JP3200338B2 - Method for producing aromatic polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aromatic polycarbonate having excellent moldability. More specifically, the present invention relates to a method for producing an aromatic polycarbonate which is inexpensive, has excellent fluidity and light resistance, and is substantially free of active chlorine and excellent in moldability.

[0002]

2. Description of the Related Art Polycarbonate has excellent mechanical properties such as impact resistance and transparency and has various uses. Known methods for producing polycarbonate include an interfacial method and a melting method in which a dihydroxy compound and a carbonic acid diester are transesterified under heating and reduced pressure.

In the former interfacial method, polycarbonate produced by using bisphenol A (2,2'-bis (4-hydroxyphenyl) propane) as a dihydroxy compound has a linear molecular structure. I have.

[0004] Since such a linear polycarbonate exhibits Newtonian fluid properties in a molten state, it is inferior in molding properties such as melt elasticity and melt strength, and it has been difficult to mold blow molded articles, hollow molded articles and the like.

As a method for improving the melting properties and moldability of such a polycarbonate, there is known a method of imparting branching properties to polycarbonate by copolymerizing a polyfunctional compound with bisphenol A. However, the polycarbonate having a branched structure has a remarkably increased melt viscosity, resulting in reduced fluidity, and as a result, it has been difficult to stably obtain a uniform molded body.

[0006] On the other hand, in the melting method, an aromatic dihydroxy compound and a carbonic acid diester are usually used as a catalyst, and a metal organic hydrochloric acid,
In the presence of inorganic hydrochloric acid, hydroxide, or alcoholate, for example, the mixture is finally heated to 250 to 300 ° C. and heated to 1 Torr.
This is a method of performing melt polycondensation under a vacuum of r or less.

This method has the advantage that the polycarbonate can be produced at a lower cost than the interface method, but the polymer is exposed to a high temperature for a long time, so that the branching reaction proceeds easily, Since a large amount of the branched structure is contained, there is a problem that the melt viscosity is remarkably increased as a result, and the fluidity and the moldability are reduced. Further, when the branching reaction progressed remarkably, a component insoluble in a solvent such as methylene chloride was sometimes formed.

Japanese Patent Application Laid-Open No. Hei 6-136112 discloses that bisphenol A is copolymerized with polyfunctional compound 2- (4-hydroxyphenyl) -2- (3'-carboxy-4'-hydroxyphenyl) propane. A method for producing a branched polycarbonate is disclosed.

However, the branched polycarbonate is
Although excellent in fluidity and moldability, the Kolbaschmit reaction for obtaining the above polyfunctional compound from bisphenol A is a reaction under high temperature and pressure, so a special device such as an autoclave is required, and as a product Since a polyvalent carboxylated compound is also produced in addition to the desired monocarboxylated compound, isolation and purification on a large scale is difficult, and there are serious problems in productivity and cost.

For this reason, there has been a demand for an inexpensive method for producing a polycarbonate resin which is excellent in moldability and fluidity and also excellent in moldability such as melt elasticity and melt strength, and which does not substantially contain active chlorine.

The inventors of the present invention have studied to solve the above-mentioned problems. As a result, by performing melt polycondensation under certain conditions, the fluidity and moldability of a moderately branched structure generated as a side reaction during the polycondensation are improved. The present inventors have found that an excellent aromatic polycarbonate can be produced at low cost, and have reached the present invention.

[0012]

That is, an object of the present invention is to contain a branched structure produced as a side reaction during polycondensation in a specific range, to be excellent in moldability and fluidity, to be inexpensive and to be substantially active chlorine. To provide a method for producing an aromatic polycarbonate containing no. Other objects and advantages of the present invention will become apparent from the following description.

[0013]

That is, according to the present invention, an aromatic dihydroxy compound and a carbonic acid diester represented by the following formula (A) are prepared by adding 1 × 1 mole of (a) the aromatic dihydroxy compound.
10 ^{-7 to} 2 × 10 ^-5 mol of alkali metal compound and / or
Or 1 × with respect to 1 mol of the alkaline earth metal compound and (b) the aromatic dihydroxy compound.
A process for producing an aromatic polycarbonate by melt polycondensation in the presence of 10 ^-3 to 1 × 10 ^-5 mol of a quaternary ammonium compound, comprising the steps of:
A polymer having an intrinsic viscosity [η] of 0.2 measured at 0 ° C. has an L / D (L represents the length of the horizontal rotation axis, and D represents the rotation diameter of the stirring blade) in the range of 2 to 30. The main repeating unit is a repeating unit represented by the following formula (I) characterized by reacting with a certain self-cleaning horizontal twin-screw reactor, and is represented by the following formulas (II) and (II)
The total of the repeating units represented by I) is from 0.001 to 0.
3 mol%, a repeating unit represented by the following formula (III) in a proportion of 0.001 mol% or more, and an intrinsic viscosity [η] measured in methylene chloride at 20 ° C. of 0.3 to 0.3
1.2 is a method for producing an aromatic polycarbonate.

[0014]

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[Where R ³ and R ⁴ are the same or different,
Hydrogen atom, alkyl group having 1 to 5 carbon atoms or 6 carbon atoms
And 10 to 10 optionally substituted aryl groups. R ⁵
Is an alkylene group having 3 to 8 carbon atoms. R ¹ and R ² are the same or different and represent a halogen atom or an alkyl group having 1 to 5 carbon atoms. m and n are the same or different;
Or 2. ]

[0016]

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Wherein X, R ¹ , R ² , m and n are the same as those in the formula (A). ]

[0018]

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Wherein X, R ¹ , R ² , m, and n are the same as in formula (A). ]

[0020]

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Wherein X, R ¹ , R ² , m and n are the same as in the formula (A). ]

In the above formula (A), R ³ and R ⁴ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an optionally substituted aryl group having 6 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. The aryl group includes a phenyl group. R ⁵ is an alkylene group having 3 to 8 carbon atoms. As the alkylene group, pentylene group, hexylene group and the like to. R ¹ and R ² are the same or different,
It represents a halogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the halogen atom include chlorine and bromine.
Examples of the alkyl group include a methyl group and a t-butyl group. m and n are the same or different and are 0, 1 or 2.

In this, R¹, R^TwoAre each hydrogen
Or R^Three, R ^FourIs methyl
It is preferably a group.

The structural units represented by the above formulas (II) and (III) are used in a process of melt-polycondensing an aromatic dihydroxy compound and a diester carbonate represented by the above formula (A) in the presence of a polycondensation catalyst. In the above, it is produced as a side reaction together with the structural unit represented by the above formula (I).

More specifically, as a first side reaction, a structural unit represented by the above formula (II) in which the ortho-position of the hydroxyl group is carboxylated by a Fries type intramolecular rearrangement reaction or a Kolbeschmidt type reaction. Is generated, and as a second step reaction, the hydroxyl group at the ortho position generated in the first step reaction undergoes a transesterification reaction, whereby a structural unit represented by the above formula (III) is formed.

However, since the hydroxyl group present in the structural unit represented by the formula (II) has low electronic and steric reactivity, the second-stage reaction hardly occurs, and the unreacted compound represented by the formula (II) In some cases, the structural unit shown may also be present in the polymer.

The structural unit represented by the above formula (II) has a concept similar to that of phenyl salicylate, which is generally used as an ultraviolet absorber, and is an aromatic polycarbonate containing the structural unit represented by the above formula (II). Is also preferable from the viewpoint of light resistance.

The above formula (II) in aromatic polycarbonate
The presence of the repeating unit represented by the above formula (III) can be easily confirmed by nuclear magnetic resonance measurement, and quantification is extremely easy due to the peak area.

In the aromatic polycarbonate produced by the present invention, the repeating structural units represented by the above formulas (II) and (III) have a specific range with respect to the main repeating structural units represented by the above formula (I). And aromatic polycarbonate. Specifically, the total of the repeating structures represented by the formulas (II) and (III) is 0.001
０．３0.3 mol%, the repeating structure represented by the above formula (III) is contained at a ratio of 0.001 mol% or more, and further the repeating structure represented by the above formula (II) and the above formula (III) is contained. Of the above formula (II)
It is preferable to contain the repeating structure represented by I) in a proportion of 0.01 mol% or more.

The total of the repeating units represented by the above formulas (II) and (III) is less than 0.001 mol%, or the amount of the repeating units represented by the above formula (III) is 0.001 mol%.
If the amount is less than mol%, improvement in fluidity and moldability cannot be expected for the linear aromatic polycarbonate.

When the total of the repeating units represented by the formulas (II) and (III) is 0.3 mol% or more, the fluidity is remarkably reduced, and the moldability is significantly reduced. In some cases, it becomes a gel-like substance insoluble in methylene chloride, which makes molding difficult.

The aromatic dihydroxy compound used in the present invention is a compound represented by the following formula (A).

[0033]

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Here, R ³ and R ⁴ are the same or different,
Hydrogen atom, alkyl group having 1 to 5 carbon atoms or 6 carbon atoms
And 10 to 10 optionally substituted aryl groups. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. The aryl group includes a phenyl group. R
⁵ is an alkylene group having 3 to 8 carbon atoms. As the alkylene group, pentylene group, hexylene group and the like to. R ¹ and R ² are the same or different and represent a halogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the halogen atom include chlorine and bromine. Examples of the alkyl group include a methyl group and a t-butyl group. m and n are the same or different and are 0, 1 or 2.

Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane, 1,1-
Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4
-Hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane,
2,2-bis (4-hydroxy-3-bromophenyl)
And bis (hydroxyaryl) alkanes such as propane.

Further, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane are also included.

Also, dihydroxyaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide;
And dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide.

Further, dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide are exemplified.

Further, dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone are used.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.

These aromatic dihydroxy compounds are often used alone, but if necessary, two or more of them can be used.

The carbonic diester used in the present invention includes an optionally substituted aryl having 6 to 10 carbon atoms,
Esters such as aralkyl, alkyl having 1 to 5 carbons, and cycloalkyl having 3 to 8 carbons are preferable.

Specific examples of the carbonic diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl Carbonate or the like is used. Of these, diphenyl carbonate is particularly preferred.

The amount of the carbonic acid diester used is 80 to 300 mol%, preferably 90 to 250 mol%, particularly preferably 90 to 20 mol%, based on the aromatic dihydroxy compound.
A range of 0 mol% is desirable.

In the present invention, the amount of the polycondensation catalyst and the amount of the polycondensation catalyst are determined by the above formula (I) which is produced as a side reaction during the polycondensation reaction.
It is preferable that the amount of the repeating unit represented by I) and the formula (III) can be controlled to a desired amount, and furthermore, an aromatic polycarbonate having good quality such as optical properties such as hue and transparency and mechanical properties. Those which can produce are preferably used. (A) 1 × per mole of aromatic dihydroxy compound
10 ^{-7 to} 2 × 10 ^-5 mol of alkali metal compound and / or
Or alkaline earth metal compound and, with respect to 1 mol (b) an aromatic dihydroxy compound, 1 ×
10 ^-3 to 1 × 10 ^-5 mol of quaternary ammonium compound is used.

Examples of the alkali metal compound include alkali metal hydroxides, hydrogen carbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, borohydrides Salts, benzoates, hydrogen phosphates, bisphenols, phenol salts and the like are mentioned. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium nitrate, potassium nitrate, lithium nitrate, sodium nitrite, Potassium nitrite, lithium nitrite, sodium nitrite, potassium nitrite, lithium nitrite, 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.

Further, as the alkaline earth metal compound,
For example, alkaline earth metal hydroxides, bicarbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, borohydrides, benzoates, phosphorus Acid hydrides, bisphenols, phenol salts and the like can be mentioned. Specifically, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate,
Calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, Barium, magnesium acetate, strontium acetate, calcium nitrate, barium nitrate, magnesium nitrate, strontium nitrate, calcium nitrite, barium nitrite, magnesium nitrite, nitrous Strontium nitrate, calcium nitrite,
Barium nitrite, magnesium sulfite, strontium sulfite, calcium cyanate, barium cyanate, magnesium cyanate, strontium cyanate, calcium thiocyanate, barium thiocyanate, magnesium thiocyanate, strontium thiocyanate, calcium stearate, barium stearate, stearin And magnesium strontium stearate.

The amount of the alkali metal compound or alkaline earth metal compound to be used is 1 × 10 ^-7 to 2 × 10 ^-5 mol, particularly preferably 1 × 10 ^-7 to 2 mol, per 1 mol of the aromatic dihydroxy compound. It can be used in an amount of × 10 ^-5 mol.

When the amount of the alkali metal compound or alkaline earth metal compound is at least 2 × 10 ^-5 mol per 1 mol of the aromatic dihydroxy compound, the compound represented by the above formula (II) contained in the obtained aromatic polycarbonate is obtained. ) And the amount of the repeating unit represented by the above formula (III) deviates from a desired range, and the moldability of the obtained aromatic polycarbonate is unpreferably reduced.

The amount of the aromatic dihydroxy compound 1
If the amount is not more than 1 × 10 ⁻⁸ mol, the polycondensation reaction does not proceed sufficiently and a high-molecular-weight aromatic polycarbonate cannot be obtained.

[0051]

Examples of the quaternary ammonium compound include tet
Lamethylammonium hydroxide, tetraethylan
Monium hydroxide, tetrabutyl ammonium hydride
Roxide, tetrabutylammonium acetate, tet
Lamethylammonium borohydride and the like.

Thermal decomposition onset temperature is 250 ° C. or less or boiling point
Quaternary ammonium compounds having a
New

The amount of the quaternary ammonium compound used is 1 × 10 ⁻³ per mole of the aromatic dihydroxy compound.
１1 × 10 ^-5 mol, preferably 1 × 10 ^{-3 to} 5 × 10 ^-5
It can be used in the molar range.

Outside the above range, the reactivity or the quality of the aromatic polycarbonate obtained is undesirably reduced.

For the purpose of obtaining a desired aromatic polycarbonate in the present invention, other metal compounds can be used in combination with the above-mentioned polycondensation catalyst. As such metal compounds, for example, metal elements belonging to groups IIB, IIIB, IVA and IVB of the periodic table and compounds thereof can be preferably used.

In the present invention, in the process of melt-polymerizing an aromatic dihydroxy compound represented by the following formula (A) and a carbonic acid diester in the presence of a polycondensation catalyst, a polymer having an intrinsic viscosity [η] of 0.2 is obtained. , L / D is 2-30
The reaction is carried out by a self-cleaning horizontal twin-screw reactor in the range of Here, the intrinsic viscosity [η] is measured at 20 ° C. in methylene chloride.

In the present invention, the intrinsic viscosity [η] is 0.2
The polymer reached is subjected to polycondensation using a self-cleaning horizontal twin-screw reactor, but other reactors and a self-cleaning horizontal twin-screw reactor can be used in combination.

This self-cleaning horizontal twin-screw reactor has two horizontal rotating shafts that rotate in the same direction, and a pair of left and right disc-shaped or wheel-shaped stirring shafts having phases shifted from each other. One or more wings are combined, and at least two or more wings are installed per rotation axis.
The surface of the reactant is renewed while maintaining a small interval so that one tip of a pair of stirring blades out of phase cleans the side surface of the other stirring blade and both stirring blades clean the inner wall of the reactor. is there.

The L / D (L: length of the horizontal rotating shaft, D: rotating diameter of the stirring blade) of the reactor is in the range of 2 to 30, preferably in the range of 2 to 15.

When L / D is 2 or less, the reaction rate becomes extremely low, so that the residence time at a high temperature becomes long, so that the amount of the repeating units represented by the above formulas (II) and (III) increases. Therefore, a desired aromatic polycarbonate cannot be obtained.

In the reaction in the reactor, the V / S (V: volume of the polymer,
(S: evaporation area of the polymer) is preferably carried out under extremely low conditions. Here, the evaporation area of the polymer (S)
Is determined as the sum of the inner surface area of the reactor and the surface area of the stirring blade.

Specifically, it is preferable that V / S is in the range of 1 mm to 50 mm, more preferably, in the range of 3 mm to 50 mm.

By performing polycondensation using the above-mentioned self-cleaning horizontal twin-screw reactor, the reaction time at a high temperature is shortened, and a desired aromatic polycarbonate can be effectively obtained.

In the present invention, the polymer having an intrinsic viscosity [η] of 0.2 supplied to the self-cleaning horizontal twin-screw reactor is produced under conventionally known polycondensation reaction conditions of an aromatic dihydroxy compound and a carbonic acid diester. It was done.

Specifically, the first-stage reaction is carried out at 80 to 250
° C, preferably 100-240 ° C, more preferably 1
The two are reacted at normal pressure at a temperature of 20 to 230 ° C. for 0 to 4 hours, more preferably 0.25 to 3 hours. Then, the reaction temperature was increased while reducing the pressure of the reaction system, and 0.1 to 10 mm
The polycondensation reaction is performed at a temperature of 200 to 290 ° C. under a reduced pressure of Hg.

There is no particular limitation on the reaction apparatus for obtaining a polymer having an intrinsic viscosity [η] of 0.2, which promotes the polycondensation reaction in a self-cleaning horizontal twin-screw reactor, and obtains a desired aromatic polycarbonate in the present invention. Any reactor can be used as long as it is a tank type, a tube type, or a tower type.

In addition, the reaction temperature was 29 throughout the entire polycondensation reaction for obtaining the desired aromatic polycarbonate, including the polycondensation reaction in the self-cleaning horizontal twin-screw reactor.
It is preferably 0 ° C. or lower. When the reaction proceeds at 290 ° C. or higher, the branching reaction proceeds to a high degree, so that a desired aromatic polycarbonate cannot be obtained, and other physical properties such as hue are not preferable.

In the present invention, the amount of metal used (unit: 10 ^-6 mol / aromatic dihydroxy compound) of the alkali metal and / or alkaline earth metal compound used and the time required for the reaction at a reaction temperature of 270 ° C. or higher (unit) : Time) is preferably in the range of 1 to 20, preferably 2 to 15.

By producing in the above range, the desired aromatic polycarbonate in which the content of the repeating units represented by the above formulas (II) and (III) is controlled can be obtained.

In the present invention, before the start of the polycondensation reaction,
It is also preferable to add various stabilizers in the molten state at least once during or after the reaction. Examples of the stabilizer include a sulfur-containing acidic compound and / or a derivative formed from the acidic compound, an epoxy compound, a phosphorus compound, and the like.

The sulfur-containing acidic compound and / or the derivative formed from the acidic compound is used in an amount of 0.01 to 500 ppm, preferably 0.01 to 300 ppm, more preferably 0.01 to 500 ppm based on the aromatic polycarbonate produced.
It can be used at a rate of １００100 ppm. The method for adding the compound to the polycondensable product is not particularly limited.

For example, the aromatic polycarbonate which is a reaction product may be added while it is in a molten state, or may be added after being pelletized once and then re-melted.

Examples of the sulfur-containing acidic compound and / or a derivative formed from the acidic compound include sulfurous acid, sulfuric acid, sulfinic acid compounds, sulfonic acid compounds, and derivatives thereof. Specifically, as the sulfuric acid derivatives, dimethyl sulfate, diethyl sulfate, sulfuric acid,
Dipropyl sulfate, dibutyl sulfate, diphenyl sulfate, dimethyl sulfite, diethyl sulfite, diphenyl sulfite, sodium dodecyl sulfate, sodium hexadecyl sulfate, dimethyl butyl hexadecyl ammonium butyl sulfate, dimethyl hexadecyl ammonium ethyl sulfate, trimethyl hexadecyl ammonium methyl sulfate, etc. be able to.

Examples of the sulfinic acid compounds include benzenesulfinic acid, toluenesulfinic acid, naphthalenesulfinic acid and the like. Examples of the sulfonic acid compound and its derivative include the following compounds. That is, benzenesulfonic acid, p
-Sulfonic acids such as toluenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p- Butyl toluenesulfonate, octyl p-toluenesulfonate, p-
Examples thereof include sulfonic acid esters such as phenyl toluenesulfonic acid, and ammonium sulfonate salts such as ammonium p-toluenesulfonate, tetrabutylphosphonium p-toluenesulfonate, and tetraphenylphosphonium dodecylbenzenesulfonate.

These compounds can be used alone or in combination. Of these, [B] pK
As the sulfur-containing acidic compound having an a value of 3 or less and a derivative formed from the acidic compound, a sulfonic acid compound or a derivative thereof is preferably used. In particular, benzenesulfonic acid, butylbenzenesulfonic acid, p-toluenesulfonic acid, Ethyl p-toluenesulfonate, butyl p-toluenesulfonate, sodium dodecyl sulfate, trimethylhexadecyl ammonium methyl sulfate, tetrabutylammonium p-toluenesulfonate, tetrabutylphosphonium p-toluenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate Is preferably used.

Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, acrylglycidylether, t-
Butylphenylglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-
Methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3', 4'-epoxycyclohexylcarboxylate 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6′-methylcyclohexylcarboxylate,
Bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate , Butadiene diepoxide, tetraphenylethylenepoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl -5-t-butyl-1,2-epoxycyclohexane,
Octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-
Dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-
Isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3 -Epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-tert-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl-4,5-epoxy-cis -1,
2-cyclohexyldicarboxylate, di-n-butyl-3-tert-butyl-4,5-epoxy-cis-1,2
-Cyclohexyldicarboxylate and the like.

These may be used alone or as a mixture of two or more. Of these, alicyclic epoxy compounds are preferably used, and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate is particularly preferably used.

In the present invention, it is preferable to add such an epoxy compound to the polycarbonate in an amount of 1 to 2000 ppm, preferably 1 to 1000 ppm.

Further, as the phosphorus compound, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphite ester can be used.

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

Examples of the phosphite include compounds represented by the following general formula.

P (OR) ₃ (wherein R represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, which may be the same or different)

As a compound represented by such a formula,
For example, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tris (2-ethylhexyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, tristearyl phosphite, tris ( Trialkyl phosphites such as 2-chloroethyl) phosphite and tris (2,3-dichloropropyl) phosphite; tricycloalkyl phosphites such as tricyclohexyl phosphite; triphenyl phosphite; tricresyl phosphite; Ethylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite, etc. Triaryl phosphites, phenyl didecyl phosphite, diphenyl decyl phosphite, diphenyl isooctyl phosphite, phenyl isooctyl phosphite, and 2-arylalkyl phosphites such as ethylhexyl diphenyl phosphite and the like.

Further, phosphites such as distearyl pentaerythrityl diphosphite and bis (2,4
-Di-t-butylphenyl) pentaerythrityl diphosphite. Among them, especially Tris (2,4-
Di-t-butylphenyl) phosphite is preferably used.

These compounds can be used alone or in combination. These may be added separately or simultaneously. In the present invention, the phosphorus compound as described above is used in an amount of 10 to 1000 ppm, preferably 50 to 500 ppm, based on the polycarbonate resin.
Can be added.

In the present invention, there is no particular limitation on the method for adding the above-mentioned epoxy compound and phosphorus compound to the polycarbonate as a reaction product. For example, these may be added while the polycarbonate as a reaction product is in a molten state, or may be added after pelletizing the polycarbonate once and then re-melting. In the former, in a molten reactor obtained after the polymerization reaction is completed, or while polycarbonate as a reaction product in the extruder is in a molten state, after adding these to form a polycarbonate, Pelletizing may be carried out through an extruder, or while the polycarbonate obtained by the polymerization reaction is pelletized from the reactor through the extruder, these compounds are added and the polycarbonate is obtained by kneading. Can be.

At this time, these compounds may be added simultaneously or separately. When these compounds are added in combination, the order of addition is not limited.

In the present invention, the polycarbonate obtained as described above is added to the polycarbonate as long as the object of the present invention is not impaired.
Heat stabilizers, ultraviolet absorbers, release agents, coloring agents, antistatic agents, slip agents, anti-locking agents, lubricants, anti-fog agents,
Natural oils, synthetic oils, waxes, organic fillers, inorganic fillers and the like may be added. Such additives may be added simultaneously with the aromatic dihydroxy compound, or may be added separately.

Specific examples of such heat-resistant stabilizers include phenol-based stabilizers, organic thioether-based stabilizers, and hindered amine-based stabilizers.

Examples of the phenol-based stabilizer include, for example, n
-Octadecyl-3- (4-hydroxy-3 ', 5'-
Di-tert-butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-)
Hydroxyphenyl) propionate] methane, 1,
1,3-Tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzylmalonate, 4-hydroxymethyl-2,6-di-t-butylphenol, etc., which are used alone They may be used alone or in combination of two or more.

As the thioether-based stabilizer, for example,
Dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- (β
-Lauryl-thiopropionate).

These may be used alone or in combination of two or more. Examples of hindered amine stabilizers include bis (2,2,6,6-tetramethyl-4).
―Piperidyl) sebacate, bis (1,2,2,6,6)
-Pentamethyl-4-piperidyl) sebacate, 1-
[2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3- Octyl-1,2,3-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1,2,2,6,2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate
6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl)
1,2,3,4-butanetetracarboxylate and the like can be mentioned.

These may be used alone or as a mixture of two or more. These heat stabilizers are used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate.
Desirably, it is used in an amount of from 0.01 to 0.3 parts by weight.

The heat stabilizer may be added in a solid state or a liquid state. It is preferable to add such a heat stabilizer while the polycarbonate is in a molten state while being cooled and pelletized from the final polymerization vessel. In this case, the heat history of the polycarbonate is reduced. Further, when heat treatment is again performed by extrusion molding, pelletizing, or the like, since the polycarbonate contains a heat stabilizer, thermal decomposition can be suppressed.

The ultraviolet absorber may be a general ultraviolet absorber and is not particularly limited. Examples thereof include a salicylic acid ultraviolet absorber, a benzophenone ultraviolet absorber,
Benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like can be given.

Specific examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate. As the benzophenone-based ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-
Carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-
Hydroxy-4-n-octoxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, 4
-Dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and the like.

Benzotriazole ultraviolet absorbers include 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, 2- (2'-hydroxy-3 ',
5'-di-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-
Hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
(t-amylphenyl) benzotriazole, 2- [2 '
-Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'-methylenebis [4
-(1,1,3,3-tetramethylbutyl) -6- (2
H-benzotriazol-2-yl) phenol].

Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate and the like. These may be used alone or as a mixture of two or more.

These ultraviolet absorbers are usually used in an amount of 0.001 to 5 parts by weight, based on 100 parts by weight of the polycarbonate.
Preferably, it can be used in an amount of 0.005 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight.

Further, the release agent may be a general release agent and is not particularly limited. For example, examples of the hydrocarbon release agent include natural and synthetic paraffins, polyethylene waxes, and fluorocarbons.

Examples of the fatty acid release agent include stearic acid,
Higher fatty acids such as hydroxystearic acid, oxy fatty acids and the like can be mentioned. Examples of the fatty acid amide release agent include fatty acid amides such as stearic acid amide and ethylenebisstearamide, and alkylenebisfatty acid amides.

Examples of the alcohol release agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols and polyglycerols.

Examples of the fatty acid ester release agent include lower alcohol esters of aliphatic acids such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters.

Examples of the silicone release agent include silicone oils. These may be used alone or in combination of two or more.

These release agents are polycarbonate 10
Usually, 0.001 to 5 parts by weight, preferably 0.005 to 1 part by weight, more preferably 0.0 to 5 parts by weight with respect to 0 parts by weight
It can be used in an amount of 1 to 0.5 parts by weight.

Further, the colorant may be a pigment or a dye. Coloring agents include inorganic and organic coloring agents, either of which may be used.
They may be used in combination.

Specific examples of the inorganic colorant include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as navy blue, and zinc chromate. , Chromates such as molybdenum red, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine blue,
Phosphates such as manganese violet; carbon such as carbon black; and metallic powder coloring agents such as bronze powder and aluminum powder.

Specific examples of the organic colorant include nitroso-type dyes such as naphthol green B, nitro-type dyes such as naphthol yellow S, lithol red and Bordeaux 10
B, phthalocyanine such as naphthol red and chromophtal yellow, phthalocyanine such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue, quinacridone violet, and dioxazine violet.

These coloring agents may be used alone or in combination. These colorants are used in an amount of usually 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ^{−5 to} 3 parts by weight, more preferably 1 × 10 ⁻⁵ to 1 part by weight, based on 100 parts by weight of the polycarbonate. It can be used in quantity.

[0111]

According to the present invention, the aromatic dihydroxy compound and the carbonic acid diester are melt-polycondensed in the presence of a polycondensation catalyst, so that a branched structure can be obtained in a specific range without using a branching agent. And an aromatic polycarbonate substantially free of active chlorine can be provided at low cost.

Further, this aromatic polycarbonate can stably obtain a molded article having good appearance and no unevenness by blow molding or the like.

[0113]

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

The methods for measuring and testing the physical properties of the aromatic polycarbonate in the following examples are shown below. Intrinsic viscosity [IV] (dl / g): 20 ° C in methylene chloride
Was measured. MFR (g / 10 minutes): Measured at a temperature of 300 ° C. and a load of 1.2 kgf according to JIS K-7210. Polymer structure: 1H-NMR GX-270 (manufactured by JEOL Ltd.) was used to examine each structural unit and its ratio. Active chlorine equivalent: measured by Dorman microanalysis. The results were all below the detection limit (1 ppm) as shown in the table. Iron content: Measured by ICP analysis. The results were all below the detection limit (1 ppm) as shown in the table. Blow-molded product appearance: After the molten resin was supplied to the mold by an extruder, the bottle was blow-molded, and the appearance of the obtained bottle was observed. Hue: Performed by observing the appearance.

Example 1 228 parts by weight of 2,2'-bis (4-hydroxyphenyl) propane (bisphenol A), 225 parts by weight of diphenyl carbonate, and 0.036 of tetramethylammonium hydroxide (25% aqueous solution) as a catalyst Parts by weight, bisphenol A disodium salt 0.00068 parts by weight (2.5 × 10 ^-6 mol / mol-
Bisphenol A) was charged in a reactor equipped with a stirrer, a decompression device, a distillation column, and the like, and stirred at 180 ° C. under a N ₂ atmosphere for 30 minutes.

Next, the pressure was gradually reduced to 30 mmHg at the same temperature, and the reaction was carried out at the same temperature and the same pressure for 30 minutes. The temperature was further increased to 270 ° C., and the pressure was gradually reduced to 1 mmHg, followed by stirring for 30 minutes. The intrinsic viscosity of the obtained reactant is [I
V] = 0.3.

Next, the reaction product was weighed with a gear pump to 20 kg.
Per hour, and fed into a self-cleaning horizontal twin-screw reactor (L / D = 5, inner volume 60 L) controlled at 280 ° C. and 0.15 mmHg to proceed with polymerization until the intrinsic viscosity [IV] = 0.5. At this time, the residence time is 60 minutes and V / S
Was 8 mm.

Next, the polymer was fed into a twin-screw extruder (L / D = 20, barrel temperature 285 ° C.) by a gear pump.
At this time, the sulfur-containing acidic compound and / or
Alternatively, 25 ppm of dodecylbenzenesulfonic acid tetrabutylphosphonium salt as the acidic compound and 100 pp of tris (nonylphenyl) phosphite as the phosphorus compound
m, Irganox 1076 as a phenolic compound
100 ppm (Ciba-Geigy) was added to the polymer.

Table 1 shows the measurement results of the physical properties and the like of the obtained polymer and molded article.

Example 2 228 parts by weight of 2,2'-bis (4-hydroxyphenyl) propane (bisphenol A), 225 parts by weight of diphenyl carbonate, and 0.036 of tetramethylammonium hydroxide (25% aqueous solution) as a catalyst Parts by weight, 0.00027 parts by weight of bisphenol A disodium salt (1 × 10 ⁻⁶ mol / mol-bisphenol A) were charged into a reactor equipped with a stirrer, a decompression device, a distillation column, and the like, and the mixture was heated at 180 ° C. and N _2. The mixture was stirred under an atmosphere for 30 minutes.

Next, the pressure was gradually reduced to 30 mmHg at the same temperature, and the reaction was carried out at the same temperature and pressure for 30 minutes. The temperature was further increased to 270 ° C., and the pressure was gradually reduced to 1 mmHg, followed by stirring for 30 minutes. The intrinsic viscosity of the obtained reactant is [I
V] = 0.3.

Next, the reaction product was weighed with a gear pump to 10 kg.
Per hour, and fed into a self-cleaning horizontal twin-screw reactor (L / D = 5, inner volume 60 L) controlled at 280 ° C. and 0.15 mmHg to proceed with polymerization until the intrinsic viscosity [IV] = 0.5. At this time, the residence time is 120 minutes, and V /
S was 8 mm.

Next, the polymer was fed into a twin-screw extruder (L / D = 20, barrel temperature 285 ° C.) by a gear pump.
At this time, the sulfur-containing acidic compound and / or
Alternatively, dodecylbenzenesulfonic acid tetrabutylphosphonium salt 10 ppm as the acidic compound and tris (nonylphenyl) phosphite 100 pp as the phosphorus compound
m, Irganox 1076 as a phenolic compound
100 ppm (Ciba-Geigy) was added to the polymer.

Table 1 shows the measurement results of the properties and the like of the obtained polymer and molded article.

[0125]

[Table 1]

Example 3 228 parts by weight of 2,2'-bis (4-hydroxyphenyl) propane (bisphenol A), 225 parts by weight of diphenyl carbonate, and 0.036 of tetramethylammonium hydroxide (25% aqueous solution) as a catalyst Parts by weight, bisphenol A disodium salt 0.00068 parts by weight (2.5 × 10 ^-6 mol / mol-
Bisphenol A) was charged in a reactor equipped with a stirrer, a decompression device, a distillation column, and the like, and stirred at 180 ° C. under a N ₂ atmosphere for 30 minutes.

Next, the pressure was gradually reduced to 30 mmHg at the same temperature, and the reaction was carried out at the same temperature and the same pressure for 30 minutes. The temperature was further increased to 270 ° C., and the pressure was gradually reduced to 1 mmHg, followed by stirring for 30 minutes. The intrinsic viscosity of the obtained reactant is [I
V] = 0.3.

Next, this reaction product was added to a 3 kg / g
The mixture was fed to a self-cleaning horizontal twin-screw reactor (L / D = 5, internal volume: 6 L) controlled at 280 ° C. and 0.15 mmHg over a period of time, and the polymerization was advanced until the intrinsic viscosity [IV] = 0.5. At this time, the residence time is 45 minutes, and V / S is 5
mm.

Next, the polymer was fed into a twin-screw extruder (L / D = 20, barrel temperature 285 ° C.) by a gear pump. At this time, the sulfur-containing acidic compound and / or tetrabutylphosphonium dodecylbenzenesulfonate 25 ppm as the acidic compound and tris (nonylphenyl) phosphite 100 as the phosphorus compound were added to the polymer.
ppm, Irganox 10 as phenolic compound
76 (manufactured by Ciba-Geigy) 100 ppm was added to the polymer.

Table 2 shows the measurement results of the properties and the like of the obtained polymer and molded article.

Example 4 228 parts by weight of 2,2'-bis (4-hydroxyphenyl) propane (bisphenol A), 225 parts by weight of diphenyl carbonate, and 0.036 of tetramethylammonium hydroxide (25% aqueous solution) as a catalyst Parts by weight, bisphenol A disodium salt 0.00068 parts by weight (2.5 × 10 ^-6 mol / mol-
Bisphenol A) was charged in a reactor equipped with a stirrer, a decompression device, a distillation column, and the like, and stirred at 180 ° C. under a N ₂ atmosphere for 30 minutes.

Next, the pressure was gradually reduced to 30 mmHg at the same temperature, and the reaction was carried out at the same temperature and pressure for 30 minutes. The temperature was further increased to 270 ° C., and the pressure was gradually reduced to 1 mmHg, followed by stirring for 30 minutes. The intrinsic viscosity of the obtained reactant is [I
V] = 0.3.

Next, this reaction product was put into a 25 kg
Per hour and into a self-cleaning horizontal twin-screw reactor (L / D = 5, internal volume 60 L) controlled at 275 ° C. and 0.2 mmHg to proceed with polymerization until the intrinsic viscosity [IV] = 0.5. At this time, the residence time was 45 minutes, and V / S was 8 mm.

Next, the polymer was fed into a twin-screw extruder (L / D = 20, barrel temperature 285 ° C.) by a gear pump. At this time, the sulfur-containing acidic compound and / or tetrabutylphosphonium dodecylbenzenesulfonate 25 ppm as the acidic compound and tris (nonylphenyl) phosphite 100 as the phosphorus compound were added to the polymer.
ppm, Irganox 10 as phenolic compound
76 (manufactured by Ciba-Geigy) 100 ppm was added to the polymer.

Table 2 shows the measurement results of the properties and the like of the obtained polymer and molded article.

[0136]

[Table 2]

Comparative Example 1 As a polycondensation catalyst, tetramethylammonium hydroxide (25% aqueous solution) 0.03
6 parts by weight, bisphenol A disodium salt 0.013
Same as Example 1 except that 6 parts by weight (5 × 10 ⁻⁵ mol / mol-bisphenol A), a sulfur-containing acidic compound and / or 500 ppm of dodecylbenzenesulfonic acid tetrabutylphosphonium salt as the acidic compound were used relative to the polymer. To produce an aromatic polycarbonate. Table 3 shows the measurement results of the physical properties of the obtained polymer.

In the obtained aromatic polycarbonate, the amount of the repeating units represented by the above formulas (II) and (III) was extremely large, and a so-called gelled product partially insoluble in methylene chloride was observed.

[0139]

[Table 3]

[Comparative Example 2] Linear polycarbonate L-1250 (manufactured by Teijin Chemicals Limited, [IV] =
0.49) was melted by an extruder and supplied to a mold.
When the bottle was blow-molded, drawdown occurred, and a good molded product could not be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Katsushi Sasaki 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Limited Iwakuni Research Center Hei 8-92365 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (5)

(57) [Claims] 1. An aromatic dihydroxy compound and a carbonic acid diester represented by the following formula (A): 1 × 1 mole of the aromatic dihydroxy compound
10 ^{-7 to} 2 × 10 ^-5 mol of alkali metal compound and / or
Or 1 × with respect to 1 mol of the alkaline earth metal compound and (b) the aromatic dihydroxy compound.
A process for producing an aromatic polycarbonate by melt polycondensation in the presence of 10 ^-3 to 1 × 10 ^-5 mol of a quaternary ammonium compound, comprising the steps of:
A polymer having an intrinsic viscosity [η] of 0.2 measured at 0 ° C. has an L / D (L represents the length of the horizontal rotation axis, and D represents the rotation diameter of the stirring blade) in the range of 2 to 30. The main repeating unit is a repeating unit represented by the following formula (I) characterized by reacting with a certain self-cleaning horizontal twin-screw reactor, and is represented by the following formulas (II) and (II)
The total of the repeating units represented by I) is from 0.001 to 0.
3 mol%, a repeating unit represented by the following formula (III) in a proportion of 0.001 mol% or more, and an intrinsic viscosity [η] measured in methylene chloride at 20 ° C. of 0.3 to 0.3
A method for producing an aromatic polycarbonate which is 1.2. Embedded image [Where R ³ and R ⁴ are the same or different and each represents a hydrogen atom,
It represents an alkyl group having 1 to 5 carbon atoms or an optionally substituted aryl group having 6 to 10 carbon atoms. R ⁵ is an alkylene group having 3 to 8 carbon atoms. R ¹ and R ² are the same or different and represent a halogen atom or an alkyl group having 1 to 5 carbon atoms. m and n are the same or different and are 0, 1 or 2. ] [Wherein, X, R ¹ , R ² , m, and n are the same as those in formula (A). ] [Wherein, X, R ¹ , R ² , m, and n are the same as those in formula (A). ] [Wherein, X, R ¹ , R ² , m, and n are the same as those in formula (A). ] 2. The L / D of the self-cleaning horizontal twin-screw reactor is 2 to 15, and the V / S of the polymer staying in the reactor (V is the volume of the polymer and S is the evaporation area of the polymer). 2. The method according to claim 1, wherein the reaction is carried out at 1 mm to 50 mm. 3. The temperature at which an aromatic dihydroxy compound and a carbonic acid diester are subjected to a melt polycondensation reaction is 290 ° C. or lower, and the amount of alkali metal and / or alkaline earth metal used (× 10 ⁻⁶ mol) 2. The method according to claim 1, wherein the product of (1 mol of aromatic dihydroxy compound) and the time (hour) required for the reaction at a reaction temperature of 270 ° C. or more is in the range of 1 to 20. 3. 4. A polymer having an intrinsic viscosity [η] of 0.2 in methylene chloride measured at 20 ° C. having an intrinsic viscosity change of 0 per hour in a reaction in a self-cleaning horizontal twin-screw reactor. 2. The method according to claim 1, wherein the value is 0.05 or more. 5. The method for producing an aromatic polycarbonate according to claim 1, wherein the chlorine content is 1 ppm or less and the iron content is 1 ppm or less.