JP2001049105A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent molding heat resistance, wet heat fatigue resistance and adhesiveness while maintaining transparency and mold release characteristics, hardly causing white defects in an optical disc substrate by making the composition include a specific aromatic polycarbonate resin and an internal mold-releasing agent in a specific ratio. SOLUTION: This composition comprises (A) 100 pts.wt. of an aromatic polycarbonate resin having <=4×10-3 relative fluorescence intensity based on a reference material at 465 nm when measured by a fluorescence spectrum (excitation wavelength 320 nm) and 10,000-50,000 viscosity-average molecular weight obtained from a dihydric phenol (e.g. homopolymer of biphenol A, etc.), and a carboxylic acid ester (e.g. diphenyl carbonate, etc.), by a melt polymerization and (B) 0.001-1.0 pt.wt. of an internal mold-releasing agent having <=5 acid value and composed of >=90 wt.% of an ester of an alcohol and a fatty acid. The composition comprises 0.0001-1 pt.wt. a phosphorus-based stabilizer which has preferably 1-11,000 ppm concentration of phosphorous acid, chlorine atom and chloride ion and is a compound of the formula [Ar1 is an (alkyl- substituted) aromatic group], etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an optical disk which is excellent in molding heat resistance, wet heat fatigue resistance and adhesiveness while maintaining the transparency inherent in a polycarbonate resin and the releasability when a release agent is added. The present invention relates to an aromatic polycarbonate resin composition obtained by a melt polymerization method in which white defects are unlikely to occur in a substrate.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used in electric parts, building material parts, automobile parts and the like because of their excellent transparency, heat resistance, heat and moisture resistance, workability, mechanical strength and the like.

[0003] As a method for producing such an aromatic polycarbonate resin, a method of directly reacting phosgene with a dihydric phenol such as bisphenol A (interfacial polymerization method),
Alternatively, there is known a method in which a dihydric phenol such as bisphenol and a diallyl carbonate such as diphenyl carbonate are transesterified in a molten state and polymerized (hereinafter, may be referred to as a melting method). Among such production methods, the method of transesterifying a dihydric phenol with diallyl carbonate has no problem in using a halogen compound such as phosgene or methylene chloride, as compared with the production by an interfacial polymerization method, and is more environmentally friendly. This is a promising technology because it has the advantages of low load and inexpensive manufacturing.

A resin composition in which a release agent is blended with a melt-polymerized polycarbonate resin is disclosed in Japanese Unexamined Patent Application Publication No. Hei. -26969. JP-A-8-73724 discloses a composition comprising a melt-polymerized polycarbonate resin having a hydroxyl group terminal and a molecular weight distribution specified, and a release agent for a partial ester of a fatty acid conventionally used for a polycarbonate resin in an interfacial polymerization method. Have been.

[0005] However, in this publication, improvement of heat resistance and reduction of molecular weight at the time of molding are described as effects of adding an acidic substance to the aromatic polycarbonate resin of the melt polymerization method. No consideration is given to controlling the polycarbonate resin in a specific fluorescence intensity range and controlling the acid value of the release agent to a specific range, and the molding heat resistance and wet heat fatigue resistance required in recent years have been considered. There is a need for improvements in adhesion, adhesion and the reduction of white defects in the optical disk substrate.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a molding resin having heat resistance, heat and humidity resistance, while maintaining the inherent transparency of a polycarbonate resin and the releasability when a release agent is added.
An object of the present invention is to provide an aromatic polycarbonate resin composition of a melt polymerization method which has excellent adhesiveness and hardly causes a white defect of about 10 to 100 μm in a spherical shape in an optical disk substrate when left under high temperature and high humidity for a long time. .

[0007]

According to the present invention, (A) when the fluorescence spectrum is measured (excitation wavelength: 320 nm), the relative fluorescence intensity at 465 nm with respect to the reference substance is 4 × 1.
0 ^-3 and a viscosity-average molecular weight of 10,000～50,
Aromatic polycarbonate resin 1 obtained by melt polymerization of dihydric phenol and carbonate
Aromatic polycarbonate resin composition comprising 00 parts by weight and (B) 0.001 to 1.0 parts by weight of an internal release agent in which the acid value is 5 or less and 90% by weight or more is an ester of an alcohol and a fatty acid. Is achieved by

Hereinafter, the present invention will be described in more detail. The aromatic polycarbonate resin used in the present invention is usually obtained by reacting a dihydric phenol with a carbonate by a melting method. Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 1,6-dihydroxynaphthalene, 2,6
-Dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2 -Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, , 2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2
-(4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis} (4-hydroxy-3, 5-dimethyl) phenyl {propane, 2,2-bis {(3,5-dibromo-4-hydroxy) phenyl} propane, 2,2-bis} (3,5
-Dichloro-4-hydroxy) phenyl} propane,
2,2-bis {(3-bromo-4-hydroxy) phenyl} propane, 2,2-bis {(3-chloro-4-hydroxy) phenyl} propane, 4-bromoresorcinol, 2,2-bis} ( 3-isopropyl-4-hydroxy) phenyl {propane, 2,2-bis {(3-phenyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-ethyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-n-propyl-4-hydroxy) phenyl} propane, 2,2-bis} (3-sec
-Butyl-4-hydroxy) phenyl} propane, 2,
2-bis {(3-tert-butyl-4-hydroxy)
Phenyl {propane, 2,2-bis} (3-cyclohexyl-4-hydroxy) phenyl} propane, 2,2-
Bis {(3-methoxy-4-hydroxy) phenyl} propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-dibromo-2,2-bis (4-hydroxyphenyl) ethylene, , 1-Dichloro-2,2-bis {(3-phenoxy-4-hydroxy) phenyl} ethylene, ethylene glycol bis (4
-Hydroxyphenyl) ether, 2,2-bis (4-
(Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) ) -2-Methylbutane, 1,1-bis (4-hydroxyphenyl)
Isobutane, 2,2-bis (4-hydroxyphenyl)
Pentane, 2,2-bis (4-hydroxyphenyl)-
4-methylpentane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1, 1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α ′
-Bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5
7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, bis {(3,5-dimethyl-4-hydroxy) phenyl} sulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide, And 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxydiphenyl ester, and these can be used alone or in combination of two or more.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(3,5-dibromo-4-hydroxy) phenyl} propane, ethylene glycol Screw (4
-Hydroxyphenyl) ether, 2,2-bis (4-
Hydroxyphenyl) hexafluoropropane, 2,2
-Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfone, bis {(3,5-dimethyl-4-hydroxy) phenyl} sulfone, 4,4'-dihydroxy Homopolymers or copolymers obtained from at least one bisphenol selected from the group consisting of diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, and 4,4'-dihydroxydiphenyl ketone are preferred, and bisphenol A is particularly preferred. Homopolymers are preferably used.

Specific examples of the carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. , Dicyclohexyl carbonate, and the like, but are not limited thereto. Preferably, diphenyl carbonate is used. These carbonates may be used alone or in combination of two or more.

In producing the aromatic polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonic acid ester by a melting method, a catalyst, a terminal terminator, an antioxidant for the dihydric phenol and the like may be used as necessary. You may. The aromatic polycarbonate resin may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid. And the resulting aromatic polycarbonate resin 2
It may be a mixture of more than one species.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, 2- (4-hydroxyphenyl) -2-
(3′-phenoxycarbonyl-4′-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2
-(3'-carboxy-4'-hydroxyphenyl) propane and the like, and among them, 1,1,1-tris (4-
Hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

The reaction by the melting method is usually a transesterification reaction between dihydric phenol and carbonic acid ester. The dihydric phenol and carbonic acid ester are mixed while heating in the presence of an inert gas to form an alcohol or alcohol. It is carried out by a method of distilling phenol. The reaction temperature depends on the boiling point of the alcohol or phenol to be produced, etc.
Usually, it is in the range of 120 to 350 ° C. In the latter stage of the reaction, the pressure of the system is reduced to about 10 to 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

In the melting method, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include (i) an alkali (earth) metal compound and / or (ii) a nitrogen-containing basic compound. Condensation using a catalyst consisting of

The alkali metal compound used as a catalyst includes, for example, hydroxides, hydrocarbons, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearic acids of alkali metals. Salts, borohydride salts, benzoates, hydrogen phosphates, bisphenols, salts of phenols and the like can be mentioned.

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, lithium borohydride, potassium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, benzoic acid Lithium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, lithium salt of phenol and the like can be mentioned.

The alkaline earth metal compound used as a catalyst includes, for example, hydroxides, hydrocarbons, carbonates, acetates, nitrates, nitrites, nitrites and the like of alkaline earth metals such as magnesium, calcium and barium. , Cyanate, thiocyanate, stearate, borohydride, benzoate, hydrogen phosphate, bisphenol, phenol salts and the like.

Among these alkali metal compounds and alkaline earth metal compounds, alkali metal compounds are suitable as a catalyst for melt polymerization.

The alkali metal compound as a catalyst can be used in a range of 10 ^-8 to 10 ^-5 mol per mol of dihydric phenol. If the amount is outside the above range, the properties of the obtained aromatic polycarbonate may be adversely affected, or a high-molecular weight aromatic polycarbonate resin may not be obtained because the transesterification does not proceed sufficiently. .

Examples of the nitrogen-containing basic compound as a catalyst include, for example, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), benzyl Ammonium hydroxides having alkyl, aryl, alkylaryl groups, such as trimethylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH) and hexadecyltrimethylammonium hydroxide, triethylamine, tributylamine, dimethylbenzylamine, hexadecyl Tertiary amines such as dimethylamine, or tetramethylammonium borohydride (Me ₄ NB
H _4), tetrabutylammonium borohydride (Bu ₄ NBH _4), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh _4), and the like basic salts such as Can be. Among them, tetramethylammonium hydroxide (Me ₄ N
OH), tetraethylammonium hydroxide (Et
₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH) are preferable, and tetramethylammonium hydroxide (Me ₄ NOH) is preferred.

The above-mentioned nitrogen-containing basic compound is preferably used in such a ratio that the amount of ammonium nitrogen atoms in the nitrogen-containing basic compound is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ equivalent per mole of dihydric phenol. A more desirable ratio is 2 ×
The ratio is 10 ^{-5 to} 7 × 10 ^-4 equivalent. A particularly desirable ratio is a ratio that is 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ equivalents with respect to the same standard.

In the present invention, if desired, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal organic acid salts, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium Compounds, organotin compounds, lead compounds,
Catalysts usually used for esterification and transesterification such as osmium compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds can be used. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is based on 1 mole of dihydric phenol as a raw material.
It is preferably selected in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents.

It is important for the melt-polymerized aromatic polycarbonate resin of the present invention to keep its relative fluorescence intensity at 4 × 10 ⁻³ or less. This relative fluorescence intensity is 4 × 10
^If it exceeds ^-3 , new problems such as a decrease in adhesiveness and printability of the aromatic polycarbonate resin sheet occur. The relative fluorescence intensity is preferably 3 × 10 ⁻³ or less, most preferably 2 × 10 ⁻³ or less.

In order to obtain an aromatic polycarbonate having a fluorescence intensity of less than a specific value with less thermal decomposition and less mechanical decomposition of the aromatic polycarbonate resin, the amount of the transesterification catalyst is specified as follows: It is preferable to deactivate the transesterification catalyst with a sulfonic acid-based compound, to regulate the ratio of the molecular terminals of the polycarbonate to the total molecular terminals of the hydroxy groups, and to block the molecular terminals of the aromatic polycarbonate.

Further, the temperature of the aromatic polycarbonate resin in the melt polycondensation reaction is always kept at 255 ° C. or less.
It is preferable to obtain an aromatic polycarbonate having a thermal intensity and a mechanical intensity which are small and a fluorescence intensity which is less than a specific value.

The stirring of the stirring blade of the polymerization tank is represented by the following formula: stirring speed = peripheral speed of the stirring blade / length of the gap between the reactor and the stirring blade [where the unit of the stirring shear speed is 1 / sec, The unit of the peripheral speed is cm / sec. The unit of the length of the gap between the stirring blades is c.
m]] and the value obtained by dividing the stirring shear rate (unit: 1 / sec) of the polymerization tank stirring blade represented by sec × c
m ² ) is preferable in order to obtain an aromatic polycarbonate with less thermal decomposition and less mechanical decomposition and a fluorescence intensity of a specific value or less.

With regard to the catalyst system in the production of these aromatic polycarbonates, a basic nitrogen compound and an alkali metal compound are used in combination, and the amount of the alkali metal compound used is reduced to 5.0 × 10 ^-6 mol or less per 1 mol of bisphenol A. By suppressing this, the transesterification reaction also proceeds industrially advantageously, and a polycarbonate having good fluidity and good color tone can be obtained.

In the polymerization reaction, in order to reduce the number of phenolic terminal groups, for example, phenol, pt-butylphenol, pt-butylphenylphenyl carbonate,
pt-butylphenyl carbonate, p-cumylphenol, p-cumylphenylphenyl carbonate, p
-Cumylphenyl carbonate, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis (phenylphenyl) carbonate, chlorophenylphenylcarbonate, bromophenylphenylcarbonate,
Nitrophenylphenyl carbonate, diphenyl carbonate, methoxycarbonylphenylphenyl carbonate, 2,2,4-trimethyl-4- (4-hydroxyphenyl) chroman 2,4,4-trimethyl-2-
It is preferred to add compounds such as (4-hydroxyphenyl) chroman and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

In the present invention, it is preferable to block the terminal of the aromatic polycarbonate resin using a terminal blocking agent. Further, it is preferable to control the terminal hydroxyl group concentration of the aromatic polycarbonate resin before adding the terminal blocking agent to 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, based on all terminals. By doing so, a specific terminal group can be introduced at a high ratio, and the effect of modifying the aromatic polycarbonate resin can be enhanced. In general, it is advantageous to use a terminal blocking agent for an aromatic polycarbonate resin having a terminal hydroxyl group concentration of 30 to 95 mol% of all terminals of the aromatic polycarbonate resin. The terminal ratio of hydroxyl groups of the aromatic polycarbonate resin before the addition of the terminal blocking agent can be controlled by the charging ratio of dihydric phenol and diphenyl carbonate as raw materials. Here, the number of moles of the terminal hydroxyl group concentration in a certain amount of the aromatic polycarbonate resin can be determined by ¹ H-NMR by a conventional method. The terminal hydroxyl group concentration of the aromatic polycarbonate resin of the present invention is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, even more preferably from 10 to 60 mol% based on all terminals.
４０40 mol%. When the concentration of the terminal hydroxyl group is in such a range, the molecular weight is reduced and the hue is improved. The terminal hydroxyl group concentration of the aromatic polycarbonate resin for optical disks is preferably from 5 to 70 mol%, more preferably from 20 to 70 mol%, even more preferably from 30 to 6 mol%, based on all terminals.
0 mol%.

In the present invention, it is preferable to use a deactivator for neutralizing the activity of the catalyst in the aromatic polycarbonate resin. Specific examples of this deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonic acid, ethylbenzenebenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, phenylbenzenebenzenesulfonic acid, p-toluenesulfonic acid. Methyl acid, p-
Sulfonates such as ethyl toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; and trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene, and methyl acrylate. Sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonate, 2-phenyl-2-butyl dodecylbenzenesulfonate, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, benzene Tetrabutylphosphonium sulfonic acid salt, Tetraethylphosphonium dodecylbenzenesulfonic acid salt, Tetrabutylphosphonium dodecylbenzenesulfonic acid salt, Tetrahexyl dodecylbenzenesulfonic acid salt Phosphonium salt, tetraoctylphosphonium dodecylbenzenesulfonate, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl Sulfate,
Tetramethyl ammonium hexyl sulfate, decyl trimethyl ammonium hexadecyl sulfate,
Examples thereof include, but are not limited to, compounds such as tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, and tetramethylammonium dodecylbenzyl sulfate. Two or more of these compounds can be used in combination.

Among the deactivators, phosphonium or ammonium salt type deactivators are themselves particularly stable even at 200 ° C. or higher. When the deactivator is added to the aromatic polycarbonate resin, the polycondensation reaction catalyst can be immediately neutralized to obtain the desired aromatic polycarbonate resin. That is, a deactivator is preferably used in an amount of 0.01 to 5 with respect to the aromatic polycarbonate formed after the polymerization blocking reaction.
At a rate of 00 ppm, more preferably 0.01 to 300
ppm, particularly preferably 0.01 to 100 ppm.

The deactivator is used in an amount of 0.5 to 5 per mole of the polycondensation reaction catalyst.
It is preferably used in a proportion of 0 mol. The method for adding the deactivator to the aromatic polycarbonate resin after terminal blocking is not particularly limited. For example, they may be added while the aromatic polycarbonate resin as a reaction product is in a molten state, or may be added after the aromatic polycarbonate resin is pelletized once and then remelted. In the former, the aromatic polycarbonate resin which is a reaction product in a polymerization tank or an extruder in a molten state obtained after the end blocking reaction is completed is added while the resin is in a molten state.

When a polymerization catalyst is used in the melt-polymerized aromatic polycarbonate resin of the present invention to accelerate the reaction, the polymerization catalyst often remains after the polymerization reaction. If the remaining catalyst is left as it is after the completion of the polymerization reaction, the catalytic activity of the polymerization catalyst has a detrimental effect on decomposition and re-reaction of the aromatic polycarbonate resin. Therefore, it is preferable to suppress such residual catalyst activity.

The aromatic polycarbonate resin of the present invention has a viscosity average molecular weight (M) of 10,000 to 50,
000, preferably 10,000 to 45,000, more preferably 12,000 to 30,000. An aromatic polycarbonate resin having such a viscosity average molecular weight is preferable because it maintains a good fluidity at the time of extrusion processing and at the same time has a certain mechanical strength with respect to the obtained aromatic polycarbonate resin composition. Further, for optical disc applications, 10,000 to 20,000 is more preferable, and 12,000 to 17,000 is most preferable.

In the present invention, the viscosity average molecular weight is such that 0.7 g of an aromatic polycarbonate resin is added to 100 ml of methylene chloride.
Is measured at 20 ° C. using a specific viscosity (η
sp).

The internal release agent in the present invention is a compound that is incorporated into a resin composition in order to improve the releasability of a resin molded product from a mold during melt molding. Examples of such an internal release agent include an internal release agent having an acid value of 5 or less and 90% by weight or more of an ester of a monohydric alcohol and a fatty acid and / or a partial ester or a whole ester of a polyhydric alcohol and a fatty acid. Can be Such an ester of a monohydric alcohol and a fatty acid is an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of a polyhydric alcohol and a fatty acid is a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

Specific examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Stearyl stearate is preferred.

Specific examples of the partial or total ester of a polyhydric alcohol and a saturated fatty acid include monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbitate stearate, monoglyceride behenate, and pentaerythritol monostearate. , Pentaerythritol tetrastearate, pentaerythritol tetraperargonate,
Examples thereof include all or partial esters of dipentaerythritol such as propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate.

Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used. In particular, stearic acid monoglyceride,
Pentaerythritol tetrastearate, a mixture of stearic acid triglyceride and stearyl stearate is preferably used. This mixture of stearic acid triglyceride and stearyl stearate preferably has a weight ratio of 60 to 80 for the former and 20 to 40 for the latter.

The amount of the fatty acid ester in the internal release agent is 90% by weight or more, preferably 95% by weight or more, when the internal release agent is 100% by weight. preferable.

If the internal release agent incorporated in the present invention contains impurities such as free fatty acids and free alcohols, the object of the present invention may not be achieved in some cases.

The fatty acid ester has an acid value of 5 or less, preferably 3 or less, more preferably 2 or less. In the case of stearic acid monoglyceride, the acid value is more preferably 1.5 or less and the purity is 95% by weight or more, and the acid value is 1.2 or less and the purity is most preferably 98% by weight or more. A known method can be used to measure the acid value of the fatty acid ester.

Examples of the internal release agent other than the above esters include:
Examples include olefin wax, olefin wax containing a carboxyl group and / or a carboxylic anhydride group, silicone oil, organopolysiloxane, paraffin wax, beeswax and the like.

The amount of the internal mold release agent of the present invention is 0.00.0 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin composition.
The amount is preferably from 0.01 to 1.0 part by weight, more preferably from 0.01 to 0.6 part by weight.

If necessary, the aromatic polycarbonate resin may be, for example, a heat stabilizer, an antioxidant, an ultraviolet absorber such as a triazole, acetophenone, or salicylate ester, a bluing agent, tetrabromobisphenol A, or tetrabromobisphenol A. Flame retardants such as low molecular weight polycarbonate of bromobisphenol A and decabromophenyl ether (3 to 15% by weight), coloring agents such as dyes, carbon black and titanium oxide (0.001 to 10% by weight), light diffusing agents and lubricants , A coumarin, a naphthalimide, an oxazole compound, and the like, a fluorescent whitening agent (0.01 to 0.1% by weight), an antistatic agent, and the like.

The aromatic polycarbonate resin composition of the present invention may be blended with a heat stabilizer in order to prevent a decrease in molecular weight and deterioration of hue during molding. Such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid,
Examples thereof include phosphonic acid and esters thereof. Specific examples include triphenyl phosphite, tris (nonylphenyl) phosphite, and tris (2,4-di-tert).
-Butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl Phosphite, monooctyldiphenyl phosphite, bis (2,6-di-ter
t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite,
Bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate , Diphenyl monoorthoxenyl phosphate, dibutyl phosphate,
Dioctyl phosphate, diisopropyl phosphate, tetrakis (4,4'-biphenylenediphosphosphinate) (2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned. These heat stabilizers may be used alone or in combination of two or more. The amount of the heat stabilizer is 0.0001 to 1 part by weight based on 100 parts by weight of the aromatic polycarbonate resin.
Part by weight is preferred, 0.0005 to 0.5 part by weight is more preferred, and 0.0001 to 0.15 is still more preferred.
0.02 to 0.1 part by weight is most preferred.

Preferred heat stabilizers of the present invention include phosphorous acid, chlorine atom and chlorine ion concentrations of 1 to 11,000 p.
pm, and a compound represented by the above formula (1) (component C-1), a compound represented by the above formula (2) (component C-2), and a compound represented by the above formula (3) (C-3 component), a compound represented by the above formula (4) (C-4 component), a compound represented by the above formula (5) (C-5 component), and a compound represented by the above formula (6) )) And at least one phosphorus stabilizer selected from the compounds represented by the formula (C-6).

Specific examples of the component C-1 of the present invention include:
Tetrakis (2,4-di-iso-propylphenyl)
-4,4'-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t
tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl) Butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,
4'-biphenylenediphosphonite, tetrakis (2,
6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert)
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
3,3'-biphenylenediphosphonite and the like,
Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and tetrakis (2,4
-Di-tert-butylphenyl) -biphenylenediphosphonite is more preferred. This tetrakis (2,4-
Di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically, tetrakis (2,4-di-tert-butylphenyl)
-4,4'-biphenylenediphosphonite (C-1-1)
Component), tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite (C
-1-2 component) and tetrakis (2,4-di-te)
More preferred is a mixture of three kinds of (rt-butylphenyl) -3,3′-biphenylenediphosphonite (component C-1-3). The mixing ratio of this mixture is such that the C-1-1 component, the C-1-2 component and the C-1-3 component are 1 in weight ratio.
00:37 to 64: 4 to 14 is preferable, and 10
The range of 0:40 to 60: 5 to 11 is more preferable.

Specific examples of the component C-2 of the present invention include:
Bis (2,4-di-iso-propylphenyl) -4-
Phenyl-phenylphosphonite, bis (2,4-di-
n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl)- 3-phenyl-phenylphosphonite bis (2,6-di-iso
-Propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3
-Phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite And bis (di-tert-butylphenyl) -phenyl-phenylphosphonite.
4-Di-tert-butylphenyl) -phenyl-phenylphosphonite is more preferred. This screw (2,4-
Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl)-
4-phenyl-phenylphosphonite (C-2-1 component) and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite (C-2
-2 components) are more preferred. The mixing ratio of this mixture is preferably in the range of 5: 1 to 4 by weight ratio of the C-2-1 component and the C-2-2 component, and more preferably in the range of 5: 2 to 3.

Specific examples of the component C-3 of the present invention include:
Tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-
Propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-t
tert-butylphenyl) phosphite, tris (2,
6-di-tert-butylphenyl) phosphite and the like, preferably tris (dialkyl-substituted phenyl) phosphite, more preferably tris (di-tert-butylphenyl) phosphite, and tris (2,4-di- (tert-Butylphenyl) phosphite is particularly preferred. The compound of the component C-3 may be one kind or a mixture of two or more kinds.

Specific examples of the component C-4 of the present invention include:
Examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and the like. Trimethyl phosphate and triphenyl phosphate are preferred, and trimethyl phosphate is most preferred.

The C-5 component of the present invention is a compound represented by the following general formula (5):

[0053]

Embedded image

[In the formula, R ₂ is an alkyl group or an aromatic group which may have an alkyl substituent, and may be the same or different. As specific examples, R ₂ is a phenyl group, a 2,4-di-tert-butylphenyl group,
A -methyl-2,6-di-tert-butylphenyl group,
Examples include phosphorus-based stabilizers such as an octadecyl group and a nonylphenyl group, preferably a 2,4-di-tert-butylphenyl group and an octadecyl group, and most preferably dioctadecylpentaerythritol diphosphite.

The C-6 component of the present invention is a compound represented by the following general formula (6):

[0056]

Embedded image

[In the formula, Ar ₄ is an aromatic group which may have an alkyl substituent, and may be the same or different. R ₃ is an alkyl group or an aromatic group which may have an alkyl substituent, and may be the same or different. As specific examples, Ar ₄ is a phenyl group, a toluyl group, a 2,4-di-tert-butylphenyl group and the like, and R ₃ is a methyl group, an ethyl group, an n-propyl group, an i- Propyl, n-butyl, t-butyl and the like. The most preferred example is dimethylphenylphosphonate.

The phosphorus-based stabilizer of the present invention comprises a C-1 component,
Phosphorus-based stabilizer composition comprising -2 component and C-3 component, or phosphorus-based stabilizer composition comprising phosphorous acid and C-3 component, or C-3 component, or C-5 component, or C-6 The components are preferred.

The C-1 component, C-2 component and C of the present invention
-3 component phosphorus-based stabilizer composition, the total of which is 1
When the content is 00% by weight, the C-1 component is 40 to 80% by weight,
0 to 25% by weight of the C-2 component and 5 to 5% of the C-3 component
A phosphorus-based stabilizer composition having 0% by weight is preferred. More preferably, the C-1 component is 40 to 80% by weight, the C-2 component is 5 to 25% by weight, and the C-3 component is 5 to 50% by weight. Most preferably, the C-1 component is 55 to 50% by weight. 80% by weight, 5 to 25% by weight of C-2 component and 5% of C-3 component
~ 45% by weight.

The phosphorus-based stabilizer composition comprising phosphorous acid and the C-3 component, when the total is 100% by weight, is 1 to 80% by weight of phosphorous acid and 20 to 99% by weight of the C-3 component. Certain phosphorus-based stabilizer compositions are preferred. More preferably, the phosphorous acid is 10 to 60% by weight and the C-3 component is 40% by weight.
~ 90% by weight, most preferably the phosphorous acid is 20 ~
45% by weight and 55 to 80% by weight of the C-3 component.

The amount of the phosphorus-based stabilizer of the present invention or the composition thereof is in the range of 0.0001 to 0.15 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.
002 to 0.15 parts by weight, more preferably 0.02 to 0.15 parts by weight.
Most preferred is a range of 2 to 0.1 parts by weight.

The content of the phosphorus-based stabilizer composition comprising phosphorous acid and the C-3 component is as follows.
0.0001 to 0.00 parts by weight of phosphorous acid
20 (preferably 0.0001 to 0.0015, more preferably 0.0001 to 0.0010) part by weight and 0.0005 to 0.0300 (preferably 0.0005 to 0. 0300, more preferably
0.0010 to 0.0200) parts by weight.

In the present invention, "chlorine atom and chlorine ion contained in the phosphorus-based stabilizer of component C-1 to component C-6 or the composition thereof (hereinafter collectively referred to as phosphorus-based stabilizer composition)" Is derived from the phosphorus-based stabilizer of the present invention or a chlorine compound contained in the composition. The chlorine compound is, for example, one generated in the stabilizer during the production process or existing from the raw material stage, and cannot be completely removed at the time of purification. These chlorine compounds are, specifically, chlorine-based solvents, chlorine-based catalysts, unreacted chlorine, by-produced hydrogen halides, by-product hydrogen halide ammonium and amine salts used during production (reaction, purification, etc.). And the like.

As a method of reducing the amount of chlorine compounds contained in the phosphorus-based stabilizer composition, there is a method of enhancing purification in the production of the stabilizer. For example, in the case of purification by washing using a solvent, it is possible to increase the number of washing solvents, increase the number of washings, or use a solvent capable of selectively dissolving a chlorine compound. In the case of purification by distillation or sublimation, there is a method of increasing the number of distillation stages by lengthening the rectification column and increasing the separation ability. In order to reduce the amount of chlorine compounds contained in the phosphorus-based stabilizer composition, it is also effective to reduce the amount of chlorine compounds immediately after completion of the synthesis reaction in the production and before purification. For example, reducing the amount of chlorine-based catalyst used, using a catalyst that does not contain chlorine, reducing the amount of chlorine-based solvent used as a reaction solvent, not using a chlorine-based solvent, and completing the reaction more completely And the like. To complete the reaction more completely, increase the reaction time, increase the reaction temperature,
When using a more active catalyst, increasing the "molar ratio of phenolic compound to chlorine compound" in the preparation of raw materials, or when there is a dehydrochlorination reaction in the production process,
Examples of the method include increasing the efficiency of capturing hydrogen chloride.

When the phosphorus-based stabilizer composition contains a "reaction product of hydrogen chloride and a hydrogen chloride scavenger", in order to reduce this, in addition to the method described above, a purification step may be used. The use of a hydrogen chloride scavenger that can be easily removed as a "reaction product of hydrogen chloride and a hydrogen chloride scavenger" can be mentioned.

In the production of the phosphorus-based stabilizer, a chlorine-based catalyst is used as a catalyst. If the chlorine-based catalyst and the chlorine-based compound derived therefrom remain in the stabilizer, a method for reducing them is as follows. In addition to the methods described above, there may be mentioned a method of selecting a catalyst which can be easily removed in the purification step as a chlorine-based catalyst.

When a chlorine-based solvent is used as a solvent in the production of the phosphorus-based stabilizer, the chlorine-based solvent in the stabilizer can be reduced by a non-chlorine-based solvent in the purification step other than the method described above. And a method of extending the drying time.

As a method for reducing the chlorine compound contained in the phosphorus-based stabilizer, it is preferable to carry out the above-mentioned method without sacrificing the production efficiency and yield of the stabilizer. However, in order to achieve the object of the present invention,
Even if the production efficiency or the yield of the stabilizer is reduced, the method described above may be carried out.

The “chlorine atom and chloride ion concentration” in the present invention can be measured by any method. Examples of the method include a chemical analysis method, a fluorescent X-ray method, a combustion chlor method, a head space gas chromatography method, and a purge and trap gas chromatography method. Among them, particularly preferred is a fluorescent X-ray method, in which chlorine atoms and chlorine ions can be measured simultaneously.

The chlorine atom and the chlorine ion concentration are 1
１11000 ppm, preferably 1-8000 p
pm, more preferably 1 to 3000 ppm.

It is industrially difficult to completely remove chlorine atoms and chlorine ions contained in the component C-1.
From an economic point of view, the concentration is 1 to 20000 ppm, preferably 1 to 14500 ppm, and more preferably 1 to 5500 ppm.

It is industrially difficult to completely remove chlorine atoms and chlorine ions contained in the component C-2.
From an economic point of view, the concentration is 1 to 20000 ppm, preferably 1 to 14500 ppm, and more preferably 1 to 5500 ppm.

It is industrially difficult to completely remove chlorine atoms and chlorine ions contained in the component C-3.
From an economic viewpoint, the concentration is 0.1 to 50 ppm, preferably 0.1 to 40 ppm, and more preferably 10 to 40 ppm.

The aromatic polycarbonate resin composition of the present invention may contain a generally known antioxidant for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3
-Laurylthiopropionate), glycerol-3-
Stearyl thiopropionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-
4-hydroxyphenyl) propionate], 1,6-
Hexanediol-bis [3- (3,5-di-tert)
-Butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,
5-di-tert-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Screw (3,5
-Di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-) (Hydroxybenzyl) isocyanurate, tetrakis (2,4-di-tert) 4,4′-biphenylenediphosphosphinate
-Butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl}
-2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The compounding amount of these antioxidants is preferably 0.0001 to 0.05 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.

The ultraviolet absorber preferably used in the present invention is, specifically, a benzophenone-based 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, -Hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-
5-sulfoxytrihydrate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2'-dihydroxy-4,4 '
-Dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybensophenone, 2-hydroxy-4-methoxy- 2′-carboxybenzophenone and the like,
In the benzotriazole series, 2- (2-hydroxy-5
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy- 3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole-2 -Yl) phenol], 2- (2-hydroxy-3,5-di-te
rt-butylphenyl) benzotriazole, 2- (2
-Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5 -Tert
-Octylphenyl) benzotriazole, 2- (2-
(Hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl),
2,2′-p-phenylenebis (1,3-benzoxazin-4-one), 2- [2-hydroxy-3- (3,
4,5,6-tetrahydrophthalimidomethyl) -5
[Methylphenyl] benzotriazole, which can be used alone or as a mixture of two or more. Preferably, 2- (2-hydroxy-5-tert)
-Octylphenyl) benzotriazole, 2- (2-
Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert)
-Butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,
3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol].

The compounding amount of the bluing agent preferably used in the present invention is 0.05 to 10 ppm, preferably 0.1 to 3 ppm of the whole resin composition. If the blending amount is too large, the bluishness of the molded product such as a sheet product becomes strong and the luminous transparency decreases, and if the blending amount is too small, the effect of the bluing agent that reduces the yellow tint and imparts natural transparency is not exhibited. There is.

As a specific bluing agent, for example, Solvent Violet 13 [CA. No
(Color index No.) 60725; Trade name “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], generic name S
solvent Violet 31 [CA. No.6821
0; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33
[CA. No. 60725; Trade name "Diaresin Blue J" manufactured by Mitsubishi Chemical Corporation], generic name Solvent
Blue 94 [CA. No. 61500; trade name "Diaresin Blue N" manufactured by Mitsubishi Chemical Corporation], generic name Solv
ent Violet 36 [CA. No. 68210; brand name "Macrolex Violet 3" manufactured by Bayer AG
R "], generic name Solvent Blue 97 [trade name" Macrolex Blue RR "manufactured by Bayer AG] and generic name Solvent Blue 45 [CA. No61
110; Trade name "Tetazole Blue RL" manufactured by Sando Co., Ltd.
S ”], Ciba Specialty Chemicals, Inc., Macrolex Violet, Triazole Blue RLS, and the like, with Macrolex Violet and Triazole Blue RLS being particularly preferred.

The light diffusing agent preferably used in the present invention may be inorganic fine particles or organic fine particles generally used in plastic light diffusing plates. For example, silica-alumina-based clay minerals such as kaolin (hydrated aluminum silicates) ,
Examples thereof include silica magnesium-based clay minerals (hydrous magnesium silicates) represented by talc, barium sulfate, calcium silicate, silica alumina, calcium carbonate, titanium oxide, silicon oxide and the like. Examples of the organic fine particles include crosslinked polyacrylate and crosslinked polystyrene having a crosslinked structure. Especially calcium carbonate, barium sulfate,
Crosslinked polyacrylates and crosslinked polystyrenes are preferred because of their excellent dispersibility in aromatic polycarbonate resins. The amount used is in the range of 0.01 to 30 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the aromatic polycarbonate resin.
There is a range of 1 to 5 parts by weight.

For blending the phosphorus-based stabilizer and additives with the aromatic polycarbonate resin of the present invention, any method is adopted. For example, after the completion of melt polymerization, a method of adding a phosphorus-based stabilizer or an additive while keeping the polycarbonate resin in a molten state, mixing with a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder, etc. The method used is appropriately used. The aromatic polycarbonate resin composition thus obtained can be used as it is or after being once pelletized by a melt extruder.

[0080]

The present invention will be further described with reference to the following examples. In the examples, parts are parts by weight,% is% by weight,
The evaluation was based on the following method.

(1) Relative Fluorescence Intensity The fluorescence intensity at 465 nm (excitation wavelength: 320 nm) of the aromatic polycarbonate resin measured under the following conditions was determined by measuring the fluorescence intensity of a reference substance, and the ratio (relative fluorescence intensity =
(Fluorescence intensity of aromatic polycarbonate resin / fluorescence intensity of reference material) was calculated. Measurement conditions Apparatus Hitachi F4500 Lamp Xe, 150W Slit width Ex / Em 2.5mm each Photomar 400W Sample (concentration) 1mg aromatic polycarbonate resin / 5ml methylene chloride Reference material: phenyl salicylate 1.0 × 10 ^-3 mg / ml Methylene chloride (2) Terminal hydroxyl group concentration A 0.02 g sample of an aromatic polycarbonate resin was dissolved in 0.4 ml of chloroform, and 1H-N was added at 20 ° C.
The terminal hydroxyl group and the terminal phenyl group were measured using MR (EX-270 manufactured by JEOL Ltd.), and the terminal hydroxyl group concentration was measured by the following formula (ii). Terminal hydroxyl group concentration (mol%) = (number of terminal hydroxyl groups / total number of terminals) × 100 (3) (3) Viscosity average molecular weight A solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride using an Ostwald viscometer. Was measured at 20 ° C., and the viscosity average molecular weight M was calculated from the following equation. ηsp / c = [η] + 0.45 × [η] ² c (where [η]
Is intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

(4) Acid value A sample is dissolved in a benzene-ethanol solution, and neutralization titration is performed with a 0.1 N KOH ethanol solution using phenolphthalein as an indicator. The acid value is determined by the following equation. Oxidation (KOH mg / g) = A × f × N × 56.11 ÷ SA: Number of ml of KOH solution required for neutralization of sample f: Potency of KOH N: Normality of KOH S: Sample weight (g) (5) Cl Content of Stabilizer Chlorine atoms and chloride ions in the stabilizer were measured by a fluorescent X-ray method.

(6) Release Load A cup-shaped molded piece was formed using a Sumitomo SS75 injection molding machine, and the protrusion load at the time of release was measured with a memoryizer. (7) Adhesion (adhesion strength) A sheet of an aromatic polycarbonate resin composition having a thickness of 2 mm was obtained using an extruder. One side of this sheet is coated with a visible light curable adhesive [Adel BENEFIX P.
C], and laminating the same sheet while extruding it to one side so that air bubbles do not enter, and then 5,000 m by a light curing device equipped with a metal halide type dedicated to visible light.
The adhesive strength of the laminate obtained by irradiating J / cm ² light was measured according to JIS K-6852 (test method for compressive shear adhesive strength of adhesive). (8) Heat resistance during molding Using an injection molding machine, pellets of the aromatic polycarbonate resin composition were molded at a molding temperature of 350 ° C. for 1 minute and “cycles for measuring hue before staying” (70 mm × 50 mm × 2 mm).
Molded. Further, after the resin was retained in the cylinder for 10 minutes, a "plate for measuring hue after retention" was obtained. The hue of the flat plate before and after the stay was measured by a color difference meter, and the color difference ΔE was determined by the following equation. The smaller the value (ΔE) shown in the table, the better the molding heat resistance.

[0084]

(Equation 1)

(9) Moisture / heat fatigue resistance Using a so-called C-type measurement sample (aromatic polycarbonate resin composition) shown in FIG.
RH atmosphere, sinusoidal frequency 1Hz, maximum load 2k
g, the following fatigue tester [manufactured by Shimadzu Corporation]
Using the Shimadzu servo pulser EHF-EC5 type], the number of times until the measurement sample was broken was measured. The larger the value (number of times until breakage) shown in the table is, the better the resistance to wet heat fatigue is.

(10) White defect after high-temperature and high-humidity treatment Disk molding machine [DISK3 MIII manufactured by Sumitomo Heavy Industries, Ltd.] using aromatic polycarbonate resin composition pellets.
Optical disc substrate (diameter 120 mm, thickness 1.2
mm). In order to reproduce the increase in white spots when left for a long time in a harsh atmosphere,
It was kept in a thermo-hygrostat controlled at a relative humidity of 85% for 1000 hours, and then the number of white defects of 20 μm or more was counted using a polarizing microscope. This is performed for 25 optical disk substrates (120 mm in diameter), and the average value is obtained.
This was taken as the number of white defects.

Reference Example 1 Bisphenol A, 228 parts by weight, 218 parts by weight of diphenyl carbonate, and a transesterification catalyst; Na2 salt of bisphenol A (1.36 ×
10 ⁻⁵ parts by weight; 0.1 μmol / 1 mol bisphenol A as Na) and tetramethylammonium hydroxide (9.1 × 10 ⁻³ parts by weight; 100 μmol / 1 m)
ol bisphenol A) was charged into a polymerization tank 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 formed phenol was distilled off. Then, the pressure was gradually reduced while the internal temperature was raised to 200 ° C., and the reaction was carried out at 50 mmHg for 30 minutes while distilling off phenol. Further, the temperature was gradually raised and reduced to 220 ° C. and 30 mmHg, and the temperature and the pressure were reduced for 30 minutes.
The temperature was repeatedly increased and reduced to 40 ° C., 10 mmHg, 250 ° C., and 1 mmHg in the same procedure as above, and the reaction was continued.

Finally, at 250-255 ° C. (always 255
° C or less), and the stirring shear rate (unit: 1 / sec) of the polymerization tank stirring blade was changed to the stirring blade radius (unit: c).
m) is divided by the square of 0.001 to 0.001 (1 / sec × c
m ² ), and the polycondensation of the polycarbonate was continued.

After completion of the polycondensation, 1.8 parts of 2-methoxycarbonylphenylphenyl carbonate was added as a terminal terminator. Thereafter, a terminal blocking reaction was performed at 255 ° C. and 1 Torr or less for 10 minutes. Next, in the molten state, 0.00029 parts (5 × 10 ⁻⁷ mol / 1 mol of bisphenol) of dodecylbenzenesulfonic acid tetrabutylphosphonium salt was added as a catalyst deactivator at 255 ° C. and 10 Torr.
The reaction was continued in the following to obtain an aromatic polycarbonate resin having a viscosity average molecular weight of 24,300, a terminal hydroxyl group concentration of 14 mol%, and a relative fluorescence intensity of 1 × 10 ⁻³ . Hereinafter, this aromatic polycarbonate resin is abbreviated as PC-1.

Reference Example 2 In PC-1, 0.00004 parts of NaOH (1 μmol / 1mo) was used as the esterification catalyst.
The same operation as in Example 1 was carried out except for changing to 1-bisphenol A) to obtain an aromatic polycarbonate resin having a viscosity average molecular weight of 24,300, a terminal hydroxyl group concentration of 16 mol%, and a relative fluorescence intensity of 2 × 10 ⁻³ . Hereinafter, this aromatic polycarbonate resin is abbreviated as PC-2.

Reference Example 3 The same operation as in PC-1 was carried out except that 2-methoxycarbonylphenylphenyl carbonate was not used as the terminal stopper, and the viscosity average molecular weight was 2
An aromatic polycarbonate resin having a terminal hydroxyl group concentration of 52 mol% and a relative fluorescence intensity of 1 × 10 ⁻³ was obtained. Hereinafter, this aromatic polycarbonate resin is abbreviated as PC-3.

Reference Example 4 The same operation as in PC-1 was carried out except that 2-methoxycarbonylphenylphenyl carbonate was not used as the terminal stopper, and the viscosity average molecular weight was 1
4,600, an aromatic polycarbonate resin having a terminal hydroxyl group concentration of 54 mol% and a relative fluorescence intensity of 1 × 10 ⁻³ was obtained. Hereinafter, this aromatic polycarbonate resin is abbreviated as PC-4.

Comparative Example 1 Bisphenol A, 22
8 parts by weight, 220 parts by weight of diphenyl carbonate and a transesterification catalyst; Na2 salt of bisphenol A (1.3
6 × 10 ⁻³ parts by weight; 10 μmol / 1 mol as Na
Bisphenol A) and tetramethylammonium hydroxide (9.1 × 10 ⁻³ parts by weight; 100 μmol / 1)
mol bisphenol A) was charged into a polymerization tank equipped with a stirrer, a distillation column and a decompression device, and the atmosphere was replaced with nitrogen.
Dissolved in. 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 pressure was gradually reduced while the internal temperature was raised to 200 ° C., and the reaction was carried out at 50 mmHg for 30 minutes while distilling off phenol. Further, the temperature was gradually raised and reduced to 220 ° C. and 30 mmHg, and the reaction was repeated at the same temperature and the same pressure for 30 minutes, and further repeated at 240 ° C., 10 mmHg, 250 ° C. and 1 mmHg in the same procedure as described above. .

Finally, a polymer was obtained at 280 ° C. to 285 ° C. while continuing the polycondensation of the carbonate. This aromatic polycarbonate resin had a viscosity average molecular weight of 24,200, a terminal hydroxyl group concentration of 51 mol%, and a relative fluorescence intensity of 6 × 10 ⁻³ . Hereinafter, this aromatic polycarbonate resin is referred to as CEX-
Abbreviated as 1.

[Comparative Reference Example 2] The same operation as in CEX-1 was carried out except that the viscosity average molecular weight of the aromatic polycarbonate resin was changed, to obtain a viscosity average molecular weight of 14,600, a terminal hydroxyl group concentration of 52 mol%, and a relative fluorescence intensity. It was 6 × 10 ^-3 . Hereinafter, this aromatic polycarbonate resin is referred to as CEX-
Abbreviated as 2.

[Examples 1 to 10, Comparative Examples 1 and 2]
The aromatic polycarbonate resin pellets described in No. 2 and the phosphorus-based stabilizer or the composition thereof were blended on a weight basis described in Tables 1 and 2, and pelletized using an extruder. Various evaluations were performed using the pellets, and the results are shown in Tables 1 and 2.

The releasing agents, phosphorus-based stabilizers and the like described in Tables 1 and 2 are as follows. -1 fatty acid ester 1 stearic acid monoglyceride (acid value 0.8, purity 97.
−2 fatty acid ester 2 Mixture of stearic acid triglyceride and stearyl stearate (the mixing ratio of the former is about 70% by weight: acid value 1.8) −3 fatty acid ester 3 pentaerythritol tetrastearate (acid value) 0.
6) -1 C-1 stabilizer tetrakis (2,4-di-t-butylphenyl) -4,
4'-biphenylenediphosphonite, tetrakis (2,
4-di-t-butylphenyl) -4,3'-biphenylenediphosphonite and tetrakis (2,4-di-t
-Butylphenyl) -3,3'-biphenylenediphosphonite 100: 50: 10 (weight ratio) mixture-2 C-2 stabilizer bis (2,4-di-tert-butylphenyl) -4-
Phenyl-phenylphosphonite and bis (2,4-
5: 3 (weight ratio) mixture of di-tert-butylphenyl) -3-phenyl-phenylphosphonite-3C-3 stabilizer Tris (2,4-di-tert-butylphenyl) phosphite (in the stabilizer) Cl content of 20 ppm and 52
ppm) -4 C-4 stabilizer trimethyl phosphate (Cl content 640 in the stabilizer)
0 ppm) -5 C-5 stabilizer dioctadecylpentaerythritol diphosphite (Cl content in the stabilizer is 5000 ppm) -6 C-6 stabilizer dimethylphenylphosphonate (Cl content in the stabilizer is 4600 ppm) -7 phosphorus Acid TNPP stabilizer tris (nonylphenyl) phosphite bluing agent 1- (4-methylphenylamino) -4-hydroxy-9,
10-anthraquinone

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

As described above, the aromatic polycarbonate resin composition of the present invention maintains the transparency inherent in the polycarbonate resin and the releasability when a release agent is added, while maintaining the heat resistance during molding, the resistance to wet heat fatigue, and the adhesiveness. It is an aromatic polycarbonate resin composition which is excellent in stiffness and hardly causes white spherical defects of about 10 to 100 μm in an optical disk substrate when left under high temperature and high humidity for a long time. Therefore, various industries such as optical discs, spectacle lenses, Fresnel lenses, artificial kidneys, bottles, automobiles, bullet trains and other vehicles and houses, window glass sheets, arcades, road walls for wind, sound and snow, and phase difference films It is used for applications, particularly useful for optical discs and sheets, and has high industrial value.

[Brief description of the drawings]

FIG. 1 is a front view of a so-called C-shaped sample used for evaluating wet heat fatigue resistance. The thickness of the sample is 3 mm. The test is performed by passing a jig of a test machine through the hole indicated by reference numeral 6 and applying a predetermined load in the vertical direction indicated by reference numeral 7.

[Explanation of symbols]

1 Center of C-shaped double circle 2 Radius of inner circle of double circle (20 mm) 3 Radius of outer circle of double circle (30 mm) 4 Center angle (60 °) indicating position of jig mounting hole 5 Gap between sample end faces (13 mm) 6 Jig mounting hole (circle 4 mm in diameter, located at center of sample width) 7 Direction of load imposed on sample during fatigue test

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08K 5/524 C08K 5/524 5/5393 5/5393 F term (Reference) 4J002 CG011 CG021 CG031 CG041 EH036 EH046 EH056 EW047 EW067 EW087 EW127 EW137 FD067 FD166 GL00 GN00 GQ00 4J029 AA09 AB01 AB04 AC01 AD01 AE01 BB04A BB05A BB10A BB12A BB12B BB13A BB13B BB13C BC06A BF17 BG06X FC02 FC12 FC14 HC02 HC04A HC05A HC05A

Claims (4)

[Claims] (A) When a fluorescence spectrum is measured (excitation wavelength: 320 nm), 465 nm with respect to a reference substance is measured.
With a relative fluorescence intensity of 4 × 10 ⁻³ or less and a viscosity average molecular weight of 10,000 to 50,000, and 100 parts by weight of an aromatic polycarbonate resin obtained by melt polymerization of a dihydric phenol and a carbonate. , (B) an internal mold release agent having an acid value of 5 or less and 90% by weight or more of an ester of an alcohol and a fatty acid;
An aromatic polycarbonate resin composition comprising parts by weight. 2. A compound (C-1) having (C) a concentration of phosphorous acid, chlorine atom and chlorine ion of 1 to 11000 ppm and represented by the following general formula (1), and a compound represented by the following general formula (2). A compound represented by the following formula (C-2 component), a compound represented by the following general formula (3) (C-3 component), a compound represented by the following general formula (4) (C-4 component), 0.0001 to 1% by weight of at least one phosphorus stabilizer selected from the compound represented by the formula (5) (C-5 component) and the compound represented by the following general formula (6) (C-6 component) The aromatic polycarbonate resin composition according to claim 1, comprising a part. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image [Wherein, Ar ₁ , Ar ₂ , and Ar ₄ are aromatic groups which may have an alkyl substituent, and may be the same or different. Ar ₃ is a dialkyl-substituted aromatic group, which may be the same or different. Further, R ₁ , R ₂ and R ₃ are an alkyl group or an aromatic group which may have an alkyl substituent, and may be the same or different. ] 3. The aromatic polycarbonate resin composition according to claim 1, wherein the carbonate ester is diphenyl carbonate. 4. The aromatic polycarbonate resin composition according to claim 1, wherein (B) an internal mold release having an acid value of 3 or less.