JP2911067B2 - Method for producing polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing polycarbonate, and more particularly to a method for producing particularly excellent hue, water resistance,
The present invention relates to a method for producing a polycarbonate capable of producing a polycarbonate that can be used for applications such as optical parts requiring transparency and automotive transparent parts.

[0002]

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

Conventionally, such a polycarbonate is prepared by a method of directly reacting an aromatic dihydroxy compound such as bisphenol A with phosgene (interfacial method), or a method of transesterifying an aromatic dihydroxy compound with a carbonic acid diester (melting method). Method).

[0004] Among them, the latter has the advantage that polycarbonate can be produced at a lower cost than the former interface method and does not use toxic substances such as phosgene.

[0005] The production method of polycarbonate by the melting method is usually carried out using an alkali metal compound, an alkaline earth metal compound or the like as a catalyst. However, in the method using a large amount of such a catalyst,
During the polycondensation, the reaction product tends to be colored, and after the polycondensation, a polycarbonate having an inferior initial color tends to be obtained. Further, the obtained polycarbonate tends to have low retention stability during molding, and the molded product tends to have low water resistance.

However, if a small amount of the above-mentioned catalyst is used, the polymerization activity may be insufficient, and it has been proposed to use another catalyst in combination. For example,
No. -14742 discloses a method in which an alkali metal compound is used in an initial condensation reaction and a quaternary ammonium compound is used in a latter stage of the condensation reaction. However, in this method, the polymerization activity was not sufficient, and a large amount of the alkali metal compound had to be used.

The present inventors have also proposed a method in which a nitrogen-containing basic compound is added to a polycondensation reaction together with an alkali metal compound or an alkaline earth metal compound (Japanese Patent Application Laid-Open No. Hei 2 (1994)).
-124934). Also in this method, it is desired that the amount of the alkali metal compound or alkaline earth metal compound used is further reduced.

For this reason, even if the amount of the alkali metal compound or alkaline earth metal compound used as the catalyst is reduced, the polycondensation reaction can be carried out while maintaining sufficient polycondensation activity, and the retention stability during melting is excellent. The emergence of a polycarbonate production method capable of producing a polycarbonate having excellent water resistance has been desired.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is intended to reduce the amount of an alkali metal compound or an alkaline earth metal compound used as a catalyst, or to use no catalyst at all. In both cases, the polycondensation reaction can be performed while maintaining sufficient polycondensation activity, little coloration occurs immediately after the polycondensation, and excellent retention stability such as heat stability and hue stability during molding, as well as water resistance and transparency It is an object of the present invention to provide a method for producing a polycarbonate capable of producing an excellent polycarbonate.

[0010]

SUMMARY OF THE INVENTION The process for producing a polycarbonate according to the present invention comprises an aromatic dihydroxy compound and a carbonic acid diester comprising (a) a nitrogen-containing basic compound and (b) an alkali metal compound and / or an alkaline earth metal compound. When producing a polycarbonate by melt polycondensation in the presence of a catalyst, the melt polycondensation is performed in two or more stages, and in the first polycondensation step, an aromatic dihydroxy compound and a carbonic acid diester are Melt polycondensation in the presence of the above catalyst, and in the second and subsequent polycondensation steps,
Further, (a) the nitrogen-containing basic compound is added at least once, and (b) the addition amount of the alkali metal compound and / or the alkaline earth metal compound is 5 × 10 ^{− 8} to 8 × 10
^-7 mol, and in the first stage polycondensation step, (a)
The nitrogen-containing basic compound is replaced with an aromatic dihydroxy compound
2.5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol based on
And in the second and subsequent polycondensation steps,
(A) Nitrogen-containing basic compound is converted from the second polycondensation step
In the total amount up to the final polycondensation step, the aromatic dihydroxy
2.5 × 10 ^{−6 to} 2.5 ×
It is characterized in that it is added in an amount of 10 ⁻³ mol .

(B) an alkali metal compound and / or
The addition amount of the alkaline earth metal compound is
5 × 10 ^{−8 to} 5 × 10 ⁻⁷ mol per 1 mol of compound
The amount is preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁷ mol.
Door is preferable.

Further, in the method for producing a polycarbonate according to the present invention, [B] a sulfonic acid compound represented by the following general formula [III] is added to the [A] polycarbonate obtained as described above. , 0.05
Preferably, it is added in an amount of from 10 to 10 ppm.

[0013]

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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 polycarbonate according to the present invention, the epoxy compound [C] is added to the polycarbonate in an amount of 1 to 200 with respect to the polycarbonate.
It is preferable to further add the [D] phosphorus compound in an amount of 10 to 1000 ppm with respect to the polycarbonate in an amount of 0 ppm.

According to the method for producing a polycarbonate according to the present invention, a polycarbonate having excellent initial color tone immediately after polycondensation, little coloring, excellent retention stability during melt molding, and improved water resistance can be obtained economically. can get.

Such a polycarbonate is suitably used for applications such as optical parts requiring particularly excellent hue, water resistance and transparency, and transparent parts for automobiles.

[0017]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing a polycarbonate according to the present invention will be specifically described. First, the aromatic dihydroxy compound and the carbonic acid diester used in the present invention will be described.

The aromatic dihydroxy compound is not particularly limited, but may be a compound represented by the following formula [I].

[0019]

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R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen or a monovalent hydrocarbon group, which may be the same or different.
p and q represent an integer of 0 to 4.

The aromatic dihydroxy compound includes:
Specific examples include the following compounds: bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2 , 2-bis (4-hydroxyphenyl)
Butane, 2,2-bis (4-hydroxyphenyl) octane,
Bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-
Bis (4-hydroxy-t-butylphenyl) propane, 2,2
Bis (hydroxyaryl) alkanes such as -bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
Dihydroxyaryl ethers such as -dimethylphenyl ether, 4,4'-dihydroxydiphenylsulfide, dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 4,
Dihydroxydiarylsulfoxides such as 4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'- Dihydroxydiaryl sulfones such as dimethyldiphenyl sulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. Further, as the aromatic dihydroxy compound, the following general formula [I
The compound represented by I] can also be used.

[0023]

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In the formula, R ₆ is a hydrocarbon group having 1 to 10 carbon atoms or a halide or halogen thereof, which may be the same or different. n is 0 to 4
Is an integer.

As the aromatic dihydroxy compound represented by the above general formula [II], specifically, resorcinol and 3-
Methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, 2,3,
Substituted resorcinols such as 4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin, catechol, hydroquinone and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-butylhydroquinone t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5,6 -Substituted hydroquinones such as -tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone.

In the present invention, 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1 'represented by the following general formula is used as the aromatic dihydroxy compound. -Spirobi- [IH-indene] -6,6'-diol can also be used.

[0027]

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These aromatic dihydroxy compounds can be used alone or in combination. Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and 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.

Examples of such a 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, 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 dicarboxylic acids or dicarboxylic acid esters may be contained alone or in combination. The carbonic acid diester as described above is usually 1.0 to 1.0 mol per 1 mol of the aromatic dihydroxy compound.
It is desirable to use it in an amount of 1.30 mol, preferably 1.01 to 1.20 mol.

In the present invention, when producing a 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 used per mole of the aromatic dihydroxy compound.
Usually, 0.03 mol or less, preferably 0.001 to 0.0.
It is used in an amount of 2 mol, more preferably 0.001 to 0.01 mol.

In the method for producing a polycarbonate according to the present invention, (a) a nitrogen-containing basic compound is used as a catalyst. Such (a) nitrogen-containing basic compounds include, for example, nitrogen-containing basic compounds that are readily decomposable or volatile at high temperatures, and specific examples include the following compounds.

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, a polycarbonate is produced by melt-polycondensing the aromatic dihydroxy compound and the carbonic acid diester in the presence of such a catalyst comprising (a) a nitrogen-containing basic compound. At this time, the melt polycondensation is carried out in two or more stages.

In the first-stage polycondensation step, the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed in the presence of (a) a catalyst comprising a nitrogen-containing basic compound. In the condensation step, (a) the nitrogen-containing basic compound is further added at least once.

Specifically, in the first stage polycondensation step, the amount is preferably 2.5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol per 1 mol of the aromatic dihydroxy compound. More preferably, (a) the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed in the presence of a nitrogen-containing basic compound added in an amount of 5 × 10 ^{-6 to} 1.25 × 10 ^-3 mol, and In the polycondensation step, (a) the nitrogen-containing basic compound,
The total amount from the second-stage polycondensation step to the last-stage polycondensation step is preferably 2.5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol per 1 mol of the aromatic dihydroxy compound. And more preferably in an amount of 5 × 10 ^{−6 to} 1.25 × 10 ⁻³ mol.

Such a polycondensation reaction between an aromatic dihydroxy compound and a carbonic acid diester comprising two or more steps can be carried out under the same conditions as conventionally known polycondensation reactions. Specifically, it is performed under the following conditions.

In the first stage polycondensation step, usually 80 to 2
At a reaction temperature of 40 ° C., preferably 100 to 230 ° C., and more preferably 120 to 220 ° C., under normal pressure, the reaction is usually carried out at a temperature of 0.2 ° C.
The aromatic dihydroxy compound is reacted with the carbonic acid diester for 1 to 5 hours, preferably 0.2 to 4 hours, more preferably 0.25 to 3 hours.

Next, in the second and subsequent polycondensation steps, the reaction is carried out while increasing the reaction temperature while reducing the pressure of the reaction system, and is usually 140 to 300 ° C., preferably 160 to 29 ° C.
At a reaction temperature of 0 ° C., more preferably 180-280 ° C., under a pressure of 200 mmHg or less,
20 ° C., 0.05 to 5 mmHg, usually 0.1 to 5
Hours, preferably 0.2-4 hours, more preferably 0.2 hours.
The reaction is performed for 25 to 3 hours.

The above-mentioned polycondensation reaction 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.

In the present invention, as described above, the catalyst comprising the nitrogen-containing basic compound (a) is used once in the initial step of the polycondensation reaction, and during the polycondensation reaction performed in the presence of the catalyst. At least once. When the catalyst is added in this manner, sufficient polycondensation activity can be maintained in each stage of the polycondensation process performed in multiple stages.

Therefore, according to the present invention, even if the total amount of the catalyst used is smaller than in the conventional case, the reaction is carried out with sufficient polycondensation activity, and the economic efficiency is improved. (A) As a catalyst, the nitrogen-containing basic compound is added to the polycondensation system as described above, and the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed.
In addition, polycarbonate having excellent residence stability during melt molding and excellent water resistance can be produced.

In the present invention, in the above melt polycondensation,
(b) An alkali metal compound and / or an alkaline earth metal compound can be added. As such an alkali metal compound and an alkaline earth metal compound, specifically, an organic acid salt, an inorganic acid salt, an oxide, a hydroxide, a hydride or an alcoholate of an alkali metal or an alkaline earth metal is preferably used. No.

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 borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate , Dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, phenol sodium salt, potassium salt, lithium salt and the like.

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 calcium carbonate. , Barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.

These compounds can be used alone or in combination. The alkali metal compound and / or alkaline earth metal compound (b) is used in an amount of 5 × 10 ⁻⁸ to 1 mol of the aromatic dihydroxy compound.
In an amount of 8 × 10 ⁻⁷ mol , preferably 5 × 10 ^{−8 to} 5 × 1
0 in an amount of ^-7 mol, more preferably 5 × 10 ^-8 ~3 × 1
It is used in an amount of ^0-7 mol.

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

In the method for producing a 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 above-mentioned melt polycondensation, can be added to [A] polycarbonate obtained after the melt polycondensation, or can be added to both. Can also. In the present invention, it is preferable to add as a catalyst during melt polycondensation.

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 a borate ester include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Is mentioned.

These compounds can be used alone or in combination. (c) When boric acid or boric acid ester is used, it is usually used in an amount of 10 ^-6 to 10 ^-4 mol based on 1 mol of the aromatic dihydroxy compound.

In the present invention, the heat resistance stability is finally improved by adding (c) a boric acid compound as a catalyst and / or to the polycarbonate (A) obtained after melt polycondensation. The polycarbonate whose fall was suppressed can be obtained.

The polycarbonate [A], which is a reaction product obtained as described above, usually has an intrinsic viscosity measured in methylene chloride at 20 ° C. of 0.10 to 1.0 dl / g.
Preferably it is 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 melt polycondensation, and is therefore preferable in terms of environmental health. In the present invention, [B] a sulfonic acid compound represented by the following general formula [III] is added to the [A] polycarbonate obtained as described above.

[0063]

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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 [III] [B] include, for example, sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, methylbenzenebenzene and methylbenzenebenzene. 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, as the [B] sulfonic acid compound, in the above general formula [III], R
⁷ is a methyl group, R ⁸ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and n is preferably a compound represented by an integer of 0 to 1. Specifically, p-toluenesulfonic acid and butyl p-toluenesulfonate are preferably used.

In the present invention, the above [B] sulfonic acid compound represented by the above general formula [III] is converted to the above [A]
It is added to the polycarbonate in an amount of 0.05 to 10 pmm, preferably 0.1 to 5 ppm, particularly preferably 0.2 to 2 ppm.

By adding the specific [B] sulfonic acid compound in such an amount to the reaction product [A] polycarbonate, the alkaline metal compound remaining in [A] polycarbonate is neutralized or weakened. As a result, it is possible to finally improve the heat resistance and obtain an improved polycarbonate in which a decrease in the molecular weight during molding is particularly suppressed.

In the method for producing a 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-epoxycyclohexylcarboxylate, 3,4-epoxy-6
-Methylcyclohexylmethyl-6'-methylsilohexylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadi Enyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate,
Butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, 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-epoxycyclohexylcarboxylate, 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-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl 4, 5-epoxy-cis-1,
2-cyclohexyldicarboxylate, di-n-butyl-3-
T-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate and the like can be mentioned.

These may be used alone or as a mixture of two or more. Of these, alicyclic epoxy compounds are preferably used, and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate is particularly preferably used.

In the present invention, such an epoxy compound [C] is added to the polycarbonate [A] by 1 to 2 times.
It is preferably added in an amount of 000 ppm, preferably in an amount of 1 to 1000 ppm.

As described above, when the epoxy compound [C] is added in the above-mentioned amount, the above-mentioned [B] is added to the polycarbonate [A].
Even if an excessive amount of the sulfonic acid compound remains, it is neutralized by reacting with the [C] epoxy compound, and finally polycarbonate having excellent hue stability, excellent heat resistance, and particularly improved water resistance is obtained. Will be obtained.

In the method for producing a 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.

Further, examples of the phosphite 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, phenyl diisooctyl 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.

In the present invention, the phosphorus compound [D] is added to the polycarbonate [A] in an amount of 10 to 100%.
It is added in an amount of 0 ppm, preferably 50-500 ppm.
In the present invention, the above-mentioned [B] sulfonic acid compound,
The method of adding the [C] epoxy compound and the [D] phosphorus compound to the reaction product [A] polycarbonate as needed is not particularly limited. For example, the reaction product [A] may be added while the polycarbonate is in a molten state, or may be added after the [A] polycarbonate is pelletized once and then remelted. In the former, while the polycondensation reaction was completed and the reaction product [A] polycarbonate in the melted reactor or extruder obtained in the melted state was added to the melted state, polycarbonate was formed by adding them. Thereafter, the compound may be pelletized through an extruder, or these compounds may be added and kneaded while the [A] polycarbonate obtained by the polycondensation reaction is pelletized from the reactor through the extruder. Thus, a polycarbonate can be obtained.

At this time, these compounds may be added simultaneously or separately. When these compounds are added in combination, the order of addition is not limited.

In the present invention, the polycarbonate obtained as described above is added to the polycarbonate as long as the object of the present invention is not impaired.
Normal heat stabilizers, UV absorbers, release agents, coloring agents, antistatic agents, slip agents, antiblocking agents, lubricants, antifog agents, natural oils, synthetic oils, waxes, as shown below,
An organic filler, an inorganic filler and the like may be added. Such additives are described in the above [B], [C] and [D].
The compounds may be added simultaneously or separately.

Specific examples of such a heat-resistant stabilizer 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 0.5 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate.
Preferably, it is used in an amount of from 0.01 to 0.3 parts by weight.

The heat stabilizer may be added in a solid state or a liquid state. Such a heat stabilizer is preferably added while the polycarbonate [A] is in a molten state while being cooled and pelletized from the final polymerization vessel. In this case, the number of heat histories received by the polycarbonate is small. In addition, when heat treatment is performed again such as extrusion molding and pelletizing, since the polycarbonate contains a heat stabilizer, thermal decomposition can be suppressed.

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

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 absorbers are usually used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 1.0 parts by weight, more preferably 0.01 to 0 parts by weight, per 100 parts by weight of the polycarbonate [A]. It can be used in an amount of 0.5 parts by weight.

Further, 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.

As the fatty acid-based release agent, 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-based 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, polyhydric alcohol esters of fatty acids, and polyglycol esters of fatty acids.

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 generally used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, and more preferably 0.01 to 0.1 part by weight, per 100 parts by weight of the polycarbonate [A]. It can be used in an amount of 5 parts 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 coloring agent 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 colorants may be used alone or in combination. These colorants are usually used in an amount of 1 × 10 ^{−6 to} 5% per 100 parts by weight of the polycarbonate [A].
It can be used in an amount of 1 part 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, the polycarbonate obtained as described above is preferably subjected 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 reduced pressure 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 the 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 reaction product polycarbonate was added to [B] if necessary.
When a reduced pressure treatment is performed after the addition of the compounds [C] and [D], a polycarbonate having reduced residual monomers and oligomers can be obtained.

[0108] In the polycarbonate obtained by performing the depressurizing treatment in this way, a molded article which is less likely to stain the mold at the time of molding, has less coloring, and is excellent in molding quality can be obtained.
As described above, the polycarbonate obtained in the present invention is:
It is less colored immediately after polycondensation, and has excellent retention stability during melt molding, does not easily undergo thermal decomposition during molding, has a low molecular weight, and has excellent hue stability. Furthermore, it is excellent in water resistance, and the transparency is not easily reduced.

Such a polycarbonate is excellent in hue stability over a long period of time and can form a molded article excellent in transparency. Therefore, it is particularly useful for optical applications such as sheets, lenses and compact discs, and for outdoor use. It can be widely and preferably used for transparent parts such as automobiles and housings of various devices.

[0110]

According to the process for producing a polycarbonate according to the present invention, (a) a catalyst comprising a nitrogen-containing basic compound is used once in the initial step of the polycondensation reaction, and once in the presence of the catalyst. A melt polycondensation reaction is performed by adding at least once during the condensation reaction.

In the method for supplying the catalyst as described above, the polycondensation reaction in each stage can be maintained at a high polymerization activity even when the total amount of the supplied catalyst is small, and the economic efficiency is improved.
In the method for producing a polycarbonate according to the present invention, a coloration is reduced immediately after polycondensation, and heat stability during molding, excellent retention stability such as hue stability, water resistance, and excellent transparency are also obtained. be able to.

Further, a specific sulfonic acid compound is added to the obtained polycarbonate, whereby a polycarbonate having improved heat resistance can be obtained. Preferably, an epoxy compound and a phosphorus compound are added to obtain a polycarbonate having further improved water resistance and hue stability.

The polycarbonate obtained by the present invention has excellent hue stability over a long period of time, has excellent water resistance, and can form a molded article having excellent transparency. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0114]

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

[Intrinsic viscosity [IV]] In methylene chloride, 2
It measured at 0 degreeC using the Ubbelohde viscometer. [Hue] Injection molded plate having a thickness of 3 mm was heated at a cylinder temperature of 290.
C., injection pressure 1000 Kg / cm, molding for 45 seconds per cycle, mold temperature 100 ° C., and measuring X, Y and Z values of Color and Color Defference Meter ND-1001 manufactured by Nippon Denshoku Industries Co., Ltd.
The yellowness [YI] was measured by a transmission method using DP.

YI = 100 (1.277X-1.060Z) / Y [Light transmittance] According to the method of ASTM D1003,
It was measured using an injection molded plate for measuring hue.

[MFR] Measured at a temperature of 300 ° C. and a load of 1.2 kg according to the method of JIS K-7210.

[Retention stability] (Melting stability test) After the resin was retained in the cylinder of the injection molding machine at a temperature of 320 ° C for 15 minutes, injection molding was performed at that temperature, and the MFR of the obtained molded plate was measured. And hue (YI) were measured.

[Water Resistance] An injection molded plate for measuring hue was immersed in water in an autoclave and placed in an oven at 125 ° C. for 5 hours.
Hold for days. The haze was measured using this test piece.

[Haze] NDH manufactured by Nippon Denshoku Industries Co., Ltd.
Using -200, the haze of the injection molded plate for hue measurement was measured.

[0121]

Example 1 Bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) (0.44 mmol) and diphenyl carbonate (manufactured by Any Corporation) (0.46 mmol) were mixed in 250 parts.
After charging into a 1-liter stirred tank and purging with nitrogen, 1
Melted at 40 ° C.

To this, 44 mmol (1 × 10 ⁻⁴ mol / mol-bisphenol A) of tetramethylammonium hydroxide and 0.1 ml of sodium hydroxide were used as catalysts.
Then, 088 mmol (2 × 10 ⁻⁷ mol / mol-bisphenol A) was added, and the mixture was stirred at 140 ° C. for 30 minutes to perform a first-stage polycondensation reaction.

Next, after the temperature was raised to 210 ° C., 66 mmol (1.5 × 10 ⁻⁴ mol / mol-bisphenol A) of tetramethylammonium hydroxide was added, and the pressure was gradually reduced to 200 mmHg. After stirring for 30 minutes, the second-stage reaction was performed.

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 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, 29
It is fed at 40 kg / hour into a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotation diameter 220 mm, internal volume 80 liter) controlled at 0 ° C. and 0.2 mmHg, and polymerized at a residence time of 30 minutes. Was.

The obtained polymer is kept in a molten state,
The mixture is fed into a twin screw extruder (L / D = 17.5, barrel temperature of 285 ° C.) by a gear pump, and 0.7 ppm of butyl p-toluenesulfonate and tris (2,4-di-t) are added to the resin. -Butylphenyl) phosphite (Mark 2112: Adeka Argus) 300 ppm, 3,4-epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (Celloxide 2021P: Daicel Chemical) 300 ppm
Was added and kneaded, the mixture was made into a strand shape through a die, and cut into a pellet by a cutter.

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

Table 1 shows the results.

[0129]

Example 2 Example 1 was repeated except that tris (2,4-di-t-butylphenyl) phosphite was not used.
A pellet made of polycarbonate was obtained in the same manner as in Example 1.

Table 1 shows the results.

[0131]

Example 3 Pellets made of polycarbonate were obtained in the same manner as in Example 2 except that 3,4-epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate was not used. .

Table 1 shows the results.

[0133]

Example 4 In Example 1, the amount of tetramethylammonium hydroxide used in the second stage reaction was changed to 44.
Mmol (1 × 10 ^-4 mol / mol-bisphenol A)
And the amount of sodium hydroxide was 0.176 mol (4
Pellets made of polycarbonate were obtained in the same manner as in Example 1 except that × 10 ⁻⁷ mol / mol-bisphenol A) was used.

[0134]

REFERENCE EXAMPLE 8 In Example 3, the amount of tetramethylammonium hydroxide used was 88 mmol (2 × 10 4 moles) in both the first-stage polycondensation reaction and the second-stage reaction.
^-4 mol / mol-bisphenol A), pellets made of polycarbonate were obtained in the same manner as in Example 3 except that the amount of sodium hydroxide was not used and butyl p-toluenesulfonate was not added.

Table 1 shows the results.

[0136]

Example 5 In Example 1, boric acid was added at the time of polymerization.
Pellets made of polycarbonate were obtained in the same manner as in Example 1 except that mmol (2.5 × 10 ⁻⁵ mol / mol-bisphenol A) was added and butyl p-toluenesulfonate was not used.

The results are shown in Table 1.

[0138]

Example 6 In Example 3, tetramethylammonium hydroxide was used in the first-stage polycondensation reaction to obtain 22
Mmol (0.5 × 10 ⁻⁴ mol / mol-bisphenol A), and in the second stage reaction, 44 mmol (1
× 10 ^-4 mol / mol-bisphenol A) and 44 mmol (1 × 10 ^-4 mol / mol-bisphenol A) were also used in the second stage reaction. A polycarbonate pellet was obtained.

Table 1 shows the results.

[0140]

Reference Example 1 In Example 1, tetramethylammonium hydroxide was used only in the first-stage polycondensation reaction.
10 mmol (2.5 × 10 ⁻⁴ mol / mol-bisphenol A) was used, not used in the second and third stage reactions, and 0.176 mmol (4 × 10 4 mmol) of sodium hydroxide was used. A pellet made of polycarbonate was obtained in the same manner as in Example 1 except that ^-7 mol / mol-bisphenol A) was used.

Table 1 shows the results.

[0142]

Reference Example 2 In Example 2, tetramethylammonium hydroxide was used only in the first-stage polycondensation reaction.
10 mmol (2.5 × 10 ⁻⁴ mol / mol-bisphenol A) was used, not used in the second and third stage reactions, and 0.176 mmol (4 × 10 4 mmol) of sodium hydroxide was used. Except for using ^-7 mol / mol-bisphenol A), pellets made of polycarbonate were obtained in the same manner as in Example 2.

Table 1 shows the results.

[0144]

Reference Example 3 In Example 3, tetramethylammonium hydroxide was used only for the first-stage polycondensation reaction.
10 mmol (2.5 × 10 ⁻⁴ mol / mol-bisphenol A) was used, not used in the second and third stage reactions, and 0.176 mmol (4 × 10 4 mmol) of sodium hydroxide was used. A pellet made of polycarbonate was obtained in the same manner as in Example 3 except that ^-7 mol / mol-bisphenol A) was used.

Table 1 shows the results.

[0146]

REFERENCE EXAMPLE 4 In Example 3, tetramethylammonium hydroxide was used only for the first-stage polycondensation reaction.
Pellets made of polycarbonate in the same manner as in Example 3 except that 10 mmol (2.5 × 10 ⁻⁴ mol / mol-bisphenol A) was used and was not used in the second and third reactions. I got

The results are shown in Table 1.

[0148]

Reference Example 5 In Example 5, tetramethylammonium hydroxide was used only in the first-stage polycondensation reaction.
Pellets made of polycarbonate were obtained in the same manner as in Example 5, except that 20 mmol (5 × 10 ⁻⁴ mol / mol-bisphenol A) was used and was not used in the second and third reactions. Was.

Table 1 shows the results.

[0150]

Reference Example 6 In Example 3, tetramethylammonium hydroxide was not used in the first-stage polycondensation reaction and the third-stage reaction, but was used only in the second-stage reaction.
Example 3 except that 0 mmol (2.5 × 10 ⁻⁴ mol / mol-bisphenol A) was used and 0.88 mmol sodium hydroxide (20 × 10 ⁻⁷ mol / mol-bisphenol A) was used. Similarly, a pellet made of polycarbonate was obtained.

Table 1 shows the results.

[0152]

Reference Example 7 A pellet made of polycarbonate was obtained in the same manner as in Reference Example 6, except that 7 ppm of butyl p-toluenesulfonate was added.

Table 1 shows the results.

[0154]

[Table 1]

[0155]

[Table 2]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomoaki Shimoda 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. , B1)

Claims (20)

(57) [Claims] 1. An aromatic dihydroxy compound and a carbonic acid diester, comprising: (a) a nitrogen-containing basic compound; and (b) an aromatic dihydric compound .
5 × 10 ⁻⁸ to 8 × 10 ⁻⁷ to 1 mol of the roxy compound
When producing a polycarbonate by melt polycondensation in the presence of a catalyst comprising a molar amount of an alkali metal compound and / or an alkaline earth metal compound, the melt polycondensation is carried out in two or more stages, In the polycondensation step of the second step, the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed in the presence of the catalyst, and in the second and subsequent polycondensation steps, (a) at least one nitrogen-containing basic compound is further added. In the first stage polycondensation step, (a) the nitrogen-containing basic compound is added in an amount of 2.
It is added in an amount of 5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol, and in the second and subsequent polycondensation steps, (a) the nitrogen-containing basic compound is removed from the second In the total amount up to the polycondensation step, per mole of the aromatic dihydroxy compound,
A method for producing a polycarbonate, characterized by adding the compound in an amount of 2.5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol. 2. An aromatic dihydroxy compound and a carbonic acid diester, comprising: (a) a nitrogen-containing basic compound; and (b) an aromatic dihydric compound .
5 × 10 ⁻⁸ to 8 × 10 ⁻⁷ to 1 mol of the roxy compound
When producing a polycarbonate by melt polycondensation in the presence of a catalyst comprising a molar amount of an alkali metal compound and / or an alkaline earth metal compound, the melt polycondensation is carried out in two or more stages, In the polycondensation step of the second step, the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed in the presence of the catalyst, and in the second and subsequent polycondensation steps, (a) at least one nitrogen-containing basic compound is further added. In the first stage polycondensation step, (a) the nitrogen-containing basic compound is added in an amount of 2.
It is added in an amount of 5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol, and in the second and subsequent polycondensation steps, (a) the nitrogen-containing basic compound is removed from the second In the total amount up to the polycondensation step, per mole of the aromatic dihydroxy compound,
2.5 × 10 ^{-6 to} 2.5 × 10 ^-3 mol, and added to the polycarbonate [A] obtained by the polycondensation. Wherein the sulfonic acid compound is added in an amount of 0.05 to 10 ppm based on the polycarbonate. Embedded image [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 a hydrocarbon group having 1 to 8 carbon atoms (hydrogen is halogen. May be substituted), and n is an integer of 0 to 3. ] 3. An aromatic dihydroxy compound and a carbonic acid diester, comprising: (a) a nitrogen-containing basic compound; and (b) an aromatic dihydroxy compound.
5 × 10 ⁻⁸ to 8 × 10 per mol of the droxy compound
^-7 moles of an alkali metal compound and / or an alkaline earth metal compound is melt-polycondensed in the presence of a catalyst to produce a polycarbonate, the melt polycondensation is carried out in two or more multi-step steps, In the first-stage polycondensation step, an aromatic dihydroxy compound and a carbonic acid diester are melt-polycondensed in the presence of the catalyst, and in the second and subsequent polycondensation steps, (a) a nitrogen-containing basic compound is further added. At least once, and in the first polycondensation step, (a) the nitrogen-containing basic compound is added in an amount of 2.
5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol, and in the second and subsequent polycondensation steps, (a) the nitrogen-containing basic compound is finally added from the second polycondensation step. The total amount up to the polycondensation step is 2.5 x 10 ^{-6 to} 2.5 x 10 ^-3 mol based on 1 mol of the aromatic dihydroxy compound. [A] polycarbonate obtained by condensation, [B] a sulfonic acid compound represented by the above general formula [III] in an amount of 0.05 to 10 ppm based on the polycarbonate, and [C] an epoxy compound in a polycarbonate. 1 for
A method for producing a polycarbonate, characterized in that it is added in an amount of about 2000 ppm. 4. An aromatic dihydroxy compound and a carbonic acid diester, comprising: (a) a nitrogen-containing basic compound; and (b) an aromatic dihydroxy compound.
5 × 10 ⁻⁸ to 8 × 10 per mol of the droxy compound
^-7 moles of an alkali metal compound and / or an alkaline earth metal compound is melt-polycondensed in the presence of a catalyst to produce a polycarbonate, the melt polycondensation is carried out in two or more multi-step steps, In the first-stage polycondensation step, an aromatic dihydroxy compound and a carbonic acid diester are melt-polycondensed in the presence of the catalyst, and in the second and subsequent polycondensation steps, (a) a nitrogen-containing basic compound is further added. At least once, and in the first polycondensation step, (a) the nitrogen-containing basic compound is added in an amount of 2.
5 × 10 ^{−6 to} 2.5 × 10 ⁻³ mol, and in the second and subsequent polycondensation steps, (a) the nitrogen-containing basic compound is finally added from the second polycondensation step. The total amount up to the polycondensation step is 2.5 x 10 ^{-6 to} 2.5 x 10 ^-3 mol based on 1 mol of the aromatic dihydroxy compound. [A] polycarbonate obtained by condensation, [B] a sulfonic acid compound represented by the above general formula [III] in an amount of 0.05 to 10 ppm based on the polycarbonate, and [C] an epoxy compound in a polycarbonate. 1 for
[D] Phosphorus compound was added to polycarbonate in an amount of
A method for producing a polycarbonate, which is added in an amount of 1000 ppm. 5. The amount of (b) the alkali metal compound and / or the alkaline earth metal compound to be added is 5 × 10 ⁻⁸ to 1 mol of the aromatic dihydroxy compound.
5. The composition according to claim 1, wherein the amount is about 5 × 10 ⁻⁷ mol.
The method for producing a polycarbonate according to any one of the above. 6. The amount of the alkali metal compound and / or the alkaline earth metal compound to be added is 5 × 10 ^{-8 to} 3 × 10 ^-7 mol per 1 mol of the aromatic dihydroxy compound. A method for producing a polycarbonate according to any one of claims 1 to 4. 7. The above two or more polycondensation steps include a first polycondensation step having a reaction temperature of 80 to 240 ° C. and a second and subsequent polycondensation steps having a reaction temperature of 140 to 300 ° C. The method for producing a polycarbonate according to any one of claims 1 to 4, comprising: 8. The method for producing a polycarbonate according to claim 1, wherein (a) the nitrogen-containing basic compound is a tetraalkylammonium hydroxide. 9. The method according to claim 1, wherein (a) the nitrogen-containing basic compound is tetramethylammonium hydroxide or tetra-n-butylammonium hydroxide. Method. 10. A nitrogen-containing basic compound having a chlorine content of 10 ppm or less and a sodium content of 20 pp.
b The method for producing a polycarbonate according to claim 1, wherein: 11. A 1 × 10 ^-6 to 1 × 10 ^-4 mole of (c) borate ester per 1 mole of an aromatic dihydroxy compound is obtained at the time of polycondensation and / or after completion of polycondensation. The method for producing a polycarbonate according to any one of claims 1 to 4, wherein the method is added to the polycarbonate obtained. 12. The method for producing a polycarbonate according to claim 2, wherein the sulfonic acid compound is added in an amount of 0.1 to 5 ppm based on the polycarbonate. 13. The process for producing a polycarbonate according to claim 2, wherein the sulfonic acid compound is added in an amount of 0.2 to 2 ppm based on the polycarbonate. 14. The sulfonic acid compound [B] in the above general formula [III], wherein R ⁷ is a methyl group, R ⁸ is hydrogen or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and n is The method for producing a polycarbonate according to any one of claims 2 to 4, wherein the sulfonic acid compound is 0 or 1. 15. The method according to claim 2, wherein the sulfonic acid compound (B) is butyl p-toluenesulfonate or p-toluenesulfonic acid. 16. The method according to claim 3, wherein the epoxy compound (C) is used in an amount of 1 to 1000 ppm based on the polycarbonate. 17. The method for producing a polycarbonate according to claim 3, wherein the epoxy compound [C] is an alicyclic epoxy compound. 18. The method according to claim 3, wherein the epoxy compound [C] is 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate. 19. The method according to claim 4, wherein the [D] phosphorus compound is an aromatic phosphite compound. 20. The [D] phosphorus compound is tris (2,4-di-t
The method for producing a polycarbonate according to claim 4, which is -butylphenyl) phosphite.