JPH059287A - Manufacture of polycarbonate - Google Patents

Abstract

PURPOSE:To provide a method for manufacturing polycarbonate, which enables the manufacture of a polycarbonate excellent in mechanical characteristics, especially impact resistance, heat resistance and transparency, and improved in residence stability and moldability without using phosgene. CONSTITUTION:In manufacturing a polycarbonate by the melt polycondensation of an aromatic dihydroxy compound and a carbonic diester in the presence of a shortstop, an alkoxy compound is used as the shortstop in such an amount that aromatic hydrocarbon units of general formula ArO- (wherein Ar is a 6-50C aromatic hydrocarbon group) can be introduced into 5-99% of the molecular terminal of the obtained polycarbonate; the melt polycondensation is effected also in the presence of a catalyst containing an alkali metal compound and/or alkaline earth metal compound, in an amount of 1X10<-8> to 1X10<-3>mol per mol of the aromatic dihydroxy compound; and an acidic compound is added to the obtained reaction product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polycarbonate, and more specifically, a polycarbonate having excellent mechanical properties such as impact resistance, transparency, hue stability, and improved residence stability. The present invention relates to a method for producing a polycarbonate capable of efficiently producing a polycarbonate.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate has excellent mechanical properties such as impact resistance, heat resistance and transparency, and is widely used in various mechanical parts, optical discs, automobile parts, etc. Has been. Further, this polycarbonate is required to have further improved performance according to each application.

By the way, the conventional polycarbonate having the above-mentioned characteristics is usually produced by an interfacial polymerization method in which an aromatic dihydroxy compound such as bisphenol-A is directly reacted with phosgene. In this method, methylene chloride is usually used during the reaction.

Thus, the use of methylene chloride and toxic phosgene is not preferable in terms of environmental hygiene.
Further, methylene chloride may remain in the obtained polycarbonate and affect the thermal stability and hue of the polycarbonate. That is, when the polycarbonate is melt-molded, residual chlorine may lower the thermal stability or cause yellowing.

By the way, such a polycarbonate usually has a high glass transition temperature (Tg), and in order to mold the polycarbonate into, for example, an optical disk, it has to be melted at a high temperature in order to improve fluidity.

[0006] Generally, when the polymer is molded at a high temperature in order to increase the production yield, the transparency or hue,
The molecular weight is lowered and the impact resistance is lowered accordingly, and the molded article is easily affected.

[0007] Therefore, the impact resistance, retention stability, and
It has been desired to develop a method capable of producing a polycarbonate having excellent moldability without using phosgene.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has excellent mechanical properties, particularly impact resistance, heat resistance, transparency, and improved retention stability and moldability. Another object of the present invention is to provide a method for producing a polycarbonate which can produce such a polycarbonate without using phosgene.

[0009]

SUMMARY OF THE INVENTION The method for producing a polycarbonate according to the present invention is a method of producing a polycarbonate by subjecting an aromatic dihydroxy compound and a carbonic acid diester to melt polycondensation in the presence of an end-capping agent. Using an alkoxy compound in an amount such that the aromatic hydrocarbon unit represented by the following general formula [I] can be introduced into 5 to 99% of the molecular ends of the obtained polycarbonate, based on 1 mol of the aromatic dihydroxy compound. 1 x 10 ^-8 to 1 x 10 ^-3
Melt polycondensation in the presence of a catalyst containing an amount of (a) an alkali metal compound and / or an alkaline earth metal compound: ArO -... [I] (wherein Ar is the number of carbon atoms). 6 to 50 aromatic hydrocarbon groups.).

In the present invention, as a catalyst, (a) an alkali metal compound and / or an alkaline earth metal compound, and (b) a nitrogen-containing basic compound and / or (c) boric acid or a boric acid ester may be used. preferable.

Further, in the present invention, it is preferable to add an acidic compound to the reaction product obtained by the melt polycondensation as described above.

[0012]

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

The aromatic dihydroxy compound used in the present invention is not particularly limited, but examples thereof include compounds represented by the following formula [II].

[0014]

[Chemical 3]

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 such aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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-methyl) Bis (hydroxyaryl) alkanes such as phenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane and 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1 -Bis (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydro Dihydroxyaryl ethers such as shea 3,3'-dimethylphenyl ether, 4,4 '
-Dihydroxydiphenyl sulfides, dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Examples thereof include dihydroxydiaryl sulfoxides such as sulfoxide, and dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone.

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

[0017]

[Chemical 4]

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

Specific examples of the aromatic dihydroxy compound represented by the above general formula [III] include resorcin and 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, and 3-t-resorcin. Butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,
Substituted resorcins such as 3,4,6-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 Mention may be made of substituted hydroquinones such as, 6-tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone.

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.

[0021]

[Chemical 5]

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

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

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

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

Such dicarboxylic acid or dicarboxylic acid ester may be contained alone or in combination. The above-mentioned carbonic acid diester is usually 1.0 to 1.3 with respect to 1 mol of the aromatic dihydroxy compound.
It is desired to be used in an amount of 0 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 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, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are preferable. Used.

When a polyfunctional compound is used, the polyfunctional compound is based on 1 mol of the aromatic dihydroxy compound.
Usually, it is not more than 0.03 mol, preferably 0.001 to 0.02.
More preferably, it is used in an amount of 0.001 to 0.01 mol.

In the present invention, when a polycarbonate is produced, an end-capping agent is used together with the above aromatic dihydroxy compound and carbonic acid diester. In the present invention, an allyloxy compound capable of introducing an end group represented by the following general formula [I] into the molecular end of the obtained polycarbonate is used as the end capping agent.

ArO -... [I] In the formula, Ar represents an aromatic hydrocarbon group having 6 to 50 carbon atoms. The aromatic hydrocarbon group is not particularly limited, and may be a condensed ring such as a phenyl group, a naphthyl group or an anthranyl group, and further, these aromatic ring and saturated hydrocarbon and / or
Alternatively, it may form a ring with a hetero atom. Further, these aromatic rings may be substituted with halogen or an alkyl group having 1 to 9 carbon atoms.

Specific examples of the terminal group represented by the above formula [I] include a phenoxy group having a skeleton represented by each of the following formulas, p-tert-butylphenoxy group and p-cumyl. Examples thereof include a phenoxy group (p-phenylisopropylphenoxy group) and a chromanylphenoxy group.

[0034]

[Chemical 6]

A phenoxy group represented by

[0036]

[Chemical 7]

A p-tert-butylphenoxy group represented by

[0038]

[Chemical 8]

A p-cumylphenoxy group (p-phenylisopropylphenoxy group) represented by

[0040]

[Chemical 9]

A chromanylphenoxy group represented by: In the present invention, the following compounds can be specifically mentioned as the compound capable of introducing the above-mentioned terminal group into the obtained polycarbonate molecule. In the compounds exemplified below, the aromatic ring or the aliphatic ring is halogen,
It may be substituted with alkyl having 1 to 9 carbon atoms.

Examples of the compound capable of introducing the phenoxy group represented by the above formula [IV] include phenol and diphenyl carbonate. Examples of the compound capable of introducing the p-tert-butylphenoxy group represented by the above formula [V] include p-tert-butylphenol, p-tert-butylphenylphenyl carbonate, p-tert-butylphenyl carbonate and the like. Can be mentioned.

Examples of the compound capable of introducing the p-cumylphenoxy group represented by the above formula [VI] include p-cumylphenol, p-cumylphenylphenyl carbonate and p-cumylphenyl carbonate. Can be mentioned.

Further, as the chromanylphenoxy group represented by the general formula [VII], the following chromanylphenoxy groups can be mentioned in more detail.

[0045]

[Chemical 10]

Specific examples of the compound capable of introducing the chromanylphenoxy group represented by the formula [VIII] include the following chroman compounds.

2,2,4-trimethyl-4- (4-hydroxyphenyl) chroman, 2,2,4,6-tetramethyl-4- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2, 3,4-Trimethyl-2-ethyl-4- (3-nonyl-4-hydroxyphenyl)-
7-nonyl-chroman, 2,2,4-trimethyl-4- (3,5-diethyl-4-hydroxyphenyl) -6-ethylchroman, 2,2,4,
6,8-Pentamethyl-4- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2,2,4-triethyl-3-methyl-4- (4-hydroxyphenyl) chroman, 2,2,4- Trimethyl-4- (3
-Bromo-4-hydroxyphenyl) chroman, 2,2,4-trimethyl-4- (3-bromo-4-hydroxyphenyl) -6-bromochroman, 2,2,4-trimethyl-4- (3,5- Dibromo-4-hydroxyphenyl) -6-bromochroman, 2,2,4-trimethyl-4- (3,5-dibromo-4-hydroxyphenyl) -6,8-
Examples thereof include dibromochroman.

Among these, especially 2,2,4-trimethyl
-4- (4-hydroxyphenyl) chroman is preferred. Specific examples of the compound capable of introducing the chromanylphenoxy group represented by the above formula [IX] include chroman compounds as shown below.

2,2,3-Trimethyl-3- (4-hydroxyphenyl) chroman, 2,2,3,6-tetramethyl-3- (3,5-dimethyl
-4-Hydroxyphenyl) chroman, 2,3,4-trimethyl
-2-Ethyl-3- (3-nonyl-4-hydroxyphenyl) -7-nonyl chroman, 2,2,3-trimethyl-3- (3,5-diethyl-4
-Hydroxyphenyl) -6-ethyl-chroman, 2,2,3,6,8-
Pentamethyl-3- (3,5-dimethyl-4-hydroxyphenyl)
Chroman, 2,3,3-triethyl-3-methyl-3- (4-hydroxyphenyl) chroman, 2,2,3-trimethyl-3- (3-bromo
-4-hydroxyphenyl) -6-bromochroman, 2,2,3-trimethyl-3- (3,5-dibromo-4-hydroxyphenyl) -6-
Bromochroman, 2,2,3-trimethyl-3- (3,5-dibromo-4
-Hydroxyphenyl) -6,8-dibromochroman and the like can be mentioned.

Of these, 2,2,3-trimethyl-3 (4-hydroxyphenyl) chroman is particularly preferable. Specific examples of the compound capable of introducing the chromanylphenoxy group represented by the above formula [X] include the chroman compounds shown below.

2,4,4-Trimethyl-2- (2-hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2- (3,5-dimethyl-2-hydroxyphenyl) chroman, 2,3, 4-Trimethyl-4-ethyl-2- (3,5-dimethyl-2-hydroxyphenyl) -7-nonyl-chroman, 2,4,4-trimethyl-2- (3,5-dimethyl-2-hydroxyphenyl)- 6-ethyl-chroman, 2,4,4,6,8-pentamethyl-2- (3,5-dimethyl-2-hydroxyphenyl) -6-ethylchroman, 2,4,4-trimethyl-2- (3 -Bromo-2-hydroxyphenyl) chroman, 2,
4,4-Trimethyl-2- (3-bromo-2-hydroxyphenyl)
-6-Bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-2-hydroxyphenyl) -6-bromochroman 2,4,4-trimethyl-2- (3,5-dibromo-2-hydroxyphenyl) -6,8-dibromochroman and the like can be mentioned.

Among these, especially 2,2,4-trimethyl
-2- (2-hydroxyphenyl) chroman is preferred. Further, specific examples of the compound capable of introducing the chromanylphenoxy group represented by the above formula [XI] include the chroman compounds shown below.

2,4,4-trimethyl-2- (4-hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2, 4,4-triethyl-2- (4-hydroxyphenyl) chroman, 2,3,4-trimethyl-4-ethyl-2- (3,5-dimethyl-4-hydroxyphenyl) -7-nonyl-chroman, 2 , 4,4-Trimethyl-2-
(3,5-Diethyl-4-hydroxyphenyl) -6-ethyl-chroman, 2,4,4,6,8-pentamethyl-2- (3,5-dimethyl-4-
Hydroxyphenyl) -6-ethylchroman, 2,4,4-trimethyl-2- (3-bromo-4-hydroxyphenyl) chroman, 2,4,4-trimethyl-2- (3-bromo-4-hydroxyphenyl) ) -6-Bromochroman, 2,4,4-trimethyl-2- (3,5-
Dibromo-4-hydroxyphenyl) -6-bromochroman,
Mention may be made of 2,4,4-trimethyl-2- (3,5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman.

Among these, especially 2,4,4-trimethyl
-2- (4-hydroxyphenyl) chroman is preferred. Each of the compounds capable of introducing the terminal group represented by the general formula [I] as described above can be used alone or in combination.

In the present invention, the above allyloxy compound is usually 0.01 to 0.2 mol, preferably 0.02 to 1 mol, relative to 1 mol of the aromatic dihydroxy compound.
It is used in an amount of 0.15 mol, more preferably 0.02 to 0.1 mol.

By using an allyloxy compound in such an amount as the end capping agent, the molecular end of the obtained polycarbonate is 1 to 95%, preferably 10 to 95%.
%, And more preferably 20 to 90%, can be blocked with the terminal group represented by the above general formula [I].

As described above, the polycarbonate in which the terminal group represented by the general formula [I] is introduced in the above proportion has excellent heat resistance and mechanical properties such as impact resistance even with a low molecular weight.

In the present invention, as the end-capping agent, an aliphatic monocarboxy compound capable of introducing an aliphatic hydrocarbon unit represented by the following general formula [XII] as needed is used together with the above allyloxy compound. May be.

[0059]

[Chemical 11]

In the formula, R is alkyl having 10 to 30 carbon atoms, which may be linear or branched,
It may be substituted with halogen. Specific examples of the compound capable of introducing the aliphatic hydrocarbon unit (aliphatic carboxyl group) represented by the above formula [XII] at the terminal of the polycarbonate molecule include an aliphatic monocarboxylic acid and an aliphatic monocarboxylic acid ester. Can be mentioned.

Specific examples of such a compound include undecanoic acid, lauric acid, tridecanoic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, and melicic acid. And alkyl monocarboxylic acid esters such as methyl ester, ethyl ester and phenyl ester of the above alkyl monocarboxylic acids such as alkyl monocarboxylic acid, methyl stearate, ethyl stearate and phenyl stearate.

These may be used alone or in combination. Of these, stearic acid, methyl stearate, ethyl stearate, phenyl stearate and the like are preferably used.

The above-mentioned aliphatic monocarboxy compound is usually used in an amount of 1 mol of the aromatic dihydroxy compound.
An amount of 0.01 to 0.20 mol, preferably 0.02
0.15 mol, more preferably 0.02 to 0.
It can be used in an amount of 10 mol.

When the total amount of the above terminal blocker containing an allyloxy compound is 0.2 mol or more per 1 mol of the aromatic dihydroxy compound, the polymerization rate tends to decrease. .

In the present invention, the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed by using the above-mentioned end capping agent. This melt polycondensation is
(a) It is carried out in the presence of a catalyst containing an alkali metal compound and / or an alkaline earth metal compound.

Specific examples of such alkali metal compounds and alkaline earth metal compounds include organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of alkali metals and alkaline earth metals. And the like are preferable.

More specifically, such alkali metal compounds include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride , Lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium Salts, dilithium salts, sodium salts of phenol, potassium salts, lithium salts and the like are used.

Specific examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, and carbonic acid. Calcium, barium carbonate,
Magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like are used.

These compounds can be used alone or in combination. Such (a) alkali metal compound and / or alkaline earth metal compound is used in an amount of 1 × 10 ⁻⁸ to 1 × with respect to 1 mol of the aromatic dihydroxy compound.
It is used in an amount of 10 ⁻³ mol, preferably 1 × 10 ⁻⁷ to 2 × 10 ⁻⁶ mol, and more preferably 1 × 10 ⁻⁷ to 8 × 10 ⁻⁷ mol.

(A) The amount of the alkali metal compound or the alkaline earth metal compound used is the aromatic dihydroxy compound 1
When the amount is 10 ⁻⁸ to 10 ⁻³ mol or less with respect to mol, the acidic compound (described later) is added in an amount that can maintain high polymerization activity and does not adversely affect the properties of the obtained polycarbonate. The basicity can be sufficiently neutralized or weakened, and a polycarbonate having excellent hue, heat resistance, water resistance and weather resistance, and excellent long-term melt stability can be obtained.

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 be used.

Examples of such a basic compound (b) include nitrogen-containing basic compounds which are easily decomposable or volatile at 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 araryl groups, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, R ₂ NH (wherein R is an alkyl group such as methyl or ethyl, an aryl group such as phenyl or toluyl). Etc.)
Secondary amines, RNH ₂ (wherein R is the same as above) primary amines, 2-methylimidazole, 2-phenylimidazole and other imidazoles,
Alternatively, ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), tetramethylammonium tetraphenylborate (Me ₄ NBPh). ₄ ) Basic salts such as.

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

As the boric acid compound (c), boric acid, boric acid ester and the like can be mentioned. As the boric acid ester, a boric acid ester represented by the following general formula is used.

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 ester 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 amounts of 10 ⁻⁵ to 10 ⁻² mol. (b) When the nitrogen-containing basic compound is used in an amount of 10 ^-6 to 10 ^-1 mol with respect to ¹ mol of the aromatic dihydroxy compound, the transesterification reaction and the polymerization reaction proceed at a sufficient rate, and the hue, It is preferable in that a polycarbonate excellent in heat resistance and water resistance can be obtained.

In addition, (c) boric acid or boric acid ester
When used, 1 mol of aromatic dihydroxy compound
On the other hand, 1 × 10^-8~ 1 x 10^-1Mol, preferably 1x
10 ^-7~ 1 x 10^-2Mol, more preferably 1 × 10^-6
~ 1 x 10^-FourUsed in molar amounts. (c) boric acid or
The amount of boric acid ester used is an aromatic dihydroxy compound
1 x 10 for 1 mole^-8~ 1 x 10^-1Used in molar amounts
Is less likely to cause a decrease in molecular weight after heat aging,
Polycarbonate with excellent hue, heat resistance and water resistance
Is preferable in that it can obtain

In particular, (a) an alkali metal compound or an alkaline earth metal compound, and (b) a nitrogen-containing basic compound,
(c) The catalyst of the combination of boric acid or boric acid ester is excellent in transparency, heat resistance and water resistance and also has improved color tone, and can form a high molecular weight polycarbonate with high polymerization activity. .

The polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester, which is carried out in the presence of such a catalyst using an end-capping agent, is carried out under the same conditions as the conventionally known polycondensation reaction conditions. be able to.

Specifically, the first step reaction 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,
The reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out, and finally the polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out at a temperature of 240 to 320 ° C. under reduced pressure of 5 mmHg or less, preferably 1 mmHg or less.

In the polycondensation reaction as described above, the terminal blocking agent can be charged together with the aromatic dihydroxy compound and the carbonic acid diester. The polycondensation reaction as described above may be carried out continuously or batchwise. Further, the reaction apparatus used for carrying out the above reaction may be a tank type, a tube type or a column type.

In the method for producing a polycarbonate according to the present invention as described above, the total chlorine content contained in the raw material as described above is 20 ppm or less, more preferably 1 ppm or less.
By setting the content to 0 ppm or less, it is possible to obtain a polycarbonate in which the transparency is not easily lowered.

The chlorine content as used herein means chlorine existing as an acid such as hydrochloric acid or a salt such as sodium chloride and potassium chloride, or chlorine contained in an organic compound such as phenylchloroformate and methylene chloride. It means the amount, and can be measured by analysis using ion chromatography or the like.

It is preferable that the total chlorine content in the raw material as described above is 20 ppm or less, since a polycarbonate having a particularly good hue can be obtained. In order to reduce the total chlorine content of the above-mentioned raw materials to 20 ppm or less, for example, these raw materials have a pH value of 6.0 to 9.0, preferably a pH value of 7.0 to 8.5. More preferably, the pH value is 7.0 to 8.0, and the temperature is 78 to 105 ° C., preferably 80 to 100 ° C., more preferably 80 to 90 ° C., if washed with warm water or a weakly basic aqueous solution. Good.

Examples of the weakly basic aqueous solution used for washing the above-mentioned raw materials are sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide, sodium hydrogen carbonate, The basic compounds such as potassium hydrogen carbonate and tetramethylammonium hydroxide should be adjusted to the specified pH.
Aqueous solutions dissolved in water are used to show the values. Among them, it is particularly preferable to use an aqueous solution of sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate.

Further, it is preferable that the raw material, especially the carbonic acid diester, is washed with warm water as described above and then further distilled before use. Further, in the present invention, the total sodium ion content contained in the above-mentioned raw material is preferably 1.0 ppm or less, more preferably 0.5 ppm or less, whereby a polycarbonate without further coloring can be obtained. it can.

The sodium ion content contained in the raw material is determined by atomic absorption analysis and inductively coupled plasma emission analysis. In order to keep the sodium ion content contained in the raw material as described above at or below the above value, a purification method such as distillation, recrystallization, an adduct method with phenol, etc. may be adopted.

In the polycarbonate thus obtained, the intrinsic viscosity [η] measured in methylene chloride at 20 ° C. is usually 0.1 to 1.0 dl / g, preferably 0.1.
It is 2 to 0.7 dl / g.

The glass transition temperature (Tg) is 100 to
The temperature is 200 ° C, preferably 120 to 180 ° C. Furthermore, the melt flow rate (MFR) is measured at a temperature of 300 ° C. and a load of 1.2 kg in accordance with the method of JIS K-7210 and is 2 g / 10.
Min or more, preferably 5 g / 10 min or more.

The polycarbonate obtained as described above usually has a main chain composed of repeating units represented by the following formula.

[0093]

[Chemical 12]

However, X, R ₄ , R ₅ , p, and q are as described in the formula [II]. The polycarbonate having a main chain as described above generally has at least two end groups such as OH groups in its molecule. In the polycarbonate obtained in the present invention, aromatic hydrocarbon units are bonded in such molecular ends in a proportion of 5 to 95%, preferably 10 to 95%, and more preferably 20 to 90%.

Polycarbonate having a molecular terminal sealed with such a unit has excellent fluidity and moldability, and has excellent mechanical properties such as impact resistance even with a low molecular weight. In the polycarbonate obtained in the present invention, the molecular terminals other than the terminal sealed with the unit represented by the above formula [I] have an aliphatic monocarboxyl group represented by the above formula [XII], and further a raw material. May be a phenolic OH group derived from the aromatic dihydroxy compound (for example, phenol derived from bisphenol-A) or may be blocked with another inert group. The total amount of the terminal groups not sealed with the unit represented by [I] is usually 1 to 95%, preferably 5 to 90%.
More preferably, the polycarbonate of the present invention is constituted at a rate of 10 to 80%.

The polycarbonate obtained in the present invention includes
Included are all polycarbonates in which the units of the general formula [I] are bonded in the above-mentioned proportions. That is,
For example, in the melt polycondensation, an aromatic carboxyl compound and a carbonic acid diester such as diphenyl carbonate are used as the end capping agent, and the aromatic hydrocarbon represented by the general formula [I] is added to the same polycarbonate. It may be a polycarbonate in which a unit and a terminal group attributed to carbonic acid diester are introduced, or a polycarbonate (1) whose end is blocked by an aliphatic hydrocarbon unit and a terminal which is blocked by another unit. Stopped polycarbonate
It may be prepared by separately preparing (2) and mixing them at a predetermined ratio.

In such a polycarbonate, in the aromatic hydrocarbon unit represented by the above formula [I] bonded to the terminal position, the ratio of the chromanyl group bonded to the terminal position is 15 to 15. A polycarbonate of 80% is preferable because it is excellent in heat resistance and moldability, and particularly excellent in impact resistance at low molecular weight.

In the method for producing a polycarbonate according to the present invention, an acidic compound is added to the reaction product thus obtained, that is, the polycarbonate. The acidic compound used in the present invention may be a Lewis acid compound, even if it is a Lewis acid compound, if it can neutralize an alkaline compound such as an alkali metal compound or an alkaline earth metal compound used as a catalyst. It may be an ester of a strong acid containing.

Particularly, the Bronsted acid compound is 2
The pKa in an aqueous solution at 5 ° C. is 5 or less, preferably 3 or less. By using an acidic compound having such a pKa value, there is an advantage that the alkali metal or alkaline earth metal used as a catalyst can be neutralized and the obtained polycarbonate can be stabilized.

Specific examples of the Lewis acid compound include boron compounds such as zinc borate and boron phosphate, and B (OC
H ₃ ) ₃ , B (OEt) ₃ , B (OPh) ₃ and other borate esters, aluminum stearates, aluminum silicates and other aluminum compounds, zirconium carbonate, alkoxide zirconium, zirconium hydroxycarboxylates and other zirconium compounds, phosphorus Gallium compounds such as gallium nitride and gallium antimonide, germanium compounds such as germanium oxide and organic germanium,
Tetra and hexaorganotin, PhOSn (Bu)
₂ Tin compounds such as OSn (Bu) ₂ OPh, antimony compounds such as antimony oxide and alkyl antimony, bismuth compounds such as bismuth oxide and alkyl bismuth,
Examples thereof include (CH ₃ COO) ₂ Zn, zinc compounds such as zinc stearate, and titanium compounds such as alkoxy titanium and titanium oxide.

In the above formula, Ph is a phenyl group, Et
Represents an ethyl group and Bu represents a butyl group. Specific examples of the Bronsted acid compound include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, adipic acid, and azelaine. Acid, dodecane 12 acid, L-ascorbic acid, aspartic acid, benzoic acid, formic acid, acetic acid, citric acid, glutamic acid,
Salicylic acid, nicotinic acid, fumaric acid, maleic acid, oxalic acid, benzenesulfinic acid, toluenesulfinic acid and benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene, methyl acrylate-sulfone Examples thereof include compounds of sulfonic acids such as modified styrene copolymer.

As the ester of an acid containing a sulfur atom,
Dimethylsulfate, diethylsulfate, p-toluenesulfonic acid methyl, ethyl, butyl, octyl or phenyl ester, benzenesulfonic acid methyl, ethyl, butyl, octyl, phenyl ester, etc.
A compound having a Ka of 3 or less is used.

Of these acidic compounds, those containing a sulfur atom, phosphorus atom, etc. are preferred, and those containing a sulfur atom are particularly preferred. Among the acidic compounds containing a sulfur atom, the compound represented by the following general formula [XIII] is particularly preferable.

[0104]

[Chemical 13]

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

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

These compounds can be used alone or in combination. Among these, as the sulfur-containing acidic compound having a pKa value of 3 or less and the derivative formed from the acidic compound, the sulfonic acid compound represented by the general formula [XIII] and its derivative are preferably used, and particularly benzene. Sulfonic acid, butyl benzene sulfonate, p-toluene sulfonic acid, ethyl p-toluene sulfonate, and butyl p-toluene sulfonate are preferably used.

Particularly preferably, butyl p-toluenesulfonate is used. The method for producing a polycarbonate according to the present invention is characterized in that the acidic compound as described above is added to the polycarbonate in an amount of 0.1 to 10 pmm, preferably 0.1 to 8 ppm.
And particularly preferably added in an amount of 0.1-5 ppm.

In the present invention, it is preferable to add an epoxy compound together with the above acidic compound. As such an epoxy compound, one epoxy group is included in one molecule.
A compound having two or more is used. The amount used is not particularly limited, but is usually 0.0001 to 0.2 part by weight, preferably 0.001 to 0.1 part by weight, based on 100 parts by weight of the reaction product polycarbonate. To be

Specific examples of such an epoxy compound include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allylglycidyl ether, t-
Butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, 2,3-epoxy Cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 4- (3,4-epoxy-5
-Methylcyclohexyl) butyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxy Rate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis -Epoxy cyclohexyl adipate,
Butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5- t-Butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexanecarboxylate, cyclohexyl-2 -Methyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-
Methylcyclohexanecarboxylate, octadecyl
-3,4-Epoxycyclohexanecarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexanecarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl
-3 ', 4'-epoxycyclohexanecarboxylate, 4,
5-epoxy tetrahydrophthalic anhydride, 3-t-butyl-4,5
-Epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexanedicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-
Examples thereof include 1,2-cyclohexanedicarboxylate, and these may be used alone or in combination of two or more kinds.

Thus, when an epoxy compound is added to the reaction product polycarbonate at the same time as the acidic compound, the excess acidic compound reacts with the epoxy compound and is neutralized, resulting in color tone, heat resistance and water resistance. An excellent polycarbonate such as is obtained.

In the method for producing a polycarbonate according to the present invention, the polycarbonate obtained as a reaction product is
There is no particular limitation on the method of adding the acidic compound and the epoxy compound as necessary, and for example, the molten compound may be kneaded by adding the acidic compound and, if necessary, the epoxy compound to the polycarbonate. The epoxy compound may be added depending on the above conditions and stirred.

More specifically, the method of adding the acidic compound and the epoxy compound is as follows. The acidic compound is directly added to the polycarbonate which is the reaction product in the reactor or the extruder in the molten state obtained after the completion of the polycondensation reaction. A method in which a compound and an epoxy compound are added separately or simultaneously as necessary and kneaded, the obtained polycarbonate is pelletized, and the pellets are fed together with an acidic compound and an epoxy compound as required to a single-screw or twin-screw extruder. Melt kneading method, the obtained polycarbonate is dissolved in a suitable solvent, for example, methylene chloride, chloroform, toluene, tetrahydrofuran, etc. to prepare a solution, in which the acidic compound and optionally an epoxy compound are separately or simultaneously prepared. Examples thereof include a method of adding and stirring.

The acidic compound and the epoxy compound may be added to the polycarbonate in the order of the acidic compound or the epoxy compound. In the present invention, the obtained polycarbonate, in addition to the acidic compound and the epoxy compound, a normal heat stabilizer, a tinuvin ultraviolet absorber, a release agent, an antistatic agent, a slip agent, an antiblocking agent, a lubricant, an antifogging agent. Agents, dyes, pigments, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like can be added within a range that does not impair the object of the present invention.

Specific examples of the heat resistance stabilizers described above include phenolic stabilizers, organic thioether stabilizers, organic phosphite stabilizers, hindered amine stabilizers, and epoxy stabilizers. be able to.

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 ( Four-
Hydroxy-3-methyl-5-t-butyl) benzyl malonate, 4-hydroxymethyl-2,6-di-t-butylphenol and the like can be mentioned. These can be used alone or in a mixture of two or more kinds. Good.

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, and these may be used alone or in combination of two or more kinds.

Examples of phosphorus stabilizers include, for example,
Aryl alkyl phosphites such as bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite, diphenyl decyl phosphite, diphenyl isooctyl phosphite, phenyl isooctyl phosphite, 2-ethylhexyl diphenyl phosphite, Trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, trinonylphosphite, tridecylphosphite, trioctadecylphosphite, distearylpentaerythrityldiphosphite, tris (2-chloroethyl) phosphite,
Trialkyl phosphites such as tris (2,3-dichloropropyl) phosphite, tricycloalkyl phosphites such as tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite, triarylphosphite such as tris (hydroxyphenyl) phosphite, trimethylphosphate, triethylphosphate, tributylphosphate, trioctylphosphate, tridecylphosphate, trioctadecylphosphate, di Trialkyl phosphates such as stearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate,
Examples thereof include tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphates, tricresyl phosphates, triaryl phosphates such as tris (nonylphenyl) phosphate, 2-ethylphenyldiphenylphosphate, and the like. You may use it in mixture of 2 or more types.

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-tetra Methylpiperidine, 2- (3,5-di-t-butyl-4-hydroxybenzyl)
-2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4
-Piperidyl), tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) 1,2,3,4-butanetetracarboxylate and the like, and these may be used alone or in combination of two or more kinds.

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

Such a heat resistance stabilizer may be added in a solid state or a liquid state. Such a heat stabilizer is preferably added while the polycarbonate is in the molten state while it is cooled from the final polymerization vessel and pelletized, and in this way the polycarbonate undergoes a small number of heat history. Further, when the heat treatment such as extrusion molding or pelletizing is performed again, since the polycarbonate contains the heat resistance stabilizer, thermal decomposition can be suppressed.

When the heat stabilizer as described above is added, an ultraviolet absorber can be added at the same time.
Such an ultraviolet absorber may be a general ultraviolet absorber and is not particularly limited, and examples thereof include salicylic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers. And so on.

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, 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-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 type ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate. These may be used alone or in combination of two or more.

These UV absorbers are usually used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of polycarbonate.
It is preferably used in an amount of 0.005 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight.

In the present invention, a releasing agent may be added at the same time when the heat resistance stabilizer as described above is added. Such a release agent may be a general release agent and is not particularly limited. For example, hydrocarbon-based releasing agents include natural and synthetic paraffins, polyethylene waxes, fluorocarbons and the like.

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

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

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

Examples of the silicone type release agent include silicone oils. These may be used alone or in combination of two or more. These release agents are used in an amount of usually 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the polycarbonate. To be

Further, when the above heat resistance stabilizer is added, a colorant may be added at the same time. Such a colorant may be a pigment or a dye. The colorant includes an inorganic colorant and an organic colorant, and either one may be used or a combination may be used.

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

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

These colorants may be used alone or in combination. These colorants are usually used in an amount of 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ^{−5 to} 3 parts by weight, and more preferably 1 × 10 ⁻⁵ to 1 part by weight, based on 100 parts by weight of polycarbonate. Used in quantity.

Further, in the present invention, it is preferable that the polycarbonate obtained by the polycondensation reaction is subjected to a reduced pressure treatment after adding an acidic compound and, if necessary, an epoxy compound.

In carrying out such a depressurization treatment, the treating device is not particularly limited, but for example, a reactor with a depressurizing device or an extruder with a depressurizing device may be used.

When the reactor is used, either a vertical tank type reactor or a horizontal tank type reactor may be used, and a horizontal tank type reactor is preferably used. When the pressure reduction treatment is carried out in the reactor as described above, the pressure is 0.05 to 750 mm.
It is carried out under the conditions of Hg, preferably 0.05 to 5 mmHg.

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

When the pressure reducing treatment is carried out in the extruder, either a single screw extruder with a vent or a twin screw extruder may be used, and the pelletizing may be performed while the pressure reducing treatment is carried out by the extruder.

When the reduced pressure treatment is carried out in the extruder,
The depressurization treatment is performed under a pressure of 1 to 750 mmHg, preferably 5 to 70.
It is carried out under the condition of 0 mmHg. In this way, by adding an acidic compound and, if necessary, an epoxy compound to the reaction product polycarbonate, and then subjecting it to a reduced pressure treatment, a polycarbonate with reduced residual monomers and oligomers can be obtained.

In the method for producing a polycarbonate according to the present invention, since a specific compound is used as an end-capping agent, sufficient impact resistance can be maintained even with a low molecular weight comparable to that of a disc grade, and heat resistance, water resistance, and It is possible to efficiently produce a polycarbonate having excellent weather resistance and transparency, and having improved flowability and moldability.

Furthermore, in the present invention, since the polycarbonate is produced by the melt polymerization method, the polycarbonate can be produced without leaving chlorine in the obtained polycarbonate.

[0144]

According to the present invention, a polycarbonate having excellent heat resistance, water resistance and weather resistance can be produced without leaving chlorine in the polycarbonate.

In the present invention, heat resistance, impact resistance,
A polycarbonate having excellent retention stability and moldability can be produced. Such polycarbonate can form a polycarbonate molded article having excellent molding quality. Further, since it is possible to provide a molded product of polycarbonate excellent in hue stability and heat resistance even during use, it is used for optical applications such as sheets, lenses, and compact discs, and outdoors such as automobiles. It can be suitably used for various purposes such as applications and housings of various devices.

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

[0147]

EXAMPLES The physical properties of the polycarbonates obtained in the following examples were measured as follows.

Intrinsic viscosity (IV): in methylene chloride (0.5 dl
/ G) Measured using an Ubbelohde viscometer at 20 ° C. Terminal group structure: 0.4 g of a sample was dissolved in 3 ml of chloroform and ¹³ C-NMR (manufactured by JEOL Ltd., G
B-270) was used to measure the structure and proportion of the terminal base.

Izod impact strength: Measured according to ASTM D256 using an injection test piece of 63.5 × 12.7 × 2 mm (rear notch). The average of 10 measured values was taken.

Yellowness (YI): L of 2 mm thick pressed sheet
The ab value is the Color and Color Defferen of Nippon Denshoku Industries Co., Ltd.
The yellowness index (YI) was calculated by the transmission method using ce Meter ND-1001 DP.

YI = (71.53a + 178.82b) / L = 100 (1.277X-1.060Z) / Y Glass transition temperature (Tg): MODEL manufactured by Perkin Elmer
Differential melting flow rate (MFR) of resin at a temperature rising rate of 10 ° C / min using a DSC-2 differential scanning calorimeter: measured in accordance with the method of JIS K-7210 under the conditions of 280 ° C and a load of 1.2 kg. did.

[0152]

Example 1 Diphenyl carbonate (Diphenyl carbonate manufactured by Bayer was washed twice with warm water having a pH of 7.0 at 80 ° C. and distilled at a yield of 90%; Na content of 10 ppb or less and chlorine content of 0.05.
ppm or less) 0.453 kmole and bisphenol A (manufactured by Nippon GE Plastics Co., Ltd. Na content of 10 ppb or less, chlorine content of 0.05 ppm or less) 0.44 kmole and 2,2,4-trimethyl-
4- (4-Hydroxyphenyl) chroman (manufactured by GE; Chroman I) (0.022 kmole) was charged into a 250-liter tank-type stirring tank, and the atmosphere was replaced with nitrogen.
Next, this was heated to 180 ° C. and stirred for 30 minutes. Then, as a catalyst, tetramethylammonium hydroxide is 0.11 mol-mol and sodium hydroxide is 0.000.
44 mol was added, the temperature was raised to 240 ° C. and the pressure was gradually lowered to 20 mmHg. The temperature and pressure were kept constant, the amount of phenol distilled was measured, and when there was no phenol distilled, the pressure was returned to atmospheric pressure with nitrogen.
The time required for the reaction was 2 hours. The intrinsic viscosity [IV] of the obtained reaction product was 0.14 dl / g.

Next, the pressure of this reaction product was increased by a gear pump and fed into a centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 290 ° C. and 2 mmHg, respectively. The prepolymer extracted from the lower part of the evaporator with a gear pump was passed through a die into a strand in a nitrogen atmosphere, cut into a pellet with a cutter. The intrinsic viscosity [IV] of this prepolymer was 0.32 dl / g.

Next, this prepolymer was treated at 293 ° C. and 0.2 m.
2-axis horizontal stirring polymerization tank controlled to mHg (L /
D = 6, stirring blade rotating diameter 150 mm, internal volume 40 liters) were fed by an extruder at 40 kg / hour and the residence time was 30
Polymerized in minutes.

Next, in the molten state, this polymer was fed into a twin-screw extruder (L / D = 17.5, barrel temperature 280 ° C.) by a gear pump, and p-toluene sulfone was added to the resin. Butyl acid (1.8 ppm) was kneaded, passed through a die to form a strand, and cut into a pellet with a cutter.

The intrinsic viscosity [IV] of the obtained polymer is
It was 0.42 dl / g. The results are shown in Table 1.

[0157]

Examples 2 to 5 Pellets were obtained in the same manner as in Example 1 except that the type and amount of catalyst and the type and amount of additive shown in Table 1 were used.

However, the final polymerization temperature in Example 3 was
Polymerization was carried out at 292 ° C. and in Examples 4 and 5 at 295 ° C. The results are shown in Table 1.

[0159]

[Examples 6 and 7] In Example 5, 0.022 kmole of p-tert-butylphenol and p-cumylphenol was charged instead of chroman I, and the final polymerization temperature was adjusted to 292 ° C and 294 ° C, respectively. Pellets were obtained in the same manner as in Example 5, except that the polymerization was carried out.

The results are shown in Table 1.

[0161]

Example 8 In Example 5, the chroman I was added to 0.02.
Example 5 except that 0.011 kmole of chroman I and 0.011 kmole of phenyl stearate were charged instead of 2 kmole, and the final polymerization temperature was 290 ° C.
Pellets were obtained in the same manner as in.

The results are shown in Table 1.

[0163]

Comparative Example 1 Pellets were obtained in the same manner as in Example 1 except that the type and amount of catalyst and the type and amount of additive shown in Table 1 were used.

The results are shown in Table 1.

[0165]

[Comparative Example 2] The same as Example 1 except that the amount of diphenyl carbonate used was changed to 0.457 kmole, the final polymerization temperature was changed to 285 ° C., and the end-capping agent Chroman I was not used. Similarly, a polycarbonate was obtained.

The results are shown in Table 1.

[0167]

[Table 1]

[0168]

[Table 2]

Claims (7)

[Claims] 1. When producing a polycarbonate by melt-polycondensing an aromatic dihydroxy compound and a carbonic acid diester in the presence of an end-capping agent, the end-capping agent is represented by the following general formula [I]. The aromatic hydrocarbon unit is used in an amount capable of being introduced into 5 to 99% of the molecular ends of the obtained polycarbonate, and the alkoxy compound is used in an amount of 1 × 10 ^{−8 with} respect to 1 mol of the aromatic dihydroxy compound.
A melt polycondensation in the presence of a catalyst containing (a) an alkali metal compound and / or an alkaline earth metal compound in an amount of ˜1 × 10 ⁻³ , and adding an acidic compound to the resulting reaction product. A method for producing a polycarbonate having: ArO -... [I] (wherein, Ar is an aromatic hydrocarbon group having 6 to 50 carbon atoms). 2. A p-cumylphenoxy group (p-phenylisopropyl group) represented by the following general formula [II] and / or a chromanylphenoxy group represented by the following general formula [III] as the terminal blocking agent. The method for producing a polycarbonate according to claim 1, wherein the group is used in an amount capable of introducing a compound that can be introduced into 5 to 99% of the molecular terminals of the obtained polycarbonate. [Chemical 1] (The aromatic ring or the aliphatic ring may be substituted with halogen or an alkyl group having 1 to 9 carbon atoms.) 3. (a) An alkali metal compound and / or an alkaline earth metal compound is added to 1 mol of an aromatic dihydroxy compound in an amount of 1 × 10 ^−7.
The method for producing a polycarbonate according to claim 1, wherein the polycarbonate is used in an amount of ˜2 × 10 ⁻⁶ . 4. A catalyst comprising (a) an alkali metal compound and / or an alkaline earth metal compound, and (b) a nitrogen-containing basic compound and / or (c) boric acid or a boric acid ester. The method for producing a polycarbonate according to claim 1. 5. A sulfur-containing acidic compound having a pKa value of 3 or less as an acidic compound, and / or
Alternatively, a derivative formed from the acidic compound is used, and the method for producing a polycarbonate according to claim 1. 6. The method for producing a polycarbonate according to claim 1, wherein a compound represented by the following general formula [XIV] is used as the acidic compound: [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 halogen. May be substituted with), and n is an integer of 0 to 3. ] 7. The method for producing a polycarbonate according to claim 1, wherein butyl p-toluenesulfonate is used as the acidic compound.