JPH06136113A - Optical molding - Google Patents

Abstract

PURPOSE:To provide an optical molding made of a copolycarbonate hardly exhibiting coloration and birefringence and excellent in moldability such as flowability and melt stability and also in clarity and mechanical characteristics and to provide an optical molding made of a copolycarbonate compsn. CONSTITUTION:An optical molding is provided which is made of a copolycarbonate obtd. by copolymerizing resorcin and/or a substd. resorcin, an arom. dihydroxy compd. other than resorcin and the substd. resorcin, and a compd. which reacts with the foregoing three dihydroxy compds. to form carbonic acid bonds. An optical molding is also provided which is made of a compsn. obtd. by compounding the copolycarbonate with additives.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optical molded article, and more specifically, to an optical molded article formed from a copolymerized polycarbonate which has excellent fluidity during molding, little coloring, and excellent transparency. The present invention relates to an optical molding formed from a composition containing a copolycarbonate.

[0002]

2. Description of the Related Art In recent years, optical discs have been used for a wide range of applications, such as optical discs for digital data, CD-ROMs, compact discs, and video, by taking advantage of their large recording capacity, non-contact reading, and high-speed access. It is used for discs.

Optical substrates such as optical discs, optical fibers, lenses, lighting fixtures and the like are required to have excellent transparency, and in particular, optical substrates only have high light transmittance in the wavelength region of the reproduction laser beam. However, the light transmittance in a wide range of wavelengths from the visible light region to the near infrared region is required.

Further, the optical substrate is also required to have characteristics such as low water absorption and heat resistance. Conventionally, an optical molded body formed of polycarbonate has been widely used as a material satisfying such characteristics.

By the way, such a molded article for optics can be obtained by molding a molten polycarbonate into a desired shape. However, upon molding, the polycarbonate has a problem that the melt viscosity is high and the fluidity is poor. It was If polycarbonate is molded into an optical substrate or the like with insufficient fluidity when melted, an optical substrate with large birefringence will be obtained.

On the other hand, when the polycarbonate is melted at a high temperature to increase its fluidity, the melt stability is lowered, and the polycarbonate is thermally decomposed during molding, so that the hue and transparency are lowered, and the mechanical properties are deteriorated. In some cases, an unsuitable molded article for optics may be obtained due to a decrease in the optical property.

For this reason, the polycarbonate optical molded article has the excellent optical characteristics originally possessed, and
Moreover, it has been desired to develop an optical molded article that is excellent in fluidity and melt stability during molding, has small birefringence, is excellent in hue and transparency, and is excellent in mechanical properties.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is excellent in moldability such as fluidity and melt stability, less coloring during molding, and excellent transparency. It is an object of the present invention to provide an optical molded body formed of a copolycarbonate having excellent mechanical properties and low birefringence, and an optical molded body formed of the copolycarbonate composition.

[0009]

SUMMARY OF THE INVENTION An optical molded article according to the present invention comprises [A] (i) resorcin and / or substituted resorcin, (ii) an aromatic dihydroxy compound other than resorcin and substituted resorcin, and (iii) these aromatic compounds. It is formed from a copolycarbonate obtained by copolymerizing the dihydroxy compounds (i) and (ii) with a compound capable of forming a carbonic acid bond.

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

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

In the above-mentioned [A] copolymerized polycarbonate, among structural units derived from an aromatic dihydroxy compound, (i) a structural unit derived from resorcin and / or a substituted resorcin is preferably 2 to 90. It is contained in an amount of mol%, more preferably in an amount of 2 to 40 mol%.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The optical molded article according to the present invention will be described below. The optical molded article according to the present invention is excellent in transparency and hue and has a small birefringence.

The optical molded article according to the present invention can be used without any particular limitation in shape, application, etc. as long as it is an optical application. Specifically, it is an optical disk for digital data, CD-R.
It is preferably used as an optical disc (optical substrate) such as OM, compact disc, video disc, optical fiber, lens, and lighting equipment.

Such an optical molded article according to the present invention is
[A] is formed from a copolycarbonate. Further, the optical molded article according to the present invention preferably comprises a copolymeric polycarbonate composition comprising a copolymeric polycarbonate [A] and an additive [B].

This [A] copolymerized polycarbonate is
(i) resorcin and / or substituted resorcin, and (ii)
Aromatic dihydroxy compounds other than resorcin and substituted resorcin, and (iii) these aromatic dihydroxy compounds
(i) and (ii) are copolymerized with a compound capable of forming a carbonic acid bond, (i) a unit derived from resorcin and / or substituted resorcin, and (ii) other than resorcin and substituted resorcin And a unit derived from a compound capable of reacting with these aromatic dihydroxy compounds (i) and (ii) to form a carbonic acid bond.

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

[0018]

[Chemical 1]

In the above formula [I], R is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or halogen, which may be the same or different. n is an integer of 0-4.

Specific examples of such (i) resorcin and / or substituted resorcin include resorcin, 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin. ,
3-phenylresorcin, 3-cumylresorcin, 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,
The structural unit derived from such (i) resorcin and / or substituted resorcin is 100 mol% when the structural unit derived from an aromatic dihydroxy compound is 100 mol%.
It is contained in an amount of less than 100 mol%, preferably 2 to 90 mol%, more preferably 2 to 40 mol%.

(Ii) The constitutional unit derived from an aromatic dihydroxy compound other than resorcin and / or substituted resorcin is not particularly limited, and is usually derived from the aromatic dihydroxy compound as described below which forms a polycarbonate. It may be a constituent unit.

[0023]

[Chemical 2]

Wherein R ¹ and R ² are hydrogen atoms or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are halogen or a monovalent hydrocarbon group, and these may be the same or different. p and q represent the integer of 0-4. ) Such (ii) aromatic dihydroxy compounds include, for example, 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 Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
-Dihydroxy aryl ethers such as dimethyl phenyl ether, 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,
4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and other dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-
Examples thereof include dihydroxydiaryl sulfones such as dimethyldiphenyl sulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferable. Further, as the compound which reacts with the aromatic dihydroxy compounds (i) and (ii) as described above and (iii) introduces a carbonic acid bond, specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, Examples thereof include carbonic acid diesters such as m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, and carbonyl halide compounds such as phosgene.

Of these, diphenyl carbonate is particularly preferable. The copolycarbonate [A] 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 above structural units. This constituent unit is polyester polycarbonate.

Examples of such dicarboxylic acid or dicarboxylic acid ester and dicarboxylic acid halide include terephthalic acid, isophthalic acid, sebacic acid, decanedioic acid,
Dodecanedioic acid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, diphenyl decanedioate, diphenyl dodecanedioate, terephthalic acid chloride, isophthalic acid chloride, sebacic acid chloride, decanedioic acid chloride, dodecanedioic acid chloride, etc. be able to.

Such polyester polycarbonate units may be present in the copolymer polycarbonate [A] in an amount of 50 mol% or less, preferably 30 mol% or less.

The copolycarbonate [A] may contain a constitutional 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 3 or more phenolic hydroxyl groups or carboxyl groups is preferable, and a compound having 3 or more phenolic hydroxyl groups is particularly preferably used. 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, 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 constituent unit is usually 3 mol% or less, preferably 0.1 to 2 mol%, when the constituent 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 ˜1 mol%.

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

Furthermore, 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 minutes,
It is preferably 8 to 50 g / 10 minutes.

The optical molded article according to the present invention formed from such a copolycarbonate has excellent mechanical properties, heat resistance, transparency and hue, as well as excellent chemical resistance and fluidity during molding. It also has excellent melt stability.

In particular, the copolymerized polycarbonate forming the optical molded article according to the present invention has an MFR (g / 10 min) as compared with a conventional polycarbonate containing no constitutional unit derived from resorcin and / or substituted resorcin. )
And has excellent moldability such as fluidity and melt stability. Therefore, the optical molded article according to the present invention is excellent in fluidity at the time of molding and can be molded without lowering transparency, hue, or molecular weight. Further, the optical molded body molded in this way has a small birefringence.

The above-mentioned [A] copolycarbonate is prepared by reacting (i) resorcin and / or substituted resorcin, (ii) another aromatic dihydroxy compound, and (iii) these aromatic dihydroxy compounds with carbonic acid. It is produced using a compound capable of forming a bond, but the production method is not particularly limited. Specifically, it is produced by an interfacial method and a solution method using a carbonyl halide such as phosgene as a compound capable of reacting with an aromatic dihydroxy compound to form a carbonic acid bond, a melting method using a carbonic acid diester, and a solid-state polymerization method. It

Of these, the melt polymerization method is preferred in the present invention, and the details thereof will be described below. In the present invention, when the copolymerized polycarbonate is produced by the melt polymerization method, (i) resorcin and / or substituted resorcin,
(ii) Another aromatic dihydroxy compound and (iii) carbonic acid diester are used.

The (i) resorcin and the substituted resorcin used in the present invention are represented by the following general formula [III].

[0040]

[Chemical 3]

In the above formula [III], R is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or a halogen, which may be the same or different. n is an integer of 0-4.

As such substituted resorcin, specifically, the above-mentioned compounds are used. Of these,
Resorcin is preferably used. These may be used alone or in combination.

In the present invention, in producing a copolymerized polycarbonate, such (i) resorcin and / or substituted resorcin are added in an aromatic dihydroxy compound,
It is used in an amount of less than 100%, preferably 2 to 90
It is used in an amount of mol%, more preferably 2-40 mol%.

The aromatic dihydroxy compound other than (ii) resorcin and / or substituted resorcin is preferably 98 to 10 mol%, more preferably 98 to 60 mol% based on 100 mol% of the aromatic dihydroxy compound. Used in quantity.

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

[0046]

[Chemical 4]

R ¹ and R ² are hydrogen atoms or monovalent hydrocarbon groups, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are halogen or a monovalent hydrocarbon group, and these may be the same or different. p and q are integers of 0-4. ) Specific 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
Specific examples of the carbonic acid diester (iii) include the compounds described above.

Of these, diphenyl carbonate is particularly preferably used. In the present invention, (iii) carbonic acid diester is added to
When the amount is 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 the dicarboxylic acid or dicarboxylic acid ester include the compounds described above. In the present invention, when a polycarbonate is produced, the carbonic acid diester as described above is 0.95 to 1.95 per 1 mol of the total amount of the aromatic dihydroxy compound.
It is desirable to use 30 moles, preferably 1.01 to 1.20 moles.

Further, in the present invention, when a polycarbonate is produced, the aromatic dihydroxy compound and the carbonic acid diester as described above are used together with 3 parts in one molecule as described above.
It is also possible to use a polyfunctional compound having one or more functional groups.

When a polyfunctional compound is used, it is usually 0.03 per 1 mol of the total amount of the aromatic dihydroxy compound.
It is used in an amount of not more than 0.001 mol, preferably 0.001 to 0.02 mol, and more preferably 0.001 to 0.01 mol.

In the present invention, the above-mentioned (i) resorcin and / or substituted resorcin, (ii) another aromatic dihydroxy compound and (iii) carbonic acid diester are used in combination with (a) an alkali metal compound and / or an alkaline earth compound. Melt polycondensation is preferably performed in the presence of a catalyst composed of a metal compound.

Specific examples of such alkali metal compounds and alkaline earth metal compounds (a) include organic acid salts and inorganic acid salts of alkali metals and alkaline earth metals,
Preferable examples include oxides, hydroxides, hydrides and alcoholates.

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

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

These compounds may be used alone or in combination.
Can be used. Such alkali metal compounds
And / or the alkaline earth metal compound (a) is an aromatic diamine.
Usually 1 × 10 with respect to 1 mol of the total amount of the hydroxy compound.
^-8~ 1 x 10 ^-3Mol, preferably 1 × 10^-7~ 1 x 10
^-FiveMol, particularly preferably 1 × 10^-7~ 2.5 × 10^-6Mo
Used in the amount of le.

When the amount of the alkali metal compound or the alkaline earth metal compound (a) used is 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol with respect to 1 mol of the total amount of the aromatic dihydroxy compound, the polymerization activity is high. An acidic compound (which will be described later) can be added in an amount that does not adversely affect the properties of the obtained copolycarbonate while being maintained, and the basicity of these compounds can be sufficiently neutralized or weakened,
It is possible to obtain a copolycarbonate having excellent hue, heat resistance, water resistance, and weather resistance, and excellent melt stability for a long time.

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

Examples of the basic compound (b) include nitrogen-containing basic compounds that are easily decomposable or volatile at high temperature, and specifically, the following compounds can be mentioned.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH ) Such as alkyl, aryl,
Ammonium hydroxides having araryl groups, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, R ₂ NH (wherein R is an alkyl group such as methyl or ethyl, an aryl group such as phenyl or toluyl). Etc.)
Secondary amines represented by RNH ₂ (wherein R is the same as above), pyridines such as pyridine, dimethylaminopyridine, 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, especially electronic tetraalkylammonium hydroxides containing 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. In the formula B (OR) _n (OH) _3-n , R is alkyl such as methyl or ethyl, aryl such as phenyl, and n is 1, 2 or 3.

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

The preferred combination used as a catalyst in the present invention includes a combination 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 the amount as described above, and (b) the nitrogen-containing basic compound is 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, relative to 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 used is 1 × 10 ⁻⁶ to 1 × 1 with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferable that the content is 0 ^-1 mol because the transesterification reaction and the polymerization reaction proceed at a sufficient rate and a copolycarbonate excellent in hue, heat resistance and water resistance can be obtained.

Thus, the 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 copolycarbonate 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 composed of 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 composed of such a combination,
The alkali metal compound or alkaline earth metal compound (a) and the nitrogen-containing basic compound (b) 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.
~ 1 x 10 ^-1 mol, preferably 1 x 10 ^-7 to 1 x 10 ^-2
It is used in an amount of 1 mol, more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol.

(C) The amount of boric acid or boric acid ester used is 1 × with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferable that it is 10 ⁻⁸ to 1 × 10 ⁻¹ mol because the molecular weight does not easily decrease after heat aging, and a copolymerized 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, (c)
The catalyst composed of boric acid or boric acid ester is excellent in transparency, heat resistance and water resistance and has an improved color tone, and can produce a high molecular weight copolycarbonate with high polymerization activity.

The polycondensation reaction of (i) resorcin and / or substituted resorcin with (ii) another aromatic dihydroxy compound and (iii) carbonic acid diester using such a catalyst is
It can be carried out under the same conditions as the conventionally known polycondensation reaction conditions of an aromatic dihydroxy compound and a carbonic acid diester.

Specifically, it is 80 to 250 ° C, preferably 100 to 230 ° C, more preferably 120 to 190 ° C.
At the temperature of 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours, under normal pressure, the aromatic dihydroxy compound and the carbonic acid diester are reacted. Then, the reaction temperature is raised while reducing the pressure of the reaction system to carry out the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally, under a reduced pressure of 5 mmHg or less, preferably 1 mmHg or less.
A polycondensation reaction of an aromatic dihydroxy compound and a carbonic acid diester is carried out at a temperature of 320 ° C.

The polycondensation reaction as described above may be carried out continuously or batchwise. Further, the reaction apparatus used for carrying out the above reaction may be a tank type, a tube type or a column type.

The copolycarbonate 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 from the viewpoint of environmental hygiene since toxic substances such as phosgene and methylene chloride are not used in the melt polycondensation of the copolymerized polycarbonate.

According to this melt polymerization method, in the copolymerized polycarbonate obtained, 100 units of the structural unit derived from the aromatic dihydroxy compound contains 90 units of the structural unit derived from (i) resorcin and / or substituted resorcin. Other methods, using (i) resorcin and / or substituted resorcin in an amount such that it exceeds mol%,
For example, a copolycarbonate excellent in hue, water resistance and heat resistance can be obtained as compared with the interfacial polymerization method and the like.

The optical molded article according to the present invention is preferably formed from a copolymeric polycarbonate composition containing the above [A] copolymeric polycarbonate and an additive [B].

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

These may be used alone or in combination of two or more. Specific examples of such (a) sulfur-containing acidic compound having a pKa value of 3 or less and derivatives formed from the acidic compound include 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,
Examples thereof include diphenyl sulfite. Examples of the sulfuric acid derivative include dimethyl sulfuric acid, diethyl sulfuric acid, dipropyl sulfuric acid, dibutyl sulfuric acid and diphenyl sulfuric acid.

Examples of sulfinic acid compounds include benzenesulfinic acid, toluenesulfinic acid and naphthalene sulphinic acid. Examples of the sulfonic acid compounds and their derivatives include compounds represented by the following general formula [V] and ammonium salts thereof.

[0083]

[Chemical 5]

In the formula, R ⁷ is a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with halogen), and R 7
⁸ is hydrogen or a hydrocarbon group having 1 to 50 carbon atoms (hydrogen may be substituted with 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 benzene sulfonic acid and p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, and benzene. Sulfonic acid 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 such as ammonium toluene sulfonate and the like can be mentioned.

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

In the present invention, (a) the sulfur-containing acidic compound and the derivative formed from the acidic compound are preferably the sulfonic acid compounds represented by the above general formula [V] and their derivatives. Furthermore, in the above general formula [V],
R ⁷ and R ⁸ are substituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms,
A compound in which n is an integer of 0 to 1 is preferably used, and specifically, benzenesulfonic acid, butyl benzenesulfonate, p-toluenesulfonic acid, ethyl p-toluenesulfonate, and p-toluenesulfonate are preferable. .

Of these, butyl p-toluenesulfonate is preferable. In the present invention, the above (a) p
A sulfur-containing acidic compound having a Ka value of 3 or less and / or a derivative formed from the acidic compound can be prepared according to the above [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
Add in the amount of m.

Examples of the (b) phosphorus compound include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphorous acid ester. Specific examples of such a phosphoric acid ester include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl). Trialkyl phosphates such as phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl phosphate, triphenyl phosphate,
Tricresyl phosphate, tris (nonylphenyl)
Triaryl phosphates such as phosphates and 2-ethylphenyldiphenyl phosphate can be mentioned.

Further, examples of the phosphite include compounds represented by the following general formula. P (OR) ₃ (In the formula, R represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. These 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-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite, triarylphosphite such as tris (hydroxyphenyl) phosphite, phenyldidecylphosphite, diphenyldecylphosphite,
Examples thereof include arylalkyl phosphites such as diphenylisooctylphosphite, phenylisooctylphosphite, and 2-ethylhexyldiphenylphosphite.

Further, as phosphite, distearyl pentaerythrityl diphosphite, bis (2,4-diester
-t-butylphenyl) pentaerythrityl diphosphite and the like.

Of these, (b) phosphorus compounds are preferably phosphites represented by the above general formula, more preferably aromatic phosphites, especially tris (2,
4-di-t-butylphenyl) phosphite is preferred.

In the present invention, the (B) phosphorus compound as described above is usually added to the [A] copolymerized polycarbonate in an amount of 1: 1.
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-butylphenyl glycidyl 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'-
Methylsirohexyl carboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, bis-epoxydicyclopentadienyl ether,
Bis-epoxy ethylene glycol, bis-epoxy cyclohexyl adipate, butadiene diepoxide, tetraphenyl ethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-
Epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-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-epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy- Examples thereof include cis-1,2-cyclohexyl dicarboxylate.

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

In the present invention, such an epoxy compound (c) is added to the above [A] copolycarbonate.
Usually in an amount of 1 to 2000 ppm, preferably 10 to 100
It is preferably added in an amount of 0 ppm.

Specific examples of the (d) phenolic stabilizer include 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) benzyl malonate, 4-hydroxymethyl-2,6-di-t-butylphenol, etc. Can be mentioned.

In the present invention, the above-mentioned (d) phenolic stabilizer is usually 10 to 1000 ppm, preferably 50 to 500 ppm based on the copolymer polycarbonate [A].
Used in ppm amounts.

As the release agent (e), a general release agent is used without particular limitation. Specifically, for example, hydrocarbon-based release agents such as natural and synthetic paraffins, polyethylene waxes and fluorocarbons, higher fatty acids such as stearic acid and hydroxystearic acid, fatty acid-based release agents such as oxyfatty acids, stearin. Acid amide,
Fatty acid amides such as ethylene bis stearamide, fatty acid amide type release agents such as alkylene bis fatty acid amides, aliphatic alcohols such as stearyl alcohol and cetyl alcohol, alcohol type release agents such as polyhydric alcohols, polyglycols and polyglycerols Molding agent, butyl stearate, fatty acid lower alcohol ester such as pentaerythritol tetrastearate, fatty acid polyhydric alcohol ester, fatty acid ester type release agent such as fatty acid polyglycol ester, silicone type release agent such as silicone oil Agents and the like.

In the present invention, the above-mentioned (e) release agent is usually 0.001 to 5 parts by weight, preferably 0.005 parts, relative to 100 parts by weight of the [A] copolymerized polycarbonate.
It can be used in an amount of 1 to 1 part by weight, more preferably 0.01 to 0.5 part by weight.

Examples of (f) boron compounds include (c) boric acid compounds as described above, and specific examples thereof include boric acid, trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, Triheptyl borate,
Examples thereof include triphenyl borate, tritolyl borate, and trinaphthyl borate.

Of these, triphenyl borate is preferred. In the copolymeric polycarbonate composition according to the present invention, the above (f) boron-based compound is used in an amount of 0.0000 per 100 parts by weight of the [A] copolymerized polycarbonate.
1 to 0.2 parts by weight, preferably 0.00005 to 0.02
It is preferably used in an amount of parts by weight.

Such a (f) boron-based compound can be used by previously adding it as one component (c) of the catalyst at the time of polymerization as described above. If a necessary amount is added at the time of polymerization, the polymerization can be performed. There is no particular need to add it later.

Such a copolycarbonate composition can be produced by kneading the respective components by a conventionally known method. For example, a method in which each component is dispersed and mixed by a high speed mixer typified 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.

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

The order of adding the additives (a), (b), (c), (d), (e), and (f) to the copolymeric polycarbonate [A] is not limited. The copolymerized polycarbonate composition obtained as described above is obtained because the above-mentioned [B] additive is added and kneaded while the copolymerized polycarbonate [A] which is a reaction product is in a molten state. The heat history of the resin composition can be reduced, and a copolycarbonate 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 the phosphorus compound, (d) phenolic stabilizer or (f) boron compound in the above amount, the alkaline catalyst remaining in the copolymerized polycarbonate [A] obtained by the polymerization reaction is moderate. Even if the (a) and (b) compounds are excessively left after being activated or weakened, they react with the (c) epoxy compound and are neutralized, further improving the retention stability during melting. The obtained copolycarbonate composition is obtained.

Such a copolycarbonate composition has improved thermal stability when melted as described above, even when pellets of the composition are remelted at the time of molding into an optical molding. Therefore, thermal decomposition is particularly suppressed, the molecular weight is less likely to decrease, and coloring is less likely to occur.

The optical molded article according to the present invention is molded from the above copolymeric 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 ordinary heat stabilizers other than the following [B] additives as long as the object of the present invention is not impaired. , UV absorbers, colorants, antistatic agents, slip agents, antiblocking agents, lubricants, antifog agents, natural oils, synthetic oils, waxes, and the like.

Such other additives may be added to the molten [A] together with the above [B], or the copolycarbonate composition once pelletized may be remelted and added. You can also The former method is preferred in the present invention.

Specific examples of such heat-resistant stabilizers include organic thioether-based stabilizers and hindered amine-based stabilizers. Examples of thioether-based stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-
Examples thereof include thiodipropionate and pentaerythritol-tetrakis- (β-lauryl-thiopropionate).

As the hindered amine stabilizer,
For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- ( 3,5-di-t-butyl-
4-Hydroxyphenyl) propionyloxy} ethyl]
-4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9- Tetramethyl-3-octyl-1,
2,3-Triazaspiro [4,5] undecane-2,4-dione, 4-
Benzoyloxy-2,2,6,6-tetramethylpiperidine, 2
-(3,5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,2 6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate and the like.

These may be used alone or in combination 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, and more preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the copolycarbonate. Used in quantity as needed.

Such a heat resistance stabilizer may be added in a solid form or a liquid form. Further, as the ultraviolet absorber, a general ultraviolet absorber is used without particular limitation, but salicylic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, etc. Used.

Examples of salicylic acid type ultraviolet absorbers include phenyl salicylate and pt-butylphenyl salicylate. Benzophenone-based UV 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 can be mentioned.

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

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

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

The colorant may be a pigment, a dye, an inorganic type or an organic type. Also, 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, molybdenum red. Chromates such as barium sulfate, carbonates such as calcium carbonate, carbonates such as calcium carbonate, silicates such as ultramarine blue, phosphates such as manganese violet, carbon such as carbon black, and metal powders such as bronze powder and aluminum powder. Examples include colorants.

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

The coloring agent is based on 100 parts by weight of [A].
Usually 1 × 10 ^{-6 to} 5 parts by weight, preferably 1 × 10 ^{-5 to} 3
It is optionally used 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 comprises a compacted disc, an optical disc, an optical fiber, a headlamp, the above-mentioned compacted disc, an optical disc, an optical fiber, a headlamp, and the like. Molded according to applications such as automotive lenses such as tail lamps, eyeglasses, cameras, and plastic lenses such as telescopes.

[0123]

The optical molded article according to the present invention formed from the above-mentioned copolymeric polycarbonate or the copolymerized polycarbonate composition is compared with the optical molded article formed from the usual bisphenol homopolycarbonate. In particular, it has excellent fluidity and melt stability during molding,
Pyrolysis is less likely to occur during molding, the molecular weight is less likely to decrease and yellowing is less likely to occur, and the hue stability is excellent and molding is performed with an excellent molding cycle.

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

[0125]

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

[Polycarbonate composition ratio] ¹ H-N
The ratio of the aromatic dihydroxy compound constitutional unit in the resin was measured by MR.

[Intrinsic viscosity [IV]] 2 in methylene chloride
It measured at 0 degreeC using the Ubbelohde viscometer. [Melt flow rate (MFR; g / 10 minutes)] JISK
According to -7210, the temperature was 250 ° C. and the load was 1.2 kg.

[Yellowness (YI)] A 3 mm thick injection-molded plate was used at a cylinder temperature of 290 ° C. and an injection pressure of 1000 kg / cm.
² , molding for 1 cycle 45 seconds, mold temperature 100 ℃,
X, Y, Z values are Color and Color manufactured by Nippon Denshoku Industries Co., Ltd.
The yellowness index (YI) was measured by a transmission method using a Defference Meter ND-1001 DP.

YI = 100 (1.277 X-1.060Z) / Y [Light transmittance] According to the method of ASTM D 1003,
It measured using the injection molding board for hue measurement.

[Haze] NDH- from Nippon Denshoku Industries Co., Ltd.
200 was used to measure the haze of the injection-molded plate for hue measurement.

[Stability of Residence] After resin was retained in a cylinder of an injection molding machine at a temperature of 320 ° C. for 15 minutes, injection molding was performed at that temperature. YI, MFR of this molded plate,
The light transmittance was measured.

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

[Moldability] Using a stamper made of nickel, a 5 inch disc was continuously shot for 100 shots at a mold temperature of 90 ° C. for 1 cycle of 5 seconds, with no fog or recording error and at a level of passing as a product. The cylinder temperature at which injection molding was possible was investigated.

[Izod impact strength] ASTM D25
According to 6, the measurement was performed using an injection test piece of 63.5 × 12.7 × 2 mm (rear notch). The number of broken pieces out of 10 test pieces was also counted.

[0135]

Example 1 0.33 kmole of bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) and resorcin (manufactured by Mitsui Petrochemical Industry Co., Ltd.) which had been purified by distillation.
11 kmole and 0.46 kmole of diphenyl carbonate (manufactured by Any Co.) were charged into a first 250 liter tank-type stirring tank, dissolved at 140 ° C., and bisphenol A was 0.12 kmole / hour so as to maintain this level. Resorcinol was fed 0.04 kilomol / hr and diphenyl carbonate was fed 0.16 kilomol / hr, and this mixed solution was fed with 0.16 hr / hr of an aromatic dihydroxy compound.
Liquid is fed to the second 50-liter tank-type stirring tank in kilomoles. The temperature of this tank type stirring tank is maintained at 180 ° C.

Tetramethylammonium hydroxide was added as a catalyst in an amount of 0.04 mol / hr and sodium hydroxide was added in an amount of 0.00016 mol / hr (1 × 10 ⁻⁶ mol / mol-aromatic dihydroxy compound), and the residence time was 30 minutes. Adjust the level so that

Next, 0.16 kilomoles of this reaction solution per hour in terms of an aromatic dihydroxy compound are sent to the following 50-liter tank-type stirring tank at a third temperature of 210 ° C. and a pressure of 200 mmHg. The level is adjusted so that the residence time is 30 minutes, and stirring is performed while distilling and removing phenol.

Next, 0.16 kilomoles of this reaction solution per hour in terms of an aromatic dihydroxy compound are fed to the following 50-liter tank-type stirring tank at a fourth temperature of 240 ° C. and a pressure of 15 mmHg. The level is adjusted so that the residence time is 30 minutes, and stirring is performed while distilling and removing phenol.

Next, the pressure of this reaction product was increased by a gear pump, and 0.16 kilomoles per hour of the aromatic dihydroxy compound was fed into the 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. Gear pump from the bottom of the evaporator to 280 ℃,
In a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotating diameter 220 mm, internal volume 80 liters) controlled at 0.2 mmHg, an hourly amount of 0.1 was calculated as an aromatic dihydroxy compound.
6 kmoles (approx. 40 kg / hour) fed in, residence time 3
It was polymerized at 0 minutes.

Next, in a molten state, this polymer was mixed with a gear pump in a twin-screw extruder (L / D = 17.5, barrel temperature 280 ° C.) at an hourly rate of 0.16 kmole (about 40 kg / hour), 0.0322 mol of butyl p-toluenesulfonate per hour (2 times the molar amount of sodium hydroxide used as a catalyst) is continuously kneaded, formed into a strand through a die, and cut with a cutter. And made into pellets.

The results are shown in Table 1.

[0142]

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

The results are shown in Table 1.

[0144]

EXAMPLE 3 In Example 1, tetramethylammonium hydroxide was used as a catalyst in an amount of 0.04 mol / h and sodium hydroxide was in an amount of 0.00016 mol / h (1 × 10 6).
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 when ( ^-6 mol / mol-aromatic dihydroxy compound) was added. The results are shown in Table 1.

[0145]

[Example 4] In Example 3, the polymerized polymer was kept in a molten state and a twin-screw extruder (L / D =
0.15 kmole (about 40 kg / hour) in terms of bisphenol A per hour at 17.5 and barrel temperature of 285 ° C., and butyl p-toluenesulfonate is added at 0.00032 per hour.
Mol (twice the amount of sodium hydroxide used as the catalyst), and at the same time, tris (2,4-di-t-butylphenyl) phosphite (Mark 2112: ADEKA ARGUS CORPORATION) was added to the copolycarbonate. Made) 300ppm,
3,4-Epoxycyclohexylmethyl-3, '4'-epoxycyclohexylcarboxylate (Celoxide 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-based mold release agent: ethyl-Petroleum-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 CORPORATION) was continuously kneaded. A pellet was obtained by the method.

The results are shown in Table 1.

[0149]

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

The results are shown in Table 1.

[0151]

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

The results are shown in Table 1.

[0153]

Comparative Examples 2 to 4 In Example 5, resorcin was not used, only 0.44 kmole 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. Pellets were obtained in the same manner as in Example 5 except for the above.

The results are shown in Table 1.

[0155]

Examples 7 and 8 In Examples 4 and 6, a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotating diameter 220 mm, controlled at 285 ° C. and 0.2 mmHg by a gear pump from the bottom of the evaporator, Same as Examples 4 and 6 as shown in Table 1 except that 0.16 kmole (about 40 kg / hour) in terms of aromatic dihydroxy compound was fed into the inner volume of 80 liters per hour and polymerization was carried out for a residence time of 30 minutes. The pellet was obtained by the method of.

The results are shown in Table 1.

[0157]

Comparative Example 5 In Example 7, resorcin was not used,
Bisphenol A (Japan GE Plastics Co., Ltd.)
Pellets were obtained in the same manner as in Example 7 except that only 0.44 kmole was used and the compounds shown in Table 1 were used in the amounts shown in Table 1.

The results are shown in Table 1.

[0159]

[Table 1]

[0160]

[Table 2]

[0161]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08K 5/55 KKM 7242-4J C08L 69/00 LPU 9363-4J G11B 7/24 526 G 7215-5D R 7215-5D

Claims (7)

[Claims] 1. (i) resorcin and / or substituted resorcin, (ii) aromatic dihydroxy compound other than resorcin and substituted resorcin, (iii) these aromatic dihydroxy compounds (i) and (ii)
An optical molded article, which is formed from a copolycarbonate obtained by copolymerizing a compound capable of reacting with and forming a carbonic acid bond. 2. The copolymerized polycarbonate comprises (i) among structural units derived from an aromatic dihydroxy compound.
The optical molded article according to claim 1, which contains a structural unit derived from resorcin and / or a substituted resorcin in an amount of 2 to 90 mol%. 3. The structural unit derived from an aromatic dihydroxy compound, wherein the copolycarbonate comprises (i)
The optical molded product according to claim 1, which contains a structural unit derived from resorcin and / or a substituted resorcin in an amount of 2 to 40 mol%. 4. [A] (i) resorcin and / or substituted resorcin, (ii) aromatic dihydroxy compound other than resorcin and substituted resorcin, (iii) these aromatic dihydroxy compounds (i) and (ii) A molded article for optics, which is formed from a copolymerized polycarbonate composition comprising a copolymerized polycarbonate obtained by copolymerizing a compound capable of reacting to form a carbonic acid bond and an additive [B]. 5. The amount of the structural unit derived from an aromatic dihydroxy compound in the copolymer polycarbonate [A] is 2 to 90 mol% of the structural unit derived from (i) resorcin and / or substituted resorcin. 5. The optical molded product according to claim 4, wherein the optical molded product is contained. 6. The copolymerized polycarbonate [A], wherein the structural unit derived from an aromatic dihydroxy compound is (i) a structural unit derived from resorcin and / or a substituted resorcin in an amount of 2 to 40 mol%. 5. The optical molded product according to claim 4, wherein the optical molded product is contained. 7. The additive [B] is (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 molded product according to claim 4, which is selected from the group consisting of (d) a phenolic stabilizer, (e) a release agent, and (f) a boron compound.