JP2000226505A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition excellent in polymer color and hydrolytic resistance, and also excellent in thermal stability and moldability by including a specific polycarbonate, a sulfonic acid compound and a partial ester of a fatty carboxylic acid and a polyhydric alcohol. SOLUTION: This composition comprises (A) 100 pts.wt. polycarbonate obtained by reacting (i) an aromatic dihydroxy compound with (ii) 1.005-1.1 mol carbonic diester based on 1 mol component (i) in the presence of 10-6 mol alkali metal or alkaline earth metal, and having 1-30 mol% terminal hydroxy group content, and 2.0-2.6 molecular weight distribution measured by a GPC, (B) 0.00001-0.01 pts.wt. sulfonic acid compound of the formula A1SOX1 [A1 is a (substituted) 1-20C hydrocarbon; X1 is an ammonium cation or a sulfonium cation], and (C) 0.005-0.1 pts.wt. partial ester of an aliphatic carboxylic acid and a polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate composition, and more particularly, to a polycarbonate composition suitable for producing optical molded articles such as optical discs and lenses. More specifically, the present invention relates to a polycarbonate composition which is excellent in polymer hue and hydrolysis resistance, and is also excellent in moldability such as a decrease in molecular weight at the time of molding, retention of hue and the like, and releasability and transferability.

[0002]

2. Description of the Related Art Polycarbonate has excellent mechanical properties such as impact resistance, and also has excellent heat resistance and transparency, and is widely used in various applications including optical parts, various mechanical parts, and automobile parts. Used.

[0003] Polycarbonate is conventionally bisphenol A
A method of directly polymerizing an aromatic dihydroxy compound such as phosgene with an organic solvent such as methylene chloride (interfacial method) or a method of transesterifying an aromatic dihydroxy compound with a carbonic acid diester (melt polycondensation method). Being manufactured.

[0004] Among them, the latter has the advantage that polycarbonate can be produced at a lower cost than the former interface method and does not use toxic substances such as phosgene.

In a conventional method for producing polycarbonate by a melt polycondensation method, an alkali metal compound, an alkaline earth metal compound or the like is usually used as a catalyst component. However, the polycarbonate resin obtained by using such a catalyst lacks thermal stability due to the remaining catalyst, and a part thereof may be decomposed at the time of melting to reduce the molecular weight or to be colored.

A method for solving this problem is disclosed in Japanese Patent Laid-Open No. 5-92.
No. 85 discloses that an aromatic dihydroxy compound and a carbonic acid diester are used to give the obtained polycarbonate the following formula (2)

[0007]

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(Where A ⁷ is a C ₁ -C ₆ hydrocarbon group optionally substituted with halogen, and A ⁸ is a C ₁ -C ₈ hydrocarbon group optionally substituted with hydrogen atom or halogen. A hydrogen group, and n is an integer of 0 to 3). A method for producing a polycarbonate by adding a sulfonic acid compound represented by the formula (1) in an amount of 0.05 to 10 ppm is disclosed.

British Patent 808,488 or British Patent 808,489 disclose a method for producing a polycarbonate by adding an acidic compound such as dimethyl sulfate or dibutyl sulfate.

However, in this method, an excess amount of the acidic compound is added to the remaining catalyst, specifically, twice or more moles. Therefore, the remaining catalyst is deactivated and stabilized. Remain in the obtained polycarbonate, resulting in a problem that the resulting polycarbonate has reduced wet heat resistance and corrodes an aluminum film deposited on an optical disc molded product.

In recent years, the demand for polycarbonate as an optical molded product has been remarkable, and for example, polycarbonate has been widely used for optical discs, information discs, optical lenses, prisms and the like. Accordingly, demands for thermal stability, releasability, transferability, and the like have been increasing more than ever.

Particularly, in the production of optical disk molded products such as compact disks and laser disks, efficient continuous production is required. When the molded product is released from the mold, if the release resistance is large, the molded product may warp and cause optical distortion. Therefore, the polycarbonate used must have excellent release properties. In order to improve the releasability, it is necessary to use a release agent. However, depending on the amount of the agent and the amount of the release agent, there is a problem that the hue at the time of molding is lowered, and the transparency of the obtained molded product is lowered. there were.

At the same time, it is required to precisely transfer the fine irregularities of the stamper, particularly in the optical disk molded product, and this requirement becomes more severe especially in the digital video disk (DVD).

It is needless to say that the releasability is also important for advanced transfer, and at the same time it is greatly affected by the fluidity of the resin. For this reason, molding tends to be performed at a molding temperature higher than before, so that the thermal stability of the resin is also required.

For this reason, usually, the polycarbonate formed into pellets or the like after production is re-melted, and a heat stabilizer is added to improve the thermal stability. However, in this method, the heat treatment is performed on the polycarbonate in a state where the heat stability is low, and the number of heat histories received by the polycarbonate is increased.

Further, the addition of the above-mentioned heat stabilizer may reduce the hydrolysis resistance of the polycarbonate, and the molded product obtained from such a polycarbonate may have reduced transparency during use.

For the above reasons, a polycarbonate composition which is excellent in polymer hue and hydrolysis resistance, and also excellent in moldability such as reduction in molecular weight during molding, heat stability such as hue retention and mold release properties and transferability. The emergence of a manufacturing method is desired.

[0018]

The present invention relates to a method for producing a polycarbonate composition, and more particularly to a polycarbonate composition suitable for producing optical molded articles such as optical discs and lenses. . More specifically, it has been found that the polycarbonate composition is excellent in polymer hue and hydrolysis resistance, and also excellent in moldability such as reduction in molecular weight during molding, heat stability such as hue retention, and releasability and transferability. The present invention has been completed.

[0019]

Means for Solving the Problems The present invention is [A] an aromatic dihydroxy compound and aromatic dihydroxy compound 1 1.005 to 1.1 mole of the carbonic acid diester moles, 10 ^-6 to 10 ^{- The} concentration of terminal hydroxyl groups obtained by reacting in the presence of an alkali metal or alkaline earth metal compound in an amount of ⁸ mol is 1 to 30 mol%,
And 100 parts by weight of a polycarbonate having a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.0 to 2.6 as measured by GPC, and [B] the following formula (1):

[0020]

A ¹ -SO ₃ X ¹ (1) (where A ¹ has 1 to 2 carbon atoms which may have a substituent)
0 is a hydrocarbon group, and X ¹ is an ammonium cation or a phosphonium cation. A) a polycarbonate-based resin composition comprising 0.00001 to 0.01 parts by weight of a sulfonic acid compound represented by the following formula: and [C] 0.005 to 0.1 parts by weight of a partial ester of an aliphatic carboxylic acid and a polyhydric alcohol. It is.

Here, the melt polycondensation product is defined as 1.0 to 1.1 mol of carbonic acid diester per 1 mol of aromatic dihydroxy compound and 10 ^-6 to 10 ^-8 mol of alkali metal or alkaline earth. All polycarbonates obtained by reacting in the presence of a metal compound are included.

The aromatic dihydroxy compound used in the present invention is not particularly limited, and various known compounds can be used. The aromatic dihydroxy compound is represented by, for example, the following formula (3)

[0023]

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A compound represented by the above formula (3)
Wherein R ¹ and R ² are the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group and a C6 to 12 carbon atom such as a phenyl group.
Are preferred. Examples of the halogen atom include chlorine, bromine and iodine.

R ⁵ is an alkylene group having 3 to 8 carbon atoms. Examples of the alkylene group include a pentylene group. In the formula, R ³ and R ⁴ are the same or different and are a halogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group and an aromatic hydrocarbon group having 6 to 12 carbon atoms such as a phenyl group.
Examples of the halogen atom include chlorine, bromine and iodine. In the formula, m and n are the same or different and represent 0 or an integer of 1 to 4.

Specifically, bis (4-hydroxydiphenyl) methane, 2,2-bis (4-hydrodiphenyl)
Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-
3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxydiphenyl) oxide, bis (3,5-dichloro-4-hydrodiphenyl) oxide , P, p'-dihydroxydiphenyl, 3,3'-
Dichloro-4,4'-dihydroxydiphenyl, bis (hydroxyphenyl) sulfone, resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, bis (4-hydroxy Phenyl) sulfide, bis (4-hydroxydiphenyl) sulfoxide, spiroglycol and the like.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. These aromatic dihydroxy compounds may be used alone,
Also, two or more kinds may be used in combination.

The carbonic diester used in the present invention is not particularly limited, and various known diesters can be used.

Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like are used. Can be
Of these, diphenyl carbonate is particularly preferably used. These carbonate diesters may be used alone or in combination of two or more.

In the production of the polycarbonate in the present invention, the carbonic acid diester is used in an amount of 1.005 to 1.1 mol, preferably 1.01 to 1.09 mol, more preferably 1 to 1 mol per mol of the aromatic dihydroxy compound. .01-
Preferably, it is used in an amount of 1.08 mole.

If the amount is out of the above range, the hue of the obtained polycarbonate is lowered, and it takes an extremely long time to obtain a desired polycarbonate, which is not preferable.

The alkali metal or alkaline earth metal compound used in the present invention is not particularly limited as long as it does not lower the hue of the obtained polycarbonate, and various known compounds can be used.

For example, alkali metal hydroxides, bicarbonates, carbonates, acetates, nitrates, nitrites, sulfites,
Examples include cyanate, thiocyanate, stearate, borohydride, benzoate, hydrogen phosphate, bisphenol, and phenol salts.

Specific examples 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 nitrate, potassium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate , Lithium cyanate, sodium thiocyanate,
Potassium thiocyanate, lithium thiocyanate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, potassium borohydride, lithium borohydride, sodium phenylated borate, sodium benzoate, potassium benzoate, benzoate Examples thereof include lithium acid, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, and lithium salt of phenol.

The above alkali metal or alkaline earth metal compound is used in an amount of 10 per mole of the aromatic dihydroxy compound.
^It is preferably used in an amount of from ^-6 to 10 ^-8 mol, preferably from 10 ^{-6 to} 5 x 10 ^-7 mol.

When the amount of the alkali metal or alkaline earth metal compound is within the above range, the polycondensation reaction activity of the aromatic dihydroxy compound and the carbonic acid diester can be maintained, and the quality of the obtained polycarbonate such as hue is adversely affected. Don't wake up. When the amount of the alkali metal or alkaline earth metal compound used as the catalyst is within the above range, the activity of these compounds can be reduced or deactivated by the sulfonic acid compound, and the hue, heat resistance, and heat resistance can be reduced. A polycarbonate having excellent quality such as hydrolyzability can be obtained.

If the amount of the alkali metal or alkaline earth metal compound is out of the above range, the quality of the polycarbonate obtained tends to decrease.

In the present invention, other basic compounds can be used as a catalyst together with the above alkali metal or alkaline earth metal compound, if desired.

As the above-mentioned basic compound, for example, those which are easily decomposed or volatile at a high temperature are preferably used.

Specific examples of the nitrogen-containing compound include tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), and tetrabutylammonium hydroxide (Bu ₄ NOH).
H), ammonium hydroxides having alkyl, aryl, alkylaryl groups and the like such as benzyltrimethylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH) and hexadecyltrimethylammonium hydroxide, triethylamine, tributylamine,
Tertiary amines such as dimethylbenzylamine and hexadecyldimethylamine, or tetramethylasimonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Me ₄ N
BPh _4), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh _4), and the like.

The sulfonic acid compound [B] used in the present invention has the following formula (1)

[0042]

A ¹ —SO ₃ X ¹ (1) (where A ¹ has 1 to 2 carbon atoms which may have a substituent)
0 is a hydrocarbon group, and X ¹ is an ammonium cation or a phosphonium cation. ), The activity of the alkali metal or alkaline earth metal compound can be reduced or deactivated, and a polycarbonate having excellent quality such as hue, heat resistance and hydrolysis resistance can be obtained. Among them, the sulfonic acid compound is represented by the following formula (1) -1

[0043]

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(Where A ² , A ³ , A ⁴ , A ⁵ , and A ⁶
Are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. ) Is preferred.

Specifically, tetramethylphosphonium hexylsulfonate, tetrabutylphosphonium hexylsulfonate, tetraoctylphosphonium hexylsulfonate, tetramethylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylsulfonate, dodecylsulfonate Acid tetraoctylphosphonium salt, benzenesulfonic acid tetramethylphosphonium salt,
Tetrabutylphosphonium benzenesulfonate, tetraoctylphosphonium benzenesulfonate, tetramethylphosphonium toluenesulfonate, tetrabutylphosphonium toluenesulfonate, tetraoctylphosphonium toluenesulfonate, tetramethylphosphonium dodecylbenzenesulfonate, dodecyl Examples include tetrabutylphosphonium benzenesulfonate and tetraoctylphosphonium dodecylbenzenesulfonate.

The amount of the sulfonic acid compound used is as follows:
Any amount may be sufficient to reduce or deactivate the activity of the alkali metal or alkaline earth metal compound used, specifically 0.00001 to 0.01 parts by weight per 100 parts by weight of the polycarbonate resin, Preferably 0.
Preferably, it is used in the range of 0005 to 0.005 parts by weight.

The above sulfonic acid compound is usually added in an excess molar amount to the alkali metal or alkaline earth metal compound in order to reduce or deactivate the activity of the alkali metal or alkaline earth metal compound. However, since the sulfonic acid compound itself is neutral or weakly acidic, the activity of the catalyst can be reduced or deactivated without lowering the quality of the obtained polycarbonate.

The partial ester of the aliphatic carboxylic acid and the polyhydric alcohol used in the present invention is 0.005 to 0.1 part by weight, preferably 0.007 to 0.08 part by weight, more preferably 0.01 to 0.01 part by weight. It can be used at ~ 0.01 parts by weight. If the ratio is outside the above range, the resulting polycarbonate resin composition has disadvantages such as a decrease in heat resistance, or a problem that sufficient mold releasability and high-grade micron-order transfer cannot be obtained.

The partial ester of an aliphatic carboxylic acid and a polyhydric alcohol is one in which at least one hydroxyl group of the polyhydric alcohol has not been reacted, and is a monoglyceride and / or a saturated monovalent fatty acid having 12 to 24 carbon atoms. Diglycerides are preferred.

The aliphatic carboxylic acid is not particularly limited, and both saturated and unsaturated aliphatic carboxylic acids can be used. The aliphatic carboxylic acid is preferably a saturated monovalent fatty acid, and particularly preferably one having 12 to 24 carbon atoms. If the number of carbon atoms is less than the above range, the produced polycarbonate-based resin composition is inferior to those in the above range, and gas is generated, which is not preferable. On the other hand, if the number of carbon atoms is larger than the above range, the releasability of the polycarbonate resin composition is inferior to those in the above range, which is not preferable. As the aliphatic carboxylic acid, specifically,
Dodecylic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachiic acid, behenic acid, lignoceric acid and the like can be mentioned.

The polyhydric alcohol is not particularly limited, and any of divalent, trivalent, tetravalent, pentavalent and hexavalent can be used. Examples thereof include ethylene glycol, glycerin, trimethylolpropane and pentaerythritol. Preferably, glycerin is particularly preferred.

The partial ester of the aliphatic carboxylic acid and the polyhydric alcohol used in the present invention can be obtained by a conventional esterification reaction.

When the above-mentioned release agent is added, the agent has an effect on various substances remaining in the polymer, for example, a residual catalyst or a catalyst deactivator. By selecting the combination of catalyst deactivator and release agent, the adverse effects of each other are minimized, and the thermal stability such as molecular weight reduction and hue retention during molding and moldability such as mold release and transferability are minimized. Thus, it is possible to provide an excellent polycarbonate composition. Further, in the present invention, the charge ratio of a specific raw material, manufactured using a specific amount of a specific catalyst,
Provided is a polycarbonate composition having a specific terminal hydroxyl group concentration and a specific molecular weight, which is excellent in moldability such as reduction in molecular weight during molding, heat stability such as hue retention, and mold release properties and transfer properties. be able to.

In the present invention, other additives which are commonly used in the polycarbonate obtained, as long as the object of the present invention is not impaired,
For example, processing stabilizers, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, metal deactivators, metal soaps, nucleating agents, antistatic agents, lubricants, flame retardants, mold release agents, fungicides Agents, coloring agents, anti-fogging agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like may be added.

Specific examples of these additives include the following. Here, as a processing stabilizer,
For example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylb-gendyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5
-Di-t-pentylphenyl) ethyl] -4,6-di-
t-pentylphenyl acrylate and the like.

Examples of the phosphorus-based antioxidant and the sulfur-based antioxidant include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and bis (2,4). -Di-t-butylphenyl)
Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetrakis (2,
4-di-t-butylphenyl) 4,4′-biphenylenediphosphite, 2,2′-ethylidenebis (4,6-
Di-t-butylphenyl) fluorophosphite, 2,
2'-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, dilauryl 3,3'-thiodipropionate, disunaaryl 3,3'-thiodipropionate, tetrakis (3-laurylthiopropionyloxy Methyl) methane and the like.

As the light stabilizer, for example, 2- (3-t-
Butyl-2-hydroxy-5-methylphenyl) -5
Chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole,
2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 2- (3,5-di-t-
Pentyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) phenyl] benzotriazole, 2- [2-hydroxy-3,5-bis ( α,
benzotriazole-based compounds such as [alpha] -dimethylbenzyl) phenyl] benzotriazole, benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxybenfozophenone, and 2,4-di-t Hydroxybenzophenone-based compounds such as -butylphenyl and 3,5-di-t-butyl-4-hydroxybenzoate; ethyl-2-cyano-
UV absorbers such as cyanoacrylate compounds such as 3,3-diphenylacrylate, nickel dibutyldithiocarbamate, nickel such as [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel Quencher and the like.

Examples of the metal deactivator include N, N '
-[3- (3,5-di-t-butyl4-hydroxyphenyl) propionyl] hydrazine and the like, and examples of the metal soaps include calcium stearate and nickel stearate.

Examples of the nucleating agent include sorbitols such as sodium di (4-t-butylphenyl) phosphonate, dibenzylidene sorbitol, and sodium salt of methylenebis (2,4-di-t-butylphenol) acid phosphate; Salt-based compounds are exemplified.

Examples of the antistatic agent include quaternary ammonium salt compounds such as (β-lauramidopropyl) trimethylammonium methyl sulfate and alkyl phosphate compounds.

Examples of the flame retardant include halogen-containing phosphates such as tris (2-chloroethyl) phosphate, halides such as hexabromocyclododecane and decabromophenyl oxide, antimony trioxide,
Metal inorganic compounds such as antimony pentoxide and aluminum hydroxide, and mixtures thereof, and the like.

The method for producing the resin composition of the present invention from each of the above components is not particularly limited. The order of blending each component is also arbitrary. For example, an ester and other optional components may be added to the polycarbonate in a molten state and kneaded,
Further, an ester and other optional components may be added to the polycarbonate solution and kneaded. More specifically, the ester and other optional components are directly or separately added to polycarbonate, which is a reaction product in a molten state reactor or extruder obtained after completion of the polymerization reaction. Or kneading by kneading, or pelletizing the obtained polycarbonate, feeding the pellets together with an ester and other optional components to a single-screw or twin-screw extruder or the like and melt-kneading. Solvents (eg, methylene chloride, chloroform,
Toluene, tetrahydrofuran, etc.) and adding the ester and other optional components to the solution separately or simultaneously and stirring the mixture. From the viewpoint of reducing the amount, it is preferable to add and knead components such as a sulfonic acid compound and an ester to the polycarbonate in a molten state obtained by melt polymerization to form pellets.

In the present invention, the polycarbonate resin composition is preferably subjected to a reduced pressure treatment. In the decompression treatment, the treatment and the apparatus are not particularly limited, and for example, a reactor with a decompression device or an extruder with a decompression device can be used. The reactor with a decompression device may be either a vertical tank reactor or a horizontal tank reactor, but a horizontal tank reactor is preferred. The extruder with a decompression device may be either a single-screw extruder with a vent or a twin-screw extruder, and it is also possible to pelletize while performing a decompression treatment with the extruder. The pressure at that time is 0.05 to 750 m when the pressure reduction treatment is performed in the reactor.
mHg, particularly preferably 0.05 to 5 mmHg, and 1 to 750 mHg when using an extruder.
mHg, particularly preferably 5 to 700 mmHg.
Such a reduced pressure treatment is preferably performed at 240 to 350 ° C., and is performed for about 5 minutes to 3 hours when using a reactor, and for about 10 seconds to 15 minutes when using an extruder. Is preferred. By subjecting the polycarbonate composition to a reduced pressure treatment in this manner, a polycarbonate composition having reduced residual monomers and oligomers can be obtained. In addition, when performing the reduced pressure treatment, water or a saturated aliphatic hydrocarbon, nitrogen or the like may be added under pressure for the purpose of reducing residual monomers and oligomers, and then the reduced pressure treatment may be performed as necessary. For example, when melt polymerization is performed using diphenyl carbonate as the carbonic acid diester, the residual amount of diphenyl carbonate in the polycarbonate can be reduced by the reduced pressure treatment.

The polycarbonate used in the present invention contains such diphenyl carbonate in an amount of 0.1 part by weight or less.
In particular, it is preferable to contain (remain) 0.02 parts by weight or less.

[0065]

The resin composition of the present invention thus obtained is excellent in polymer hue and hydrolysis resistance, and also has thermal stability and releasability such as retention of hue with reduced molecular weight during molding.
Also excellent in moldability such as transferability.

[0066]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Examples 1-3 and Comparative Examples 3-5 Bisphenol A (hereinafter BPA) 228 parts by weight, diphenyl carbonate (hereinafter DPC) 223 parts by weight, tetramethylammonium hydroxide 0.009 parts by weight, bisphenol A 0.00014 parts by weight of disodium salt was charged into a reaction vessel equipped with a stirrer, a distillation column, and a decompression device, and was replaced with nitrogen. After stirring for 30 minutes,
The internal temperature was raised to 180 ° C., the reaction was performed at an internal pressure of 100 mmHg for 30 minutes, and the generated phenol was distilled off.

Then, the internal temperature was raised to 200 ° C. and the pressure was gradually reduced, and the reaction was carried out while distilling off phenol at 50 mmHg for 30 minutes. Further, gradually raise the temperature to 0 ° C. and 30 mmHg,
Reduce the pressure, at the same temperature and under the same pressure for 30 minutes, and further at 240 ° C.
The temperature was repeatedly increased and reduced to 10 mmHg, 260 ° C. and 1 mmHg in the same procedure as described above, and the reaction was continued. Finally 2
The polycondensation of the polycarbonate was continued at a temperature of 70 ° C.

The obtained polycarbonate had a viscosity average molecular weight of 15,500 and a terminal hydroxyl concentration of 15
%, And the molecular weight distribution (weight average molecular weight / number average molecular weight) by GPC measurement is 2.2.

Next, in the molten state, this polymer was inserted into a twin-screw extruder (L / D 17.5, barrel temperature 270 ° C.) using a gear pump, and the sulfonic acid compound and the aliphatic compound shown in Table 1 were added to the polymer. A predetermined amount of a partial ester of a carboxylic acid and a polyhydric alcohol and, if necessary, the additives described in Table 1 are added and kneaded, and the mixture is made into a strand through a die.
It was cut into pellets by a cutter.

Comparative Example 1 228 parts by weight of BPA, DP
It carried out like Example 1 except having used C217 weight part. The molecular weight of the obtained polycarbonate is 15,5.
The terminal hydroxy concentration was 50%, and the molecular weight distribution measured by GPC was 2.2.

Comparative Example 2 228 parts by weight of BPA, DP
Example 1 except that 231 parts by weight of C, 0.009 parts by weight of tetramethylammonium hydroxide, and 0.000034 parts by weight of disodium bisphenol A were used.
Was performed in the same manner as described above. The molecular weight of the obtained polycarbonate was 15,500, the terminal hydroxyl concentration was 3 mol%, and the molecular weight distribution measured by GPC was 3.0.

[Comparative Examples 6 and 7] As ester compounds,
The procedure was performed in the same manner as in Example 1 except that glycerin tristearate pentaerythritol tetrastearate was used.

[Evaluation of Obtained Pellets] The pellets obtained above were evaluated as follows. (1) Hue: b value A molded plate having a thickness of 2 mm was prepared from the obtained pellets by injection molding (cylinder temperature 320 ° C., mold temperature 80 ° C., cycle time 35 seconds), and manufactured by Nippon Denshoku Industries Co., Ltd. Co
lor and Color Difference M
b value was measured using eter Z-300A.

(2) Release Property Using a nickel stamper, the cylinder temperature was set to 34.
0, a compact disk substrate of φ120 was continuously used by a CD molding machine under the condition of a mold temperature of 80 ° C. and a cycle of 7 seconds.
000 shots were formed, and the remainder of the disk or sprue in the mold was evaluated as a defective rate (%).

(3) Transferability The pits transferred to the disk substrate obtained by the method (1) were observed and evaluated with an optical microscope (× 800). For each of the examples and comparative examples, 10 disk substrates were evaluated.

(4) Stain on the stamper According to the method (1), the state of the mold and the stamper after 10,000 shots were visually observed and evaluated.

(5) Thermal stability Under the molding conditions of (1), the molding was stopped for 15 minutes, the resin was retained, molding was started again, and the hue and surface condition of the obtained disk substrate were evaluated. The surface state was visually observed. Hue (YI) is obtained from Nippon Denshoku Industries Co., Ltd.
r and Color Difference Met
er ND-1001DP.

(6) Humidity and heat stability (boiling water resistance) The disc substrate obtained by the method of (1) was heated at 120 ° C. ×
The decrease in molecular weight after 50-hour wet heat treatment was evaluated.

[0080]

[Table 1]

[0081]

[Table 2]

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Wataru Funakoshi 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. Inside the Iwakuni Research Center (72) Inventor Katsushi Sasaki 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Shares F term in the Iwakuni Research Center (reference) 4J002 CG011 EH057 EV236 EW176 GS02

Claims (3)

[Claims] 1. [A] an aromatic dihydroxy compound and 1.005 to 1 mole of the aromatic dihydroxy compound
When a terminal hydroxyl group concentration of 1 to 30 mol% is obtained by reacting 1.1 mol of carbonic acid diester in the presence of an alkali metal or alkaline earth metal compound in an amount of 10 ^-6 to 10 ^-8 mol. Polycarbonate 10 having a molecular weight distribution measured by GPC of 2.0 to 2.6
0 parts by weight and [B] the following formula (1): A ¹ —SO ₃ X ¹ (1) (where A ¹ has 1 to 2 carbon atoms which may have a substituent)
0 is a hydrocarbon group, and X ¹ is an ammonium cation or a phosphonium cation. A) a sulfonic acid compound represented by the formula (1), and 0.005 to 0.1 parts by weight of [C] a partial ester of an aliphatic carboxylic acid and a polyhydric alcohol. 2. [B] The sulfonic acid compound is represented by the following formula (1):
-1 (Where A ² , A ³ , A ⁴ , A ⁵ , and A ⁶ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms). The polycarbonate resin composition according to claim 1, wherein 3. The method according to claim 1, wherein [C] the partial ester of an aliphatic carboxylic acid and a polyhydric alcohol is a monoglyceride and / or diglyceride of a saturated monovalent fatty acid having 12 to 24 carbon atoms. Polycarbonate resin composition.