JP3043828B2 - Polycarbonate composition - Google Patents

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 more particularly, to a polycarbonate composition which is excellent in heat stability and hue stability during molding and can form a molded article excellent in transparency and water resistance. .

[0002]

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

By the way, in the conventional polycarbonate,
At the time of melt molding, a part thereof is thermally decomposed, and the molecular weight may be reduced or colored, and the thermal stability may be lacking. For this reason, a heat resistance stabilizer is usually blended with polycarbonate to improve the heat stability at the time of melting. However, in the case of a polycarbonate containing a heat stabilizer, water resistance tends to decrease, and in a molded article obtained from such a polycarbonate, transparency may decrease when used.

[0004] Therefore, there has been a demand for a polycarbonate composition which is excellent in heat stability and hue stability at the time of molding and can form a molded article having excellent water resistance and transparency.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above prior art, and has excellent heat stability and hue stability during molding, as well as excellent transparency and water resistance. It is an object of the present invention to provide a polycarbonate composition capable of forming a molded article.

[0006]

SUMMARY OF THE INVENTION The polycarbonate composition according to the present invention comprises: [A] (a) 1 mole of the aromatic dihydroxy compound in total
And an alkali metal compound in an amount of 10 ^-8 to 10 ^-3 mol
And / or the presence of a catalyst containing an alkaline earth metal compound
In the presence, an aromatic dihydroxy compound and a carbonic acid diester
A polycarbonate obtained by melt polycondensation and formed from with respect to the polycarbonate [A], [B] sulfur-containing acidic compound pKa value of the amount 0.1~5ppm is 3 or less and / or acidic compound And [C] a phosphorus compound in an amount of 10 to 1000 ppm, and [D] an epoxy compound in an amount of 1 to 2000 ppm.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate composition according to the present invention will be specifically described below. The polycarbonate composition according to the present invention, [A] polycarbonate,
[B] a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound;
It consists of [C] a phosphorus compound and [D] an epoxy compound.

The polycarbonate [A] used in the present invention can be prepared by a method of reacting an aromatic dihydroxy compound with phosgene in the presence of a solvent and a deoxidizing agent, or a method of reacting an aromatic dihydroxy compound with a carbonic acid diester such as diphenyl carbonate. It can be produced by a method of melting under heating and reacting under high temperature and reduced pressure (melting method).

In the present invention, the polycarbonate produced by the latter melting method is particularly preferably used. Specifically, such [A] polycarbonate can be produced, for example, by melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester as shown below.

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

[0011]

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R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen or a monovalent hydrocarbon group, which may be the same or different.
p and q represent an integer of 0 to 4. ) 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 (4-hydroxy 1-methylphenyl)
Bis (hydroxyaryl) alkanes such as propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis Bis (hydroxyaryl) cycloalkanes such as (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 Dihydroxyaryl ethers such as' -dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide; dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; and 4,4'-dihydroxydiphenyl Dihydroxydiarylsulfoxides such as sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfoxide, 4,4 ′ Dihydroxydiarylsulfones such as -dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

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

[0015]

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

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

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

[0019]

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

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

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

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

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

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

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

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

The polyfunctional compound is usually used in an amount of 0.03 mol or less, preferably 0.001 to 0.02 mol, more preferably 0.001 to 0.01 mol, per mol of the aromatic dihydroxy compound.
It is used in an amount of 0.01 mol.

The above-mentioned aromatic dihydroxy compound and diester carbonate are melt-polycondensed in the presence of a catalyst to produce polycarbonate.
(a) It is preferable to use an alkali metal compound and / or an alkaline earth metal compound.

Specific examples of the alkali metal compound and the alkaline earth metal compound include organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides and alcoholates of alkali metals and alkaline earth metals. And the like.

As such an alkali metal compound,
More specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate , Potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid Examples include dilithium hydrogen, disodium salt, dipotassium salt, dilithium salt of bisphenol A, phenol sodium salt, potassium salt, and lithium salt.

Specific examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, and 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 alkali metal compound and / or alkaline earth metal compound (a) is used in an amount of 10 ^-8 to 10 based on 1 mol of the aromatic dihydroxy compound.
^-3 mol, preferably 10 ^-7 to 2 × 10 ^-6 mol .

Further, as the catalyst, (b) a basic compound and / or (c) a boric acid compound may be used together with the above-mentioned (a) the alkali metal compound and / or the alkaline earth metal compound.

Examples of the basic compound (b) include nitrogen-containing basic compounds which are easily decomposable or volatile at a high temperature, and specific examples thereof include the following compounds.

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 araryl group and the like, tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine, R ₂ NH (where R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and toluyl) Etc.)
A primary amine represented by RNH ₂ (where R is the same as defined above), imidazoles such as 2-methylimidazole and 2-phenylimidazole,
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 ) ₄ ) Basic salts such as.

Of these, tetraalkylammonium hydroxides, especially tetraalkylammonium hydroxides for electronic use, which contain few metal impurities, are preferably used.

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

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

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

When the above-mentioned (b) nitrogen-containing basic compound is used, (b) the nitrogen-containing basic compound is 10 ^-6 to 10 ^-1 mol or less per 1 mol of the aromatic dihydroxy compound. , Preferably in an amount of 10 ^-5 to 10 ^-2 mol.

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

These may be used as a catalyst, for example, by combining (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound, and further comprising (a) an alkali metal compound and / or an alkali metal compound. An 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) an alkali metal compound and / or an alkaline earth metal compound with (b) a nitrogen-containing basic compound allows the polycondensation reaction to proceed at a sufficient rate, Can be produced with high polymerization activity, which is preferable.

Further, a catalyst combining the above three is preferable because it can produce a polycarbonate which 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 performed under the same conditions as conventionally known polycondensation reaction conditions.

Specifically, the first-stage reaction is carried out at 80 to 25
0 ° C., preferably 100-230 ° C., more preferably 120-190 ° C., for 0-5 hours, preferably 0 ° C.
The aromatic dihydroxy compound is reacted with the carbonic acid diester under normal pressure for up to 4 hours, more preferably 0 to 3 hours. Next, the reaction temperature was increased while reducing the pressure of the reaction system,
The reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out, and finally, 5 mmHg or less, preferably 1 mmHg or less.
The polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is performed at 240 to 320 ° C. under the following reduced pressure.

The above-mentioned polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

In the polycarbonate [A] used in the present invention, the intrinsic viscosity measured in methylene chloride at 20 ° C. is as follows:
Usually, 0.10 to 1.0 dl / g, preferably 0.30 to 0.1 dl / g.
It is 65 dl / g.

Next, the [B] sulfur-containing acidic compound constituting the polycarbonate composition according to the present invention and having a pKa value of 3 or less and / or a derivative formed from the acidic compound will be described.

In the present invention, examples of the sulfur-containing acidic compound [B] 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 sulfuric acid derivative include dimethyl sulfate, diethyl sulfate, sulfuric acid, dipropyl sulfate, dibutyl sulfate, diphenyl sulfate, dimethyl sulfite, diethyl sulfite, diphenyl sulfite, and the like.

Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid, and naphthalene sulfinic acid. Further, as the sulfonic acid compound and its derivative, the following general formula [II
And the ammonium salts thereof.

[0052]

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[Wherein, R ⁷ is a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted by halogen);
R ⁸ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted by halogen);
Is an integer of 0 to 3. ] Examples of such sulfonic acid compounds and derivatives thereof include the following compounds.

Sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, p -Sulfonate esters such as ethyl-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; and ammonium sulfonates such as ammonium p-toluenesulfonate.

Further, besides the sulfonic acid compound represented by the above general formula [III], trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene,
Sulfonic acids such as methyl acrylate-sulfonated styrene copolymer.

These compounds can be used alone or in combination. Of these, [B] p
As the sulfur-containing acidic compound having a Ka value of 3 or less and the derivative formed from the acidic compound, the above-mentioned general formula [II]
The sulfonic acid-based compound represented by I] and derivatives thereof are preferably used, and benzenesulfonic acid, butylbenzenesulfonate, p-toluenesulfonic acid, ethyl p-toluenesulfonate and butyl p-toluenesulfonate are particularly preferably used. Can be

Particularly preferably, butyl p-toluenesulfonate is used. The polycarbonate composition according to the present invention comprises: [B] a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound,
It is contained in an amount of 0.1 to 5 ppm .

In the present invention, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphite are used as the [C] phosphorus compound constituting the polycarbonate composition. Can be.

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

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

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

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

The polycarbonate composition according to the present invention comprises:
The above [C] phosphorus compound is added to the [A] polycarbonate in an amount of 10 to 1000 ppm, preferably 50 to 1000 ppm.
It is contained in an amount of 500 ppm.

Next, the epoxy compound [D] constituting the polycarbonate composition will be described. In the present invention,
[D] As the epoxy compound, a compound having one or more epoxy groups in one molecule is used.

As such epoxy compounds, specifically, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl 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'-epoxycyclohexyl carboxylate, 4- (3,4
-Epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 3,4-
Epoxy-6-methylcyclohexylmethyl-6′-methylsilohexylcarboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, diglycidyl ester of phthalic acid,
Diglycidyl ester of hexahydrophthalic acid, bis-
Epoxy dicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane , 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N- Butyl-2,2-dimethyl-3,
4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-
Methylcyclohexyl 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-cyclohexyldicarboxylate, di
-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate.

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

These may be used alone or as a mixture of two or more. The polycarbonate composition according to the present invention contains the epoxy compound [D] in an amount of 10 to 1000 ppm, preferably 50 to 800 ppm, based on the polycarbonate [A].

The polycarbonate composition according to the present invention comprises:
[A] polycarbonate as described above, and [B] pKa
It is prepared from a sulfur-containing acidic compound having a value of 3 or less and / or a derivative formed from the acidic compound, [C] a phosphorus compound, and [D] an epoxy compound, but the preparation method is not particularly limited. For example, a method in which [B], [C] and [D] are added separately or simultaneously to a molten polycarbonate [A] in a reactor or an extruder and kneaded, or the obtained polycarbonate is pelletized. And feeding the pellets together with [B], [C] and [D] to a single-screw or twin-screw extruder and melt-kneading them, dissolving the obtained polycarbonate in an appropriate solvent such as toluene, tetrahydrofuran, etc. Is prepared, and [B], [C] and [D] are separately or simultaneously added to the solution, followed by stirring. [A] polycarbonate, [B],
The order of adding [C] and [D] does not matter.

The polycarbonate composition according to the present invention comprises:
As long as the object of the present invention is not impaired, the composition may contain ordinary heat stabilizers, ultraviolet absorbers, release agents, coloring agents and the like as shown below.

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

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

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

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

These may be used alone or as a mixture of two or more. These heat stabilizers are used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight, per 100 parts by weight of the polycarbonate [A]. Is desirably used.

Such a heat stabilizer may be added in a solid state or a liquid state. It is preferable to add such a heat stabilizer while the polycarbonate is in a molten state while being cooled and pelletized from the final polymerization vessel. In this case, the heat history of the polycarbonate is reduced. In addition, when heat treatment is performed again such as extrusion molding and pelletizing, since the polycarbonate contains a heat stabilizer, thermal decomposition can be suppressed.

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

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

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

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

The polycarbonate composition according to the present invention comprises:
Such an ultraviolet absorber was used as [A] polycarbonate 1
Usually, 0.001 to 5 parts by weight, preferably 0.005 to 1.0 parts by weight, more preferably 0.005 parts by weight, per 100 parts by weight.
It may be contained in an amount of from 0.01 to 0.5 part by weight.

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

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

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

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

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

The polycarbonate composition according to the present invention comprises:
Such a release agent is generally used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, more preferably 0.01 to 1 part by weight, per 100 parts by weight of the polycarbonate [A].
It may be contained in an amount of 0.5 parts by weight.

The coloring agent 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. , Chromates such as molybdenum red, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine blue,
Phosphates such as manganese violet; carbon such as carbon black; and metallic powder coloring agents such as bronze powder and aluminum powder.

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

These coloring agents may be used alone or in combination. These colorants are usually contained in the polycarbonate composition in an amount of 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ⁻⁶ parts by weight, per 100 parts by weight of the polycarbonate [A].
^10-5 to 3 parts by weight, and more preferably be contained in an amount of 1 × 10 ^-5 to 1 part by weight.

Further, the polycarbonate composition according to the present invention may contain an antistatic agent, as long as the object of the present invention is not impaired.
It may contain a slip agent, an anti-blocking agent, a lubricant, an anti-fogging agent, a natural oil, a synthetic oil, a wax, an organic filler, an inorganic filler, and the like.

The polycarbonate composition according to the present invention contains the sulfur-containing acidic compound [B] having a pKa value of 3 or less and / or a derivative formed from the acidic compound in an amount of less than 5 ppm as described above. As compared with the conventional polycarbonate, the thermal stability, particularly at the time of melting, is improved. In such a polycarbonate composition, thermal decomposition hardly occurs even in a molten state for a long time,
In particular, the molecular weight does not easily decrease during molding. Further, the polycarbonate composition has excellent hue stability and is hardly colored during molding.

Further, the polycarbonate composition according to the present invention is characterized in that [B] a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound and [C] an acidic compound such as a phosphorus compound. Despite containing, it is neutralized by [D] epoxy compound and is excellent in water resistance.

The polycarbonate composition according to the present invention is excellent in heat stability and hue stability during molding, and is excellent in water resistance and transparency over a long period of time during use. Can be formed.

[0095]

Industrial Applicability The polycarbonate composition according to the present invention has excellent heat stability during molding, excellent hue stability, and a molded article having excellent water resistance and transparency over a long period of time even during use. Can be formed.

Therefore, the molded product obtained by molding the polycarbonate composition according to the present invention is required to have transparency, hue stability, etc., especially for optical molded products such as sheets, lenses and compact discs. It can be widely used for applications.

[0097]

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

In this specification, the limiting viscosity [IV], MFR, hue [YI],
Light transmittance, haze, retention stability, and water resistance are measured as follows.

[Intrinsic viscosity [IV]] In methylene chloride, 2
It measured at 0 degreeC using the Ubbelohde viscometer. [MFR]
According to the method of JIS K-7210, temperature 300 ° C,
It was measured under 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, a mold temperature of 100 ° C., and the X, Y and Z values were determined by Nippon Denshoku Industries Co., Ltd. Colorand Color Defference Met
The yellowness [YI] was measured by a transmission method using er ND-1001 DP.

YI = 100 (1.277X-1.060Z) / Y [Light Transmittance] Measured according to the method of AASTM D1003 using an injection molded plate for hue measurement.

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

[Retention stability] After the resin was retained in the cylinder of the injection molding machine at a temperature of 320 ° C for 15 minutes, injection molding was performed at that temperature, and the MFR and hue (Y
I), the light transmittance was measured.

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

[0105]

Example 1 Bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) 0.44 kmole and diphenyl carbonate (manufactured by Any Corporation) 0.46 kmole were charged into a 250-liter stirred tank and purged with nitrogen. , 14
Dissolved at 0 ° C.

Next, the temperature was raised to a temperature of 180 ° C.
11 mol and 0.00044 mol of sodium hydroxide (1 × 10 ⁻⁶ mol / mol-bisphenol A)
Stir for 0 minutes.

Next, the temperature was raised to 210 ° C. and gradually lowered to 200 mmHg.
At the same time as the temperature was raised to 40 ° C., the temperature and pressure were kept constant by gradually lowering the pressure to 15 mmHg, and the amount of phenol distilled out was measured. When there was no more phenol distilled out, the pressure was returned to atmospheric pressure with nitrogen. The time required for the reaction was 1 hour.
The intrinsic viscosity [IV] of the obtained reaction product is 0.15 dl / g.
Met.

Next, the pressure of the reaction product was increased by a gear pump and sent to a centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. From the bottom of the evaporator, use a gear pump at 290 ° C.
2-axis horizontal stirring polymerization tank (L
/ D = 3, stirring blade rotation diameter 220 mm, internal volume 80 liter) at a rate of 40 kg / hour and polymerization for a residence time of 30 minutes.

Next, in a molten state, the polymer was fed to a twin-screw extruder (L / D = 17.5, barrel temperature: 285 ° C.) using a gear pump, and p-toluene sulfone was added to the resin. 1.8 ppm of butyl acid, 300 ppm of tris (2,4-di-t-butylphenyl) phosphite (Mark 2112: manufactured by Adeka Argus Co.), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (Ceroxide 2021P: manufactured by Daicel Chemical) 300 ppm
Was kneaded, passed through a die to form a strand, and cut with a cutter into pellets.

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

[0111]

Example 2 Pellets were obtained in the same manner as in Example 1 except that the polymerization temperature was changed to 280 ° C.

Table 1 shows the results.

[0113]

Examples 3 and 4 Pellets were obtained in the same manner as in Example 1 except that the compounds shown in Table 1 were used in place of butyl p-toluenesulfonate in the amounts shown in Table 1. Was.

Table 1 shows the results.

[0115]

[0116]

[0117]

Comparative Example 1 Except that in Example 1, tris (2,4-di-t-butylphenyl) phosphite and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate were not added. A pellet was obtained in the same manner as in Example 1.

Table 1 shows the results.

[0119]

Comparative Example 2 Pellets were obtained in the same manner as in Example 1, except that 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate was not added.

Table 1 shows the results.

[0121]

Comparative Example 3 Pellets were obtained in the same manner as in Example 1 except that tris (2,4-di-t-butylphenyl) phosphite was not added.

Table 1 shows the results.

[0123]

Comparative Example 4 Pellets were obtained in the same manner as in Example 1, except that butyl p-toluenesulfonate was not added.

Table 1 shows the results.

[0125]

Comparative Example 5 In Example 1, butyl p-toluenesulfonate, tris (2,4-di-t-butylphenyl) phosphite and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxy were used. Pellets were obtained in the same manner as in Example 1 except that no rate was added.

Table 1 shows the results.

[0127]

Comparative Example 6 Pellets were obtained in the same manner as in Example 1, except that butyl p-toluenesulfonate was used in the amounts shown in Table 1.

Table 1 shows the results. [Comparative Example 7] In Example 1, butyl p-toluenesulfonate was added as shown in Table 1.
Except for using the amount described in the above, the same method as in Example 1 was used.
To obtain a pellet. Table 1 shows the results.

[0129]

[Table 1]

[0130]

[Table 2]

Continued on the front page (72) Inventor Kimiyoshi Miura 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Kazuhiko Yamamoto Waka-machi, Kuga-gun, Yamaguchi Prefecture No. 6 1-2 Ki, Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-47-12993 (JP, A) JP-A-53-64262 (JP, A) (58) Fields investigated (Int. Cl. ^7, DB name) C08L 69/00

Claims (10)

(57) [Claims] [1] (A) (a) Total amount of aromatic dihydroxy compound
10 ^-8 to 10 ^-3 mole of alkali gold per mole
Contains genus compounds and / or alkaline earth metal compounds
An aromatic dihydroxy compound and carbonic acid in the presence of
A polycarbonate obtained by melt polycondensation of a diester with a sulfur-containing acid having a pKa value of 0.1 to 5 ppm with respect to the polycarbonate [A] of 0.1 to 5 ppm or less; A polycarbonate composition comprising a compound and / or a derivative formed from the acidic compound, [C] a phosphorus compound in an amount of 10 to 1000 ppm, and [D] an epoxy compound in an amount of 1 to 2000 ppm. 2. [A] The polycarbonate comprises an aromatic dihydroxy compound and a carbonic acid diester, and (a) 10 ^{-7 with} respect to 1 mole of the aromatic dihydroxy compound.
A polycarbonate obtained by melt polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of a catalyst containing an alkali metal compound and / or an alkaline earth metal compound in an amount of up to 2 × 10 ⁻⁶ mol. The polycarbonate composition according to claim 1, which is present. 3. [B] The sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound is a compound represented by the following general formula [III]. The polycarbonate composition according to claim 1 or 2: 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). And n is an integer of 0 to 3. 4. [B] The sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound is butyl p-toluenesulfonate. The polycarbonate composition according to any one of the above. 5. The polycarbonate composition according to claim 1, wherein the phosphorus compound [C] is contained in an amount of 50 to 500 ppm based on the polycarbonate [A]. 6. The polycarbonate composition according to claim 1, wherein the phosphorus compound [C] is an aromatic phosphite compound. 7. [C] The phosphorus compound is tris (2,4-di-t-
The polycarbonate composition according to any one of claims 1 to 6, wherein the composition is (butylphenyl) phosphite. 8. The polycarbonate composition according to claim 1, wherein the epoxy compound [D] is contained in an amount of 10 to 1000 ppm based on the polycarbonate [A]. 9. The polycarbonate composition according to claim 1, wherein the epoxy compound [D] is an alicyclic epoxy compound. 10. The [D] epoxy compound is 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate.
The polycarbonate composition according to any one of the above.