulfonic acid compound represented by the following general formula [VII], with respect to the reaction products A method for producing a copolymerized polycarbonate, which is added in an amount of 0.05 to 10 ppm. Embedded image [In the formula, R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms (hydrogen may be substituted by halogen), and R ⁸ is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms (hydrogen is halogen. May be substituted), and n is an integer of 0 to 3. ] 6. An aromatic dihydroxy compound represented by the above general formula [IV] and an aromatic dihydroxy compound represented by the above general formula [V] in a molar ratio of 99: 1 to 10:90. The aromatic dihydroxy compound represented by the general formula [VI] is used in an amount of 80 mol or less based on 100 mol of the total amount of the compound represented by the formula [V] and the compound represented by the formula [VI]. an aromatic dihydroxy compound containing an amount, and a carbonic acid diester, mixture was allowed to melt co polycondensation in the presence of an alkaline compound catalyst, a sulfonic acid compound represented by [B] above general formula [VII], the reaction product A method for producing a copolymerized polycarbonate, characterized in that it is added in an amount of 0.05 to 10 ppm to the product . 7. An aromatic dihydroxy compound represented by the general formula [IV] and an aromatic dihydroxy compound represented by the general formula [V] in a molar ratio of 99: 1 to 10:90. and aromatic dihydroxy compounds, and carbonic acid diester, mixture was allowed to melt co polycondensation in the presence of an alkaline compound catalyst, [B] the above general formula sulfonic acid compound represented by [VII], with respect to the reaction products The epoxy compound [C] is added to the reaction product in an amount of 0.05 to 10 ppm,
A method for producing a copolymerized polycarbonate, which is added in an amount of 000 ppm. 8. An aromatic dihydroxy compound represented by the above general formula [IV] and an aromatic dihydroxy compound represented by the above general formula [V] in a molar ratio of 99: 1 to 10:90. The aromatic dihydroxy compound represented by the general formula [VI] is used in an amount of 80 mol or less based on 100 mol of the total amount of the compound represented by the formula [V] and the compound represented by the formula [VI]. Of the aromatic dihydroxy compound and the carbonic acid diester in the presence of an alkaline compound catalyst, [B] the sulfonic acid compound represented by the above general formula [VII] [C] epoxy compound is added to the reaction product in an amount of from 0.05 to 10 ppm based on the reaction product.
A method for producing a copolymerized polycarbonate, which is added in an amount of 000 ppm. 9. An aromatic dihydroxy compound represented by the above general formula [IV] and an aromatic dihydroxy compound represented by the above general formula [V] in a molar ratio of 99: 1 to 10:90. Copolycondensation of an aromatic dihydroxy compound and a diester carbonate in the presence of an alkaline compound catalyst
After the reaction , [B] the sulfonic acid compound represented by the general formula [VII] is added to the reaction product in an amount of 0.05 to 10 ppm, and the [C] epoxy compound is added to the reaction product. And 1-2
[D] Phosphorus compound was added to the reaction product in an amount of
A process for producing a copolymerized polycarbonate, which is added in an amount of 00 ppm. 10. An aromatic dihydroxy compound represented by the general formula [IV] and an aromatic dihydroxy compound represented by the general formula [V] in a molar ratio of 99: 1 to 10:90. The aromatic dihydroxy compound represented by the general formula [VI] is used in an amount of 80 mol or less based on 100 mol of the total amount of the compound represented by the formula [V] and the compound represented by the formula [VI]. an aromatic dihydroxy compound containing an amount, and a carbonic acid diester, mixture was allowed to melt co polycondensation in the presence of an alkaline compound catalyst, a sulfonic acid compound represented by [B] above general formula [VII], the reaction product relative things, in an amount of 0.05-10, an epoxy compound [C], to the reaction product, 1-2
[D] Phosphorus compound was added to the reaction product in an amount of
A process for producing a copolymerized polycarbonate, which is added in an amount of 00 ppm. 11. In the copolycondensation, (a) a nitrogen-containing basic compound is used in an amount of 5 × 10 ^{−5 to} 7.5 × 10 ⁻⁴ per mole of an aromatic dihydroxy compound as an alkaline compound catalyst.
11. The method according to claim 3, wherein the alkali metal compound and / or the alkaline earth metal compound are used in an amount of 5 × 10 ⁻⁸ to 8 × 10 ⁻⁷ mol in a molar amount. A method for producing the copolymerized polycarbonate according to any one of the above. 12. 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol of (c) borate ester per 1 mol of aromatic dihydroxy compound during copolycondensation and / or after completion of copolycondensation The method for producing a copolymerized polycarbonate according to any one of claims 3 to 10, wherein the method is added to a copolymerized polycarbonate which is a reaction product.