JPH051144A - Copolymerized polycarbonate and its production - Google Patents

Abstract

PURPOSE:To obtain the subject carbonate having improved flowability in melt- forming without lowering the heat-resistance and good hue by polymerizing a specific bisphenol compound mixture and a carbonic acid diester in the presence of an alkaline compound catalyst under melting. CONSTITUTION:The objective copolymerized polycarbonate can be produced by the melt-copolymerization condensation of (A) an aromatic dihydroxy compound mixture containing (i) an aromatic dihydroxy compound of formula I and (ii) an aromatic dihydroxy compound of formula II at a molar ratio of 99:1 to 91:9 and (B) a carbonic acid diester such as diphenyl carbonate in the presence of (C) an alkaline catalyst such as sodium hydroxide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a copolymerized polycarbonate and a method for producing the same, and more specifically, a copolymerized polycarbonate which does not impair the heat resistance and good hue originally possessed by the polycarbonate and which has improved fluidity during melt molding. The present invention relates to a polycarbonate and a method for producing a copolycarbonate capable of producing such a copolycarbonate.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate has excellent mechanical properties such as impact resistance, 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 characteristics are usually produced by an interfacial polymerization method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene.

By the way, when such a polycarbonate is molded into, for example, an optical disk, it is melted at a high temperature and used in order to improve fluidity. Generally, the longer the melting time of a polymer at a high temperature, the more the polymer tends to be affected by the molded article such as the decrease in transparency or hue.
Therefore, if it is possible to improve the flowability of the polycarbonate, it becomes possible to obtain a molded product that is less affected by the heat during molding, the molding cycle is faster, and the moldability such as the production yield is improved. Become.

As a material for improving the fluidity of such a polycarbonate, for example, JP-A-60-243115 is used.
The publication discloses a copolymerized polycarbonate obtained by using bisphenol E represented by the following general formula [IV] together with bisphenol A as an aromatic dihydroxy compound.

[0006]

[Chemical 4]

However, the copolymerized polycarbonate disclosed in this publication has problems that the heat resistance inherent in the polycarbonate is lowered and that the polycarbonate is easily colored.

Therefore, it has been desired to develop a copolycarbonate having improved flowability and moldability without impairing the inherent properties such as heat resistance of polycarbonate.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and improved the fluidity at the time of melt molding without impairing the heat resistance and good hue originally possessed by polycarbonate. An object of the present invention is to provide a copolycarbonate and a method for producing a copolycarbonate capable of producing such a copolycarbonate.

[0010]

The copolymerized polycarbonate according to the present invention comprises a repeating constitutional unit represented by the following general formula [I]:
The repeating constitutional unit represented by the following general formula [II] is
It is characterized in that it is contained in a molar ratio of 9: 1 to 91: 9.

[0011]

[Chemical 5]

The method for producing a copolycarbonate according to the present invention comprises the steps of preparing an aromatic dihydroxy compound represented by the following general formula [III] and an aromatic dihydroxy compound represented by the following general formula [IV]: 99: It is characterized in that the aromatic dihydroxy compound contained in a molar ratio of 1 to 91: 9 and the carbonic acid diester are subjected to melt copolycondensation in the presence of an alkaline compound catalyst.

[0013]

[Chemical 6]

In the method for producing a copolycarbonate according to the present invention, [A] a copolycarbonate which is a reaction product, and [B] a sulfonic acid compound represented by the following general formula [V] into a copolycarbonate. To 0.05
It is preferably added in an amount of 10 ppm.

[0015]

[Chemical 7]

[V] [In the formula, R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms (hydrogen may be substituted with halogen), and R ⁸ is hydrogen or 1 to 8 carbon atoms. Is a hydrocarbon group (wherein hydrogen may be substituted with halogen), and n is an integer of 0 to 3. ]
Further, in the method for producing a copolycarbonate according to the present invention, the [A] copolycarbonate, which is a reaction product, and the [C] epoxy compound, together with the [B] sulfonic acid compound, are added to the copolycarbonate in an amount of 1 to 1. Two
It is preferable to add the phosphorus compound [D] in an amount of 000 ppm to the copolymerized polycarbonate in an amount of 10 to 1000 ppm.

Further, in the method for producing a copolycarbonate according to the present invention, as the alkaline compound catalyst, (a) the nitrogen-containing basic compound is added in an amount of 5 × 10 ^{−5 to} 7.5 × with respect to 1 mol of the aromatic dihydroxy compound. It is preferred to add in an amount of 10 ⁻⁴ mol and / or (b) the alkali metal compound and / or the alkaline earth metal compound in an amount of 5 × 10 ⁻⁸ to 8 × 10 ⁻⁷ mol.

The copolycarbonate according to the present invention is
It contains the structural unit derived from the specific aromatic dihydroxy compound in the specific amount as described above. Such a copolycarbonate does not impair the heat resistance and good hue inherent to the polycarbonate, and is also excellent in fluidity during melt molding.

In the method for producing a copolycarbonate according to the present invention, copolycondensation is carried out in the presence of an alkaline compound catalyst, and a [B] sulfonic acid specific to the [A] copolycarbonate, which is a reaction product, is preferably used. The compound, the [C] epoxy compound and the [D] phosphorus compound are added.

According to such a method, the copolycarbonate according to the present invention can be easily produced.

[0021]

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

[0022]

[Chemical 8]

In the copolymerized polycarbonate according to the present invention, the repeating constitutional unit represented by the general formula [I] and the repeating constitutional unit represented by the general formula [II] are mixed in a molar ratio of 9
The content is 9: 1 to 91: 9, preferably 97: 3 to 92: 8.

The copolycarbonate according to the present invention is
It contains the repeating structural unit represented by the general formula [II] in a specific amount as described above, and is excellent in the heat resistance inherent in polycarbonate, the good hue, and the excellent fluidity during melt molding. There is. As described above, the copolymerized polycarbonate according to the present invention, which has excellent fluidity, is unlikely to undergo thermal decomposition during melt-molding, and thus is unlikely to have a reduced molecular weight and difficult to be colored. Such a copolycarbonate has excellent hue stability over a long period of time,
A molded article having excellent transparency can be formed.

The method for producing such a copolycarbonate will be specifically described below. 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 copolycarbonate.

In the present invention, as the aromatic dihydroxy compound, a compound represented by the following formula [III] (bisphenol A) and a compound represented by the following formula [IV] (4,4'-dihydroxydiphenyl-1, 1-ethane; bisphenol E) is used.

[0027]

[Chemical 9]

In the present invention, such [III] and [I
The aromatic dihydroxy compound represented by V] is used in a molar ratio of 99: 1 to 91: 9, preferably 97: 3 to 92: 8.

The carbonic acid diester used in the present invention includes
Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate,
Examples thereof include dimethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate.

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

The above carbonic acid 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.

Examples of such dicarboxylic acid or dicarboxylic acid ester include terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as diphenyl terephthalate and diphenyl isophthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, diphenyl sebacate, decanedioic acid Diphenyl, aliphatic dicarboxylic acids such as diphenyl dodecanedioate, cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,
3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclophenyldicarboxylic acid diphenyl, 1,2-cyclobutanedicarboxylic acid diphenyl, 1,3- Cyclobutanedicarboxylic acid diphenyl, 1,2-cyclopentanedicarboxylic acid diphenyl, 1,3-cyclopentanedicarboxylic acid diphenyl, 1,2-cyclohexanedicarboxylic acid diphenyl, 1,3-cyclohexanedicarboxylic acid diphenyl, 1,4-cyclohexanedicarboxylic acid Examples thereof include alicyclic dicarboxylic acids such as diphenyl.

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

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

Examples of the (a) nitrogen-containing basic compound include, for example, nitrogen-containing basic compounds that are easily decomposable or volatile at high temperature. Specifically, the following compounds are listed. You can

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) and the like, ammonium hydroxides having an alkyl group, an aryl group, an aryl group, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, R ₂ NH (wherein R is methyl, Secondary amines represented by alkyl such as ethyl, aryl groups such as phenyl and toluyl, primary amines represented by RNH ₂ (wherein R is the same as above), and 2-methylimidazole, Imidazoles such as 2-phenylimidazole, ammonia, tetra Methylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ), etc. Basic salt.

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

The nitrogen-containing basic compound (a) 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 such sodium impurities, particularly 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, such a nitrogen-containing basic compound (a) is used in an amount of 5 × 1 per 1 mol of the aromatic dihydroxy compound in total.
It is preferably used in an amount of 0 ^{-5 to} 7.5 x 10 ^-4 mol.

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

Immediately after copolycondensation, (a) a nitrogen-containing basic compound as a catalyst is added to the copolycondensation system in an amount as described above to melt-copolycondense the aromatic dihydroxy compound and the carbonic acid diester. It is possible to produce a copolycarbonate that is less colored and has excellent retention stability during melt molding and excellent water resistance.

As the alkali metal compound and the alkaline earth metal compound (b) used in the present invention, specifically, organic acid salts of alkali metal and alkaline earth metal,
Preferred are inorganic acid salts, oxides, hydroxides, hydrides, alcoholates and the like.

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, sodium acetate. , Potassium acetate, lithium acetate,
Sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl 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 salt, dilithium salt, sodium salt of phenol, potassium salt, and lithium salt.

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 carbonic acid. 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) alkaline gold
Group compounds and / or alkaline earth metal compounds are
5 per 1 mol of the total amount 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) is 240 ° C., preferably 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 lower. It is preferable to add these (b) metal compounds under such conditions, since it becomes possible to obtain a copolycarbonate having a high molecular weight, little coloring, and excellent water resistance.

In the method for producing a copolycarbonate according to the present invention, it is preferable to use (c) 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. It can also be added to both. In the present invention, it is preferably added as a catalyst during melt copolycondensation.

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

In the formula B (OR) _n (OH) _3-n , R is alkyl such as methyl or ethyl, aryl such as phenyl, and n is 1, 2 or 3.

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

When boric acid or boric acid ester (c) is used in the present invention, it is used in an amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol with respect to 1 mol of the aromatic dihydroxy compound.

In the present invention, as a catalyst, (a) a nitrogen-containing basic compound and (b) an alkali metal compound and / or an alkaline earth metal compound are combined, and (b) a nitrogen-containing basic compound, A combination of b) an alkali metal compound and / or an alkaline earth metal compound, and (c) boric acid or a borate ester can be preferably used in combination.

A catalyst obtained by combining (a) the nitrogen-containing basic compound and (b) the alkali metal compound and / or the alkaline earth metal compound in the above-mentioned amounts is sufficient for the copolycondensation reaction to proceed at a sufficient rate. Is preferable because a high-molecular weight copolycarbonate can be produced with high polymerization activity.

(C) a boric acid compound as a catalyst and /
Alternatively, by adding it to the reaction product [A] copolycarbonate after melt copolycondensation, it is possible to finally obtain a copolycarbonate having improved heat resistance stability and particularly suppressed decrease in molecular weight during molding. Become.

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

Specifically, in the first stage, 80 to 2
40 ° C., preferably 100 to 230 ° C., more preferably 120 to 220 ° C., 0.1 to 5 hours, preferably 0.2 to 4 hours, more preferably 0.25 to 3 hours under normal pressure, The aromatic dihydroxy compound and the carbonic acid diester are reacted.

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

Next, the reaction temperature is raised while reducing the pressure of the reaction system, and finally, under a reduced pressure of 0.05 to 5 mmHg, 2
A copolycondensation reaction between an aromatic dihydroxy compound and a carbonic acid diester is carried out at 40 to 320 ° C.

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

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

As described above, the production method according to the present invention does not use toxic substances such as phosgene and methylene chloride at the time of copolycondensation, and is therefore preferable in terms of environmental hygiene. In the present invention, it is preferable to add [B] a sulfonic acid compound represented by the following general formula [V] to the [A] copolymerized polycarbonate that is a reaction product as described above.

[0062]

[Chemical 10]

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

Specific examples of such a sulfonic acid compound represented by the general formula [V] [B] include, for example, sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid, methyl benzene sulfonate, and benzene. Ethyl sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, butyl p-toluene sulfonate, octyl p-toluene sulfonate, p-toluene Mention may be made of sulfonates such as phenyl sulfonate.

Further, trifluoromethanesulfonic acid,
Sulfonic acid compounds such as naphthalene sulfonic 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 [V] is added to the above [A] copolymerized polycarbonate in an amount of 0.
It is preferably added in an amount of from 05 to 10 pmm, preferably from 0.1 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 amount of the alkaline metal compound remaining in the [A] copolymerized polycarbonate becomes moderate. Ultimately, it is possible to obtain a copolymerized polycarbonate having improved retention stability and water resistance by being added or weakened.

In the method for producing a copolycarbonate according to the present invention, it is preferable to add the [C] epoxy compound together with the [B] sulfonic acid compound. As such a [C] epoxy compound, a compound having one or more epoxy groups in one molecule is used. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butyl phenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 3 , 4-Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4 '
-Epoxy cyclohexyl carboxylate, 4- (3,4-
Epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl
3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylsiloxylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, phthalic acid diglycidyl ester, Hexahydrophthalic acid diglycidyl ester, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octylepoxytalate, epoxidized polybutadiene, 3 , 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-cyclohexyl dicarboxylate, di
Examples include -n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate.

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

[0070]

[Chemical 11]

[VI] These may be used alone or in combination of two or more. In the present invention, such a [C] epoxy compound is
1 to 20 relative to the above [A] copolymerized polycarbonate
It is desirable to add it in an amount of 00 ppm, preferably 10 to 1000 ppm.

Thus, when the [C] epoxy compound is added in the above amount, even if the [B] sulfonic acid compound remains excessively in the [A] copolymerized polycarbonate, it reacts with the [C] epoxy compound. As a result, a copolycarbonate that is neutralized and has particularly improved water resistance can be obtained.

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

Specific examples of such a phosphoric acid ester include 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 Mention may be made of triaryl phosphates such as phenyldiphenyl phosphate.

Examples of the phosphite ester include compounds represented by the following general formula. P (OR) ₃ (In the formula, R represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. These 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-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite, triarylphosphite such as tris (hydroxyphenyl) phosphite, phenyldidecylphosphite, diphenyldecylphosphite,
Examples thereof include arylalkyl phosphites such as diphenylisooctylphosphite, phenylisooctylphosphite, and 2-ethylhexyldiphenylphosphite.

Further, as phosphite, distearyl pentaerythrityl diphosphite, bis (2,4-diester
-t-butylphenyl) pentaerythrityl diphosphite and the like.

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

These may be added separately or at the same time. 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 it in the amount of ppm.

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

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

At this time, each of these compounds may be added simultaneously or separately. Further, the order of adding each of these compounds does not matter. In the present invention, the copolycarbonate obtained as described above, to the extent that the object of the present invention is not impaired, the following ordinary heat stabilizers, ultraviolet absorbers, release agents, colorants, antistatic agents are provided. Agents, slip agents, anti-blocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like may be added. Such additives are
The [B] and [C] and [D] compounds may be added at the same time 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) benzyl malonate,
4-hydroxymethyl-2,6-di-t-butylphenol and the like can be mentioned, and these may be used alone or in combination of two or more kinds.

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

These may be used alone or in admixture of two or more. Examples of hindered amine-based stabilizers 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} -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 etc. can be mentioned.

These may be used alone or in combination 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, and more preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the copolycarbonate. It is preferably used in a quantity.

Such heat resistance stabilizer may be added in the form of solid or liquid. Such a heat stabilizer is preferably added while the [A] copolycarbonate is in a molten state while being cooled and pelletized from the final polymerization vessel. Not many times. Further, when the heat treatment such as extrusion molding or pelletizing is performed again, since the copolycarbonate contains a heat-resistant stabilizer,
Thermal decomposition can be suppressed.

The UV absorber may be a general UV absorber and is not particularly limited, and examples thereof include salicylic acid UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, and cyanoacrylate UV absorbers. An agent etc. can be mentioned.

Specific examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate. Benzophenone-based UV 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 can be mentioned.

Examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole and 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 can be mentioned. .

Examples of the cyanoacrylate type ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate. Even if these are used alone,
You may use it in mixture of 2 or more types.

These ultraviolet absorbers are usually used in an amount of 0.001 per 100 parts by weight of the [A] copolymerized polycarbonate.
It can be used in an amount of about 5 to 5 parts by weight, preferably 0.005 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight.

Further, the release agent may be a general release agent and is not particularly limited. For example, hydrocarbon-based releasing agents include natural and synthetic paraffins, polyethylene waxes, fluorocarbons and the like.

As the fatty acid-based release agent, stearic acid,
Examples thereof include higher fatty acids such as hydroxystearic acid and oxyfatty acids. Examples of the fatty acid amide-based release agent include stearic acid amide, fatty acid amides such as ethylene bis stearoamide, and alkylene bis fatty acid amides.

Examples of the alcohol-based releasing agent include stearyl alcohol, cetyl alcohol and other aliphatic alcohols, polyhydric alcohols, polyglycols, polyglycerols and the like.

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

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

These releasing agents are usually used in an amount of 0.001-5 with respect to 100 parts by weight of the [A] copolymerized polycarbonate.
It can be used in an amount of parts by weight, preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight.

Further, the colorant may be a pigment or a dye. The colorant includes an inorganic colorant and an organic colorant, whichever may be used.
You may use it in combination.

Specific examples of the inorganic colorants include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as dark blue, and zinc chromate. , Chromate such as molybdenum red, sulfate such as barium sulfate, carbonate such as calcium carbonate, silicate such as ultramarine blue,
Examples thereof include phosphates such as manganese violet, carbon such as carbon black, and metal powder colorants such as bronze powder and aluminum powder.

Specific examples of the organic colorant include nitroso type such as naphthol green B, nitro type such as naphthol yellow-S, resole red and bordeaux 10.
Examples thereof include azo colorants such as B, naphthol red, and chromophthal yellow, phthalocyanine colorants such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue, quinacridone violet, and dioxazine violet.

These colorants may be used alone or in combination. These colorants are usually used in an amount of 1 × 10 6 with respect to 100 parts by weight of the [A] copolymerized polycarbonate.
^{-6 to} 5 parts by weight, preferably 1 x 10 ^{-5 to} 3 parts by weight, more preferably 1 x 10 ^-5 to 1 part by weight.

Further, in the present invention, it is preferable to subject the copolymerized polycarbonate obtained as described above to a pressure reduction treatment. In carrying out such a depressurization treatment, the treating device is not particularly limited, but for example, a reactor with a depressurizing device or an extruder with a depressurizing device may be used.

When the 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 the pressure reduction treatment is carried out in the reactor as described above, the pressure is 0.05 to 750 mm.
Hg is preferably carried out under the condition of 0.05 to 5 mmHg.

Such pressure reduction treatment is preferably carried out for about 10 seconds to 15 minutes when using an extruder, and for about 5 minutes to 3 hours when using a reactor. Further, the depressurization treatment is preferably performed at a temperature of about 240 to 350 ° C.

When the pressure reducing treatment is carried out 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 pressure reducing treatment is carried out by the extruder.

When the reduced pressure treatment is carried out in the extruder,
The depressurization treatment is performed under a pressure of 1 to 750 mmHg, preferably 5 to 70.
It is carried out under the condition of 0 mmHg. In this way, the copolymerized polycarbonate, which is a reaction product, preferably contains the [B] sulfonic acid compound and the [C] epoxy compound,
[D] After adding a phosphorus compound, if a reduced pressure treatment is performed,
A copolycarbonate having reduced residual monomers and oligomers can be obtained. Such a copolycarbonate is unlikely to cause mold stains during molding, can form a molded product with excellent molding quality, and can reduce the frequency of mold replacement.

In the method for producing a copolycarbonate according to the present invention, as described above, the aromatic dihydroxy compound containing the specific dihydroxy compound in the specific amount and the carbonic acid diester are melt-copolycondensed. In the present invention, the copolymerized polycarbonate obtained after copolycondensation,
It is preferable to add a specific sulfonic acid compound, and further an epoxy compound and a phosphorus compound.

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

[0110]

As described above, the copolymerized polycarbonate according to the present invention contains the constituent unit derived from the specified aromatic dihydroxy compound in a specified amount.

In the copolycarbonate having such a constitution, the fluidity during melt molding is improved while maintaining the heat resistance and good hue originally possessed by the polycarbonate.

In the method for producing a copolycarbonate according to the present invention, an aromatic dihydroxy compound containing a specific dihydroxy compound in a specific amount and a carbonic acid diester are melt-copolycondensed.

According to such a method for producing a copolycarbonate according to the present invention, while maintaining the heat resistance and good hue originally possessed by polycarbonate as described above,
A copolymerized polycarbonate having improved flowability and moldability during melt molding can be easily produced.

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

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

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

[0117]

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

[Intrinsic viscosity [IV]] 2 in methylene chloride
It measured at 0 degreeC using the Ubbelohde viscometer. [Yellowness (YI)] A cylinder temperature of 320 ° C., injection pressure of 1000 kg: cm, injection cycle plate of 3 mm thickness, 1 cycle 4
Molded for 5 seconds at a mold temperature of 90 ° C, and set the X, Y, and Z values for the Color and Color Defference Meter N manufactured by Nippon Denshoku Industries Co., Ltd.
The yellowness index [YI] was measured by a transmission method using D-1001 DP.

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

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

[MFR (g / 10 minutes)] JIS K-7
According to the method of No. 210, it was measured at a temperature of 300 ° C. and a load of 1.2 Kg.

[Heat deformation temperature (HDT)] 0.5 × 0.5 ×
A 5 inch injection test specimen was measured under a load of 264 psi.

[Dwelling 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 MFR and yellowness (YI) of the obtained molded plate were measured. [Water resistance] A 3 mm thick injection-molded plate is immersed in water in an autoclave and kept in an oven at 125 ° C for 5 days.
Haze was measured using this test piece.

[0124]

Example 1 404.8 mol of the compound of the formula [III] (bisphenol A) and 35.2 mol of the compound of the formula [IV] (bisphenol E) were mixed with 460 mol of diphenyl carbonate and stirred in a 250-liter tank. It was charged in a tank, replaced with nitrogen, and then melted at 140 ° C.

As a catalyst, 110 mmol of tetramethylammonium hydroxide (2.5.times.10.sup.- ⁴ mol / mol-aromatic dihydroxy compound) and 0.176 mmol of sodium hydroxide (4.times.10.sup.- ⁷ mol / mol) were used as catalysts. Mol-aromatic dihydroxy compound), and at 140 ° C., 30
After stirring for 1 minute, the first step reaction was carried out.

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 reaction. Next, the temperature was raised to 240 ° C., the pressure was gradually reduced to 15 mmHg, and the mixture was stirred for 1 hour to carry out the third stage reaction.

The pressure of the obtained reaction product was increased by a gear pump, and the reaction product was fed into 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, the reaction product was controlled from the bottom of the evaporator by a gear pump at 290 ° C. and 0.2 mmHg in a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotating diameter 220 mm,
It was fed into an inner volume of 80 liters) at a rate of 40 kg / hr and polymerized for a residence time of 30 minutes.

The obtained polymer was kept in a molten state,
This polymer was added to a twin-screw extruder (L / D = 1 with a gear pump).
7.5, barrel temperature 285 ° C.), 0.7 ppm of butyl p-toluenesulfonate and tris (2,4-di-t-butylphenyl) phosphite (mark
2112: 300 ppm of Adeka Argus Co., Ltd., 300 ppm of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (Celoxide 2021P: Daicel Chemical Co., Ltd.) were added and kneaded, and then kneaded through a die. It was made into a strand shape and cut into pellets by a cutter.

Tetramethylammonium hydroxide is 20% commercially available as electronic grade.
An aqueous solution was used. Na content in the aqueous solution is 9 ppb, C
The l content was 3 ppm.

The results obtained are shown in Table 1.

[0132]

Example 2 In Example 1, 413.6 mol of the compound of the formula [III] (bisphenol A) was added to the compound of the formula [I
Example 1 was repeated except that 26.4 mol of the compound [V] (bisphenol E) was used.

The results obtained are shown in Table 1.

[0134]

Example 3 In Example 1, 422.4 mol of the compound of formula [III] (bisphenol A) was added to the compound of formula [I
Example 1 was repeated except that 17.6 mol of the compound [V] (bisphenol E) was used.

The results obtained are shown in Table 1.

[0136]

Example 4 The procedure of Example 1 was repeated except that tris (2,4-di-t-butylphenyl) phosphite was not used.
The same procedure as in Example 1 was performed.

The results obtained are shown in Table 1.

[0138]

Example 5 Example 4 was repeated except that 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate was not used.

The results obtained are shown in Table 1.

[0140]

Example 6 In Example 5, sodium hydroxide was used in an amount of 0.088 mmol (2 × 10 ⁻⁷ mol / mol-aromatic dihydroxy compound) and butyl p-toluenesulfonate was not used. The same procedure as in Example 5 was performed.

The results obtained are shown in Table 1.

[0142]

Example 7 In Example 1, boric acid was added at the time of polymerization.
The procedure of Example 1 was repeated except that the amount of mmol (2.5 × 10 ⁻⁵ mol / mol-aromatic dihydroxy compound) was added and butyl p-toluenesulfonate was not used.

The results obtained are shown in Table 1.

[0144]

COMPARATIVE EXAMPLE 1 Example 1 was repeated except that 440 mol of the compound of formula [III] (bisphenol A) was used and the compound of formula [IV] (bisphenol E) was not used. The same was done.

The results obtained are shown in Table 1.

[0146]

Comparative Example 2 In Example 1, 374 mol of the compound of formula [III] (bisphenol A) was added to the compound of formula [IV].
Example 1 was repeated except that 66 mol of the compound (bisphenol E) was used.

The results obtained are shown in Table 1.

[0148]

[Table 1]

Claims (21)

[Claims] 1. A repeating constitutional unit represented by the following general formula [I] and a repeating constitutional unit represented by the following general formula [II] are contained in a molar ratio of 99: 1 to 91: 9. A copolymerized polycarbonate characterized by: [Chemical 1] 2. An aromatic dihydroxy compound represented by the following general formula [III] and an aromatic dihydroxy compound represented by the following general formula [IV] are contained in a molar ratio of 99: 1 to 91: 9. A method for producing a copolycarbonate, which comprises melt-copolycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of an alkaline compound catalyst. [Chemical 2] 3. An aromatic dihydroxy compound represented by the above general formula [III] and an aromatic dihydroxy compound represented by the above general formula [IV] are contained in a molar ratio of 99: 1 to 91: 9. The aromatic dihydroxy compound and the carbonic acid diester are subjected to melt copolycondensation in the presence of an alkaline compound catalyst to give a reaction product [A] copolymerized polycarbonate [B] represented by the following general formula [V]. Sulfonic acid compound is added to the copolymerized polycarbonate in an amount of 0.05 to 1
A method for producing a copolycarbonate, which comprises adding the same in an amount of 0 ppm. [Chemical 3] · · · [V] wherein, R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms (hydrogen may be substituted with halogen), R ⁸ is hydrogen or a hydrocarbon of 1 to 8 carbon atoms Is a group (hydrogen may be substituted with halogen), and n is an integer of 0 to 3. ] 4. An aromatic dihydroxy compound represented by the general formula [III] and an aromatic dihydroxy compound represented by the general formula [IV] are contained in a molar ratio of 99: 1 to 91: 9. The aromatic dihydroxy compound and the carbonic acid diester are subjected to melt copolycondensation in the presence of an alkaline compound catalyst to give a reaction product [A] copolymerized polycarbonate [B] represented by the above general formula [V]. Sulfonic acid compound is added to the copolymerized polycarbonate in an amount of 0.05 to 1
A method for producing a copolycarbonate, which comprises adding the [C] epoxy compound in an amount of 1 ppm to 2000 ppm with respect to the copolycarbonate in an amount of 0 ppm. 5. An aromatic dihydroxy compound represented by the general formula [III] and an aromatic dihydroxy compound represented by the general formula [IV] are contained in a molar ratio of 99: 1 to 91: 9. The aromatic dihydroxy compound and the carbonic acid diester are subjected to melt copolycondensation in the presence of an alkaline compound catalyst to give a reaction product [A] copolymerized polycarbonate [B] represented by the above general formula [V]. Sulfonic acid compound is added to the copolymerized polycarbonate in an amount of 0.05 to 1
In an amount of 0 ppm, the [C] epoxy compound is used in the amount of 1 to 2000 ppm of the [D] phosphorus compound in the copolymerized polycarbonate, and in the amount of 10 ppm of the copolymerized polycarbonate.
A method for producing a copolycarbonate, which comprises adding 1000 ppm. 6. In the copolycondensation, (a) the nitrogen-containing basic compound is used in an amount of 5 × 10 ^{−5 to} 7.5 × 10 ⁻⁴ mol per mol of the aromatic dihydroxy compound as an alkaline compound catalyst. , And / or (b) an alkali metal compound and /
Alternatively, an alkaline earth metal compound is added to 5 × 10 ⁻⁸ to 8 × 10.
^-7 mol, added in an amount of ⁷ mol.
4. The method for producing the copolycarbonate according to 4 or 5. 7. The above (b) alkali metal compound and / or alkaline earth metal compound is added in an amount of 1 × 10 ^{−7 to} 7 × 10 ⁻⁷ mol with respect to 1 mol of the aromatic dihydroxy compound. The method for producing the copolycarbonate according to claim 2, 3, 4, or 5. 8. The addition of the above-mentioned (b) alkali metal compound and / or alkaline earth metal compound in an amount of 1 × 10 ^{−7 to} 6 × 10 ⁻⁷ mol with respect to 1 mol of an aromatic dihydroxy compound. The method for producing the copolycarbonate according to claim 2, 3, 4, or 5. 9. The method for producing a copolycarbonate according to claim 2, wherein (a) the nitrogen-containing basic compound is tetraalkylammonium hydroxide. 10. The copolymerization according to claim 2, 3, 4 or 5, wherein (a) the nitrogen-containing basic compound is tetramethylammonium hydroxide or tetra-n-butylammonium hydroxide. Method for producing polycarbonate. 11. (a) The chlorine content in the nitrogen-containing basic compound is 10 ppm or less, and the sodium content is 20 ppb.
It is the following, The manufacturing method of the copolycarbonate of Claim 2, 3, 4 or 5. 12. 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol of (c) boric acid ester per 1 mol of an aromatic dihydroxy compound, during and / or at the end of copolycondensation. The method for producing a copolycarbonate according to claim 2, 3, 4, or 5, wherein the post-reaction product is added to the copolycarbonate. 13. The method for producing a copolycarbonate according to claim 3, 4 or 5, wherein the sulfonic acid compound [B] is used in an amount of 0.1 to 5 ppm with respect to the copolycarbonate. . 14. The method for producing a copolycarbonate according to claim 3, 4 or 5, wherein the sulfonic acid compound [B] is used in an amount of 0.2 to 2 ppm with respect to the copolycarbonate. . 15. A sulfonic acid compound [B] in the above general formula [V], R ⁷ is a methyl group, R ⁸ is hydrogen or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and n is It is a sulfonic acid compound which is 0 or 1, The manufacturing method of the copolycarbonate of Claim 3, 4 or 5 characterized by the above-mentioned. 16. The method for producing a copolycarbonate according to claim 3, wherein the sulfonic acid compound [B] is butyl p-toluenesulfonate or p-toluenesulfonic acid. 17. The method for producing a copolycarbonate according to claim 4 or 5, wherein the epoxy compound [C] is used in an amount of 1 to 1000 ppm with respect to the copolycarbonate. 18. The method for producing a copolycarbonate according to claim 4, wherein the [C] epoxy compound is an alicyclic epoxy compound. 19. The method for producing a copolycarbonate according to claim 4, wherein the [C] epoxy compound is 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate. Method. 20. The method for producing a copolycarbonate according to claim 5, wherein the phosphorus compound [D] is an aromatic phosphite compound. 21. [D] phosphorus compound is tris (2,4-di-t
-Butylphenyl) phosphite, The method for producing a copolycarbonate according to claim 5, wherein