JPH08134341A - Polycarbonate composition and its production - Google Patents

Abstract

PURPOSE: To obtain a polycarbonate composition, excellent in thermal stability in molding, retention stability such as hue stability, weather, water, impact and heat resistances and transparency and useful as mechanical parts, etc., by adding a specific salt to pellets of a polycarbonate and kneading the resultant mixture. CONSTITUTION: This polycarbonate composition is obtained by adding (B) a salt of a strong acid compound having <=3pKa with a basic compound containing nitrogen, represented by the formula [A is a 1--56C (halogen-substituted) hydrocarbon; R<7> to R<10> are each H or a 1-18C (halogen-substituted) hydrocarbon] and more preferably adding (C) an additive such as a heat stabilizer or an epoxy compound to (A) pellets of a polycarbonate prepared by melt polycondensing an aromatic dihydroxy compound such as bis(4-hydroxyphenyl) methane with a carbonic acid diester in the presence of preferably 1×10<--8> to 1×10<-3> mol (based on 1mol aromatic dihydroxy compound) basic catalyst such as an alkali(alkaline earth) metallic compound and kneading the resultant mixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate composition and a method for producing the same, and more specifically, it has excellent retention stability such as heat stability and hue stability during molding, and also has excellent weather resistance and water resistance. It relates to an excellent polycarbonate composition and a method for producing the same.

[0002]

2. Description of the Related Art Polycarbonate has excellent mechanical properties such as impact resistance, heat resistance and transparency, and is widely used for various mechanical parts, optical discs, automobile parts and the like. There is.

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.

By the way, in the conventional polycarbonate,
At the time of melting, a part thereof may be thermally decomposed to lower the molecular weight or to be colored, which may result in lack of retention stability.

As a method for improving the residence stability of such a polycarbonate, conventionally, in the melt polycondensation method, the aromatic dihydroxy compound and the carbonic acid diester are melted in the presence of an alkaline compound catalyst. After condensation, while the reaction product polycarbonate is in a molten state, by kneading an additive according to the purpose of use, a method of reducing the number of heat history received by the polycarbonate during the production (Japanese Patent Laid-Open No. 4-103626). JP-A-4-175368 and JP-A-4-328124, after melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of an alkaline compound catalyst, and then adding an acidic compound. ) Is disclosed.

The present inventors further studied the method for producing polycarbonate by the melt polycondensation method, and found that the aromatic dihydroxy compound and the carbonic acid diester were melt-polycondensed in the presence of a basic catalyst. A polycarbonate composition comprising the obtained polycarbonate and a salt of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound,
The inventors have found that the present invention is further excellent in retention stability such as heat stability and hue stability during molding, and is also excellent in weather resistance and water resistance, and has completed the present invention.

[0008]

OBJECT OF THE INVENTION The present invention provides a polycarbonate composition which is excellent in heat stability during molding, retention stability such as hue stability and the like, and is also excellent in weather resistance, water resistance and transparency, and a method for producing the same. Is intended.

[0009]

SUMMARY OF THE INVENTION A polycarbonate composition according to the present invention comprises a polycarbonate [A] obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a basic catalyst, and a strong acid having a pKa of 3 or less. It is characterized by comprising a salt [B] of a compound and a nitrogen-containing basic compound.

The polycarbonate composition according to the present invention is
It is preferable to contain an additive [C] together with a salt [B] of a strong acid compound having a pKa of 3 or less as described above and a nitrogen-containing basic compound.

In the method for producing a polycarbonate composition according to the present invention, a salt [B] of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound, and an additive [C] which is optionally blended. May be added while the polycarbonate [A] obtained by melt polycondensation of the aromatic dihydroxy compound and the carbonic acid diester in the presence of a basic catalyst is in a molten state, or in the presence of a basic catalyst. Alternatively, pellets of polycarbonate [A] obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester may be remelted and added.

Since such a polycarbonate composition is not easily decomposed by heat during molding, it is excellent in transparency and hue stability, mechanical properties, water resistance and weather resistance.

[0013]

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

[A] Polycarbonate In the present invention, first, an aromatic dihydroxy compound and a carbonic acid diester are melt-polycondensed in the presence of a basic catalyst to produce a [A] polycarbonate.

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

[0016]

Embedded image

In the formula, 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 represented by the above formula 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 Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
-Dihydroxy aryl ethers such as dimethyl phenyl ether, 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,
4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and other dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-
Examples thereof include dihydroxydiaryl sulfones such as dimethyldiphenyl sulfone.

As the aromatic dihydroxy compound,
A compound represented by the following general formula [II] can also be used.

[0019]

[Chemical 4]

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 to 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.

[0023]

Embedded image

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. 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 and dibutyl. Examples thereof include carbonate and dicyclohexyl carbonate.

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

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

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

Two or more kinds of such dicarboxylic acid or dicarboxylic acid ester may be contained in the carbonic acid diester. In the present invention, when melt polycondensation is performed using an aromatic dihydroxy compound and a carbonic acid diester, the carbonic acid diester is usually 1.0 to 1.30 mol, preferably 1 to 1 mol of the aromatic dihydroxy compound. It is preferably used in an amount of 0.01 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 0.03 mol or less, preferably 0.001 to 0.02 mol, and more preferably 0.001 mol, per 1 mol of the aromatic dihydroxy compound.
Used in an amount of ˜0.01 mol.

In the present invention, the above-mentioned aromatic dihydroxy compound and carbonic acid diester are melt-polycondensed in the presence of a basic catalyst to obtain a polycarbonate [A]. As the basic catalyst, (a) an alkali metal compound 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 in combination of two or more kinds. Such (a) alkali metal compound and / or alkaline earth metal compound is used in an amount of 1 × 10 ⁻⁸ to 1 × 1 with respect to 1 mol of the aromatic dihydroxy compound.
It is desirable that it is used in an amount of 0 ^-3 mol, preferably 10 ^-7 to 2 × 10 ^-6 mol, and more preferably 10 ^-7 to 1 × 10 ^-6 mol.

When (a) an alkali metal compound or an alkaline earth metal compound is used as a catalyst in an amount as described above, a polycarbonate can be produced with a high polymerization activity, and an amount which does not adversely affect the obtained polycarbonate will be described later. The acidic compounds described above can be added to sufficiently neutralize or weaken the basicity of these compounds.

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 an aryl group, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, trioctylamine, tridodecylamine, trioctadecylamine, R ₂ NH (wherein R is methyl, Alkyl groups such as ethyl, aryl groups such as phenyl and toluyl, etc.), primary amines represented by RNH ₂ (wherein R is as defined above), 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-
Pyridines such as pyrrolidinopyridine, imidazoles such as 2-methylimidazole, 2-phenylimidazole, and 2-dimethylaminoimidazole, or ammonia, tetramethylammonium borohydride (Me ₄ N
BH ₄ ), tetrabutylammonium borohydride (B
u ₄ NBH ₄ ), basic salts such as tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ).

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

(B) The nitrogen-containing basic compound is used in an amount of 1 × 10 ^-6 to 1 × 10 ^{-1 with} respect to 1 mol of the aromatic dihydroxy compound.
It is preferably used in an amount of not more than 1 mol, preferably 1 × 10 ⁻⁵ to 1 × 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.

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

Specific examples of such 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
1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol, preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol, and more preferably 1 × with respect to mol.
It is used in an amount of 10 ⁻⁶ to 1 × 10 ⁻⁴ mol.

In the present invention, the base catalyst is preferably (b) a nitrogen-containing basic compound together with (a) an alkali metal compound and / or an alkaline earth metal compound as described above, 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 boric acid ester are used.

As described above, when the basic catalyst is used in combination with (a) the alkali metal compound and / or the alkaline earth metal compound in the above-mentioned amount of (b) the nitrogen-containing basic compound, the aromatic compound is It is preferable because the polycondensation reaction between the dihydroxy compound and the carbonic acid diester can proceed at a sufficient rate, and a high-molecular weight polycarbonate can be produced with high polymerization activity.

Furthermore, it is more preferable to use a combination of the above three amounts in order to produce a polycarbonate that is less likely to cause a decrease in 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. The reactor used for carrying out the above reaction may be of a tank type, a tube type, a column type or a horizontal 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, in the present invention, the
Since toxic substances such as phosgene and methylene chloride are not used in the production of bone, it is preferable from the viewpoint of environmental hygiene. Polycarbonate composition The polycarbonate composition according to the present invention comprises the polycarbonate [A] obtained as described above, and a salt [B] of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound. ,
If necessary, it comprises an additive [C].

Strong acid compound having pKa of 3 or less and nitrogen-containing base
Salt with Basic Compound [B] The salt of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound used in the present invention will be described.

[B] A salt consisting of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound is hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, or pyrroline. Acid, polyphosphoric acid, sulfuric acid, sulfite, thiosulfate, dimethyl sulfite, diethyl sulfite, dipropyl sulfite, dibutyl sulfite, diphenyl sulfite, dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, diphenyl sulfate,
Aromatic sulfonic acids such as benzenesulfinic acid, toluenesulfinic acid, naphthalene sulphinic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, diisobutylnaphthalenesulfonic acid, Methyl sulfonic acid,
Alkyl sulfonic acids such as ethyl sulfonic acid and propyl sulfonic acid, α-olefin sulfonic acids, sulfonated polystyrenes, strong acid compounds having a PKa of 3 or less such as methyl acrylate-sulfonated styrene copolymer, and the catalyst are described above. Nitrogen-containing basic compounds such as tetramethylammonium hydroxide (Me ₄ NOH),
Tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (M
e) ₃ NOH), etc., ammonium hydroxides having alkyl, aryl, araryl groups, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, trioctylamine, tridodecylamine, trioctadecylamine. , R ₂ NH (wherein R is an alkyl group such as methyl or ethyl, or an aryl group such as phenyl or toluyl)
Secondary amines represented by RNH ₂ (wherein R is the same as above), pyridines such as 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 2 -Salts with imidazoles such as methyl imidazole, 2-phenyl imidazole and 2-dimethylamino imidazole, or with ammonia.

The strong acid compound having a PKa of 2 or less is preferably a salt of a strong acid compound having a sulfonic acid compound and a nitrogen-containing basic compound, and more preferably the following general formula [II
It is preferably a sulfonate compound represented by I].

[0059]

[Chemical 6]

[In the formula, A represents a hydrocarbon group having 1 to 56 carbon atoms (alkyl, aryl or cycloalkyl), and hydrogen may be substituted with halogen. R ⁷ ,
R ^8, R ^9, R ¹⁰ is hydrogen or the same or different numbers from 1 to 18 hydrocarbon group having a carbon (hydrogen may be substituted with halogen). ] Particularly preferably, a sulfonate compound represented by the following general formula [IV] is used.

[0061]

[Chemical 7]

[In the formula, R ¹¹ is a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with halogen),
n is an integer of 0-3. R < ⁷ >, R < ⁸ >, R < ⁹ > and R < ¹⁰ > are hydrogen or the same or different hydrocarbon groups having 1 to 18 carbon atoms (hydrogen may be substituted with halogen). The following compounds can be mentioned as such a sulfonate compound.

Ammonium benzene sulfonate, ammonium salts such as ammonium p-toluene sulfonate, methyl ammonium benzene sulfonate, ethyl ammonium benzene sulfonate, propyl ammonium benzene sulfonate, methyl ammonium p-toluene sulfonate, p-toluene sulfonic acid Primary ammonium salts such as ethylammonium, propylammonium p-toluenesulfonate, butylammonium p-toluenesulfonate, octylammonium p-toluenesulfonate, phenylammonium p-toluenesulfonate, dimethylammonium benzenesulfonate, benzenesulfonic acid Diethyl ammonium, dipropyl ammonium benzenesulfonate, dimethyl ammonium p-toluenesulfonate, p-
Secondary ammonium salts such as diethylammonium toluenesulfonate, dipropylammonium p-toluenesulfonate, dibutylammonium p-toluenesulfonate, dioctylammonium p-toluenesulfonate, diphenylammonium p-toluenesulfonate, trimethylammonium benzenesulfonate , Triethylammonium benzenesulfonate, tripropylammonium benzenesulfonate, trimethylammonium p-toluenesulfonate, triethylammonium p-toluenesulfonate, tripropylammonium p-toluenesulfonate,
Tertiary ammonium salts such as tributylammonium p-toluenesulfonate, trioctylammonium p-toluenesulfonate, triphenylammonium p-toluenesulfonate, tetramethylammonium benzenesulfonate, tetraethylammonium benzenesulfonate, tetrapropylbenzenesulfonate Ammonium, tetramethylammonium p-toluenesulfonate, tetraethylammonium p-toluenesulfonate, tetrapropylammonium p-toluenesulfonate, tetrabutylammonium p-toluenesulfonate, tetraoctylammonium p-toluenesulfonate, p-toluenesulfone Quaternary ammonium salts such as acid tetraphenylammonium,
And so on.

These compounds can be used alone or in combination. Furthermore, the above general formula [I
V], R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are preferably substituted aliphatic hydrocarbon groups having 1 to 8 carbon atoms, and n is a sulfonate compound represented by an integer of 0 to 1.

Specifically, tetramethylammonium benzenesulfonate, tetraethylammonium benzenesulfonate, tetrapropylammonium benzenesulfonate, tetramethylammonium p-toluenesulfonate, tetraethylammonium p-toluenesulfonate,
tetrapropylammonium p-toluenesulfonate, p-
Quaternary ammonium salts such as tetrabutylammonium toluenesulfonate, tetraoctylammonium p-toluenesulfonate and tetraphenylammonium p-toluenesulfonate are preferably used.

Particularly in the present invention, tetramethylammonium p-toluenesulfonate, tetraethylammonium p-toluenesulfonate, tetrapropylammonium p-toluenesulfonate and tetrabutylammonium tetrabutylammonium p-toluenesulfonate are preferably used.

The polycarbonate composition according to the present invention is
The salt [B] of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound as described above is (a) an amount of an alkali metal compound and / or an alkaline earth metal compound as a basic catalyst, It is preferably contained in an amount of 1 to 20 mole times, preferably 1 to 10 mole times, and particularly preferably 1 to 8 mole times.

Thus, the polycarbonate composition has p
When a salt of a strong acid compound having a Ka of 3 or less and a nitrogen-containing basic compound is contained, the basic catalyst in the polycarbonate is formed by the salt [B] of the strong acid compound having a pKa of 3 or less and the nitrogen-containing basic compound. A polycarbonate composition which is neutralized, has excellent retention stability during melting, and has excellent hue, transparency, water resistance and weather resistance can be obtained.

In the present invention, the above polycarbonate composition is prepared by adding the salt [B] of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound to the polycarbonate [A] and kneading. can do.

In the present invention, the above-mentioned salt [B] can be added after pelletizing the polycarbonate [A] obtained by the polycondensation reaction as described above, but particularly as described above. The polycarbonate [A] obtained by the polycondensation reaction is preferably added while it is in a molten state in the reactor or the extruder. The polycarbonate composition is usually obtained by pelletizing.

The polycarbonate [A] and the salt [B] are kneaded by a single-screw extruder, a twin-screw extruder, a static mixer.
And the like, and these kneaders can be effectively used with or without a vent.

Preferably, in order to obtain a polycarbonate composition by adding salt [B] and kneading while the reaction product polycarbonate [A] is in a molten state as described above. Specifically, for example, after the salt [B] is added to the polycarbonate [A] obtained by the polycondensation reaction in the reactor to form a polycarbonate composition, it may be pelletized through an extruder, Further, while the polycarbonate [A] obtained by the polycondensation reaction is pelletized from the reactor through the extruder, salt [B] may be added and kneaded to obtain a polycarbonate composition. .

Generally, when polycarbonate is used, pellets of polycarbonate are remelted and various additives such as a heat resistance stabilizer are blended. In the polycarbonate composition obtained in the present invention, since the thermal stability at the time of melting is improved as described above, it has excellent retention stability at the time of melting, and various additives may be blended or molded. At this time, even if the pellet made of the polycarbonate composition is re-melted, the thermal decomposition is particularly suppressed, so that the molecular weight is less likely to decrease and the coloring is less likely to occur.

[C] Additive In addition, the polycarbonate composition according to the present invention may contain the additive [C] together with the salt [B] as described above within a range not impairing the object of the present invention. preferable.

Specific examples of the additive [C] used in the present invention include a wide range of additives generally added to polycarbonate depending on the purpose of use.
Heat resistance stabilizer, epoxy compound, ultraviolet absorber, release agent,
Examples thereof include colorants, antistatic agents, slip agents, antiblocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like.

Among these, as the additive [C], the following (i) heat stabilizer, (ii) epoxy compound, (iii) ultraviolet absorber, (iv) release agent and (v) ) Colorants are preferably used. These can be used in combination of two or more kinds.

(I) Heat Resistant Stabilizer Specific examples of the (i) heat resistant stabilizer used in the present invention include phosphorus compounds, phenolic stabilizers, organic thioether stabilizers, hindered amine stabilizers, and the like. Can be mentioned.

As the phosphorus compound, phosphoric acid, phosphorous acid,
Hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid esters and phosphorous acid esters can be used. As such a phosphoric acid ester, specifically, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate,
Trialkyl phosphates such as distearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate , Triaryl phosphates such as tris (nonylphenyl) phosphate and 2-ethylphenyldiphenylphosphate.

Further, 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 phosphite such as tris (2,3-dichloropropyl) phosphite, tricycloalkyl phosphite such as tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl ) Triaryl phosphites such as phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite, phenyldidecylphosphite,
Diphenyldecyl phosphite, diphenylisooctyl phosphite, phenylisooctyl phosphite,
Examples thereof include arylalkyl phosphites such as 2-ethylhexyl diphenyl phosphite.

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

Of these, the phosphorus compound is preferably a phosphite represented by the above general formula, more preferably an aromatic phosphite, particularly tris (2,4-diester).
-t-Butylphenyl) phosphite is preferably used.

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.

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.

As the hindered amine stabilizer,
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,2 6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate and the like.

These heat resistance stabilizers may be used in combination of two or more kinds. In the present invention, (i) heat stabilizer,
[A] 0.0 with respect to 100 parts by weight of polycarbonate
It is desirable that it is used in an amount of 01 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, and more preferably 0.01 to 0.3 parts by weight.

The heat stabilizer (i) may be added in the form of solid or liquid. (i) The heat stabilizer is
It is preferable to add [A] while the polycarbonate is in a molten state while being cooled from the final polymerization vessel and pelletized.

(Ii) Epoxy Compound In the present invention, a compound having one or more epoxy groups in one molecule is used as the (ii) epoxy compound. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-
Butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexylcarboxy Rate, 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'-methylsiloxyhexyl carboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, diglycidyl ester of phthalic acid,
Hexahydrophthalic acid diglycidyl ester, bis-
Epoxy dicyclopentadienyl ether, bis-epoxy ethylene glycol, bis-epoxy cyclohexyl adipate, butadiene diepoxide, tetraphenyl ethylene 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-
Methyl cyclohexyl carboxylate, octadecyl
-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-
3 ', 4'-epoxycyclohexylcarboxylate, 4,5-
Epoxy tetrahydrophthalic anhydride, 3-t-butyl-4,5-
Epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, di
Examples include -n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate.

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

These may be used alone or in combination of two or more. In the present invention, such an (ii) epoxy compound is added to the polycarbonate [A] in an amount of 1 to 2
It is preferable to add it in an amount of 000 ppm, preferably 10 to 1000 ppm.

In particular, when the (ii) epoxy compound is used as the additive [C], the (ii) epoxy compound is added after the addition of the salt [B], and the salt which is an excessively added acid salt [ It is preferable to neutralize B]. In this way, by neutralizing the salt [B] which may remain excessively in the polycarbonate composition with the (ii) epoxy compound, a polycarbonate composition excellent in water resistance and transparency can be obtained.

(Iii) Ultraviolet Absorber Examples of the ultraviolet absorber (iii) include general ultraviolet absorbers, and are not particularly limited. For example, salicylic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based Examples thereof include an ultraviolet absorber and a cyanoacrylate-based ultraviolet absorber.

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 UV 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.

In the present invention, the (iii) ultraviolet absorber is usually 0.0 to 100 parts by weight of the polycarbonate [A].
It can be used in an amount of 01 to 5 parts by weight, preferably 0.005 to 1.0 parts by weight, more preferably 0.01 to 0.5 parts by weight.

(Iv) Release Agent 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 release agent include lower fatty acid alcohol esters such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters.

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

In the present invention, the releasing agent (iv) is usually 0.001 to 100 parts by weight of the polycarbonate [A].
It can be used in an amount of 5 parts by weight, preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight.

(V) Colorant The (v) colorant may be a pigment or a dye. The coloring agent includes an inorganic coloring agent and an organic coloring agent, and any one of them may be used or a combination thereof may be used.

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. , 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, condensed polycyclic colorants such as indanthrone blue, quinacridone violet, and dioxazine violet.

These colorants may be used alone or in combination. In the present invention, the colorant (v) is usually 1 × 1 with respect to 100 parts by weight of the polycarbonate [A].
It can be used in an amount of 0 ^{-6 to} 5 parts by weight, preferably 1 x 10 ^{-5 to} 3 parts by weight, and more preferably 1 x 10 ^-5 to 1 part by weight.

In the present invention, when the above salt [B] and, if necessary, the additive [C] are added to the reaction product polycarbonate [A], these physical properties are Is used by diluting with a polycarbonate powder to an extent that does not impair, or a polycarbonate carbonate master pellet containing a high concentration of [B] and [C] is prepared in advance,
The master pellets can be added to finally produce a polycarbonate composition containing the target concentrations of [B] and [C].

[0107]

According to the present invention, it is possible to reliably and efficiently produce a polycarbonate composition excellent in retention stability such as heat stability and hue stability during melting.

The polycarbonate composition obtained according to the present invention does not easily undergo thermal decomposition at the time of molding so that the molecular weight thereof is not easily lowered, and it is hardly yellowed and has excellent hue stability.

Furthermore, according to the present invention, since the basic catalyst remaining in the polycarbonate is neutralized and stabilized, when other additives are added, the characteristics originally possessed by the additives are obtained. A polycarbonate composition having excellent heat resistance, weather resistance, water resistance and the like can be obtained without impairing the heat resistance.

The polycarbonate composition produced by the method of the present invention is used as a general molding material in addition to building materials such as sheets, automotive headlamp lenses, optical lenses such as eyeglasses, and optical recording materials. Is preferably used as.

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

[0112]

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] A press-molded plate having a thickness of 3 mm was molded at a molding temperature of 290 ° C., an injection pressure was 1000 kg / cm, and one cycle was 45.
Seconds, mold temperature is 100 ° C, and X, Y, and Z values are Color and Color Defference Meter ND manufactured by Nippon Denshoku Industries Co., Ltd.
The yellowness index [YI] was measured by a transmission method using -1001 DP.

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.
The haze of the press-molded plate for hue measurement was measured using -200.

[Stability] The resin was retained in the cylinder of the injection molding machine at a temperature of 340 ° C. for 15 minutes, and injection molding was performed at that temperature to obtain the MFR and hue (Y) of the molded plate.
I), the light transmittance 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.

[Weather resistance] An injection-molded plate for hue measurement was provided with a sunshine weatherometer (manufactured by Suga Test Machine 〓: 63 ° C,
Carbon arc light source, 2 minutes 18 minutes rain)
After holding for 1000 hours, the hue (YI) and light transmittance were measured.

[0120]

EXAMPLE 1 Bisphenol A [2,2-bis (4-hydroxyphenyl) propane] (manufactured by Nippon GE Plastics Co., Ltd.) 0.44 kmole and diphenyl carbonate (manufactured by Any Co.) 0.46 kmole It was charged in a 250-liter tank-type stirring tank, and after nitrogen substitution, it was melted at 140 ° 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 3
Stirred for 0 minutes.

Next, the temperature was raised to 210 ° C. and, at the same time, gradually lowered to 200 mmHg and 30 minutes later, the temperature was raised to 2
The temperature was raised to 40 ° C. and, at the same time, gradually lowered to 15 mmHg, the temperature and pressure were kept constant, and the amount of phenol to be distilled out was measured. When the phenol to be distilled out was exhausted, 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 raised 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. From the bottom of the evaporator with a gear pump at 290 ℃, 0.
Biaxial horizontal stirring polymerization tank controlled to 2 mmHg (L
/ D = 3, stirring blade rotating diameter 220 mm, internal volume 80 liters) was fed at 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 tetramethylammonium p-toluenesulfonate ( An acidic compound salt) was added and kneaded so as to have a molar amount twice that of sodium hydroxide used, kneaded into a strand shape through a die, and cut into a pellet with a cutter.

The intrinsic viscosity [IV] of the obtained polymer was 0.49 dl / g. The results are shown in Table 1.

[0126]

Examples 2, 3 and 4 The same as Example 1 except that tetramethylammonium p-toluenesulfonate was replaced by the salt shown in Table 1 and the amount shown in Table 1 was used. A pellet was obtained by the method.

The results are shown in Table 1.

[0128]

Example 5 In Example 1, the polymer was directly extracted as a strand form from the biaxial horizontal stirring polymerization tank and cut into a pellet by a cutter.

Next, tetrabutylammonium p-toluenesulfonate was added to the pellets in an amount of twice the molar amount of sodium hydroxide, and the mixture was kneaded at 285 ° C. in a usual twin-screw extruder. Pellets were obtained.

[0130]

Comparative Example 1 Pellets were obtained in the same manner as in Example 1 except that tetramethylammonium p-toluenesulfonate was not added.

The results are shown in Table 1.

[0132]

Comparative Example 2 Same as Example 1 except that in Example 1, butyl p-toluenesulfonate, which is an acidic compound ester, was used in the amount shown in Table 1 instead of tetramethylammonium p-toluenesulfonate. The pellet was obtained by the method of.

The results are shown in Table 1.

[0134]

[Comparative Example 3] The same as Example 5 except that butyl p-toluenesulfonate, which is an acidic compound ester, was used in place of tetramethylammonium p-toluenesulfonate in the amount described in Table 1 in Example 5. The pellet was obtained by the method of.

The results are shown in Table 1.

[0136]

[Example 6] In Example 3, tetraethylammonium p-toluenesulfonate was added in an amount twice that of sodium hydroxide, and tris (2,4-di-t) was added.
-Butylphenyl) phosphite (Mark 2112: manufactured by ADEKA ARGUS CORPORATION) 500 ppm, n-octadecyl-3- (4-hydroxy-3,5, -di-t-butylphenyl) propionate (Mark AO50: ADEKA ARGAS) (Made by the company) 500ppm,
3,4-Epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (Celoxide 2021P:
Daicel Chemical Co., Ltd.) 500ppm, 2- (2'-hydroxy-5 ')
-t-octylphenyl) benzotriazole (Ciasolv UV5411: Sun Chemical Co., Ltd.) 3000 ppm, silicone release agent (TSF437: Toshiba Silicone Co., Ltd.) 3000
ppm, colorant (Plast Violet 8840: Bayer)
0.5 ppm was kneaded, and pellets were obtained by the same method as in Example 1.

The results are shown in Table 1.

[0138]

Example 7 Pellets were obtained in the same manner as in Example 6 except that tetrabutylammonium p-toluenesulfonate was used instead of tetraethylammonium p-toluenesulfonate.

The results are shown in Table 1.

[0140]

Comparative Example 4 In Example 6, except that tetramethylammonium p-toluenesulfonate was replaced with butyl p-toluenesulfonate which is an acidic compound ester,
Pellets were obtained by the same method as in Example 6.

The results are shown in Table 1.

[0142]

[Table 1]

[0143]

[Table 2]

[0144]

[Table 3]

[0145]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Nagai 2-2 Kinugaoka, Moka-shi, Tochigi Japan Japan Plastics Co., Ltd.

Claims (13)

[Claims] 1. A polycarbonate [A] obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a basic catalyst, a strong acid compound having a pKa of 3 or less, and a nitrogen-containing basic compound. A polycarbonate composition comprising a salt [B]. 2. A polycarbonate [A] obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a basic catalyst, a strong acid compound having a pKa of 3 or less, and a nitrogen-containing basic compound. A polycarbonate composition comprising a salt [B] and an additive [C]. 3. A pellet of polycarbonate [A] obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a basic catalyst, has a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound. A method for producing a polycarbonate composition, which comprises adding a salt [B] with a compound and kneading. 4. Pellets of a polycarbonate [A] obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a basic catalyst, have a strong acid compound having a pKa of 3 or less, and a nitrogen-containing basic compound. A method for producing a polycarbonate composition, comprising adding a salt [B] with a compound and an additive [C] and kneading. 5. A polycarbonate (A) obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a basic catalyst, and a strong acid compound having a pKa of 3 or less while the polycarbonate [A] is in a molten state. A method for producing a polycarbonate composition, comprising adding a salt [B] with a nitrogen-containing basic compound and kneading. 6. A strong acid compound having a pKa of 3 or less while a polycarbonate [A] obtained by melt polycondensation of an aromatic dihydroxy compound and a carbonic acid diester in the presence of a basic catalyst is in a molten state. A method for producing a polycarbonate composition, comprising adding a salt [B] with a nitrogen-containing basic compound and an additive [C] and kneading. 7. The basic catalyst is 1 × 10 ^{−8 with} respect to 1 mol of the aromatic dihydroxy compound.
The polycarbonate composition according to claim 1 or 2, which comprises (i) an alkali metal compound and / or an alkaline earth metal compound in an amount of ^-1 x 10 ^-3 mol. 8. The basic catalyst is 1 × 10 ^{−7 with} respect to 1 mol of the aromatic dihydroxy compound.
The polycarbonate composition according to claim 1 or 2, which comprises (i) an alkali metal compound and / or an alkaline earth metal compound in an amount of ˜2 × 10 ⁻⁶ mol. 9. A salt of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound is 1 to 20 mol times the amount of an alkali metal compound and / or an alkaline earth metal compound as a basic catalyst. The polycarbonate composition according to claims 1 to 4, characterized in that it is used in an amount of. 10. The polycarbonate composition according to claim 1, wherein the strong acid compound is a sulfonic acid compound having a pKa of 2 or less. 11. The salt [B] of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound is a compound represented by the following general formula [III]. Polycarbonate composition described: [In the formula, A is a hydrocarbon group having 1 to 56 carbon atoms (alkyl, aryl or cycloalkyl), and hydrogen may be substituted with halogen. R ⁷ , R ⁸ , R ⁹ , R ¹⁰
Is hydrogen or the same or different hydrocarbon group having 1 to 18 carbon atoms (hydrogen may be substituted with halogen). ] 12. The salt [B] of a strong acid compound having a pKa of 3 or less and a nitrogen-containing basic compound is a compound represented by the following general formula [IV]. The polycarbonate composition described in: [In formula, R < ¹¹ > is a C1-C50 hydrocarbon group (hydrogen may be substituted by halogen), and n is an integer of 0-3. R < ⁷ >, R < ⁸ >, R < ⁹ > and R < ¹⁰ > are hydrogen or the same or different hydrocarbon groups having 1 to 18 carbon atoms (hydrogen may be substituted with halogen). ] 13. The additive [C] is at least one selected from the group consisting of heat resistance stabilizers, epoxy compounds, ultraviolet absorbers, release agents and colorants. The polycarbonate composition according to.