JP3171876B2 - Optical polycarbonate composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate composition for optical use, and more particularly, to a resin composition having less coloring during molding.
The present invention relates to an optical polycarbonate composition capable of forming a molded article having excellent transparency.

[0002]

In recent years, optical disks have a large recording capacity,
It is used for various versatile uses, for example, optical disks for digital data, CD-ROMs, compact disks, video disks, etc., taking advantage of the advantages of non-contact reading and high-speed access.

[0003] Such optical substrates as optical disks, optical fibers, lenses, lighting equipment and the like are required to be transparent. In particular, the optical substrates not only have high light transmittance in the wavelength region of reproduction laser light, but also have high transparency. It is required to transmit light having a wavelength ranging from a visible light region to a near infrared region.

Further, characteristics such as low water absorption and heat resistance are required, and polycarbonate resin [A] is often used as a plastic material satisfying these characteristics. However, the conventional [A] polycarbonate resin may be colored at the time of molding, so that the obtained [A] polycarbonate resin substrate, lens and the like are inferior in transparency.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to solve the above-mentioned problems and to provide a polycarbonate composition for optical use which is capable of obtaining a molded article having little coloring during molding and excellent in transparency. It is intended to provide.

[0006]

SUMMARY OF THE INVENTION The optical polycarbonate composition according to the present invention has an intrinsic viscosity of 0.2 measured at 20 ° C. in methylene chloride.
[A] 100 parts by weight of a polycarbonate resin of 30 to 0.65 dl / g, and [B] a boron-based compound in an amount of 0.000001 to 0.2 parts by weight.
In an amount, [C] a sulfonic acid compound having a pKa value of 3 or less and / or a derivative formed from the compound is 0.00
001 to 0.0005 parts by weight, and [D] a phosphorus compound in an amount of 0.1 parts by weight or less, and / or [E] an epoxy compound in a quantity of 0.001 to 0.005 parts by weight. .1 part by weight.

The optical polycarbonate composition according to the present invention has less coloring at the time of molding, and a molded product obtained from the composition has characteristics such as excellent transparency, heat resistance and water resistance. Is particularly suitable for optical applications.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the optical polycarbonate composition according to the present invention will be described in detail.

First, the polycarbonate resin [A] forming the polycarbonate composition for optical use according to the present invention will be described. [A] The polycarbonate resin according to the present invention is a method of reacting an aromatic organic dihydroxy compound with phosgene in the presence of a solvent and a deoxidizing agent, and a method of reacting an aromatic organic dihydroxy compound with a carbonic acid diester such as diphenyl carbonate. Can be produced by a method of melting by heating and reacting under high temperature and reduced pressure (melting method).
Those produced by the latter melting method are particularly preferably used.

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

[0011]

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Specific examples of the aromatic organic dihydroxy group compound include the following compounds: bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, etc. Bis (hydroxyaryl) alkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane 4,4'-dihydroxydiphenyl ether, dihydroxyaryl ethers such as 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3 Dihydroxydiaryl sulfides such as' -dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl Dihydroxydiaryl sulfones such as sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

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

[0014]

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

Specific examples of the aromatic organic dihydric compound represented by the general formula [II] include resorcinol and
3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3,
Substituted resorcinols such as 4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin, catechol, hydroquinone and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-butylhydroquinone t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5,6 -Substituted hydroquinones such as -tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone.

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

[0018]

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These aromatic organic dihydroxy compounds are:
They 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, and dicyclohexyl. Carbonate and the like can be mentioned.

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

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

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

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

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

The polyfunctional compound is usually used in an amount of not more than 0.03 mol, preferably 0.001 to 0.02 mol, more preferably 0.001 mol, per 1 mol of the aromatic organic dihydroxy compound.
It is used in an amount of .about.0.01 mol.

In the production of polycarbonate, a compound capable of introducing the following terminal group into the obtained polycarbonate [A] is used together with the above-mentioned aromatic organic dihydroxy compound and carbonic acid diester. it can.

-OH: a hydroxyl group represented by [III], and / or

[0030]

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In the present invention, specific examples of the compound capable of introducing the above terminal group into the obtained polycarbonate molecule include the following compounds. In the compounds exemplified below, the aromatic ring or the aliphatic ring may be substituted with halogen or 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 a 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], more specifically, the following chromanylphenoxy groups can be mentioned.

[0035]

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Specific examples of such a compound into which the chromanylphenoxy group represented by the formula [VIII] can be introduced 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, 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-dibromochroman Rukoto can.

Of these, in particular, 2,2,4-trimethyl
-4- (4-Hydroxyphenyl) chroman is preferred. In addition, specific examples of the compound into which the chromanylphenoxy group represented by the above formula [IX] can be introduced include the chroman compounds shown below.

2,2,3-trimethyl-3- (4-hydroxyphenyl) chroman, 2,2,3,6-tetramethyl-3- (3,5-dimethyl-4-hydroxyphenyl) chroman, 3,4-trimethyl-2-ethyl-3- (3-nonyl-4-hydroxyphenyl) -7-nonylchroman, 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.

Of these, 2,2,3-trimethyl-3 (4-hydroxyphenyl) chroman is particularly preferred. Further, specific examples of the compound into which the chromanylphenoxy group represented by the above formula [X] can be introduced include the following chroman compounds.

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.

Of these, especially 2,2,4-trimethyl
2- (2-Hydroxyphenyl) chroman is preferred. Further, specific examples of the compound into which the chromanylphenoxy group represented by the above formula [XI] can be introduced include the following chroman compounds.

2,4,4-trimethyl-2- (4-hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2- (3,5-dimethyl-4-hydroxyphenyl) chroman, 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-hydroxy Phenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo 4-hydroxyphenyl) -6,8-dibromochroman Rukoto can.

Of these, especially 2,4,4-trimethyl
2- (4-Hydroxyphenyl) chroman is preferred. Each compound capable of introducing a terminal group represented by each of the above formulas can be used alone or in combination.

The catalyst used in the above-mentioned melting method is disclosed, for example, in Japanese Patent Application No. Hei.
The compounds proposed in the specification of No. 8 can be used, and specifically, (a) organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides of metals such as alkali metals and alkaline earth metals Alternatively, an alcoholate or the like can be preferably used.

As such an alkali metal compound,
Specifically, 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 boron hydroxide, sodium borohydride,
Sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, sodium salt of phenol, Potassium salts, lithium salts and the like are used.

Further, as the alkaline earth metal compound,
Specifically, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, acetic acid Calcium, 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 an alkali metal compound and / or alkaline earth metal compound (a) is used in an amount of 1 × 10 ⁻⁸ to 1 mol of an aromatic organic dihydroxy compound.
1 × 10 ⁻³ , preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻⁶ mol,
More preferably, it is used in an amount of 1 × 10 ⁻⁷ to 8 × 10 ⁻⁷ .

As the catalyst, together with the above-mentioned (a) the alkali metal compound and / or the alkaline earth metal compound
(b) A basic compound may be used. Examples of such a basic compound (b) include a nitrogen-containing compound, specifically, tetramethylammonium hydroxide (Me ₄ N
OH), tetraethylammonium hydroxide (Et
₄ NOH), tetrabutylammonium hydroxide alkyl such (Bu ₄ NOH), trimethylbenzylammonium hydroxide _{(φ-CH 2 (Me)} NOH), aryl, ammonium hydroxide oxides having like Aruariru group, trimethylamine, triethylamine, Tertiary amines such as dimethylbenzyldiamine and triphenylamine; secondary amines represented by R ² NH (where R is an alkyl group such as methyl and ethyl; and aryl groups such as phenyl and toluyl); RNH ₂ primary amines represented by (wherein R is as defined above) or ammonia, tetramethylammonium borohydride (Me ₄ NBH _4),, tetrabutylammonium borohydride (Bu ₄ NBH _4), tetrabutylammonium tetraphenyl Borate (Bu ₄ NBPh _4),
Tetramethylammonium tetraphenylborate (B
Basic salts such as u ₄ NBPh ₄ ) are used.

Of these, tetraammonium hydroxides are particularly preferably used. In the present invention, as the catalyst, for example, a combination of (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound, and (a) an alkali metal compound and / or an alkaline earth metal And a combination consisting of a compound, (b) a nitrogen-containing basic compound, and (c) boric acid or at least one of borate esters.

When a catalyst comprising such a combination is used, (a) the alkali metal compound and / or the alkaline earth metal compound is used in the amounts described above, and (b) the nitrogen-containing basic compound is an aromatic compound. 1 × 10 ^-6 to 1 × 10 ^-1 mol, preferably ¹ mol, per 1 mol of the organic dihydroxy group compound
It is preferably used in an amount of from ^10-5 to ^1-10-2 mol.

As described above, the catalyst in which (a) the alkali metal compound and / or the alkaline earth metal compound is combined with (b) the nitrogen-containing basic compound can produce a high molecular weight polycarbonate with high polymerization activity. it can.

The (c) boric acid or borate ester will be described later as [B] boron compound. The polycondensation reaction between the aromatic organic dihydroxy group compound and the carbonic acid diester using such a catalyst is performed under the same conditions as the conventionally known polycondensation reaction between the aromatic organic dihydroxyl compound and the carbonic acid diester. Specifically, the first-stage reaction is carried out at 80 to 250 ° C, preferably 100 to 230 ° C.
More preferably, at a temperature of 120 to 190 ° C. for 0 to 5 hours, preferably 0 to 4 hours, more preferably 0.25.
The two are allowed to react at normal pressure for ~ 3 hours.

Next, the reaction temperature was increased while reducing the pressure of the reaction system to carry out the reaction between the aromatic organic dihydric compound and the carbonic acid diester, and finally the reaction was carried out at 240 to 320 ° C. under a reduced pressure of 0.05 to 5 mmHg. A polycondensation reaction between the aromatic organic dihydroxy compound and the carbonic acid diester is performed at a temperature.

The reaction between the aromatic organic dihydroxy group compound and the carbonic acid diester as described above may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

In the case of such a polycarbonate resin [A], the intrinsic viscosity measured in methylene chloride at 20 ° C. is 0.1%.
30 to 0.65 dl / g, preferably 0.32 to 0.62 dl
/ G is desirable.

If the intrinsic viscosity is too large, the fluidity is reduced, so that molding must be performed at a resin temperature of 400 ° C. or higher. For this reason, decomposition of the resin cannot be avoided, causing problems such as silver streaks and impairing the transparency of the molded product.

On the other hand, if the intrinsic viscosity is too low, problems such as deterioration of heat resistance and strength, easiness of crystallization, and other physical properties and molding problems are caused. [A] The polycarbonate resin preferably has the following terminal groups as described above.

-OH: a hydroxyl group represented by [III], and / or

[0060]

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In the polycarbonate resin [A] used in the present invention, the above formulas [III], [IV], [V], [V]
Although the ratio of the terminal groups represented by I] and [VII] is arbitrary,
The proportion of the hydroxyl group terminal represented by the general formula [II] which is blocked is preferably 50% or less, more preferably 30% or less.
The following is preferred.

The polycarbonate composition for optical use according to the present invention is obtained by adding the polycarbonate resin [A] as described above.
[C] A sulfonic acid compound having a pKa value of 3 or less is compounded.

As the [C] sulfonic acid compound having a pKa value of 3 or less and / or a derivative thereof blended in the optical polycarbonate composition, a compound represented by the following general formula [XII] is preferably used. be able to.

[0064]

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[Wherein R ⁰ is a hydrocarbon group having 1 to 20 carbon atoms (hydrogen may be substituted by halogen);
R ¹ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted by halogen);
Is an integer. ] Examples of such sulfonic acid compounds and derivatives thereof include the following compounds.

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

Further, trifluoromethanesulfonic acid,
Naphthalene sulfonic acid, sulfone compound polystyrene,
Sulfonic acid compounds such as methyl acrylate-sulfonated styrene copolymer can be mentioned.

These compounds can be used alone or in combination. Optical poly according to the present invention
In the carbonate composition, [A] polycarbonate
Sulfonic acid having a [C] pKa value of 3 or less for the resin
The compounding amount of the compound and / or its derivative is determined according to [A]
0.00000 per 100 parts by weight of the carbonate resin
1 to 0.0005 parts by weight.

Such [C] sulfonic acid compound and
And / or the derivative was blended in the amount described above.
[A] Polycarbonate resin has improved heat resistance,
In addition, a decrease in molecular weight during molding is suppressed.

The polycarbonate for optical use according to the present invention
[D] phosphorus compound and / or
[E] An epoxy compound is blended. [D] Phosphorus esters and phosphites are specifically used as the phosphorus compound. Such a [D] phosphorus compound is a process stabilizer (antioxidant) for polycarbonate.

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

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

Further, examples of the phosphite include distearyl pentaerythrityl diphosphite and bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite.

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

In the present invention, the phosphorus compound [D] is compounded in an amount of 0.1 part by weight or less based on 100 parts by weight of the polycarbonate resin [A]. [E]
As an epoxy compound , one epoxy group is contained in one molecule.
Compounds having at least one compound are used. The amount used is 0.001 to 100 parts by weight of the polycarbonate.
It is preferably contained in an amount of 0.1 part by weight, preferably 0.001 to 0.08 part by weight. As such an epoxy compound, specifically, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxy Cyclohexanecarboxylate, 3,4-epoxy-6-
Methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, 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-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3,4-dimethyl-1,2-
Epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-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-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 can be mentioned.

These may be used alone or in combination of two or more. More polycarbonate composition according to the present invention, the [D] phosphorus compound and / or [E] with an epoxy compound [B] boron compound is contained.

As such a [B] boron compound,
Is preferably a compound represented by the following general formula:
You. B (OR ³ ) _n (OH) _3-n wherein R ³ is a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon
A hydrogen group or an aromatic hydrocarbon group, and n is 1, 2 or
Or 3.

[B] Specific examples of the boron-based compound include
Are boric acid, trimethyl borate, triethyl borate,
Tributyl borate, trihexyl borate, trihept borate
Chill, triphenyl borate, tolyl borate, boric acid
Trinaphthyl and the like can be mentioned.

Of these, triphenyl borate is preferred.
Used. Compounding amount of such a boron-based compound [B]
Is [A] per 100 parts by weight of the polycarbonate resin,
0.000001 to 0.2 part by weight, preferably 0.0000
Desirably, the amount is 5 to 0.02 parts by weight.

Such a boron-based compound [B] is described above.
As a component of the catalyst during polymerization
It can be used by adding the necessary amount during polymerization.
There is no particular need to add it after polymerization.

[B] The amount of the boron-based compound is as described above.
[A] Polymer before or after polymerization as one component of catalyst
If compounded in the carbonate resin,
[A] To prevent coloring of the polycarbonate resin composition
Can be.

Further , [B] a boron compound and [C] p
A sulfonic acid compound having a Ka value of 3 or less and / or
Is combined with a derivative formed from the compound.
The molded polycarbonate composition is
Coloring of the carbonate composition is particularly prevented.
You.

The above-mentioned [B] boron compound and [C] sulfonic acid compound having a pKa value of 3 or less and / or a derivative formed from the compound may be used in an excessively large amount. In some cases, the water resistance of the polycarbonate composition may decrease.

In the present invention, the method of adding the [D] phosphorus compound and the [E] epoxy compound to the [A] polycarbonate resin is not particularly limited. For example, when the [A] polycarbonate resin is produced by a melting method. [A] polycarbonate resin in a molten state, the above [B],
The acidic compound [C], the phosphorus compound [D] and the epoxy compound [E] may be added and kneaded, and the acidic compound [B] and [C] may be added to the solution [A] of the polycarbonate resin. [D] A phosphorus compound and [E] an epoxy compound may be added and stirred. More specifically, the above-mentioned [B], [C] , [ C] , [A] are directly added to the polycarbonate resin, which is a reaction product in a reactor or an extruder in a molten state obtained after completion of the polycondensation reaction. D] and [E] are separately or simultaneously added and kneaded, or the obtained [A] polycarbonate resin is pelletized, and the resulting pellet is mixed with [B], [C] , [D] and [E]. A method of melt kneading by supplying to a single or twin screw extruder,
Further, the obtained polycarbonate is dissolved in an appropriate solvent, for example, methylene chloride, chloroform, toluene, tetrahydrofuran or the like to prepare a solution, and [B], [C] and the epoxy compound are separately or simultaneously added to the solution. Stirring can be mentioned.

The order in which the above compounds are added to the polycarbonate resin [A] does not matter. In the polycarbonate composition to which the [E] epoxy compound is added simultaneously with the sulfonic acid compound as described above, [B] or [B] which excessively remains in the polycarbonate composition
[C] The sulfonic acid-based compound reacts with the epoxy compound to be neutralized, so that a molded article excellent in color tone, heat resistance, water resistance and the like can be formed.

The above-mentioned polycarbonate composition contains a heat stabilizer, a weather stabilizer, a release agent, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, Oils, waxes, organic fillers, inorganic fillers and the like can be blended within a range that does not impair the purpose of the present invention.

In the present invention, the above-mentioned polycarbonate composition is preferably subjected to a reduced pressure treatment. When performing such a decompression treatment, the treatment apparatus is not particularly limited. For example, a reactor with a decompression device may be used, or an extruder with a decompression device may be used.

When a reactor is used, either a vertical tank reactor or a horizontal tank reactor may be used, and a horizontal tank reactor is preferably used. When performing the decompression treatment in the above-mentioned reactor, the pressure is 0.05 to 750 mmH.
g, preferably 0.05 to 5 mmHg.

When the depressurizing treatment is performed in the extruder, any of a vented single-screw extruder and a twin-screw extruder may be used, and the pelletizing may be performed while the depressurizing treatment is performed by the extruder.

When the vacuum treatment is performed in the extruder,
The reduced pressure treatment is performed under a pressure of 1 to 750 mmHg, preferably 5 to 700 mmHg.
It is performed under the condition of mmHg. When the polycarbonate composition is subjected to a reduced pressure treatment in this manner, a polycarbonate composition with reduced residual monomers and oligomers can be obtained.

For example, when a polycarbonate resin is produced by carrying out melt polymerization using diphenyl carbonate as a carbonic acid diester, the reaction product [A] polycarbonate resin is subjected to such a decompression treatment. The residual amount of diphenyl carbonate can be reduced.

In the polycarbonate composition used in the present invention, such diphenyl carbonate is used in an amount of 0.1 part by weight or less, preferably 0.01 part by weight or less, per 100 parts by weight of the polycarbonate resin [A] in the polycarbonate composition. It is preferably contained (residual) in an amount.

Incidentally, such a reduced pressure treatment may be carried out before adding the acidic compound and, if necessary, the epoxy compound to the polycarbonate resin [A].

[0094]

According to the polycarbonate resin composition for optical use of the present invention, [B] a boron-based compound is contained in an amount of 0.000001 to 0.2 per 100 parts by weight of the polycarbonate resin.
[C] A sulfonic acid compound having a pKa value of 3 or less and / or a derivative thereof is 0.00000 in parts by weight .
It is blended in an amount of 1 to 0.0005 parts by weight.

The optical polycarbonate composition according to the present invention has such characteristics as being less colored at the time of molding and being able to form a molded article having excellent transparency, heat resistance and water resistance. It is most suitable as an optical material such as a substrate of an optical disc and a lens.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. In this specification, [A] the intrinsic viscosity [IV], MFR, hue [YI], light transmittance, haze, retention stability, and water resistance of the polycarbonate resin composition are measured as follows. .

[Intrinsic viscosity [IV]] The intrinsic viscosity was measured in methylene chloride at 20 ° C using an Ubbelohde viscometer. [MFR] Based on the method of JIS K-7210, at a temperature of 300 ° C.
It was measured under a load of 1.2 kg.

[Hue] A 3 mm-thick injection molded plate was molded at a cylinder temperature of 290 ° C., an injection pressure of 1000 kg / cm, a cycle of 45 seconds, and a mold temperature of 10
Molded at 0 ° C, and the X, Y and Z values were determined by Nippon Denshoku Industries
The yellowness [YI] was measured by a transmission method using a Colorand Color Defference Meter ND-1001 DP.

YI = 100 (1.277X-1.060Z) / Y [Light Transmittance] The light transmittance was measured using an injection molded plate for measuring hue according to the method of ASTM D1003.

[Haze] The haze of an injection molded plate for measuring hue was measured using NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd.

[Retention stability] After the resin was retained in the cylinder of the injection molding machine at a temperature of 320 ° C for 15 minutes, injection molding was performed at that temperature, and the MFR, hue (YI) and light transmission of the molded plate were obtained. The rate was measured.

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

[Mold dirt] Using a nickel stamper, cylinder temperature 32
After forming a 5-inch disk for 500 shots continuously at 0 ° C., 9 seconds per cycle, and a mold temperature of 90 ° C., the stamper was visually observed, then immersed in acetone to measure up to 10 cc, and subjected to high-speed chromatography. In (HPLC), the absorption at a wavelength of 254 nm was measured with a UV detector to determine the amounts of the monomer and oligomer.

[Terminal Group Structure] A sample (0.4 g) was dissolved in 3 ml of chloroform.
At 40 ° C., ¹³ C-NMR (GX-2 manufactured by JEOL Ltd.)
Using 70), the structure and proportion of the terminal groups were measured.

[0105]

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

Next, this was heated to a temperature of 180 ° C., and tetramethylammonium hydroxide was added as a catalyst to a temperature of 0.1%.
11 mol (2.5 × 10 ⁻⁴ mol / mol-bisphenol A) and 0.0444 mol (1
× 10 ^-6 mol / mol-bisphenol A) was added, and 30
Stir for a minute.

Next, the temperature was raised to 210 ° C. and gradually lowered to 200 mmHg.
At the same time as the temperature was raised to 40 ° C., the pressure was gradually lowered to 15 mmHg to keep the temperature and pressure constant, and the amount of phenol distilled out was measured. When the amount of phenol distilled out disappeared, the pressure was returned to atmospheric pressure with nitrogen. The time required for the reaction was 1 hour.
The intrinsic viscosity [η] of the obtained reaction product was 0.12 dl / g.

Next, the pressure of the reaction product was increased by a gear pump and sent to a centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. From the bottom of the evaporator, use a gear pump at 280 ° C,
2-axis horizontal stirring polymerization tank (L
/ D = 3, stirring blade rotation diameter 220 mm, internal volume 80 liter) at a rate of 40 kg / hour and polymerization for a residence time of 30 minutes.

Next, in a molten state, this polymer was fed to a twin-screw extruder (L / D = 17.5, barrel temperature 280 ° C.) by a gear pump, and p-toluenesulfonic acid was added to the resin. Butyl 2 ppm (0.
0002 parts by weight), kneaded, passed through a die to form a strand, and cut with a cutter into pellets.

The intrinsic viscosity (IV) of the obtained polymer was 0.36 dl / g. The results are shown in Table 1.

[0111]

Examples 1 and 2 and Reference Example A In Reference Example 1, the type and amount of the catalyst and the type and amount of the additives were as described in Table 1, and the pellets were obtained in the same manner as in Reference Example 1. I got

The results are shown in Table 1. However, in Example 1 ,
2 and Reference Example A , the final polymerization temperature was
Polymerization was performed at 2 ° C.

The amounts of additives and catalyst in the polymer were calculated from the charged composition.

[0114]

REFERENCE EXAMPLE 2 Bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) (0.44 mmol) and diphenyl carbonate (manufactured by Any Corporation) (0.46 mmol) were charged into a 250-liter stirred tank, and the mixture was purged with nitrogen. , 14
Melted at 0 ° C.

Then, the temperature is raised to a temperature of 180 ° C., 0.11 mol of triphenyl borate is added, and the mixture is stirred for 30 minutes. Next, 0.11 mol of tetramethylammonium hydroxide (2.5 × 10 ⁻⁴ mol / mol-bisphenol A) and 0.0004 of sodium hydroxide were used as catalysts.
Add 4 mol (1 × 10 ⁻⁴ mol / mol-bisphenol A) and stir for 30 minutes.

Next, the temperature was raised to 210 ° C. and gradually lowered to 200 mmHg.
At the same time as the temperature was raised to 40 ° C., the pressure was gradually lowered to 15 mmHg to keep the temperature and pressure constant, and the amount of phenol distilled out was measured. When the amount of phenol distilled out disappeared, the pressure was returned to atmospheric pressure with nitrogen. The time required for the reaction was 1 hour.
The intrinsic viscosity [η] of the obtained reaction product was 0.15 dl / g.

Next, the pressure of the reaction product was increased by a gear pump and sent to a centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. From the bottom of the evaporator, use a gear pump at 280 ° C,
2 axis horizontal stirring polymerization tank (L
/ D = 3, stirring blade rotation diameter 220 mm, internal volume 80 liter) at a rate of 40 kg / hour and polymerization for a residence time of 30 minutes.

Thereafter, butyl p-toluenesulfonate was added to 2
After adding ppm, stirring was continued at 280 ° C. and 0.2 mmHg for another 30 minutes. (Decompression treatment) The intrinsic viscosity (IV) of the obtained polymer was 0.36 dl / g.

[0119]

REFERENCE EXAMPLE 3 The polymer obtained in Reference Example 2 was fed into a twin-screw extruder (L / D = 17.5, barrel temperature 285 ° C.) by a gear pump while keeping the polymer in a molten state. The phosphorus compound and the epoxy compound were added to the resin in the amounts shown in Table 1 and kneaded. The mixture was made into a strand through a die, and cut with a cutter to obtain pellets.

The intrinsic viscosity (IV) of the obtained polymer was 0.36 dl / g. The results are shown in Table 1.

[0121]

Example 4 Example 2 was repeated except that bisphenol A and diphenyl carbonate were charged, 0.022 mmol of p-cumylphenol (manufactured by Mitsui Texaco) and the final polymerization temperature was 287 ° C. Pellets were obtained in the same manner as in Example 2.

The results are shown in Table 1.

[0123]

Example 5 In Example 4 , instead of p-cumylphenol, 2,2,4-trimethyl-4- (4-hydroxyphenyl) chroman (manufactured by Nippon GE Plastics Co., Ltd.);
Chroman I) Implemented except that 0.022 mmol was charged
Pellets were obtained in the same manner as in Example 4 .

The results are shown in Table 1.

[0125]

Examples 6 to 8, Reference Example B Examples 2, 3, and 5
Using the resin composition obtained in Example A , a mold stain test was performed. The results are shown in Table 2.

[0126]

REFERENCE EXAMPLE 3 Additives as shown in Table 2 were added to phosgene polycarbonate powder (IV; 0.36 dl / g) using phenol as a terminal blocking agent manufactured by GE Plastics Co., Ltd. Compounded to the amount shown in Table 2 and single screw extruder (L / D = 31, temperature: 280 ° C)
To obtain pellets.

Table 1 shows the results.

[0128]

Reference Example 4 Using the resin composition of Reference Example 3, a mold stain test was performed. The results are shown in Table 2.

[0129]

[Table 1]

[0130]

[Table 2]

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08K 5/524 C08K 5/55 5/55 B41M 5/26 Y (72) Inventor Takashi Nagai 6-chome Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture No. 1-2 in Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-61-255929 (JP, A) JP-A-53-64262 (JP, A) JP-A-1-146950 (JP, A) 63-314269 (JP, A) JP-A-2-175723 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 69/00 B41M 5/26 C08K 3/24 C08K 5/42

Claims (8)

(57) [Claims] [A] Per 100 parts by weight of a polycarbonate resin having an intrinsic viscosity of 0.30 to 0.65 dl / g measured in methylene chloride at 20 ° C., [B] a boron-based compound in an amount of 0.000001 to 0.2% by weight. Parts and the [C] pKa value is 3 or less, the sulfonic acid compound and / or the derivative formed from the compound is 0.00
001 to 0.0005 parts by weight, and [D] a phosphorus compound in an amount of 0.1 parts by weight or less, and / or [E] an epoxy compound in a quantity of 0.001 to 0.005 parts by weight. An optical polycarbonate composition, which is blended in an amount of 0.1 part by weight. 2. The polycarbonate composition according to claim 1, wherein the polycarbonate resin [A] has a terminal group represented by the following general formula. Embedded image 3. The polycarbonate composition according to claim 1, wherein the polycarbonate resin (A) is a polycarbonate obtained by melt polycondensation of an aromatic organic dihydroxy compound and a carbonic acid diester. 4. The polycarbonate resin (A) comprises an aromatic organic dihydroxy compound and a carbonic acid diester in an amount of 1 × 10 ⁻⁸ per mole of the aromatic organic dihydroxy compound.
A polycarbonate obtained by 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 up to 1 × 10 ^-3 mol. 2. The polycarbonate composition according to 1. 5. The polycarbonate resin as set forth in claim 1, wherein the polycarbonate resin comprises an aromatic organic dihydroxy compound and a carbonic acid diester in an amount of 1 × 10 1 mole per mole of the aromatic organic dihydroxy compound.
^A polycarbonate obtained by 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 ^{-7 to} 2 × 10 ^-6 mol. The polycarbonate composition according to claim 1. 6. [C] The sulfonic acid compound having a pKa value of 3 or less or a derivative formed from the compound is a compound represented by the following general formula [I]. 2. The optical polycarbonate composition according to item 1. Embedded image [In the formula, R ⁰ is a hydrocarbon group having 1 to 20 carbon atoms (hydrogen may be substituted by halogen), and R ¹ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen is halogen. May be substituted), and n is an integer of 0 to 3. ] 7. The [C] sulfonic acid compound represented by the formula [I] or a derivative formed from the compound is benzenesulfonic acid or p-toluenesulfonic acid, or methyl, ethyl, butyl, octyl thereof. The polycarbonate composition for optical use according to claim 6, which is an ester. 8. The optical polycarbonate composition according to claim 1, wherein the boron compound [B] is a compound represented by the following general formula. B (OR ³ ) _n (OH) _3-n (wherein, R ³ is a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group;
Or 3. )