JPH059286A - Manufacture of polycarbonate composition - Google Patents

Abstract

PURPOSE:To provide a method for manufacturing a polycarbonate composition which is excellent in residence stability, such as hue stability and thermal stability, when molded and enables efficient manufacture of polycarbonate moldings excellent in water resistance and transparency. CONSTITUTION:A method for manufacturing a polycarbonate composition, which comprises subjecting an aromatic dihydroxy compound and a carbonic diester to melt polycondensation in the presence of a catalyst containing an alkali metal compound and/or alkaline earth metal compound, in an amount of 10<-8> to 10<-3>mol per mol of the aromatic dihydroxy compound, adding a phosphorus compound to the reaction product comprising a polycarbonate while it is in a molten state to give a melt mixture, pelletizing the melt mixture, and kneading the pellets together with an additive again.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a polycarbonate composition, and more specifically to a molded article which is excellent in retention stability such as hue stability and thermal stability at the time of molding and also excellent in water resistance. The present invention relates to a method for producing a polycarbonate composition capable of efficiently producing a polycarbonate composition.

[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, etc. Has been.

Conventionally, such a polycarbonate has a method of directly reacting an aromatic dihydroxy compound such as bisphenol with phosgene (interfacial method) or a method of transesterifying an aromatic dihydroxy compound and a carbonic acid diester (melting method). ) Is manufactured by.

Of these, the latter is advantageous in environmental hygiene because it has the advantage of being able to produce polycarbonate at a lower cost than the former interface method and does not use toxic substances such as phosgene.

Generally, the polycarbonate obtained by the polycondensation reaction is pelletized, then distributed to each small lot according to the purpose of use, remelted and added with various additives according to the purpose. It is used by being colored.

By the way, in the conventional polycarbonate,
At the time of melting, the composition may be colored or the molecular weight may be reduced, resulting in lack of retention stability. For this reason, when a pellet made of polycarbonate is remelted, a heat resistance stabilizer or the like is usually added to improve the thermal stability. However, in this method, the polycarbonate is subjected to heat treatment in a state of low thermal stability.

Further, the addition of the above heat-resistant stabilizer may reduce the water resistance of the polycarbonate, and the molded product obtained from such a polycarbonate may have decreased transparency during use.

Therefore, a polycarbonate composition capable of efficiently forming a molded article having excellent hue stability during molding, retention stability such as heat stability, and excellent water resistance and transparency according to the purpose of use. The advent of a method for producing a polycarbonate capable of producing a product is desired.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is excellent in retention of stability such as hue stability and heat stability at the time of molding, water resistance and transparency. Another object of the present invention is to provide a method for producing a polycarbonate composition capable of producing a polycarbonate composition capable of efficiently forming an excellent molded article according to the purpose of use.

[0010]

SUMMARY OF THE INVENTION In the method for producing a polycarbonate composition according to the present invention, an aromatic dihydroxy compound and a carbonic acid diester are used in an amount of 1 mol per 1 mol of the aromatic dihydroxy compound.
After melt polycondensation in the presence of a catalyst containing (a) an alkali metal compound and / or an alkaline earth metal compound in an amount of 0 ^-8 to 10 ^-3 mol, the reaction product [A] polycarbonate is The present invention is characterized in that the molten mixture obtained by adding the phosphorus compound [B] is molded into pellets while in the molten state, and then the pellets and the additive [E] are kneaded again.

The method for producing a polycarbonate composition according to the present invention preferably comprises the above [B] phosphorus compound,
[C] A sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, and a [D] epoxy compound are added.

According to the method for producing a polycarbonate composition of the present invention, first, while the polycarbonate, which is a reaction product obtained by melt polycondensation, is in a molten state,
The above [B] phosphorus compound and preferably [C], [D]
By adding a compound, pellets having improved retention stability such as hue stability and heat resistance stability are obtained. Therefore, when remelting the pellets, it is possible to prevent the polycarbonate composition from being colored or thermally decomposed.

As described above, pellets composed of a polycarbonate melt mixture having improved water resistance as well as retention stability such as hue stability and thermal stability before pelletizing are used in small lots in the next step. Re-kneading can be efficiently performed according to the purpose.

More preferably, the epoxy compound [D] is added to obtain a polycarbonate composition having improved water resistance. INDUSTRIAL APPLICABILITY The polycarbonate composition obtained according to the present invention is less colored during molding, and can efficiently form a molded article excellent in transparency and water resistance.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a polycarbonate composition according to the present invention will be specifically described below.

First, in the present invention, an aromatic dihydroxy compound and a carbonic acid diester are melt-polycondensed in the presence of a catalyst to produce a polycarbonate. The aromatic dihydroxy compound is not particularly limited, but may be a compound represented by the following formula [I].

[0017]

[Chemical 2]

R ¹ and R ² are hydrogen atoms or monovalent hydrocarbon groups, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are halogen or a monovalent hydrocarbon group, and these may be the same or different.
p and q represent the integer of 0-4. ) Specific examples of the aromatic dihydroxy compound 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 ( Bis (hydroxyaryl) such as 4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane and 2,2-bis (4-hydroxy-3-bromophenyl) propane ) Alkanes, 1,1-bis (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiene Dihydroxy aryl ethers such as phenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, etc. Dihydroxydiaryl sulfides, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and other dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenyl sulfone, 4,4 ' -Dihydroxydiaryl sulfones such as dihydroxy-3,3'-dimethyldiphenyl sulfone.

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

[0020]

[Chemical 3]

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

Specific examples of the aromatic dihydroxy compound represented by the above general formula [II] include resorcin and 3-
Methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3,
Substituted resorcins such as 4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromoresorcinol, catechol, hydroquinone and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3- 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 can be mentioned.

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

[0024]

[Chemical 4]

These aromatic dihydroxy compounds can be used alone or in combination. Specific 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, dicyclohexyl. Carbonate etc. can be mentioned.

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 1.0 to 1 mol with respect to 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 a polycarbonate is produced, 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 described above.

As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferable, and a compound containing 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, 1,
Examples include 3,5-benzenetricarboxylic acid and pyromellitic acid.

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

The polyfunctional compound is usually used in an amount of 0.03 mol or less, preferably 0.001 to 0.02 mol, and more preferably 0.001 mol, based on 1 mol of the aromatic dihydroxy compound.
Used in an amount of 0.01 mol.

The polycarbonate used in the present invention is
It is obtained by melt polycondensation of the above aromatic dihydroxy compound and carbonic acid diester in the presence of a catalyst. Such catalysts include (a) alkali metal compounds and /
Alternatively, it is preferable to use an alkaline earth metal compound.

As the alkali metal compound and the alkaline earth metal compound, specifically, organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of alkali metals and alkaline earth metals are preferable. Can be mentioned.

More specifically, as the alkali metal compound, 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, bisphenol A disodium salt, 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. Such an (a) alkali metal compound and / or alkaline earth metal compound is used in an amount of 10 ^-8 to 10 based on 1 mol of the aromatic dihydroxy compound.
^-3 mol, preferably used in an amount of 10 ^-7 to 2 × 10 ^-6 mol.

As described above, when (a) an alkali metal compound or an alkaline earth metal compound is used as a catalyst in an amount of 10 ^-8 to 10 ^-3 mol with respect to 1 mol of an aromatic dihydroxy compound, high polymerization is achieved. The basic compounds of these compounds can be sufficiently neutralized or weakened by adding the acidic compounds described below in an amount that does not adversely affect the obtained polycarbonate while producing the polycarbonate with activity.

In the present invention, the catalyst as described above is used.
(a) together with an alkali metal compound and / or an alkaline earth metal compound, (b) a basic compound and / or
(c) A boric acid compound can also be used.

Examples of such a basic compound (b) include nitrogen-containing basic compounds which are easily decomposable or volatile at high temperature, and specifically, the following compounds can be mentioned.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH ) Such as alkyl, aryl,
Ammonium hydroxides having araryl groups, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, R ₂ NH (wherein R is an alkyl group such as methyl or ethyl, an aryl group such as phenyl or toluyl). Etc.)
Secondary amines, RNH ₂ (wherein R is the same as above) primary amines, 2-methylimidazole, 2-phenylimidazole and other imidazoles,
Alternatively, ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh). ₄ ) Basic salts such as.

Of these, tetraalkylammonium hydroxides, especially electron-use tetraalkylammonium hydroxides containing few metal impurities, are preferably used.

When the (b) nitrogen-containing basic compound is used as the catalyst, the (b) nitrogen-containing basic compound is preferably 10 ^-6 to 10 ^-1 mol or less, preferably ¹ to ¹ mol of the aromatic dihydroxy compound. Is used in an amount of 10 ⁻⁵ to 10 ⁻² mol.

As the boric acid compound (c), boric acid, boric acid ester and the like can be mentioned. Examples of the borate ester include borate esters represented by the following general formula.

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

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

When (c) boric acid or boric acid ester is used as a catalyst, the aromatic dihydroxy compound 1
10 ^-8 to 10 ^-1 mol, preferably 10 ^-7 mol per mol
It is used in an amount of 10 ⁻² to 10 ⁻² mol, more preferably 10 ⁻⁶ to 10 ⁻⁴ mol.

These are, for example, (a) alkali metal compounds and / or alkaline earth metal compounds and
(b) a combination of nitrogen-containing basic compounds, and (a) an alkali metal compound and / or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid or a borate ester. Can be preferably used in combination.

As described above, the catalyst obtained by combining (a) the alkali metal compound and / or the alkaline earth metal compound and (b) the nitrogen-containing basic compound in the above-mentioned use amount is sufficient for the polycondensation reaction. It is preferable that the high-molecular weight polycarbonate can be produced with high polymerization activity by advancing at a high speed.

Furthermore, the catalysts in which the above three are combined in the above-mentioned use amounts are preferable because they can produce a polycarbonate which is less likely to cause a decrease in the molecular weight after heat aging. In the presence of such a catalyst, the polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester can be carried out under the same conditions as the conventionally known polycondensation reaction conditions.

Specifically, the reaction in the first step is carried out at 80 to 25
0 ° C., preferably 100 to 230 ° C., more preferably 120 to 190 ° C., 0 to 5 hours, preferably 0
The aromatic dihydroxy compound and the carbonic acid diester are reacted under atmospheric pressure for -4 hours, more preferably 0-3 hours. Then increase the reaction temperature while reducing the pressure of the reaction system,
Aromatic dihydroxy compound and carbonic acid diester are reacted, and finally 5 mmHg or less, preferably 1 mmHg
The polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out at 240 to 320 ° C. under the following reduced pressure.

The polycondensation 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.

In the polycarbonate obtained as a reaction product as described above, the intrinsic viscosity measured in methylene chloride at 20 ° C. is usually from 0.10 to 1.0 dl / g, preferably from 0.30 to 0.3. It is 65 dl / g.

As described above, the manufacturing method according to the present invention does not use toxic substances such as phosgene and methylene chloride in the melt polycondensation, and is therefore preferable in terms of environmental hygiene. In the present invention, the [B] phosphorus compound below is added immediately after the polycondensation reaction without cooling the reaction product [A] polycarbonate obtained as described above. That is, the [B] phosphorus compound is directly added while the [A] polycarbonate, which is the reaction product in the molten reactor or extruder obtained after the completion of the polycondensation reaction, is in the molten state.

At this time, together with the [B] phosphorus compound, a sulfur-containing acidic compound having a [C] pKa value of 3 or less and / or a derivative formed from the acidic compound, as described later, and a [D] epoxy compound. Is preferably added.

First, the phosphorus compound [B] will be described. As the phosphorus compound [B], 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, 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 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, as the [B] 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) phosph is particularly preferable. Fight is preferably used.

In the present invention, the above [B] phosphorus compound is added to the [A] polycarbonate in an amount of 10 to 100.
It is added in an amount of 0 ppm, preferably 50 to 500 ppm.
Next, the sulfur-containing acidic compound having a [C] pKa value of 3 or less and / or the derivative formed from the acidic compound used in the present invention will be described.

In the present invention, examples of the sulfur-containing acidic compound [C] and the derivative formed from the acidic compound include sulfurous acid, sulfuric acid, sulfinic acid compounds, sulfonic acid compounds and derivatives thereof. Specifically, examples of the sulfite derivative include dimethyl sulfite, diethyl sulfite, dipropyl sulfite, dibutyl sulfite, diphenyl sulfite, and the like.

Examples of the sulfuric acid derivative include dimethyl sulfuric acid, diethyl sulfuric acid, dipropyl sulfuric acid, dibutyl sulfuric acid and diphenyl sulfuric acid. Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid, and naphtherensulfinic acid.

Examples of the sulfonic acid compounds and their derivatives include compounds represented by the following general formula [III] and their ammonium salts.

[0066]

[Chemical 5]

In the formula, R ⁷ is a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with halogen), and R 7
⁸ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with halogen), and n is an integer of 0 to 3.

Examples of such sulfonic acid compounds and their derivatives include the following compounds. Sulfonic acids such as benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-
Methyl toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl ester p-toluenesulfonate, ammonium sulfonate such as ammonium p-toluenesulfonate .

In addition to the sulfonic acid compound represented by the above general formula [III], trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene,
Mention may be made of sulfonic acid compounds such as methyl acrylate-sulfonated styrene copolymers.

These compounds can be used alone or in combination. In the present invention, as the [C] sulfur-containing acidic compound and the derivative formed from the acidic compound, the sulfonic acid compound represented by the general formula [III] and its derivative are preferably used. Further, in the general formula [III], R ⁷ and R ⁸ are preferably substituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms, and n is a compound represented by an integer of 0 to 1. Specifically, benzene sulfonic acid, butyl benzene sulfonate, p-toluene sulfonic acid, ethyl p-toluene sulfonate, and butyl p-toluene sulfonate are preferably used.

Particularly, in the present invention, butyl p-toluenesulfonate is preferably used. In the present invention, the sulfur-containing acidic compound having a [C] pKa value of 3 or less as described above and / or a derivative formed from the acidic compound are
0.1 to 10 pmm against the above [A] polycarbonate
, Preferably 0.1 to 8 ppm, particularly preferably 0.1 to
Add in an amount of 5 ppm.

In the present invention, as the [D] 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'-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'-methylsiloxyhexylcarboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, phthalic acid Diglycidyl ester of hexahydrophthalic acid Diester, bis-epoxydicyclopentadienyl ether, bis-epoxy ethylene glycol,
Bis-epoxy cyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxytalate, 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-epoxy tetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxy tetrahydrophthalic anhydride, diethyl 4,5- Epoxy-cis-1,2-cyclohexyl dicarboxylate, di-n-butyl-3-t-butyl-
4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate and the like can be mentioned.

Of these, alicyclic epoxy compounds are preferably used, and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate is particularly preferably used.

These may be used alone or in combination of two or more. In the present invention, such a [D] epoxy compound is added to the above [A] polycarbonate in an amount of 1 to
It is preferably added in an amount of 2000 ppm, preferably 10 to 1000 ppm.

In the present invention, as described above, immediately after the polycondensation reaction of the obtained reaction product [A] polycarbonate without cooling, the above [B] phosphorus compound and preferably [C], [C], D] compound is added,
The resulting molten mixture is pelletized. Specifically, for example, after adding the [B], [C] and [D] compounds to the [A] polycarbonate obtained by the polycondensation reaction in the reactor, it may be pelletized through an extruder. Also, while the [A] polycarbonate obtained by the polycondensation reaction is pelletized from the reactor through the extruder,
[B], [C] and [D] compounds may be added.
The order of adding the [B], [C] and [D] compounds does not matter.

The pellets composed of [A], [B] and preferably [C] thus obtained have a neutralized or weakened alkaline catalyst remaining in the polycarbonate, In particular, retention stability such as hue stability and thermal stability during melting is improved. Further, by adding the [D] epoxy compound, even if the [B] and [C] compounds excessively remain in the pellet, these react with the [D] epoxy compound and are neutralized, Pellets of the molten mixture with improved water resistance and transparency are obtained.

Such pellets are re-kneaded in the next step, for example, with an additive depending on the purpose of use. However, since the retention stability is improved as described above, coloring or Thermal decomposition is suppressed. Further, the water resistance is also improved.

In the present invention, the pellets thus obtained are re-kneaded together with the [E] additive to produce a polycarbonate composition. At this time, it is preferable to divide into small lots according to the purpose of use and re-knead together with additives according to the purpose.

The kneading can be performed with a single screw extruder, a twin screw extruder, a Brabender, or the like. The kneading temperature is usually 200 to 380 ° C, preferably 220 to 360 ° C.

Such an [E] additive varies depending on the purpose and is not particularly limited, but examples thereof include the following additives. In addition, in this re-kneading, the above-mentioned [B], [C] and [D] compounds may be added, if necessary.

Examples of the [E] additives used for re-kneading in the present invention include the following ordinary heat resistance stabilizers, ultraviolet absorbers, release agents, colorants, flame retardants, antistatic agents. Examples thereof include agents, slip agents, anti-blocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers, glass powder, and inorganic fillers such as glass fibers.

Specific examples of the heat resistance stabilizers described above include phenolic stabilizers, organic thioether stabilizers, hindered amine stabilizers, and the like.

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 resistance stabilizers are 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.005 parts by weight, based on 100 parts by weight of the polycarbonate.
It is preferably used in an amount of 01 to 0.3 part by weight.

Such heat resistance stabilizer may be added in the form of solid or liquid. 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. Can be mentioned.

Specific examples of the salicylic acid type 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-based 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 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, based on 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, 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 releasing agent include lower fatty acid esters of aliphatic acids such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters.

Examples of the silicone 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 to 5 parts by weight, preferably 0.005 to 1 part by weight, and more preferably 0.01 to 0.00 parts by weight, based on 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. 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 navy 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 to} 5 with respect to 100 parts by weight of [A] polycarbonate.
It can be used in an amount of 1 part by weight, preferably 1 × 10 ^{−5 to} 3 parts by weight, and more preferably 1 × 10 ⁻⁵ to 1 part by weight.

As described above, in the present invention, after the polycondensation reaction, pelletized as a molten mixture having improved heat stability. Then, the pellets thus obtained are re-kneaded together with an additive depending on the purpose of use to obtain a polycarbonate composition.

Therefore, the polycarbonate composition according to the purpose can be efficiently produced without re-kneading to make it yellow or reduce the molecular weight.

The polycarbonate composition thus obtained can be efficiently used according to the intended purpose, is less likely to yellow during molding, is excellent in hue stability, and is resistant to thermal decomposition, and has a molecular weight of Is hard to drop.

Further, the polycarbonate composition containing an epoxy compound has particularly improved water resistance,
Transparency does not easily deteriorate.

[0106]

EFFECTS OF THE INVENTION According to the present invention, it is possible to produce a polycarbonate composition having excellent retention stability such as thermal stability and hue stability during melting.

The polycarbonate composition obtained according to the present invention is excellent in heat stability during molding, is excellent in hue stability for a long time even in use, and is excellent in water resistance and transparency. A molded body can be efficiently formed. The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0108]

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

[Intrinsic viscosity [IV]] 2 in methylene chloride
It measured at 0 degreeC using the Ubbelohde viscometer. [MFR] Based on the method of JIS K-7210, it was measured at a temperature of 300 ° C. and a load of 1.2 kg.

[Hue] An injection-molded plate having a thickness of 3 mm was molded at a cylinder temperature of 290 ° C., an injection pressure of 1000 kg / cm, a cycle of 45 seconds and a mold temperature of 100 ° C. Co., Ltd. Color and Color Defference Met
measured by transmission method using er ND-1001 DP, yellowness [Y
I] was measured.

YI = 100 (1.277X-1.060Z) / Y [Light transmittance] According to the method of ASTM D 1003,
It measured using the injection molding board for hue measurement.

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

[Stability] The resin was allowed to stay in the cylinder of the injection molding machine at a temperature of 320 ° C. for 15 minutes, and then injection molding was performed at that temperature to obtain MFR, hue (YI), and light transmission of the molded plate. The rate was measured.

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

[Additives] The additives used are shown below. Heat-resistant stabilizer: Mark 2112 [made by ADEKA ARGUS; tris (2,4-di-t-butylphenyl) phosphite Mark AO-50 [made by ADEKA ARGUS; n-octadecyl-3-
(4'-Hydroxy-3 ', 5'-di-t-butylphenyl) propionate] UV absorber: Siasolv UV 5411 [American Cynamid; 2- (2'-hydroxy-5'-t-octylphenyl] ) Benzotriazole] Release agent: TSF 437 (manufactured by Toshiba Silicone; silicone type) Epoxy stabilizer: Celoxide 2021P (manufactured by Daicel Chemical; Alicyclic Diepoxycarboxylate) Coloring agent: Plast Violet 8840 (Arimoto) (Chemical company; styrene type)

[0116]

Example 1 0.44 kmole of bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) and 0.46 kmole of diphenyl carbonate (manufactured by Any Co.) were placed in a 250 liter tank type stirring tank, and after nitrogen replacement, 140
Melted at ° C.

Next, this was heated to a temperature of 180 ° C., and tetramethylammonium hydroxide as a catalyst was added to 0.2%.
11 mol and 0.00044 mol of sodium hydroxide (1 × 10 ⁻⁶ mol / mol-bisphenol A) were added and 3
Stir for 0 minutes.

Next, the temperature is raised to 210 ° C. and, at the same time, gradually lowered to 200 mmHg, and after 30 minutes, the temperature is set to 24.
While raising the temperature to 0 ° C. and gradually lowering it to 15 mmHg, the temperature and pressure were kept constant and the amount of phenol distilled out was measured. At the time when there was no phenol distilled out, the pressure was returned to atmospheric pressure with nitrogen. The time required for the reaction was 1 hour. The intrinsic viscosity [η] of the obtained reaction product was 0.15 dl / g.

Next, the pressure of this reaction product was increased by a gear pump and 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. Gear pump from the bottom of the evaporator at 290 ℃, 0.2
Biaxial horizontal stirring polymerization tank controlled to mmHg (L / D
= 3, stirring blade rotation diameter 220 mm, internal volume 80 liters)
At a rate of 40 Kg / hour and polymerized for a residence time of 30 minutes.

Next, in the molten state, this polymer was fed into a twin-screw extruder (L / D = 17.5, barrel temperature 285 ° C.) by a gear pump, and p-toluenesulfone was added to the resin. Butyl acid 1.8 ppm, tris (2,4-di-t-butylphenyl) phosphite (Mark2112: manufactured by ADEKA ARGUS CORPORATION) 300 ppm, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (celoxide 2021P) : Daicel Chemical Industries, Ltd.) 300
ppm was kneaded, passed through a die to form a strand, and cut with a cutter to form a pellet.

Next, the additives shown in Table 1 were added to the pellets in the amounts shown in Table 1, and the pellets were mixed with a conventional single-screw extruder.
Re-kneading was performed at 5 ° C to obtain pellets. The intrinsic viscosity (IV) of the obtained polymer was 0.49 dl / g.

The results are shown in Table 1.

[0123]

Examples 2 and 3 In the same manner as in Example 1 except that immediately after the polymerization, the compounds shown in Table 1 were used in place of butyl p-toluenesulfonate in the amounts shown in Table 1. Pellets were obtained, and the additives shown in Table 1 were added in the amounts shown in Table 1 and re-kneaded in the same manner as in Example 1 to obtain pellets.

The results are shown in Table 1.

[0125]

Example 4 Pellets were prepared in the same manner as in Example 1 except that butyl p-toluenesulfonate and tris (2,4-di-t-butylphenyl) phosphite were used immediately after polymerization. Then, the additives shown in Table 1 were added and remixed in the same manner as in Example 1 except that the amounts shown in Table 1 were added to obtain pellets.

The results are shown in Table 1.

[0127]

Example 5 In Example 1, immediately after polymerization, tris (2,
Pellets were obtained in the same manner as in Example 1 except that only 4-di-t-butylphenyl) phosphite was used, and the additives shown in Table 1 were added in the amounts shown in Table 1 to Example 1. Pellets were obtained by re-kneading in the same manner as in.

The results are shown in Table 1.

[0129]

Example 6 In Example 1, immediately after polymerization, tris (2,
4-di-t-butylphenyl) phosphite, pellets were obtained in the same manner as in Example 1 except that only Celoxide 2021P was used, and the additives shown in Table 1 were added in the amounts shown in Table 1. Re-kneading was carried out in the same manner as in Example 1 to obtain pellets.

The results are shown in Table 1.

[0131]

[Examples 7 and 8] Pellets were obtained in the same manner as in Example 1 except that butyl p-toluenesulfonate was used in the amount described in Table 1 immediately after the polymerization, and the additions shown in Table 1 were obtained. The agent was added in the amounts shown in Table 1 and re-kneaded in the same manner as in Example 1 to obtain pellets.

The results are shown in Table 1.

[0133]

Example 9 Pellets were obtained in the same manner as in Example 1 except that the colorant was not used during the re-kneading.

The results are shown in Table 1.

[0135]

Comparative Example 1 In Example 1, immediately after the polymerization, tris (2,
Pellets were obtained in the same manner as in Example 1 except that 4-di-t-butylphenyl) phosphite was not added.
The additives shown in Table 1 were added in the amounts shown in Table 1 and re-kneaded in the same manner as in Example 1 to obtain pellets.

The results are shown in Table 1.

[0137]

Comparative Example 2 In Example 1, immediately after polymerization, tris (2,
Pellets were obtained in the same manner as in Example 1 except that 4-di-t-butylphenyl) phosphite and Celoxide 2021P were not added, and the additives shown in Table 1 were added in the amounts shown in Table 1. And kneading was carried out in the same manner as in Example 1 to obtain pellets.

The results are shown in Table 1.

[0139]

Comparative Example 3 Pellets were obtained in the same manner as in Example 1 except that only Celoxide 2021P was added immediately after the polymerization, and the additives shown in Table 1 were added in the amounts shown in Table 1. And kneading was carried out in the same manner as in Example 1 to obtain pellets.

The results are shown in Table 1.

[0141]

Comparative Examples 4 and 5 Pellets were obtained in the same manner as in Example 1 except that nothing was added immediately after polymerization, and the additives shown in Table 1 were added in the amounts shown in Table 1. Was re-kneaded in the same manner as in Example 1 to obtain pellets.

The results are shown in Table 1.

[0143]

Comparative Example 6 Pellets were obtained in the same manner as in Comparative Example 5, except that the colorant was not used during re-kneading.

The results are shown in Table 1.

[0145]

[Table 1]

[0146]

[Table 2]

[0147]

[Table 3]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kimiyoshi Miura             6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture             Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Kazuhiko Yamamoto             6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture             Mitsui Petrochemical Industry Co., Ltd.

Claims (14)

[Claims] 1. An aromatic dihydroxy compound and a carbonic acid diester are added in an amount of 10 ^-8 to 1 with respect to 1 mol of the aromatic dihydroxy compound.
After melt polycondensation in the presence of a catalyst containing (a) an alkali metal compound and / or an alkaline earth metal compound in an amount of 0 ^-3 mol, the reaction product [A] polycarbonate is in a molten state. In the meantime, after the molten mixture obtained by adding the [B] phosphorus compound is molded into pellets, the pellets and the [E] additive are re-kneaded, and a method for producing a polycarbonate composition. 2. An aromatic dihydroxy compound and a carbonic acid diester are added in an amount of 10 ⁻⁸ to 1 with respect to 1 mol of the aromatic dihydroxy compound.
After melt polycondensation in the presence of a catalyst containing (a) an alkali metal compound and / or an alkaline earth metal compound in an amount of 0 ^-3 mol, the reaction product [A] polycarbonate is in a molten state. In the meantime, after the [B] phosphorus compound and the [C] sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound are added, a molten mixture obtained is molded into pellets. A method for producing a polycarbonate composition, comprising: re-kneading the pellet and the [E] additive. 3. An aromatic dihydroxy compound and a carbonic acid diester are added in an amount of 10 ⁻⁸ to 1 with respect to 1 mol of the aromatic dihydroxy compound.
After melt polycondensation in the presence of a catalyst containing (a) an alkali metal compound and / or an alkaline earth metal compound in an amount of 0 ^-3 mol, the reaction product [A] polycarbonate is in a molten state. In the meantime, a melt obtained by adding [B] a phosphorus compound, [C] a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, and [D] an epoxy compound A method for producing a polycarbonate composition, which comprises molding the mixture into pellets and then re-kneading the pellets and the [E] additive. 4. (a) An alkali metal compound and / or an alkaline earth metal compound is added in an amount of 10 ⁻⁷ to 2 with respect to 1 mol of an aromatic dihydroxy compound.
Use in an amount of × 10 ^-6 mol.
4. The method for producing the polycarbonate composition according to any one of 3 above. 5. The phosphorus compound [B] is added to the reaction product [A] polycarbonate in an amount of 10 to 1000 ppm.
The method for producing a polycarbonate composition according to any one of claims 1 to 4, wherein the method is used in an amount of. 6. An aromatic phosphite ester compound is used as the [B] phosphorus compound.
A method for producing the polycarbonate composition according to any one of 1. 7. A [B] phosphorus compound as tris (2,4-di)
-T-Butylphenyl) phosphite is used, The manufacturing method of the polycarbonate composition in any one of Claims 1-6 characterized by the above-mentioned. 8. A sulfur-containing acidic compound having a [C] pKa value of 3 or less and / or a derivative formed from the acidic compound is added to a reaction product [A] polycarbonate.
Use in an amount of 0.1 to 10 ppm.
7. The method for producing a polycarbonate composition according to any one of 7 to 7. 9. A sulfur-containing acidic compound having a [C] pKa value of 3 or less and / or a derivative formed from the acidic compound is added to a reaction product [A] polycarbonate.
2. Use in an amount of 0.1 to 5 ppm.
9. A method for producing the polycarbonate composition according to any one of items 8 to 8. 10. A compound represented by the following general formula [III] is used as a sulfur-containing acidic compound having a [C] pKa value of 3 or less and / or a derivative formed from the acidic compound. A method for producing the polycarbonate composition according to any one of claims 1 to 9: In the formula, R ⁷ is a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with halogen), and R ⁸ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen is substituted with halogen). May be included), and n is an integer of 0 to 3. 11. A butyl p-toluenesulfonate is used as a sulfur-containing acidic compound having a [C] pKa value of 3 or less and / or a derivative formed from the acidic compound. A method for producing the polycarbonate composition according to any one of 1. 12. The epoxy compound [D] is added to the reaction product [A] polycarbonate of 1 to 2000 pp.
The method for producing a polycarbonate composition according to any one of claims 1 to 11, which is used in an amount of m. 13. An alicyclic epoxy compound is used as the [D] epoxy compound.
A method for producing the polycarbonate composition according to any one of 1. 14. The polycarbonate composition according to claim 1, wherein 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate is used as the [D] epoxy compound. Method of manufacturing things.