JP3302056B2 - Optical molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article for optical use, and more particularly, to a molded article for optical use formed from a copolymerized polycarbonate having excellent fluidity during molding, little coloring and excellent transparency. The present invention relates to an optical molded article formed from a composition containing a copolymerized polycarbonate.

[0002]

2. Description of the Related Art In recent years, optical disks have been used in a wide range of applications, such as optical disks for digital data, CD-ROMs, compact disks, and videos, by taking advantage of their large recording capacity, non-contact readout, and high-speed access. Used for disks and the like.

[0003] Such optical substrates such as optical disks, optical fibers, lenses, lighting equipment and the like are required to have excellent transparency. In particular, optical substrates only have high light transmittance in the wavelength range of reproduction laser light. In addition, light transmittance in a wide range of wavelengths from a visible light region to a near infrared region is required.

The optical substrate is also required to have characteristics such as low water absorption and heat resistance. Conventionally, optical molded articles formed from polycarbonate have been widely used to satisfy such characteristics.

[0005] Incidentally, such an optical molded article can be obtained by molding a molten polycarbonate into a desired shape. However, at the time of molding, the polycarbonate has a problem that the melt viscosity is high and the flowability is poor. Was. If polycarbonate is molded into an optical substrate or the like with insufficient fluidity at the time of melting, an optical substrate having large birefringence will be obtained.

On the other hand, if the polycarbonate is melted at a high temperature to increase the fluidity, the melt stability is reduced, and the polycarbonate is thermally decomposed at the time of molding to lower the hue and transparency, and the mechanical properties are reduced. In some cases, a molded article for optical use may be incompatible with the molded article for optical use.

For this reason, the polycarbonate-based optical molded article has excellent optical characteristics inherently,
In addition, there has been a demand for an optical molded article having excellent fluidity and melt stability during molding, low birefringence, excellent hue and transparency, and excellent mechanical properties.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above prior art, and has excellent moldability such as fluidity and melt stability, has little coloring during molding, and has excellent transparency. An object of the present invention is to provide an optical molded article formed from a copolymerized polycarbonate having excellent mechanical properties and low birefringence, and an optical molded article formed from a copolymerized polycarbonate composition.

[0009]

SUMMARY OF THE INVENTION The optical molded article according to the present invention comprises (A) (i) resorcinol, (ii) an aromatic dihydroxy compound other than resorcinol and substituted resorcinol, and (iii) these aromatic dihydroxy compounds (i). And (ii) a carbonate diester compound capable of forming a carbonic acid bond with an alkali metal compound and / or an alkaline earth metal compound, wherein 1 × 10 ⁻⁷ to 2 × 10 ⁻⁷ to 1 mol of the aromatic dihydroxy compound . It is formed from a copolymerized polycarbonate which is copolymerized in the presence of catalyst (a) used in an amount of 5 × 10 ^-6 mol .

The molded article for optical use according to the present invention is preferably formed from a copolymerized polycarbonate composition containing an additive [B] in addition to the copolymerized [A].

This [B] additive is preferably (A)
a sulfur-containing acidic compound having a pKa value of 3 or less and / or
Alternatively, the compound is selected from the group consisting of a derivative formed from the acidic compound, (b) a phosphorus compound, (c) an epoxy compound, (d) a phenol-based stabilizer, (e) a release agent, and (f) a boron-based compound.

The above-mentioned (A) copolymerized polycarbonate preferably contains (i) a structural unit derived from resorcinol in an amount of preferably 2 to 90 mol% among structural units derived from an aromatic dihydroxy compound. , More preferably 2
It is contained in an amount of ４０40 mol%. It is formed from a copolymerized polycarbonate obtained by copolymerization.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, an optical molded article according to the present invention will be described. The optical molded article according to the present invention is excellent in transparency and hue and has low birefringence.

The molded article for optical use according to the present invention is not particularly limited in shape and use as long as it is used for optical purposes. Specifically, an optical disc for digital data, a CD-R
It is suitably used as an optical disk (optical substrate) such as an OM, a compact disk, and a video disk, an optical fiber, a lens, and a lighting fixture.

Such an optical molded article according to the present invention comprises:
[A] It is formed from a copolymerized polycarbonate. The molded article for optical use according to the present invention is preferably made of a copolymerized polycarbonate composition comprising an additive [B] in addition to the copolymerized [A].

The [A] copolymerized polycarbonate comprises (i) resorcinol, (ii) an aromatic dihydroxy compound other than resorcinol and substituted resorcinol, and (iii) these aromatic dihydroxy compounds (i) and (ii)
A diester carbonate compound capable of forming a carbonic acid bond by reacting with an alkali metal compound and / or an alkaline earth metal compound, wherein 1 × 10 ^{−7 to} 2.5 × 10 ^{− In} the presence of catalyst (a) used in an amount of ⁶ moles , copolymerized in the presence of (i) units derived from resorcinol, and (ii) derived from aromatic dihydroxy compounds other than resorcinol and substituted resorcinol And (iii) these aromatic dihydroxy compounds (i) and (ii)
And a unit derived from a carbonic acid diester compound capable of forming a carbonic acid bond by reacting with

[A] The copolymerized polycarbonate will be described below. Such a structural unit derived from (i) resorcin or substituted resorcin is represented by the following general formula [I].

[0018]

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In the above formula [I], R 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 an integer of 0-4.

Specific examples of (i) resorcinol and / or substituted resorcinol include resorcinol, 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, and 3-t-butylresorcinol. ,
3-phenylresorcinol, 3-cumylresorcinol, 2,3,4,5-
Tetrafluororesorcin, 2,3,4,5-tetrabromoresorcin and the like can be mentioned.

Of these, resorcin is particularly preferred. In the [A] copolymerized polycarbonate according to the present invention,
Such a structural unit derived from (i) resorcinol and / or substituted resorcinol, when the structural unit derived from an aromatic dihydroxy compound is 100 mol%,
Although it is contained in an amount of less than 100 mol%, it is preferably contained in an amount of 2 to 90 mol%, more preferably 2 to 40 mol%.

(Ii) Structural units derived from aromatic dihydroxy compounds other than resorcinol and / or substituted resorcinol are not particularly limited, and are usually derived from the following aromatic dihydroxy compounds which form polycarbonate. May be a structural unit.

[0023]

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Wherein R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen or a monovalent hydrocarbon group, which may be the same or different. p and q represent an integer of 0 to 4. Examples of such (ii) aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl)
Butane, 2,2-bis (4-hydroxyphenyl) octane,
Bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-
Bis (4-hydroxy-t-butylphenyl) propane, 2,2
Bis (hydroxyaryl) alkanes such as -bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
Dihydroxyaryl ethers such as -dimethylphenyl ether, 4,4'-dihydroxydiphenylsulfide, dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 4,
Dihydroxydiarylsulfoxides such as 4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-
And dihydroxydiarylsulfones such as dimethyldiphenylsulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred. Examples of the compound that reacts with the aromatic dihydroxy compounds (i) and (ii) to introduce a carbonic acid bond (iii) include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m- cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, carbonic acid diester such as dicyclohexyl carbonate
No.

Of these, diphenyl carbonate is particularly preferred. The [A] copolymerized polycarbonate according to the present invention may contain a structural unit derived from a dicarboxylic acid, a dicarboxylic acid ester or a dicarboxylic acid halide, in addition to the structural units described above. This structural unit is a polyester polycarbonate.

Examples of such a dicarboxylic acid or dicarboxylic acid ester or dicarboxylic acid halide include terephthalic acid, isophthalic acid, sebacic acid, decandioic acid, and the like.
Dodecane diacid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, diphenyl decane diacid, diphenyl dodecane diacid, terephthalic chloride, isophthalic chloride, sebacic chloride, decane diacid chloride, dodecane dichloride and the like. be able to.

[A] In the copolymerized polycarbonate, such a polyester polycarbonate unit may be present in an amount of 50 mol% or less, preferably 30 mol% or less.

Also, [A] the copolymerized polycarbonate may contain a structural unit derived from a polyfunctional compound having three or more functional groups in one molecule, as long as the object of the present invention is not impaired. Good.

As such a polyfunctional compound, a compound having three or more phenolic hydroxyl groups or carboxyl groups is preferable, and a compound having three or more phenolic hydroxyl groups is particularly preferably used. Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane,
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) -heptane-2,1,3,5-tri (4 -Hydroxyphenyl) benzene, 2,2-bis- [4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, etc. Is mentioned.

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

Such a structural unit is usually 3 mol% or less, preferably 0.1 to 2 mol%, when the structural unit derived from the aromatic dihydroxy compound in the copolymerized polycarbonate is 100 mol%. Preferably 0.1
It may be present in an amount of １1 mol%.

The above-mentioned [A] copolymerized polycarbonate has a glass transition temperature (Tg) of usually from 100 to 15;
It is 0 degreeC, Preferably it is 110-135 degreeC. The thermal decomposition temperature is usually 350 to 380 ° C, preferably 360 to 380 ° C.
380 ° C.

Further, in accordance with JIS K 7210,
The melt flow rate (MFR) measured under the conditions of a temperature of 300 ° C. and a load of 1.2 kg is usually 5 to 100 g / 10 min.
Preferably it is 8 to 50 g / 10 minutes.

The optical molded article according to the present invention formed from such a copolymerized polycarbonate has excellent mechanical properties, heat resistance, transparency and hue, as well as excellent chemical resistance and fluidity during molding. Also, it has excellent melting stability.

In particular, the copolymerized polycarbonate forming the optical molded article according to the present invention has a MFR (g / 10 min.) Which is smaller than that of a conventional polycarbonate containing no structural unit derived from resorcinol and / or substituted resorcinol. )
And excellent in moldability such as fluidity and melt stability. For this reason, the optical molded article according to the present invention is excellent in fluidity at the time of molding, and is molded without decreasing transparency, hue, or molecular weight. Further, the optical molded body molded in this way has a small birefringence.

The above-mentioned [A] copolymerized polycarbonate can be produced by reacting (i) resorcinol and / or substituted resorcinol, (ii) other aromatic dihydroxy compounds, and (iii) these aromatic dihydroxy compounds. It is produced using a carbonic acid diester compound capable of forming a bond,
The manufacturing method is not particularly limited. Specifically, it is produced by a melting method using a carbonic acid diester as a compound capable of forming a carbonic acid bond by reacting with an aromatic dihydroxy compound, a solid phase polymerization method, or the like.

In the present invention, of these, the melt polymerization method is preferable, and the details thereof will be described below. In the present invention, when producing a copolymerized polycarbonate by a melt polymerization method, (i) resorcinol and / or substituted resorcinol,
(ii) Other aromatic dihydroxy compounds and (iii) carbonic acid diester are used.

(I) Resorcinol and substituted resorcinol used in the present invention are represented by the following general formula [III].

[0040]

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In the above formula [III], R 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 an integer of 0-4.

As such a substituted resorcinol, specifically, the aforementioned compounds are used. Of these,
Resorcin is preferably used. These may be used alone or in combination.

In the present invention, when producing a copolymerized polycarbonate, such (i) resorcinol and / or substituted resorcinol is contained in an aromatic dihydroxy compound.
It is used in an amount of less than 100%, but preferably
%, More preferably 2 to 40 mol%.

(Ii) The aromatic dihydroxy compound other than resorcinol and / or substituted resorcinol is preferably 98 to 10 mol%, more preferably 98 to 60 mol%, when the aromatic dihydroxy compound is 100 mol%. Used in quantity.

The aromatic dihydroxy compound other than (ii) resorcinol and / or substituted resorcinol is not particularly limited, but is usually a compound represented by the following formula [IV], and further, a phenyl group represented by the following [IV]: Examples thereof include compounds in which an aliphatic group or a halogen group is substituted.

[0046]

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Wherein R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen or a monovalent hydrocarbon group, which may be the same or different. p and q are integers of 0-4. Examples of the (ii) aromatic dihydroxy compound include the compounds described above.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. Also
(iii) Specific examples of the carbonic acid diester include the compounds described above.

Of these, diphenyl carbonate is particularly preferably used. In the present invention, when producing a copolymerized polycarbonate, (iii) the carbonic acid diester is
When it is set to 00 mol%, the 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.

Specific examples of such a dicarboxylic acid or dicarboxylic acid ester include the compounds described above. In the present invention, when producing a polycarbonate, the above-mentioned carbonic acid diester is used in an amount of 0.95 to 1.95 based on 1 mol of the aromatic dihydroxy compound in total.
It is desirably used in an amount of 30 mol, preferably 1.01 to 1.20 mol.

Further, in the present invention, when producing a polycarbonate, together with the aromatic dihydroxy compound and the carbonic acid diester as described above, 3
Polyfunctional compounds having more than one functional group can also be used.

When a polyfunctional compound is used, it is usually 0.03 with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferably used in an amount of 0.001 to 0.02 mol, more preferably 0.001 to 0.01 mol.

In the present invention, (i) resorcinol and / or substituted resorcinol as described above, (ii) other aromatic dihydroxy compound and (iii) diester carbonate are combined with (a) an alkali metal compound and / or an alkaline earth compound. It is preferable to carry out the melt polycondensation in the presence of a catalyst comprising an analogous compound.

Examples of the alkali metal compound and the alkaline earth metal compound (a) include organic acid salts and inorganic acid salts of alkali metals and alkaline earth metals.
Oxides, hydroxides, hydrides or 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 compounds may be used alone or in combination.
Can be used. Such alkali metal compounds and
And / or an alkaline earth metal compound (a)
Usually, 1 × 10
^-8~ 1 × 10 ^-3Mol, preferably 1 × 10^-7~ 1 × 10
^-FiveMol, particularly preferably 1 × 10^-7~ 2.5 × 10^-6Mo
Used in the amount of oil.

When the amount of the alkali metal compound or the alkaline earth metal compound (a) is from 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol per 1 mol of the total amount of the aromatic dihydroxy compound, the polymerization activity is increased. While maintaining, it is possible to add an acidic compound (described below) in an amount that does not adversely affect the properties of the obtained copolymerized polycarbonate, thereby sufficiently neutralizing or weakening the basicity of these compounds,
A copolymerized polycarbonate having excellent hue, heat resistance, water resistance, and weather resistance and excellent long-term melt stability can be obtained.

In the present invention, as a catalyst, together with (a) the alkali metal compound and / or alkaline earth metal compound described above, (b) a basic compound and / or
(c) Boric acid compounds can be used.

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

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH) ), Such as alkyl, aryl,
Ammonium hydroxides having an araryl group and the like, tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine, R ₂ NH (where R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and toluyl) Etc.)
In secondary amines represented, primary amines represented by RNH ₂ (wherein R is as defined above), pyridine, dimethylaminopyridine, pyridine such as pyrrolidinopyridine, 2-methylimidazole, 2-phenyl imidazoles such as imidazole, or ammonia, tetramethylammonium borohydride (Me ₄ NBH _4), tetrabutylammonium borohydride (Bu ₄ NBH _4), tetrabutylammonium tetraphenylborate (Bu ₄ N
BPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄₎ basic salts, such as.

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

Examples of the boric acid compound (c) include boric acid and boric acid esters represented by the following general formula. B (OR) _n (OH) _{3-n In the} formula, R is alkyl such as methyl and ethyl, aryl such as phenyl and the like, 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.

Preferred combinations used as a catalyst in the present invention include a combination consisting of (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound.

At this time, (a) an alkali metal compound and / or
Alternatively, the alkaline earth metal compound is used in an amount as described above, and (b) the nitrogen-containing basic compound is 1 × 10 ^-6 to 1 × 10 ^-1 mol, based on 1 mol of the total amount of the aromatic dihydroxy compound, It is preferably used in an amount of 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol. (b) The amount of the nitrogen-containing basic compound to be used is 1 × 10 ⁻⁶ to 1 × 1 per 1 mol of the total amount of the aromatic dihydroxy compound.
The amount of 0 to ¹ mol is preferred in that the transesterification reaction and the polymerization reaction proceed at a sufficient rate, and a copolymerized polycarbonate having excellent hue, heat resistance and water resistance can be obtained.

As described above, a catalyst obtained by combining (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound is excellent in heat resistance and water resistance and has improved color tone. A high molecular weight copolymerized polycarbonate having excellent transparency can be produced with high polymerization activity.

Further, in the present invention, a catalyst comprising a combination of (a) an alkali metal compound and / or an alkaline earth metal compound and (c) boric acid or a borate ester, and (a) an alkali metal compound and / or Alternatively, a catalyst comprising a combination of an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid or a borate ester is preferably used.

In a catalyst comprising such a combination,
(a) The alkali metal compound or alkaline earth metal compound and (b) the nitrogen-containing basic compound are preferably used in the amounts described above.

(C) Boric acid or boric acid ester is 1 × 10 ^{-8 with} respect to 1 mol of the total amount of the aromatic dihydroxy compound.
１1 × 10 ^-1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-2
Mole, more preferably 1 × 10 ^-6 to 1 × 10 ^-4 mole.

(C) The amount of boric acid or boric acid ester used is 1 × with respect to 1 mole of the total amount of the aromatic dihydroxy compound.
The molar ratio of 10 ^-8 to 1 × 10 ^-1 is preferred because a molecular weight is less likely to be reduced after heat aging, and a copolymer polycarbonate excellent in hue, heat resistance and water resistance can be obtained.

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

The polycondensation reaction between (i) resorcinol and / or substituted resorcinol and (ii) other aromatic dihydroxy compound and (iii) carbonic acid diester using such a catalyst is as follows:
The reaction can be carried out under the same conditions as conventionally known polycondensation reaction conditions between an aromatic dihydroxy compound and a carbonic acid diester.

Specifically, 80 to 250 ° C., preferably 100 to 230 ° C., more preferably 120 to 190 ° C.
The aromatic dihydroxy compound is reacted with the carbonic acid diester at a temperature of 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours under normal pressure. Next, the reaction temperature is increased while reducing the pressure of the reaction system, and the reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out. Finally, the reaction is carried out under a reduced pressure of 5 mmHg or less, preferably 1 mmHg or less.
A polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is performed at a temperature of about 320 ° C.

The above-mentioned polycondensation reaction may be carried out in a continuous manner or in a batch manner. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The copolymerized polycarbonate thus obtained usually has an intrinsic viscosity [η] of 0.2 to 1.2 dl.
/ G, preferably 0.3 to 1.0 dl / g. The production method as described above is preferable in terms of environmental hygiene because toxic substances such as phosgene and methylene chloride are not used in the melt polycondensation of the copolymerized polycarbonate.

Further, according to this melt polymerization method, in the obtained copolymerized polycarbonate, 90 moles of the structural units derived from (i) resorcinol and / or substituted resorcinol per 100 moles of the structural units derived from the aromatic dihydroxy compound. The use of (i) resorcinol and / or substituted resorcinol in such an amount as to exceed mol%,
For example, a copolymerized polycarbonate having excellent hue, water resistance and heat resistance as compared with an interfacial polymerization method or the like can be obtained.

The molded article for optical use according to the present invention is preferably formed from a copolymerized polycarbonate composition containing an additive [B] in addition to the above-mentioned [A] copolymerized polycarbonate.

Examples of such additives [B] include (a)
a sulfur-containing acidic compound having a pKa value of 3 or less and / or
Or a derivative formed from the acidic compound, (b) a phosphorus compound, (c) an epoxy compound, (d) a phenol-based stabilizer, (e) a release agent, (f) a boron-based compound, and the like.

These may be used alone or in combination of two or more. Such (a) sulfur-containing acidic compounds having a pKa value of 3 or less and derivatives formed from the acidic compounds include, specifically, sulfurous acid, sulfuric acid, sulfinic acid compounds, sulfonic acid compounds and derivatives thereof. Is mentioned.

As the sulfite derivative, dimethyl sulfite,
Diethyl sulfite, dipropyl sulfite, dibutyl sulfite,
Diphenylsulfite and the like. Examples of the sulfuric acid derivative include dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, diphenyl sulfate and the like.

Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid, naphthalenesulfinic acid and the like. Examples of the sulfonic acid compound and its derivative include a compound represented by the following general formula [V] and an ammonium salt thereof.

[0083]

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In the formula, R ⁷ is a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted by halogen);
⁸ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted by halogen), and n is an integer of 0 to 3.

Specific examples of such sulfonic acid compounds and derivatives thereof include sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butylbenzenesulfonate and benzene. Sulfonate esters such as octyl sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, butyl p-toluene sulfonate, octyl p-toluene sulfonate, phenyl p-toluene sulfonate, p -Ammonium sulfonate salts such as ammonium toluene sulfonate.

Further, in addition to the sulfonic acid compound represented by the general formula [V], trifluoromethanesulfonic acid,
Sulfonic acid compounds such as naphthalene sulfonic acid, sulfonated polystyrene, and methyl acrylate-sulfonated styrene copolymer are exemplified.

In the present invention, as the sulfur-containing acidic compound and the derivative formed from the acidic compound, a sulfonic acid compound represented by the above general formula [V] and its derivative are preferable. Further, in the general formula [V],
R ⁷ and R ⁸ each represent a substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms;
Compounds in which n is an integer of 0 to 1 are preferably used, and specifically, benzenesulfonic acid, butylbenzenesulfonate, p-toluenesulfonic acid, ethyl p-toluenesulfonate, and butyl p-toluenesulfonate are preferred. .

Of these, butyl p-toluenesulfonate is preferred. In the present invention, (a) p
The sulfur-containing acidic compound having a Ka value of 3 or less and / or a derivative formed from the acidic compound is converted into the above-mentioned [A]
0.1 to 10 ppm with respect to the copolymerized polycarbonate,
Preferably 0.1 to 8 ppm, particularly preferably 0.1 to 5 pp
m.

(B) Phosphorus compounds include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphate esters and phosphite esters. Specific examples of such a phosphate include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, and 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 and triaryl phosphates such as 2-ethylphenyldiphenyl phosphate and the like.

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

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

Of these, the (b) phosphorus compound is preferably a phosphite represented by the above general formula, more preferably an aromatic phosphite, especially tris (2,
4-Di-t-butylphenyl) phosphite is preferred.

In the present invention, the above-mentioned (b) phosphorus compound is usually added to [A]
It is added in an amount of 0 to 1000 ppm, preferably 50 to 500 ppm.

(C) As the epoxy compound, a compound having one or more epoxy groups in one molecule is used. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 3 , 4-Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4
-(3,4-epoxy-5-methylcyclohexyl) butyl-3 ',
4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-
Methylsilohexyl carboxylate, 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-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-
Epoxy-5-methylcyclohexylcarboxylate,
Octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ′, 4′-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3 ′, 4′-epoxycyclohexylcarboxylate, 4,5-epoxy tetrahydrophthalic anhydride, 3-
t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy- Cis-1,2-cyclohexyldicarboxylate and the like.

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

In the present invention, such an epoxy compound (c) is used for the above [A] copolymerized polycarbonate.
Usually in an amount of 1 to 2000 ppm, preferably 10 to 100 ppm
Preferably, it is added in an amount of 0 ppm.

(D) Specific examples of the phenolic stabilizer include, for example, n-octadecyl-3- (4-hydroxy-3 ', 5'
-Di-t-butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl- 4-hydroxy-5-t-butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzylmalonate, 4-hydroxymethyl-2,6-di-t-butylphenol, etc. No.

In the present invention, the above-mentioned (d) phenol-based stabilizer is used in an amount of usually 10 to 1000 ppm, preferably 50 to 500 ppm, based on [A] copolymerized polycarbonate.
Used in ppm amounts.

(E) As the release agent, a general release agent is used without any particular limitation. Specifically, 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, stearin Acid amide,
Fatty acid amides such as ethylenebisstearamide, fatty acid amide release agents such as alkylenebisfatty acid amides, aliphatic alcohols such as stearyl alcohol and cetyl alcohol, and alcoholic release agents such as polyhydric alcohols, polyglycols and polyglycerols Mold release agents, fatty acid ester release agents such as aliphatic acid lower alcohol esters such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters and fatty acid polyglycol esters, and silicone release agents such as silicone oils Agents and the like.

In the present invention, the release agent (e) is usually 0.001 to 5 parts by weight, preferably 0.005 part by weight, per 100 parts by weight of the copolymer (A).
To 1 part by weight, more preferably 0.01 to 0.5 part by weight.

Examples of the (f) boron compounds include the above-mentioned boric acid compounds (c), and specific examples thereof include boric acid, trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, and the like. Triheptyl borate,
Triphenyl borate, tolyl borate, trinaphthyl borate and the like can be mentioned.

Of these, triphenyl borate is preferred. In the copolymerized polycarbonate composition according to the present invention, the (f) boron-based compound as described above contains 0.000 parts per 100 parts by weight of [A] the copolymerized polycarbonate.
1 to 0.2 part by weight, preferably 0.00005 to 0.02
It is preferably used in parts by weight.

Such a (f) boron compound can be used by adding it in advance as one component (c) of the catalyst at the time of polymerization, as described above. There is no particular need to add it later.

Such a copolymerized polycarbonate composition can be produced by kneading the components by a conventionally known method. For example, a method in which each component is dispersed and mixed by a high-speed mixer represented by a turnbull mixer or a Henschel mixer, and then melt-kneaded by an extruder, a Banbury mixer, a roll, or the like is appropriately selected.

In producing the copolymerized polycarbonate composition, the reaction product [A] in a molten reactor or extruder obtained after completion of the polycondensation reaction.
While the copolymerized polycarbonate is in the molten state,
[B] It is preferable to add and knead the additive. Specifically, for example, after adding a [B] additive to a [A] copolymerized polycarbonate obtained in a polycondensation reaction in a reactor to form a copolymerized polycarbonate composition, a pelletizing process is performed through an extruder. Alternatively, while the [A] copolymerized polycarbonate obtained by the polycondensation reaction is pelletized from the reactor through an extruder, [B] additives are added, and these are kneaded. It may be a copolymerized polycarbonate composition.

[A] The order of adding the additives (a), (b), (c), (d), (e) and (f) to the copolymerized polycarbonate is not limited. The copolymerized polycarbonate composition obtained as described above is obtained because the additive [B] is added and kneaded while the copolymerized polycarbonate [A], which is the reaction product, is in a molten state. The heat history of the resin composition can be reduced, and a copolymer polycarbonate composition with less hue deterioration and heat deterioration can be obtained.

As described above, the additive [B], that is, (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound;
By adding (b) a phosphorus compound, (d) a phenol-based stabilizer or (f) a boron-based compound in the above amount, the alkaline catalyst remaining in the [A] copolymerized polycarbonate obtained by the polymerization reaction becomes medium. And (2) even if the compounds (a) and (b) remain excessively, they react with the epoxy compound (c) to be neutralized, thereby further improving the retention stability during melting. The obtained copolymerized polycarbonate composition is obtained.

Such a copolymerized polycarbonate composition has improved thermal stability as described above even when pellets made of the composition are re-melted when molded into an optical molded article. Therefore, thermal decomposition is particularly suppressed, the molecular weight is hardly reduced, and coloring is difficult.

The molded article for optical use according to the present invention is molded from the above copolymerized polycarbonate composition with excellent fluidity and melt stability. Further, the copolymerized polycarbonate and the copolymerized polycarbonate composition forming the optical molded article according to the present invention are, as long as the object of the present invention is not impaired, ordinary heat stabilizers other than the following [B] additives. , An ultraviolet absorber, a colorant, an antistatic agent, a slip agent, an antiblocking agent, a lubricant, an antifogging agent, a natural oil, a synthetic oil, a wax, and the like.

Such other additives can be added to [A] in a molten state together with the above-mentioned [B], or the pelletized copolymerized polycarbonate composition is re-melted and added. You can also. In the present invention, the former method is preferred.

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

The hindered amine stabilizers include:
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) propionyloxydiethyl]
-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
Bis (1,2,2,6,6-pentamethyl-4-piperidyl)-(3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2,2, 6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate.

These may be used alone or as a mixture of two or more. These heat stabilizers are used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the copolymerized polycarbonate. It is used as needed in an amount.

Such a heat stabilizer may be added in a solid state or in a liquid state. As the UV absorber, a general UV absorber is used without any particular limitation. Examples thereof include salicylic acid-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and cyanoacrylate-based UV absorbers. Used.

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

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

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

The ultraviolet absorber is usually used in an amount of 0.001 to 5 parts by weight, preferably 0.005 parts by weight, per 100 parts by weight of [A].
To 1.0 part by weight, more preferably 0.01 to 0.5 part by weight, if necessary.

The colorant may be a pigment or a dye, and may be inorganic or organic. These may be used in combination. Specific examples of inorganic colorants include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as navy blue, zinc chromate, and molybdenum red. Such as chromate, sulfate such as barium sulfate, carbonate such as calcium carbonate, silicate such as ultramarine blue, phosphate such as manganese violet, carbon such as carbon black, and metal powder such as bronze powder and aluminum powder. Coloring agents and the like.

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, azo-based such as naphthol red and chromophtal yellow, phthalocyanine-based such as phthalocyanine blue and fast sky blue, and condensed polycyclic-based coloring agents such as indanthrone blue, quinazodone violet, and dioxazine violet.

The coloring agent was used in 100 parts by weight of [A].
Usually 1 × 10 ^{-6 to} 5 parts by weight, preferably 1 × 10 ^{-5 to} 3 parts by weight
It is used as needed in an amount of 1 part by weight, more preferably 1 × 10 ^-5 to 1 part by weight.

The optical molded article according to the present invention can be obtained by molding a conventionally known polycarbonate from the above-mentioned copolymerized polycarbonate or the copolymerized polycarbonate composition by a molding method as described above for the compact disk, optical disk, optical fiber, headlamp, Molded according to the application such as automotive lenses such as tail lamps, plastic lenses such as glasses, cameras and telescopes.

[0123]

The optical molded article according to the present invention formed from the above-mentioned copolymerized polycarbonate or the copolymerized polycarbonate composition is compared with an optical molded article formed from a normal bisphenol homopolycarbonate. Excellent flowability and melt stability, especially during molding,
It is hardly thermally decomposed during molding, has a low molecular weight, is hardly yellowed, has excellent hue stability, and is molded in an excellent molding cycle.

The optical molded article according to the present invention is as follows.
It has excellent transparency and mechanical properties, and has low birefringence, and is used for a wide range of optical applications. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0125]

EXAMPLES In the present specification, the composition of the copolymerized polycarbonate, the intrinsic viscosity [IV], the ratio of the terminal groups, and the moldability and appearance of the copolymerized polycarbonate composition are measured as follows.

[Composition ratio of polycarbonate] ¹ H-N
The ratio of the aromatic dihydroxy compound constituent unit in the resin was measured by MR.

[Intrinsic viscosity [IV]] In methylene chloride, 2
It measured at 0 degreeC using the Ubbelohde viscometer. [Melt flow rate (MFR; g / 10 min)] JISK
It was measured at a temperature of 250 ° C. and a load of 1.2 kg in accordance with −7210.

[Yellowness (YI)] An injection molded plate having a thickness of 3 mm was placed at a cylinder temperature of 290 ° C. under an injection pressure of 1000 kg / cm.
^2. Molded at a mold temperature of 100 ° C for 45 seconds per cycle.
X, Y, and Z values are calculated using Nippon Denshoku Industries Co., Ltd.
The yellowness (YI) was measured by a transmission method using a Defference Meter ND-1001 DP.

YI = 100 (1.277 X−1.060 Z) / Y [Light transmittance] According to the method of ASTM D 1003,
It was measured using an injection molded plate for measuring hue.

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

[Residence 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. YI, MFR,
The light transmittance was measured.

[Water Resistance] An injection molded plate for measuring hue was immersed in water in an autoclave and placed in an oven at 120 ° C. for 5 hours.
Hold for days. The haze was measured using this test piece.

[Moldability] Using a nickel stamper, a 5-inch disk was continuously shot for 100 shots at a mold temperature of 90 ° C. for 5 seconds in a cycle of 5 seconds, without fogging or recording error, and at a level acceptable as a product. The cylinder temperature at which injection molding was possible was examined.

[Izod impact strength] ASTM D25
According to No. 6, the measurement was performed using an injection test piece of 63.5 × 12.7 × 2 mm (rear notch). The number of broken pieces in 10 test pieces was also counted.

[0135]

Example 1 0.33 mmol of bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) and resorcin (distilled and refined) (manufactured by Mitsui Petrochemical Industries, Ltd.)
11 mmol and 0.46 mmol of diphenyl carbonate (manufactured by Any Co.) were charged into a first 250-liter stirred tank at 140 ° C., and 0.12 mmol / h of bisphenol A was added so as to maintain this level. While feeding resorcinol at a rate of 0.04 km / h and diphenyl carbonate at a rate of 0.16 km / h, the mixed solution was fed at 0.16 hr / hr in terms of aromatic dihydroxy compound.
The solution is fed to the second 50-liter stirred tank in kilomoles. The temperature of this tank type stirring tank is maintained at 180 ° C.

As catalysts, 0.04 mol / h of tetramethylammonium hydroxide and 0.00016 mol / h of sodium hydroxide (1 × 10 ⁻⁶ mol / mol-aromatic dihydroxy compound) were added, and the residence time was 30 minutes. Adjust the level so that it becomes as desired.

Next, this reaction solution is fed to the next 50-liter stirred tank at a third temperature of 210 ° C. and a pressure of 200 mmHg at a rate of 0.16 kmol / hour in terms of an aromatic dihydroxy compound. The level is adjusted so that the residence time is 30 minutes, and the mixture is stirred while phenol is distilled off.

Next, this reaction solution is fed into a 50-liter stirred tank at a temperature of 240 ° C. and a pressure of 15 mmHg at a rate of 0.16 km / h in terms of an aromatic dihydroxy compound. The level is adjusted so that the residence time is 30 minutes, and the mixture is stirred while phenol is distilled off.

Next, the pressure of the reaction product was increased by a gear pump, and the reaction product was fed into a centrifugal thin-film evaporator in an amount of 0.16 kmol / hour in terms of an aromatic dihydroxy compound, to proceed the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. 280 ° C by gear pump from the bottom of the evaporator,
0.1 hour in terms of aromatic dihydroxy compound in a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotation diameter 220 mm, internal volume 80 liters) controlled to 0.2 mmHg.
6 kilomoles (about 40 kg / hour) each, and residence time 3
Polymerization was performed at 0 minutes.

Next, in the melted state, the polymer was fed to a twin-screw extruder (L / D = 17.5, barrel temperature 280 ° C.) using a gear pump at 0.16 kmol (about an aromatic dihydroxy compound) per hour. 40 kg / hour), and kneaded continuously with 0.00032 mol / h of p-toluene butyl sulphonate (2 times the molar amount of sodium hydroxide used as a catalyst), made into a strand through a die, and cut with a cutter. To obtain pellets.

Table 1 shows the results.

[0142]

Example 2 In Example 1, 0.264 mmol of bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) and 0.1 mol of resorcinol (manufactured by Mitsui Petrochemical Industries, Ltd.) were used.
Pellets were obtained in the same manner as in Example 1 except that 176 mmol was used.

Table 1 shows the results.

[0144]

EXAMPLE 3 In Example 1, 0.04 mol / h of tetramethylammonium hydroxide and 0.00016 mol / h of sodium hydroxide (1 × 10
^(-6 mol / mol-aromatic dihydroxy compound) Pellets were obtained in the same manner as in Example 1 except that 0.004 mol of triphenyl borate was added at the same time. Table 1 shows the results.

[0145]

Example 4 In Example 3, a twin-screw extruder (L / D =
17.5, a barrel temperature of 285 ° C.) was fed at a rate of 0.16 kmol (about 40 kg / hour) in terms of bisphenol A per hour, and butyl p-toluenesulfonate was fed at 0.00032 per hour.
Moles (twice the molar amount of sodium hydroxide used as a catalyst), and at the same time, tris (2,4-di-t-butylphenyl) phosphite (Mark 2112: Adeka Argas) Manufactured) 300ppm,
3,4-epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (Celloxide 2021P:
Pellets were obtained in the same manner as in Example 3, except that 300 ppm of Daicel Chemical Co., Ltd. and 1000 ppm of Hitec 164 (hydrocarbon release agent: ethyl-petrolatum-additives) were continuously kneaded.

The results are shown in Table 1.

[0147]

Example 5 In Example 4, together with other additives,
Same as Example 4 except that 300 ppm of n-octadecyl-3- (4-hydroxy-3 ', 5'-di-t-butylphenyl) propionate (Mark AO 50: manufactured by Adeka Argus) was continuously kneaded. Pellets were obtained by the method.

The results are shown in Table 1.

[0149]

Example 6 In Example 4, 0.22 mmol of bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) and 0.2 of resorcinol (manufactured by Mitsui Petrochemical Industries, Ltd.) were used.
Pellets were obtained in the same manner as in Example 4 except that 2 mmol was used.

Table 1 shows the results.

[0151]

Comparative Example 1 In Example 1, resorcin was not used.
Bisphenol A (Nihon GE Plastics Co., Ltd.)
Pellets were obtained in the same manner as in Example 1 except that only 0.44 mmol was used.

Table 1 shows the results.

[0153]

Comparative Examples 2 to 4 In Example 5, without using resorcinol, only 0.44 mmol of bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) was used, and the compounds shown in Table 1 were used in the amounts shown in Table 1. Except for the above, pellets were obtained in the same manner as in Example 5.

The results are shown in Table 1.

[0155]

Embodiments 7 and 8 In Embodiments 4 and 6, a two-shaft horizontal stirring polymerization tank (L / D = 3, stirring blade rotation diameter 220 mm, controlled at 285 ° C. and 0.2 mmHg by a gear pump from the lower part of the evaporator, The same as in Examples 4 and 6, as shown in Table 1, except that 0.16 kilomol (about 40 kg / hour) in terms of an aromatic dihydroxy compound was fed into an hourly amount of 80 liters and polymerized at a residence time of 30 minutes. A pellet was obtained by the method described above.

Table 1 shows the results.

[0157]

Comparative Example 5 In Example 7, resorcin was not used.
Bisphenol A (Nihon GE Plastics Co., Ltd.)
Pellets were obtained in the same manner as in Example 7 except that only 0.44 mmol of the compound shown in Table 1 was used and the amount of the compound shown in Table 1 was used.

The results are shown in Table 1.

[0159]

[Table 1]

[0160]

[Table 2]

[0161]

[Table 3]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takashi Nagai 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Gee Plastics Co., Ltd. (56) References JP-A-63-3021 (JP) , A) JP-A-63-10623 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (7)

(57) [Claims] (1) resorcinol, (ii) an aromatic dihydroxy compound other than resorcinol and substituted resorcinol, (iii) these aromatic dihydroxy compounds (i) and (ii)
A diester carbonate compound capable of forming a carbonic acid bond by reacting with an alkali metal compound and / or an alkaline earth metal compound, wherein 1 × 10 ^{−7 to} 2.5 × 10 ^{− A} molded article for optical use, characterized by being formed from a copolymerized polycarbonate obtained by copolymerization in the presence of a catalyst (a) used in an amount of ⁶ mol . 2. The copolymeric polycarbonate according to claim 1, wherein the structural unit derived from an aromatic dihydroxy compound is (i)
The optical molded article according to claim 1, comprising a structural unit derived from resorcinol in an amount of 2 to 90 mol%. 3. The copolymerized polycarbonate according to claim 1, wherein the structural unit derived from an aromatic dihydroxy compound is (i)
The optical molded product according to claim 1, further comprising a structural unit derived from resorcin in an amount of 2 to 40 mol%. (A) (i) resorcinol, (ii) an aromatic dihydroxy compound other than resorcinol and substituted resorcinol, (iii) these aromatic dihydroxy compounds (i) and (ii)
A diester carbonate compound capable of forming a carbonic acid bond by reacting with an alkali metal compound and / or an alkaline earth metal compound, wherein 1 × 10 ^{−7 to} 2.5 × 10 ⁻ An optical composition characterized by being formed from a copolymerized polycarbonate composition comprising a copolymerized polycarbonate obtained by copolymerization in the presence of a catalyst (a) used in an amount of ⁶ mol and [B] an additive. Moldings. 5. The copolymer (A) is characterized in that, among the structural units derived from an aromatic dihydroxy compound, (i) a structural unit derived from resorcin is 2-90.
The optical molding according to claim 4, wherein the molding is contained in an amount of mol%. 6. The (A) copolymerized polycarbonate may comprise (i) 2 to 40 structural units derived from resorcinol among structural units derived from an aromatic dihydroxy compound.
The optical molding according to claim 4, wherein the molding is contained in an amount of mol%. 7. The additives [B] include: (a) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, (b) a phosphorus compound, (c) an epoxy compound, The optical molding according to claim 4, wherein the molding is selected from the group consisting of (d) a phenol-based stabilizer, (e) a release agent, and (f) a boron-based compound.