JP3358899B2 - Copolycarbonates, copolycarbonate compositions and methods for their manufacture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel copolycarbonate, a copolycarbonate composition which is excellent in heat resistance, hue, transparency and the like, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate is widely used because it has excellent mechanical properties such as impact resistance, and also has excellent heat resistance and transparency.

Such a polycarbonate is usually prepared by directly reacting bisphenol A (aromatic dihydroxy compound) with phosgene (interfacial method), or by melting an aromatic dihydroxy compound such as bisphenol A and a diester carbonate such as diphenyl carbonate. It is manufactured by a melting method in which a transesterification reaction (polycondensation reaction) is performed in a state.

[0004] Among them, when polycarbonate is produced by a melting method, it is not necessary to use phosgene as a raw material, and the polycarbonate can be produced at a lower cost than the interface method.

[0005] By the way, as described above, a conventional polycarbonate usually produced using bisphenol A as an aromatic dihydroxy compound has a glass transition temperature (Tg) of about 150 ° C. Such polycarbonates
For example, heat resistance is insufficient for use in optical materials that are exposed to high temperatures, such as automotive headlamps.
Depending on the application, even better heat resistance is desired.
Polycarbonate may be colored during production or melt molding.

Therefore, polycarbonates and polycarbonate compositions having excellent heat resistance and high hue and transparency that can be used even under high temperature conditions, and such polycarbonates and polycarbonate compositions can be obtained. The emergence of a method for producing polycarbonate has been desired.

[0007]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a novel copolycarbonate and copolycarbonate composition having excellent heat resistance and excellent hue and transparency. It is an object of the present invention to provide products and methods for producing them.

[0008]

SUMMARY OF THE INVENTION The copolycarbonate according to the present invention comprises
A novel copolycarbonate having (i) a structural unit represented by the following formula [I] and (ii) a structural unit represented by the following formula [II].

[0009]

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Wherein R ^a , R ^b , R ^c and R ^d are
A halogen atom, a hydrocarbon group having 1 to 10 carbon atoms or 1 to 10 carbon atoms in which at least a part thereof is substituted by halogen;
Wherein R ^a , R ^b , R ^c and R ^d are
They may be the same or different, and R ^b and R ^c may be hydrogen atoms.

[0011] p and q are integers from 0 to 3 each represent a number of substituents, when 2 or 3, R ^a s or R ^d each other may be the same or different. ).
The copolycarbonate according to the present invention is characterized in that the above (i) the structural unit represented by the formula [I] and (ii) the structural unit represented by the formula [II] are 98/2 to 1/99 [(i) / (Ii)].

The intrinsic viscosity [IV] of the copolycarbonate according to the present invention is preferably from 0.2 to 1.2 dl / g. Copolycarbonate according to the present invention as described above,
Excellent heat resistance and hue.

In the method for producing a copolycarbonate according to the present invention, for example, an aromatic dihydroxy compound represented by the following general formula [Ia], an aromatic dihydroxy compound represented by the following general formula [IIa], and a carbonic acid diester are
(a) The above copolycarbonate is produced by melt polycondensation in the presence of a catalyst containing an alkali metal compound and / or an alkaline earth metal compound.

[0014]

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(In the formula, R ^a , R ^b , R ^c , R ^d , p and q are the same as in the formula [II].) The copolycarbonate composition according to the present invention has the above-mentioned [ It is formed from [A] a copolycarbonate, [B] an acidic compound, and if necessary, [C] an epoxy compound.

In the method for producing a copolycarbonate composition according to the present invention, the aromatic dihydroxy compound represented by the above general formula [Ia] and the above general formula [II]
a) The aromatic dihydroxy compound represented by a) is melt-polycondensed with a carbonic acid diester in the presence of an alkaline compound catalyst, and the obtained [A] copolycarbonate is treated with [B]
It is characterized by adding an acidic compound and, if necessary, an epoxy compound [C].

In the present invention, as described above, it is preferable to add a [B] acidic compound and, if necessary, an [C] epoxy compound to the [A] copolycarbonate and then to perform a vacuum treatment.

The copolycarbonate composition according to the present invention is excellent in heat resistance and hue, excellent in molding retention stability, water resistance and weather resistance, and also excellent in stability when left in a molten state for a long time.

Further, in producing the copolycarbonate composition according to the present invention, when a vacuum treatment is performed during the production,
The amount of residual monomers or oligomers in the polymer is reduced, so that mold contamination during molding can be reduced, and a copolycarbonate composition excellent in molding stability and the like can be obtained.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The copolycarbonate, the copolycarbonate composition according to the present invention and the method for producing them will be described below in detail.

The co Polycarbonate copolycarbonate according to the present invention, as shown below
A novel polycarbonate having (i) a structural unit represented by the formula [I] and (ii) a structural unit represented by the formula [II].

[0022]

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Wherein R ^a , R ^b , R ^c and R ^d are
A halogen atom, a hydrocarbon group having 1 to 10 carbon atoms or 1 to 10 carbon atoms in which at least a part thereof is substituted by halogen;
Wherein R ^a , R ^b , R ^c and R ^d are
They may be the same or different, and R ^b and R ^c may be hydrogen atoms.

[0024] p and q are integers from 0 to 3 each represent a number of substituents, when 2 or 3, R ^a s or R ^d each other may be the same or different. ).
In the copolycarbonate according to the present invention, the structural unit (i) represented by the formula [I] and the structural unit (ii) represented by the formula [II] are randomly arranged.

The hydrocarbon group having 1 to 10 carbon atoms includes, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl , Nonyl, decyl, phenyl, methylphenyl, butylphenyl, naphthyl and the like.

The structural unit represented by the above formula [I]
(i) is an aromatic dihydroxy compound [I
a] and carbonic acid diester or phosgene.

[0027]

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Specific examples of the aromatic dihydroxy compound represented by the formula [Ia] include bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl) methane.
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
-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Bis (hydroxyaryl) cycloalkanes, dihydroxyaryl ethers such as 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfides such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 '
Dihydroxydiarylsulfoxides such as -dimethyldiphenylsulfoxide; and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferably used. Further, the structural unit (ii) represented by the above formula [II] includes an aromatic dihydroxy compound [II
a] and carbonic acid diester or phosgene.

[0030]

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Such an aromatic dihydroxy compound [II
Specific examples of a] include the following compounds. 3,6-dihydroxyxanthene, 2,6-dihydroxyxanthene, 2,7-dihydroxyxanthene, 3,6-dihydroxy-9,9-dimethylxanthene, 2,6-dihydroxy-9,
9-dimethylxanthene, 2,7-dihydroxy-9,9-dimethylxanthene, 3,6-dihydroxy-9,9-diethylxanthene, 3,6-dihydroxy-2,7,9,9-tetramethylxanthene, 3 , 6-Dihydroxy-9,9-dimethyl-2,7-dichloroxanthene, 3,6-dihydroxy-9,9-dimethyl-2,4,5,7-tetrachloroxanthene, 3,6-dihydroxy-9, 9-dimethyl-2,4,5,7-tetrabromoxanthene and the like.

Of these, 3,6-dihydroxy-
9,9-Dimethylxanthene is preferred. The copolycarbonate according to the present invention comprises (i) a structural unit represented by the formula [I] and (ii) a structural unit represented by the formula [II]:
98/2 to 1/99, preferably 95/5 to 5/95, and particularly preferably 90/10 to 10/90 [(i) / (ii)].

The copolycarbonate containing the structural units (i) and (ii) in such a ratio is excellent in moldability and has sufficiently improved heat resistance as compared with a general polycarbonate derived from bisphenol A. I have. If the content of the structural unit (ii) is less than 2 mol%, the copolycarbonate may not be sufficiently improved in heat resistance.

The copolycarbonate according to the present invention comprises the aromatic dihydroxy compounds [Ia] and [II]
a) and structural units (i) and (ii) derived from carbonic acid diester or phosgene, and may contain a unit derived from dicarboxylic acid or dicarboxylic acid ester within a range not to impair the object of the present invention.

Examples of such a dicarboxylic acid or dicarboxylic acid ester include terephthalic acid, isophthalic acid, sebacic acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, and diphenyl decandioate. And diphenyl dodecane diacid.

The copolycarbonate according to the present invention has a unit derived from a dicarboxylic acid or a dicarboxylic acid ester as described above, for example, when the unit derived from a carbonic acid diester is taken as 100 mol%, 50 mol% or less, preferably 30 mol% or less. % Or less.

The copolycarbonate derived from such a dicarboxylic acid or dicarboxylic acid ester, an aromatic dihydroxy compound, and a carbonic acid diester or phosgene is also called a polyester copolycarbonate.

Further, the copolycarbonate according to the present invention comprises:
A unit derived from a polyfunctional compound having three or more functional groups in one molecule may be contained within a range not to impair the object of the present invention. As the polyfunctional compound, a compound having three or more phenolic hydroxyl groups or carboxyl groups in one molecule is preferable, and in particular, a compound having three or more phenolic hydroxyl groups is preferred.
Is preferred.

Specific examples of such polyfunctional compounds include, 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, phloroglucin, 4,6-dimethyl
-2,4,6-tri- (4-hydroxyphenyl) -2-heptane,
1,3,5-tri (4-hydroxyphenyl) benzene, 2,2-bis-4,4- (4,4'-dihydroxyphenyl) -cyclohexylpropane, trimellitic acid, 1,3,5-benzenetricarboxylic Acid, pyromellitic acid and the like.

Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene are preferred. .

In the copolycarbonate according to the present invention, when the unit derived from such a polyfunctional compound is defined as 100 mol% with respect to the unit derived from an aromatic dihydroxy compound, it is 3 mol% or less, preferably 0.1 to 2 mol%. Mol%, more preferably 0.1 to 1 mol%.

The intrinsic viscosity [IV] of the copolycarbonate according to the present invention as described above is desirably 0.2 to 1.2 dl / g, preferably 0.3 to 0.8 dl / g. This IV value is a value measured in methylene chloride (0.5 dl / g) at 20 ° C. using an Ubbelohde viscometer.

The copolycarbonate of the present invention has a glass transition temperature (Tg) of 150 to 190 ° C., preferably 16 to 190 ° C.
Desirably, the temperature is 5 to 185 ° C. The heat distortion temperature (HDT) of the copolycarbonate according to the present invention is 135.
To 175 ° C, preferably 150 to 170 ° C.

The copolycarbonate according to the present invention has a yellowness (YI) of usually 3 or less, preferably 2.5 or less. This yellowness (YI) can be determined as follows.

A 3 mm-thick pressed sheet of copolycarbonate was used as a sample, and was manufactured by Nippon Denshoku Industries Co., Ltd.
fference Meter ND-1001 DP
The value, Y value, and Z value are measured. These values are substituted into the following equation to calculate the YI value.

YI = (100 / Y) × (1.277X)
−1.060Z) As described above, the copolycarbonate according to the present invention has a high glass transition temperature (Tg) and a high heat distortion temperature (HDT) and is excellent in heat resistance, and is compared with ordinary bisphenol A polycarbonate. More excellent heat resistance.

Further, the copolycarbonate according to the present invention comprises:
Low yellowness, excellent hue and excellent transparency. Copolycarbonate production method The copolycarbonate according to the present invention as described above can be produced by a method using phosgene, or can be produced by a solid-state polymerization method of a copolycarbonate oligomer. It is preferable to produce the copolycarbonate by a suitable melting method.

In the present invention, an aromatic dihydroxy compound represented by the above formula [Ia], an aromatic dihydroxy compound represented by the above formula [IIa], and a carbonic acid diester are
(a) It is preferable to produce the above copolycarbonate by melt polycondensation in the presence of a catalyst containing an alkali metal compound and / or an alkaline earth metal compound.

The aromatic dihydroxy compound used in the melt polycondensation reaction includes the compounds represented by the general formulas [Ia] and [IIa] as described in the description of the structural units of the copolycarbonate. Among these, as the aromatic dihydroxy compound represented by the general formula [Ia], 2,2-bis (4-hydroxyphenyl) propane is preferably used, and as the aromatic dihydroxy compound represented by the general formula [IIa], Is preferably 3,6-dihydroxy-9,9-dimethylxanthene.

Specific examples of the carbonic acid diester used in the present invention include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, Dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like can be mentioned.

Of these, diphenyl carbonate is particularly preferred. In the present invention, the carbonic acid diester as described above may contain the above-mentioned dicarboxylic acid or dicarboxylic acid ester in an amount of 50 mol% or less, preferably 30 mol% or less in 100 mol% of the carbonic acid diester. Good.

In the present invention, in producing a copolycarbonate, the above-mentioned carbonic acid diester is used in an amount of 1.0 to 1.3 with respect to a total of 1 mole of the aromatic dihydroxy compound.
It is preferably used in an amount of 0 mol, preferably 1.01 to 1.20 mol, more preferably 1.01 to 1.10 mol.

In the present invention, when producing a copolycarbonate, an aromatic dihydroxy compound [Ia],
Along with the aromatic dihydroxy compound [IIa] and the carbonic acid diester, the above-mentioned polyfunctional compound having three or more functional groups in one molecule can also be used.

Such a polyfunctional compound is usually used in an amount of not more than 0.03 mol, preferably from 0.001 to 0.02 mol, more preferably from 0.001 to 0.01 mol, per 1 mol of the total of the aromatic dihydroxy compound. Desirably, they are used in molar amounts.

In the method for producing a copolycarbonate according to the present invention, the aromatic dihydroxy compound and the carbonic acid diester are subjected to the polymerization in the presence of a catalyst containing (a) an alkali metal compound and / or an alkaline earth metal compound. Condensation reaction.

As (a) the alkali metal compound and / or the alkaline earth metal compound (hereinafter also referred to as (a) the alkali compound), specifically, an organic acid salt of an alkali metal or an alkaline earth metal, Inorganic acid salts, oxides,
Hydroxides, hydrides, and alcoholates are preferred.

More specifically, such alkali metal compounds include 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, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium Salts, dilithium salts, phenol sodium salts, 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 carbonate. 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 may be used in combination of two or more.
No. In the present invention, (a) the alkali compound is an aromatic diamine.
1 × 10 with respect to the total of 1 mol of the hydroxy compound^-8~ 1
× 10^-3Mol, preferably 5 × 10^-8~ 2 × 10 ^-6Mo
, More preferably 1 × 10^-7~ 1 × 10^-6Molar amount
Used in

As described above, the alkali compound (a) was used in an amount of 1 × 10 ⁻⁸ to 1 × 1 per mole of the aromatic dihydroxy compound.
When used in an amount of 0 to ³ mol, a copolycarbonate excellent in hue while maintaining high polymerization activity can be produced. In addition, an acidic compound is added to the produced copolycarbonate to prepare a copolycarbonate composition as described later. In this case, the acidic compound is added to the basicity of the alkali compound in an amount that does not adversely affect the properties of the copolycarbonate. Can be sufficiently neutralized or weakened, and a copolycarbonate composition 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 (a)
(B) Nitrogen-containing basic compound together with alkali compound, (c)
Boric acid compounds can also be used. Such (b) nitrogen-containing basic compounds include, for example, easily decomposable or volatile nitrogen-containing basic compounds at high temperatures, and specific examples include the following compounds.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (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), pyridines such as 4-dimethylaminopyridine, 4-diethylaminopyridine, and 4-pyrrolidinopyridine; -Imidazoles such as -methylimidazole and 2-phenylimidazole, or ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenyl borate (Bu ₄ NBPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄₎ basic salts, such as.

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

The (b) nitrogen-containing basic compound as described above is
10 moles per mole of the aromatic dihydroxy compound
^-6 to 10 ^-1 mol, preferably 10 ^-5 to 10 ^-2 mol, can be used.

Examples of the boric acid compound (c) include boric acid and boric acid esters. As the borate ester, a borate 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 esters include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tolyl borate, and trinaphthyl borate. Is mentioned.

The (c) boric acid or boric acid ester is used in an amount of 10 ^-8 to 10 ^-1 mol, preferably 10 ^-7 to 10 ^-2 mol, more preferably 10 ^-7 to 10 ^-1 mol, per mol of the aromatic dihydroxy compound. Preferably, it can be used in an amount of 10 ^-6 to 10 ^-4 mol.

In the present invention, as a catalyst,
(a) an alkali compound, (b) a combination of a nitrogen-containing basic compound, (a) an alkali compound, and (c) a combination of boric acid or borate, and further, (a) an alkali compound, It is preferable to use a combination of (b) a nitrogen-containing basic compound and (c) boric acid or a borate ester.

As a catalyst (a) with an alkali compound
(b) When a nitrogen-containing basic compound is used in combination, the polycondensation reaction can be performed with high activity, and heat resistance, water resistance,
A high-molecular weight copolycarbonate having excellent hue and transparency can be produced.

When (c) boric acid or boric acid ester is used in combination with (a) an alkali compound, the transesterification reaction and the polycondensation reaction can proceed at a sufficient speed, and the hue, heat resistance and water resistance can be improved. The copolycarbonate excellent in the above can be produced. In particular, it is preferable that the amount of the (c) boric acid or boric acid ester used is as described above, because a copolycarbonate which is unlikely to cause a decrease in molecular weight after heat aging is obtained.

In the present invention, the following acidic catalysts can be used in combination with the above-mentioned catalysts. Examples of the acidic catalyst include Lewis acid compounds. Specific examples thereof include zinc borate, zinc acetate, zinc oxalate, zinc phenylacetate, zinc chloride, zinc sulfate, zinc nitrate, zinc carbonate, zinc oxide, and hydroxide. Zinc compounds such as zinc, zinc stearate, zinc-chromium oxide and zinc-chromium-copper oxide; cadmium compounds such as cadmium acetate, cadmium oxalate, cadmium oxide, and cadmium stearate; silicon oxide; silica alumina; silica magnesia Such as silicon compounds, germanium oxides, germanium compounds such as germanium hydroxide, stannous acetate, stannous oxalate, tin octylate, stannous chloride, stannic chloride, stannous oxide, stannic oxide , Tin compounds such as tetraphenyltin, lead acetate, lead borate, lead citrate,
Lead compounds such as lead hydroxide, lead oxide, lead phosphate, lead phthalate, lead stearate, antimony acetate, antimony oxalate, triphenylantimony, antimony trioxide, antimony pentoxide, triphenoxyantimony, trimethoxyantimony, Antimony compounds such as antimony trichloride; bismuth compounds such as bismuth acetate, bismuth oxalate, triphenyl bismuth, bismuth trioxide, and bismuth trichloride; titanium trichloride, titanium tetrachloride, titanium dioxide, tetraphenoxy titanium, and tetraisopropoxy titanium And the like.

The polycondensation reaction between an aromatic dihydroxy compound and a carbonic acid diester using such a catalyst is carried out under the same conditions as conventionally known polycondensation reaction between an aromatic dihydroxy compound and a carbonic acid diester. Can be.

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 is increased while the pressure in the reaction system is reduced, and the reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out.
The polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is performed at a temperature of 240 to 320 ° C. under a reduced pressure of not more than mmHg.

The above 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.

Copolycarbonate Composition The copolycarbonate composition according to the present invention comprises the above-mentioned [A] copolycarbonate and [B] an acidic compound.

The copolycarbonate composition according to the present invention preferably further contains [C] an epoxy compound. [A] The copolycarbonate contains (a) an alkali metal compound or an alkaline earth metal compound used as a catalyst during production as described above.

The acidic compound [B] used in the present invention is
As long as (a) the alkali metal compound or alkaline earth metal compound in such [A] copolycarbonate can be neutralized, even a Lewis acid compound can be used as a Bronsted acid compound or a strong acid ester containing a sulfur atom. There may be.

The acidic compound [B] used in the present invention includes:
The pKa in the aqueous solution at 25 ° C. is preferably 3 or less. Use of an acidic compound having such a pKa value has the advantage that the alkali metal or alkaline earth metal used as a catalyst can be neutralized and the obtained copolycarbonate can be stabilized.

Specific examples of the Lewis acid compound include boron compounds such as zinc borate and boron phosphate, and B (OC
Borate esters such as H ₃ ) ₃ , B (OEt) ₃ and B (OPh) ₃ ; aluminum compounds such as aluminum stearate and aluminum silicate; zirconium carbonate;
Alkoxide zirconium, zirconium compounds such as zirconium hydroxycarboxylate, gallium phosphide,
Gallium compounds such as gallium antimonide, germanium compounds such as germanium oxide and organogermanium, tetra or hexaorganotin, PhOSn (B
_{u) 2 OSn (Bu) 2} OPh tin compounds such as antimony oxide, antimony compounds such as alkyl antimony, bismuth oxide, bismuth compounds such as an alkyl _{bismuth, (CH 3 COO) 2 Zn} , zinc compounds such as zinc stearate, Examples thereof include titanium compounds such as alkoxytitanium and titanium oxide.

In the above formula, Ph represents a phenyl group, Et represents an ethyl group, and Bu represents a butyl group. As the Bronsted acid compound, specifically, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, adipic acid, azelaic acid, Dodecanoic 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, benzenesulfonic acid, p -Compounds of sulfonic acids such as toluenesulfonic acid, trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene, and methyl acrylate-sulfonated styrene copolymer.

Examples of the acid ester containing a sulfur atom include:
Specifically, pKa of an acid residue portion such as methyl, ethyl, butyl, octyl or phenyl ester of dimethyl sulfate, diethyl sulfate, p-toluenesulfonic acid, or methyl, ethyl, butyl, octyl or phenyl ester of benzenesulfonic acid is Up to three compounds are used.

Among such acidic compounds [B], acidic compounds containing a sulfur atom, a phosphorus atom and the like are preferred, and acidic compounds containing a sulfur atom are particularly preferred.
These may be used in combination of two or more.

The copolycarbonate composition according to the present invention is capable of neutralizing the acidic compound [B] as described above with respect to [A] the alkalinity of the alkali compound (a) remaining in the copolycarbonate or the effect of the neutralization. It is sufficient if it is contained in an amount that can weaken, specifically,
[A] It is contained in the copolycarbonate in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, per 1 mol of the alkali compound (a).

Particularly, when the acidic compound [B] is a Lewis acid or 3
In the case of a Bronsted acid having a higher pKa, it is used in an amount of 0.1 to 50 mol, preferably 0.1 to 30 mol, and the [B] acidic compound has a pKa of 3 or less. Alternatively, when it is an ester of an acid containing a sulfur atom, it is used in an amount of 0.1 to 50 mol, preferably 0.1 to 15 mol, more preferably 0.1 to 7 mol.

The copolycarbonate composition according to the present invention may contain a specific amount of water.
Preferably 10 to 500 ppm, more preferably 20 to 3 ppm
It may contain water in an amount of 00 ppm.

As described above, the copolycarbonate composition containing the specific amount of water together with the acidic compound [B] can be used as the [A]
The neutralization efficiency of the basic catalyst in the copolycarbonate is increased, the retention stability during melting is further improved, and the hue, transparency, water resistance and weather resistance are also improved.

If the content of water is more than 1000 ppm, hydrolysis of the polycarbonate is likely to occur, and the physical properties of the polycarbonate may be deteriorated. In the copolycarbonate composition according to the present invention, the [C] epoxy compound is used in an amount of 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 [A] copolycarbonate. It is desirable to contain it in the amount of parts.

Examples of the epoxy compound [C] used in the present invention include compounds having one or more epoxy groups in one molecule. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether , Allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxy 2,3-epoxycyclohexylmethyl 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-
Methylcyclohexanecarboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid,
Bis-epoxydicyclopentadienyl ether, bis
-Epoxy ethylene 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-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-epoxy Cyclohexyl-3 ', 4'-epoxycyclohexanecarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1, 2-cyclohexanedicarboxylate, di-n-butyl-3-t-butyl-4,5-
Epoxy-cis-1,2-cyclohexanedicarboxylate and the like.

These may be used in combination of two or more. As described above, the copolycarbonate composition containing the [C] epoxy compound is neutralized by reacting the [C] epoxy compound with the [C] epoxy compound, even if the [B] acidic compound remains excessively, It has excellent heat resistance and excellent hue, transparency, water resistance and weather resistance.

The copolycarbonate composition according to the present invention not only has excellent heat resistance, hue, transparency, water resistance and weather resistance, but also has excellent hue stability for a long time during use. Since a molded article of polycarbonate can be provided, it can be suitably used for optical applications such as sheets, lenses and compact discs, outdoor applications such as automobiles, and housings for various devices.

As described above, the copolycarbonate composition according to the present invention is obtained by copolymerizing the aromatic dihydroxy compound [Ia], the aromatic dihydroxy compound [IIa], and the carbonic acid diester with the polycarbonate [A]. And the obtained [A] copolycarbonate is
It is produced by adding [B] an acidic compound and, if necessary, [C] an epoxy compound.

In the method for producing a copolycarbonate composition according to the present invention, [A] obtained as a polycondensation reaction product is obtained.
The method for adding the acidic compound [B] and the epoxy compound [C] to the copolycarbonate is not particularly limited. For example, [B] is added to the [A] copolycarbonate in a molten state,
[C] may be added and kneaded, and [B] and [C] may be added to the solution of the copolycarbonate [A] and stirred.

More specifically, [A] in the melted reactor or extruder obtained after completion of the polycondensation reaction.
A method in which the [B] acidic compound and, if necessary, the [C] epoxy compound are separately or simultaneously added to the copolycarbonate and kneaded. The obtained [A] copolycarbonate is pelletized, and the resulting pellet is mixed with the [B] acidic compound. And if necessary, supplying the epoxy compound together with the [C] epoxy compound to a single-screw or twin-screw extruder and melt-kneading it. The obtained [A] copolycarbonate is mixed with a suitable solvent such as methylene chloride, chloroform, toluene, tetrahydrofuran and the like. Dissolution is carried out to prepare a solution, and the [B] acidic compound and, if necessary, the [C] epoxy compound are separately or simultaneously added to the solution, followed by stirring.

The order of adding the acidic compound [B] and the epoxy compound [C] to the copolycarbonate [A] may be either order. In the method for producing a copolycarbonate composition according to the present invention, the [A] copolycarbonate obtained by the polycondensation reaction as described above includes:
After adding the acidic compound [B] and the epoxy compound [C] as needed, it is preferable to apply a reduced pressure treatment.

[0097] The decompression treatment of the copolycarbonate composition is as follows.
For example, the reaction can be performed using a reactor equipped with a pressure reducing device, an extruder equipped with a pressure reducing device, or the like. As a reactor with a decompression device,
Either a vertical tank reactor or a horizontal tank reactor may be used, and a horizontal tank reactor is preferably used.

It is preferable that the decompression treatment is performed at a temperature of about 240 to 350 ° C. When the decompression treatment is performed in a reactor as described above, 0.05 to 750 mmHg
Preferably, under pressure conditions of 0.05 to 5 mmHg, for 5 minutes to
It is preferable to carry out for about 3 hours.

When the decompression treatment is performed in an extruder, it is 1 to 750 mmHg, preferably 5 to 700 mmHg.
It is preferably performed for about 10 seconds to 15 minutes under the pressure condition of g. As the extruder, any of a vented single-screw extruder and a twin-screw extruder may be used, and the copolycarbonate composition may be pelletized while being subjected to a reduced pressure treatment by the extruder.

By adding an acidic compound and, if necessary, an epoxy compound to the copolycarbonate as a reaction product and subjecting the copolycarbonate to a reduced pressure treatment, a copolycarbonate composition having reduced residual monomers and oligomers can be obtained. Can be.

The copolycarbonate composition according to the present invention contains a heat stabilizer, as long as the object of the present invention is not impaired.
Including UV absorbers, release agents, antistatic agents, slip agents, anti-blocking agents, lubricants, anti-fog agents, dyes, pigments, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers, etc. May be.

Among them, the following heat stabilizers, ultraviolet absorbers, release agents, coloring agents, etc. are preferably used. These can be used in combination of two or more.

Specific examples of such heat stabilizers include phenol stabilizers, organic thioether stabilizers,
Examples include organic phosphite-based stabilizers, hindered amine-based stabilizers, and epoxy-based stabilizers.

Examples of the phenol 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) benzylmalonate, 4-hydroxymethyl-2,6-di-t-butylphenol and the like.

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).

Examples of the organic phosphite-based stabilizer include bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite, diphenyldecyl phosphite, diphenylisooctyl phosphite, and phenylisooctyl phosphite. , Arylalkyl phosphites such as 2-ethylhexyl diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, distearyl pentaeryth Trialkyl phosphites such as lithyl diphosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite, and tricyclophosphites such as tricyclohexyl phosphite Chloroalkyl phosphite,
Triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite Such as triaryl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate, tris (2,3- Trialkyl phosphates such as dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate Chromatography, tris (nonylphenyl) phosphate, triaryl phosphates such as 2-ethylphenyl diphenyl phosphate.

Further, as the hindered amine-based stabilizer,
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- ( 3,5-di-t-butyl
-4-hydroxyphenyl) propionyloxy {ethyl] -4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 8 -Benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6 -Tetramethylpiperidine, 2- (3,5-di-t-butyl-4-hydroxybenzyl)
Bis (1,2,2,6,6-pentamethyl-4-2-n-butylmalonate
-Piperidyl), tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) 1,2,3,4-butanetetracarboxylate.

These may be used in combination of two or more. These heat stabilizers may be added in a solid state or in a liquid state. The copolycarbonate composition according to the present invention contains 0.001 to 5 parts by weight of a heat stabilizer based on 100 parts by weight of [A] copolycarbonate.
It may be contained in an amount of preferably 0.005 to 0.5 part by weight, more preferably 0.01 to 0.3 part by weight.

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,
Benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like can be given.

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-benzotriazole-2-
Il) phenol].

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate and the like. These may be used in combination of two or more.

The copolycarbonate composition according to the present invention is characterized in that the ultraviolet absorbent is [A] copolycarbonate 100
0.001 to 5 parts by weight, preferably 0.005 to 1.0 parts by weight, and more preferably 0.01 to 5 parts by weight based on parts by weight.
It may be contained in an amount of 0.5 parts by weight.

As the release agent, those generally known as release agents are widely used without any particular limitation. For example, hydrocarbon release agents such as natural and synthetic paraffins, polyethylene waxes and fluorocarbons, higher fatty acids such as stearic acid and hydroxystearic acid, fatty acid release agents such as oxy fatty acids, stearic acid amide, ethylene bis Fatty acid amides such as stearoamide, fatty acid amide release agents such as alkylenebisfatty acid amides, aliphatic alcohols such as stearyl alcohol and cetyl alcohol, alcoholic release agents such as polyhydric alcohols, polyglycols and polyglycerols Fatty acid ester release agents such as fatty acid lower alcohol esters such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters and fatty acid polyglycol esters, and silicones such as silicone oils Can be used system release agent, it may be used in combination of two or more of these.

The copolycarbonate composition comprises a releasing agent,
[A] It is contained 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 copolycarbonate. You may.

The colorant may be a pigment or a dye, and may be any of an inorganic colorant and an organic colorant, or a combination thereof.

Specific examples of the inorganic coloring agent 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 metal powder coloring agents such as bronze powder and aluminum powder.

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

In the copolycarbonate composition according to the present invention, the colorant is used in an amount of usually 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × ^10-6 parts by weight, per 100 parts by weight of [A] copolycarbonate.
^10-5 to 3 parts by weight, and more preferably may be contained in an amount of 1 × 10 ^-5 to 1 part by weight.

In the present invention, when the above-mentioned other components, especially the heat-resistant stabilizer, are added while the copolycarbonate [A] is in the molten state as in the case of [B] or [C], the thermal history during the production is increased. It is preferable because a copolycarbonate composition with a small number of times can be produced. Moreover, since the pellets of the obtained copolycarbonate composition contain a heat-resistant stabilizer, thermal decomposition during remelting can be suppressed.

In the polycarbonate or copolycarbonate composition according to the present invention as described above, other polymers, compounding agents and the like can be blended and used according to the purpose.

[0122]

The novel copolycarbonate according to the present invention has excellent heat resistance and excellent hue and transparency.

According to the method for producing a copolycarbonate according to the present invention, the above copolycarbonate can be produced at low cost. Further, since phosgene or the like is not used, it is preferable in terms of safety and health.

Further, the copolycarbonate composition according to the present invention is excellent in heat resistance, transparency and hue, and particularly excellent in hue stability for a long time during use. The polycarbonate or copolycarbonate composition of the present invention is suitably used as a general molding material, as well as a building material such as a sheet, an optical lens such as an automobile headlamp lens, glasses, an optical recording material, and the like.

[0125]

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

The physical properties of the copolycarbonate and the molded product obtained in the following examples were measured as follows. Intrinsic viscosity [IV]; in methylene chloride (0.5 dl / g)
It measured at 20 degreeC using the Ubbelohde viscometer.

Light transmittance: A 3 mm-thick press sheet was measured using NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd. Haze: A 3 mm-thick press sheet was measured using NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd.

Yellowness [YI]: Color and Defference manufactured by Nippon Denshoku Industries Co., Ltd.
X value, Y measured by transmission method using Meter ND-1001 DP
The values and Z values were calculated by substituting into the following equation.

YI = (100 / Y) × (1.277X
-1.060Z) Glass transition temperature (Tg); MODEL manufactured by PerkinElmer
It was determined by performing differential thermal analysis of the resin at a heating rate of 10 ° C./min using a DSC-2 differential scanning calorimeter.

Heat distortion temperature (HDT): 0.5 × 0.5 × 5
(Inch) injection specimens were measured under a load of 264 psi.

[0131]

[Example 1] 5 equipped with a nickel (Ni) stirring blade
In a 00 ml glass reactor, bisphenol A (B
PA; a compound represented by the formula [Ia]): 0.45 mol;
3,6-dihydroxy-9,9-dimethylxanthene (formula [II
a)) and 0.16 mol of diphenyl carbonate are added under N ₂ atmosphere, and
Stirred at 0 ° C. for 30 minutes.

Then, a 15% aqueous solution of tetramethylammonium hydroxide was added in an amount of ^2.5 × 10 ^-4 mol of tetramethylammonium hydroxide to 1 mol of the aromatic dihydroxy compound in total, and sodium hydroxide was added. was added in an amount of 1 × 10 ^-6 mol per total 1 mol of aromatic dihydroxy compound, N ₂ atmosphere, 180
Transesterification was performed at 30 ° C. for 30 minutes.

Thereafter, the temperature was raised to 210 ° C., the pressure was gradually reduced to 200 mmHg for 1 hour, and the temperature was further raised to 240 ° C. and 200 mmHg for 20 minutes, and the pressure was gradually increased to 150 mmHg.
The reaction was continued for 20 minutes by reducing the pressure to Hg, further reduced to 100 mmHg for 20 minutes, reduced to 15 mmHg for 15 minutes, heated to 270 ° C, and finally reduced to 0.5 mmHg for 1.5 hours. And the intrinsic viscosity [IV] is 0.50 dl /
g of copolycarbonate was obtained.

The glass transition temperature (Tg) of the obtained copolycarbonate is 160 ° C., and the yellowness (YI) is 1.
It was 5. Table 1 shows the physical properties measured for the copolycarbonate.

Before removing the polymer from the reactor, butyl p-toluenesulfonate was added in an amount twice as much as that of the added sodium hydroxide, followed by stirring for 15 minutes to obtain a copolycarbonate composition. The intrinsic viscosity [IV], Tg, and YI of this copolycarbonate composition were the same as those of the above copolycarbonate.

[0136]

Example 2 In Example 1, bisphenol A (B
PA) and 0.36 mol of 3,6-dihydroxy-9,9-dimethylxanthene, and the final reaction temperature was 280 ° C., except that copolycarbonate and A copolycarbonate composition was obtained.

The intrinsic viscosity [IV] of the obtained copolycarbonate was 0.50 dl / g, and the glass transition temperature (T
g) was 170 ° C. and the yellowness (YI) was 1.6. Table 1 shows the physical properties measured for the copolycarbonate.

The intrinsic viscosity of the copolycarbonate composition [I
V], Tg and YI were the same as in the above copolycarbonate.

[0139]

Example 3 In Example 1, bisphenol A (B
PA) and 0.16 mol of 3,6-dihydroxy-9,9-dimethylxanthene, and the final reaction temperature was 290 ° C., except that copolycarbonate and A copolycarbonate composition was obtained.

The intrinsic viscosity [IV] of the obtained copolycarbonate was 0.50 dl / g, and the glass transition temperature (T
g) was 190 ° C. and the yellowness (YI) was 1.7. Table 1 shows the physical properties measured for the copolycarbonate.

The intrinsic viscosity of the copolycarbonate composition [I
V], Tg and YI were the same as in the above copolycarbonate.

[0142]

Comparative Example 1 In the same manner as in Example 1, except that the compound represented by the formula [IIa] was not used as the aromatic dihydroxy compound and only 0.6 mol of bisphenol A (BPA) was used. Polycarbonate was obtained.

The obtained polycarbonate had an intrinsic viscosity [IV] of 0.50 dl / g and a glass transition temperature (T
g) was 149 ° C. and the yellowness (YI) was 1.5. Table 1 shows the physical properties measured for this polycarbonate.
Shown in

[0144]

[Table 1]

(56) References JP-A-3-162413 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 EUROPAT (QUESTEL)

Claims (6)

(57) [Claims] (1) A structural unit represented by the following formula [I]:
(ii) a copolycarbonate having a structural unit represented by the following formula [II]: (Wherein, Ra, Rb, Rc and Rd are a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group having 1 to 10 carbon atoms in which at least a part thereof is substituted by halogen; Rb, Rc and Rd may be the same or different, and Rb and Rc may be hydrogen atoms, p and q are each an integer of 0 to 3 representing the number of substituents, and 2 Or in the case of 3, Ra or Rd may be the same or different.) (2) a structural unit represented by the formula (I): (ii)
The structural unit represented by the formula [II] is represented by the following formula:
The copolycarbonate according to claim 1, wherein the copolycarbonate is contained in a molar ratio of [(i) / (ii)]. 3. The copolycarbonate according to claim 1, wherein the intrinsic viscosity [IV] is 0.2 to 1.2 dl / g. 4. [A] The copolycarbonate according to claim 1 and [B] an acidic compound, wherein the acidic compound [B] is contained in [A] the copolycarbonate. Or a total of 1 alkaline earth metal compounds
A copolycarbonate composition characterized in that it is present in an amount of from 0.1 to 50 mol per mol. 5. An aromatic dihydroxy compound represented by the above general formula [Ia], an aromatic dihydroxy compound represented by the above general formula [IIa], and a carbonic acid diester are obtained by: (a) an alkali metal compound and / or an alkali A process for producing a copolycarbonate composition, comprising: performing a melt polycondensation in the presence of a catalyst containing an earth metal compound; and adding an acidic compound [B] to the obtained [A] copolycarbonate. 6. An aromatic dihydroxy compound represented by the above general formula [Ia], an aromatic dihydroxy compound represented by the above general formula [IIa], and a carbonic acid diester are obtained by: (a) an alkali metal compound and / or an alkali A copolycarbonate composition obtained by melt polycondensation in the presence of a catalyst containing an earth metal compound, adding [B] an acidic compound to the obtained [A] copolycarbonate, and then subjecting the copolycarbonate to vacuum treatment. Production method.