JP2001253943A - Aromatic polycarbonate, method of producing the same, and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic polycarbonate having high durability and excellent in color tone, transparency and mechanical strength, especially an aromatic polycarbonate having high durability and stability in use under conditions of high temperatures and high humidities for a long period, and to provide a method of producing the aromatic polycarbonate and uses thereof. SOLUTION: This aromatic polycarbonate has <=100 ppb content of sodium element and <=70 ppb content of each element of Ni, Pb, Cr, Mn and Fe. (1) each content of Na element is controlled to <=52 ppb and (2) the concentration of each element of Fe, Cr, Mn, Ni and Pb is controlled to <=40 ppb in each raw material, and further (3) a specific catalyst is controlled to a specified amount based on the content of Fe in the raw materials, in the method of producing the polycarbonate comprising polycondensing an aromatic dihydroxy compound with carbonic diesters.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate having a low content of a specific metal element and having high durability and stability especially for a long time under high temperature and high humidity conditions, a process for producing the same, and a process for producing the same. Related to the molded product.

[0002]

2. Description of the Related Art Aromatic polycarbonate is an engineering plastic excellent in hue, transparency and mechanical strength. In recent years, its applications have been diversified, and the environmental conditions in which it is used are also widening.Therefore, high durability and stability that maintain the above-mentioned features even when used for a long time under high temperature and high humidity conditions are required. ing.

[0003] It has been pointed out that conventional aromatic polycarbonates have problems in durability and stability due to a decrease in molecular weight and deterioration of hue and transparency due to long-term use under high temperature and high humidity conditions. A decrease in molecular weight decreases the mechanical strength of the polymer, and a decrease in hue and transparency significantly reduces the advantages of aromatic polycarbonate.

[0004] Deterioration due to wet heat is not clear even if the chemical structure of trace impurities contained in the polymer, especially the chemical species present, is unknown, but there is concern about the influence of metal compounds. The method and the effect of reducing the metal content on heat stability have been studied.

Japanese Patent Application Laid-Open No. 5-148355 discloses that the iron-containing weight is 5 ppm or less and the sodium-containing weight is 1 ppm.
The following aromatic polycarbonates are disclosed, and JP-A-6-32885 discloses a polycarbonate having a total content of iron, chromium and molybdenum of 10 ppm or less and a total content of nickel and copper of 50 ppm or less.

JP-A-2-175722 discloses that a polycarbonate having an improved color tone can be obtained by reducing the content of hydrolyzable chlorine, sodium ion and iron ion in the raw material.

Japanese Patent Application Laid-Open No. 11-310630 discloses a method for producing an aromatic polycarbonate by reducing the amount of impurities contained in bisphenol A as a raw material to 10 parts per billion by weight of iron and 40 ppm by weight of chroman-based impurities. It has improved color tone, heat stability and gel, and has achieved some results.

In each case, in the examples where the optimum conditions are realized, the disclosed metal content is ppm
It is still on the order and is insufficient to maintain the good hue, transparency and mechanical strength of the aromatic polycarbonate for a long time under the severe wet heat conditions disclosed in the present invention.

[0009] The metal species targeted for reduction as impurities are limited to sodium, iron, and some transition metals. However, reduction of the content of these metals alone is required under severe conditions required. Realization of durability and stability is insufficient.

Further, according to the study of the present inventors, the stability of the polymer is not merely a matter of reducing the amount of impurities, but the relation between the amount of specific impurities contained in the raw material and the constitution of the transesterification catalyst, and It has also been found that the structural properties of the polycarbonate molecule are also important factors. Heretofore, attempts have been made to reduce the number of terminal phenolic hydroxyl groups in a polycarbonate molecule, but nothing more has been done.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to maintain good hue, transparency and mechanical strength for a long period of time under moist heat conditions which have never been considered before.
An object of the present invention is to provide an aromatic polycarbonate having excellent durability and stability. Another object of the present invention is to provide a method for industrially and advantageously producing the aromatic polycarbonate of the present invention. Still another object of the present invention is to provide a molded article, such as an injection molded article, comprising the aromatic polycarbonate of the present invention. Still other objects and advantages of the present invention will become apparent from the following description.

[0012]

According to the present invention, the above objects and advantages of the present invention are as follows. First, the main repeating unit is represented by the following formula (1).

[0013]

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(Wherein R ₁ and R ₂ are each independently
Hydrogen atom, alkyl group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 alkoxy group, C6-C20 cycloalkyl group, C6-C20 aryl group, C6-C20 cycloalkoxy group or C6-C20 aryloxy group, m and n are Is independently an integer of 0 to 4, and X is a single bond, an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, or a cycloalkylene having 6 to 20 carbon atoms. Group, cycloalkylidene group having 6 to 20 carbon atoms or 6 to 20 carbon atoms
Or an alkylene arylene alkylene group having 6 to 20 carbon atoms. ) Wherein the terminal group consists essentially of an aryloxy group (A) and a phenolic hydroxyl group (B), and their molar ratio (A) / (B) is 9
5/5 to 40/60 with melt viscosity stability of 0.5%
And the content of sodium metal element is 100p
pb or less, and Ni, Pb, Cr, Mn and F
This is achieved by an aromatic polycarbonate characterized in that the content weight of each first element of e is 70 ppb or less.

According to the present invention, the above objects and advantages of the present invention are secondly achieved by a molded article of the aromatic polycarbonate of the present invention.

The object and advantages of the present invention are as follows.
An aromatic dihydroxy compound and a carbonic acid diester are added to at least one basic compound selected from the group consisting of a) a nitrogen-containing basic compound and a phosphorus-containing basic compound per 1 mol of the aromatic dihydroxy compound; 00
0 μ chemical equivalent and a) aromatic dihydroxy compound 1
A method for producing a polycarbonate by performing polycondensation in the presence of a catalyst containing 0.05 to 5 μm equivalent of at least one compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound per mole, ) Na metal element content weight is each 52 ppb or less,
And 2) an aromatic dihydroxy compound and a carbonic acid diester having a content of the first element of each of Fe, Cr, Mn, Ni and Pb of 40 ppb or less, and 3) a basic compound per 1 mole of the aromatic dihydroxy compound. Is used in an amount not exceeding 20 × (Fe ^* ) + 200 with respect to the total weight Fe ^* (ppb) of Fe contained in the aromatic dihydroxy compound and the carbonic acid diester. Achieved by

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The aromatic polycarbonate of the present invention has a main repeating structure represented by the following formula (1):

[0018]

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(Wherein R ₁ and R ₂ are each independently
C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 cycloalkyl group, C6-carbon
An aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, m and n are integers of 0 to 4, X is a single bond, an oxygen atom, Group, alkylene group having 1 to 20 carbon atoms, alkylidene group having 2 to 20 carbon atoms, 6 to 20 carbon atoms
A cycloalkylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and an alkylene arylene alkylene group having 6 to 20 carbon atoms. Wherein the terminal group consists essentially of an aryloxy group (A) and a phenolic hydroxyl group (B), and their molar ratio (A) / (B) is 95/5 to 40/60; And the melt viscosity stability is 0.5% or less.

According to the present invention, the specific elements contained in the aromatic polycarbonate are divided into groups based on the magnitude of the influence thereof, and their contents are defined below the specific values, so that the conventional elements can be considered. Provided is an aromatic polycarbonate having excellent durability, stability, and transparency when used for a long period of time under unusually severe moist heat conditions.

In the present invention, the trace elements which are contained as impurities in the aromatic polycarbonate and the raw materials and are problematic include sodium and sodium based on the degree of influence on the durability, color tone and transparency of the obtained aromatic polycarbonate. , Were classified into the following first to fourth groups.

The elements belonging to each group are as follows. 1st element; Ni, Pb, Cr, Mn and Fe 2nd element; Cu, Zn, Pd, In, Si and Al 3rd element; Ti 4th element; P, N, S, Cl and Br Aromatic polycarbonates have good durability and stability under long-term use under severe high-temperature and high-humidity conditions.
00 ppb or less, and the content weight of each of the first elements is 70 ppb or less.

Further, among such aromatic polycarbonates, in order to have more excellent durability and stability, the content of the sodium metal element is preferably 70 ppb or less.
More preferably, it is 20 ppb or less. Further, the content weight of each of the first elements is preferably 40 ppb or less, more preferably 20 ppb or less, particularly preferably 10 ppb or less.

The terminal groups of the aromatic polycarbonates according to the invention consist essentially of aryloxy groups (A) and phenolic hydroxyl groups (B) and their molar ratio (A).
/ (B) is 95/5 to 40/60. The preferred molar ratio (A) / (B) is 90/10 to 50/50, more preferably 85/15 to 60/40, and particularly preferably 8
0/20 to 70/30.

In the present invention, in order for the aromatic polycarbonate to have more excellent durability and stability, the phenolic terminal hydroxyl group concentration; (H) (eq / ton-polycarbonate) is the first element (Ni, Pb, Cr). , Mn and F
e) the sum of the content weights;） with respect to the first element (ppb)
It is preferable that the following relationship (H) ≦ Σthe first element.

Further, among such aromatic polycarbonates, in order to have more excellent durability and stability, (H)
Is (H) ≦ 0.5 × (Σfirst element) with respect to Σfirst element
Is more preferable.

Further, in order to obtain an aromatic polycarbonate having better durability and stability among such aromatic polycarbonates, the content of each of the second elements is preferably not more than 20 ppb, and The content weight of the element is preferably 1 ppb or less, and more preferably the content weight of each with the fourth element is 1 ppm or less.

The viscosity stability (as defined below) of the molten polymer of the aromatic polycarbonate of the present invention is 0.5%
It is as follows. When this value is larger than 0.5%, hydrolysis degradation of the aromatic polycarbonate is promoted. In order to secure practical hydrolysis resistance, it is sufficient to set this value to 0.5% or less. For that purpose, it is preferable that the aromatic polycarbonate of the present invention is stabilized in melt viscosity, particularly after polymerization, by using a melt viscosity stabilizer described later. Here, the melt viscosity stability is evaluated by the absolute value of the change in the melt viscosity measured at 300 ° C. for 30 minutes at a shear rate of 1 rad / sec under a nitrogen stream, and is expressed as a rate of change per minute.

The aromatic polycarbonate of the present invention may be produced by any conventionally known methods such as a melt polymerization method and an interfacial polymerization method. However, the process, cost including raw materials, and polymerization solvents such as chlorinated hydrocarbons are required. It is preferable to use a method in which an aromatic dihydroxy compound and a carbonic acid diester are melt-polycondensed from the viewpoint that they can be used without using a harmful compound such as phosgene as a carbonate-forming compound.

In the melting method, an aromatic dihydroxy compound (hereinafter may be referred to as BPA) and a carbonic acid diester (hereinafter may be referred to as DPC) may be formed under a normal pressure and / or reduced pressure nitrogen atmosphere in the presence of a transesterification catalyst. This is performed by stirring while heating to distill off alcohol or phenol generated from the carbonic acid diester. The reaction temperature varies depending on the boiling point of the product and the like, but is usually in the range of 120 to 350 ° C. to remove alcohol or phenol generated by the reaction, and preferably 180 to 350 ° C. in order to obtain an aromatic polycarbonate with less impurities.
280 ° C, more preferably 250 to 2 ° C.
It is in the range of 70 ° C.

At the latter stage of the reaction, the pressure of the system is reduced to facilitate the distillation of the alcohol or phenol formed. The internal pressure of the system at the latter stage of the reaction is preferably 133.3 Pa (1 mmH
g) or less, and more preferably 66.7 Pa (0.5
mmHg) or less.

In the present invention, as a method of the present invention for producing an aromatic polycarbonate, an aromatic dihydroxy compound (BPAs) and a carbonic acid diester (DPCs) are used.
As described above, a) at least one basic compound (hereinafter may be referred to as NCBA) selected from the group consisting of a nitrogen-containing basic compound and a phosphorus-containing basic compound,
~ 1,000μ chemical equivalents / mol of BPAs, and
A) a catalyst containing 0.05 to 5 μchemical equivalents / one mole of BPA containing at least one compound selected from the group consisting of an alkali metal compound and an alkaline earth metal compound (hereinafter sometimes referred to as AMC). A method for producing an aromatic polycarbonate by heat melting and polycondensation in the presence is provided. In the method of the present invention, the weight of each element belonging to the first element group, wherein the weight of the Na metal element in each of the BPAs and DPCs is 52 ppb or less, more preferably 35 ppb or less, particularly preferably 6 ppb or less. BPAs and DPCs having a concentration of 40 ppb or less, more preferably 23 ppb or less, particularly preferably 6 ppb or less are used. Also, N
The amount of CBA used (μ chemical equivalent / 1 mol of BPAs) is Fe
^* (Total weight of Fe content of DPCs and BPAs; ppb)
Should not exceed (20 × Fe ^* + 200).

The weight concentration of each of the second elements contained in the DPCs and BPAs is preferably 10%.
ppb or less is desirable.

The weight concentration of each of the third elements contained in DPCs and BPAs is preferably 1 pp.
b and the weight concentration of each of the fourth elements is 1
Desirably, it is ppm.

As a raw material, BPAs and DPCs having the above-mentioned specific element content of not more than a specific value are used together, and further, a specific amount ratio of N to the iron content weight is increased.
According to the present invention, an aromatic polycarbonate having excellent durability can be obtained by using a CBA catalyst. The metal content weight in the known raw materials is pp
m level, the metal content weight in the raw material defined in the present invention was lower by one order,
80 ppb, the specific metal elements contained in the raw materials are further divided into groups based on the magnitude of the influence, and their content weights are respectively specified below a specific value, and the content weight of the specific nonmetallic elements is reduced. Stipulate, and furthermore, a specific amount ratio of NCBA to the iron content weight in the raw material
By using a catalyst, excellent durability in long-time use under moist heat conditions of a degree that was not previously thought,
It has made it possible to produce an aromatic polycarbonate having stability and transparency.

In particular, it is surprising that the use of a specific amount of the NCBA catalyst with respect to the iron impurities improves the impact resistance during the heat resistance test.

In the present invention, BP used as a raw material
When bisphenol A (hereinafter sometimes referred to as BPA) is used as A, an aromatic polycarbonate having a better color tone can be produced by defining the concentration of organic impurities. That is, as a BPA, a specific high-performance liquid chromatographic analysis (adsorbent in which 15% (as carbon content) octadecyl group is bonded to high-purity spherical silica gel having a pore diameter of 100 Å (inertsil ODS-3 type adsorbent manufactured by GL Sciences Inc.) ) Packed with a 4.6 mm inner diameter and 250 mm long column at 40 ° C ±
According to a high performance liquid chromatograph maintained at 0.1 ° C., a 0.1% phosphoric acid aqueous solution was used as eluent A and acetonitrile was used as eluent B. Eluent A: eluent B for 5 minutes from the start of measurement Is measured so that the total flow rate of the eluent A and the eluent B is 0.9 ml / min, and the total flow rate is kept constant. A gradient operation is performed in which the ratio is continuously increased, and the ratio of the eluent B is increased so that the ratio of the eluent A to the eluent B becomes 0: 1 by 55 minutes after the start of the measurement. (Analysis of BPA by an analyzer) From 15.5 minutes to 24 minutes, the sum of the absorption peak areas of the eluting compound group (hereinafter abbreviated as compound group A) is 2.
This method uses BPA of 0 × 10 ⁻³ or less, more preferably 1.0 × 10 ⁻³ or less.

More preferably, in the above-mentioned specific high performance liquid chromatography analysis, the sum of the absorption peak areas of the compound group eluted between 22 minutes and 24 minutes (hereinafter abbreviated as compound group B) is a ratio to the absorption peak area of BPA. 5
× 10 ^-5 (50 ppm) or less, more preferably, in the above analysis, the sum of the absorption peaks of compounds having a molecular weight of 307 to 309 eluted between 22 minutes and 24 minutes is BPA
2 × 10 ⁻⁵ (20 pp)
m) The following method uses BPA.

More preferably, 1-naphthols represented by the following formula (2):

[0040]

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(Wherein R ₃ and R ₄ are each independently a methyl, ethyl, n-propyl, isopropyl group or an isopropenyl group). The content is 2 × 10 ^-4 weight per 1 weight part of BPA. Parts or less, more preferably 1 ×
This is a method using BPA which is 10 ^-4 or less. In addition,
In the above formula (2), each of R ₃ and R ₄ is 2 to 8 other than 1-position (substituted by a hydroxyl group) of the naphthalene ring.
It can be linked to any of the positions without duplication.

More preferably, the following formula (3)

[0043]

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Wherein R _{5 to} R ₇ are each independently an alkyl group having 1 to 4 carbon atoms, R ₈ and R ₉ are each independently an alkyl group having 1 to 4 carbon atoms; p and q are each independently an integer of 0 to 4), and the content of the paraflavan compound is 5 × 10 ⁻⁵ parts by weight or less based on 1 part by weight of BPA, and the following formula (4)

[0045]

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Wherein R _{10 to} R ₁₂ are each independently an alkyl group having 1 to 4 carbon atoms, R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 4 carbon atoms; s and t are each independently an integer of 0 to 4.) This is a method using BPA in which the content of the codimer derivative represented by the following formula is 5 × 10 ⁻⁵ parts by weight or less based on 1 part by weight of BPA.

More preferably, as BPA, the following formula (5)

[0048]

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Wherein R _{15 to} R ₁₇ are each independently an alkyl group having 1 to 4 carbon atoms, R ₁₈ is each independently an alkyl group having 1 to 4 carbon atoms, and a is 0 ~
4 is an integer. Is less than 1 × 10 ^-5 parts by weight based on 1 part by weight of BPA;
And the following equation (6)

[0050]

Embedded image

(Where R₁₉And R₂₀Are independently charcoal
An alkyl group having a prime number of 1 to 4; _{twenty one}And R_{twenty two}Haso
Each independently represents an alkyl group having 1 to 4 carbon atoms;
And b and c are each independently an integer of 0 to 4. )
The content of xanthenes represented by
1 × 10^-FiveHow to use BPA which is less than parts by weight
It is.

The 1-naphthols represented by the formula (2)
For example, 2,4-dimethyl-1-hydroxynaphthalene,
2,6-dimethyl-1-hydroxynaphthalene, 2,7
-Dimethyl-1-hydroxynaphthalene, 3,6-dimethyl-1-hydroxynaphthalene, 2-isopropyl-
1-hydroxynaphthalene, 6-isopropenyl-1-
Hydroxynaphthalene.

The paraflavan compound represented by the formula (3) is, for example, 2- (4-hydroxyphenyl) -2,4,
4-trimethylchroman, 2- (3-methyl-4-hydroxyphenyl) -2,4,4-trimethylchroman,
2- (3,5-dimethyl-4-hydroxyphenyl)-
2,4,4-trimethylchroman, 2- (3,5-dimethyl-4-hydroxyphenyl) -2,4,4-trimethylchroman, 2- (3-methyl-4-hydroxyphenyl) -2,4 4,8-tetramethylchroman.

The codimer derivative represented by the formula (4) is
For example, 4- (4-hydroxyphenyl) -2,2,4-
Trimethyl chroman, 4- (3-methyl-4-hydroxyphenyl) -2,2,4-trimethyl chroman, 4-
(3,5-dimethyl-4-hydroxyphenyl) -2,
2,4-trimethylchroman, 4- (3,5-dimethyl-4-hydroxyphenyl) -2,2,4-trimethylchroman, 4- (3-methyl-4-hydroxyphenyl) -2,4,4 8-tetramethylchroman.

The chromene compound represented by the formula (5) is, for example, 2,2,4-trimethylchroman- (3) -ene,
2,2-dimethyl-4-ethylchroman- (3) -ene, 2,2-dimethyl-4-ethylchroman- (3)-
Ene, 2,2,6-trimethylchroman- (3) -ene, 2,2-dimethyl-6-ethylchroman- (3)-
Ene, 2,2,4,6-tetramethylchroman- (3)
-Ene, 2,2,4-trimethyl-7-butylchroman- (3) -ene.

The xanthenes represented by the formula (6) are, for example, 9,9-dimethylxanthene, 2-butyl-
9,9-dimethylxanthene, 3-methyl-9,9-diethylxanthene, 9,9-diethylxanthene, 9-
Methylxanthene and 2,6,9,9-tetramethylxanthene.

Bisphenol A is produced by subjecting acetone and excess phenol to dehydration condensation in the presence of an acid catalyst such as a homogeneous acid such as hydrochloric acid or a solid acid such as an ion exchange resin. Bisphenol A obtained by such a production method is easily obtained as a commercial product, and the compounds (impurities) represented by the above formulas (2) to (6)
Is usually contained.

In the present invention, conventionally known dihydroxy compounds can be suitably used as the BPA. For example, 2,2-bis (4-hydroxyphenyl) propane (ie, BPA), bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, 1,1-
Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl ) Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and aromatic rings of these compounds Examples thereof include compounds in which an alkyl group or an aryl group is substituted. Among them, BPA is particularly preferred from the viewpoint of cost. These may be used alone or in combination of two or more.

The DPCs include, for example, diphenyl carbonate (hereinafter sometimes referred to as DPC), bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, DPC is preferable from the viewpoint of cost.

An aromatic polycarbonate having a small content of a specific metal element as an impurity and excellent in durability, color tone and transparency as described above can be obtained by purifying BPAs and DPCs used as raw materials. Alternatively, it can be obtained by purifying an aromatic polycarbonate.

The BPAs and DPCs used as raw materials can be purified by a known purification method, for example, a single or combination of purification methods such as distillation, extraction and recrystallization.

In addition to these methods, a method in which the raw material is purified by a long-term sublimation method at a temperature as low as possible is also preferable. In addition to sublimation, it is more preferable to use various combinations of the above-mentioned purification methods.

According to these methods, the conventional method in which the content of the impurity element as described above is at the ppm level is
It can be reduced to a ppb level which is 1,000 times or less. In addition, the content of the above-mentioned organic impurities, which has not been noticed in the past, can be reduced to a predetermined value.

The aromatic polycarbonate can be purified by a purification method such as washing and reprecipitation of the polymer solution with water. In the water washing of the polymer, it is preferable to sufficiently dehydrate the polymer solution after the washing. As a dehydration method, for example, silica gel treatment and filtration using a fine pore filter are used. The polymer is reprecipitated by adding a polymer poor solvent such as methanol or acetonitrile to a polymer solution in a solvent such as methylene chloride or 1-methyl-2-pyrrolidinone (hereinafter sometimes referred to as NMP). At that time, in order to obtain a polymer having a higher degree of purification, it is preferable to gradually add the poor solvent over a long period of time.

That is, in order to obtain an aromatic polycarbonate containing a small amount of impurity elements, it is preferable to produce a polymer using the raw material purified by the above-mentioned raw material purification method, and to further purify the obtained polymer by the above-mentioned method. .

In order to obtain the aromatic polycarbonate having a small amount of impurity elements of the present invention, it is preferable to use a high-purity solvent having a very small content of impurity elements in the purification of raw materials and polymers. Therefore, for example, a solvent for the electronics industry can be used.

In the present invention, in the transesterification melt polymerization of the aromatic polycarbonate, it is preferable to use a specific catalyst, ie, at least one base selected from the group consisting of: a) a nitrogen-containing basic compound and a phosphorus-containing basic compound. A catalyst comprising at least one compound selected from the group consisting of an acidic compound (NCBA) and a) at least one compound (AMC) selected from the group consisting of an alkali metal compound and an alkaline earth metal compound is used.

Specific examples of the catalyst NCBA include nitrogen-containing salts.
Tetramethylammonium hydroxy as basic compound
Do (Me_FourNOH), tetrabutylammonium hydro
Oxide (Bu_FourNOH), benzyltrimethylammonium
Um hydroxide (φ-CH_Two(Me)_ThreeNOH), Heki
Like sadecyltrimethylammonium hydroxide
Possesses an alkyl, aryl or alkylaryl group
Ammonium hydroxides; tetramethylammonium
Acetate, tetraethylammonium phenoki
Sid, tetrabutylammonium carbonate, benzyltri
Methyl ammonium benzoate, hexadecyl trimethyi
Alkyl and aryl such as luammonium ethoxide
Or basic ammonium having an alkylaryl group, etc.
Um salt; triethylamine, dimethylbenzylamine,
Tertiary amines such as hexadecyldimethylamine;
And tetramethylammonium borohydride (Me
_FourNBH_Four), Tetrabutylammonium tetraphenyl
Borate (Bu_FourNBPh _Four), Tetramethylammonium
Mutetraphenyl borate (Me_FourNBPh_Four)
Basic salts can be mentioned.

Specific examples of the phosphorus-containing basic compound include, for example, tetrabutylphosphonium hydroxide (Bu ₄
POH), benzyltrimethylphosphonium hydroxide (φ-CH ₂ (Me) ₃ POH), phosphonium hydroxides having an alkyl, aryl, alkylaryl group and the like such as hexadecyltrimethylphosphonium hydroxide, and tetrabutylphosphonium borohydride ( (Bu ₄ PBH ₄ ), tetrabutylphosphonium tetraphenylborate (Bu ₄ PBPh ₄ ), tetramethylphosphonium tetraphenylborate, (Me ₄
Basic salts such as PBPh ₄ ) can be mentioned.

The above-mentioned NCBA has a basic nitrogen atom or a basic phosphorus atom in an amount of 10 to 1,
It is preferable to use it at a ratio of 000 μ chemical equivalent. A more preferable usage ratio is a ratio that results in a chemical equivalent of 20 to 500 μ with respect to the same standard. A particularly desirable ratio is a ratio that results in a chemical equivalent of 50 to 500 μ with respect to the same standard.

In particular, at this time, in order to improve the hue of the obtained aromatic polycarbonate, the amount of NCBA used should be (20%) based on the total weight of iron contained in the raw materials DPCs and BPAs; Fe ^* (ppb). × Fe ^* + 200) μ
It has been found that it is effective to use so as not to exceed the chemical equivalent. Particularly preferably, (20 × Fe ^* + 150)
It is within the range not exceeding μ chemical equivalent.

Although the reason is not clear, it is presumed that iron contained in the raw material DPCs and BPAs interacts with NCBA in some way to deteriorate the color tone of the aromatic polycarbonate. In this sense, it is preferable to reduce the contents of various impurity elements as much as possible.

Further, in the present invention, in order to realize the effect of reducing impurities in the raw material in the color tone and stability of the polymer, AMC is used in combination with NCBA.
As MC, a compound containing an alkali metal compound is preferably used. Such an alkali metal compound is preferably used in the range of 5 × 10 ^{−8 to} 5 × 10 ⁻⁶ chemical equivalent as an alkali metal element per 1 mol of BPAs. By using a catalyst having such a quantitative ratio, a branching reaction, a main chain cleavage reaction, or a main chain cleavage reaction that is easily generated during a polycondensation reaction without impairing a molecular terminal blocking reaction or a polycondensation reaction rate, is performed in a device during molding processing. It is preferable because undesired phenomena such as generation of foreign matter and burning can be effectively suppressed.

If the ratio is outside the above range, there is a problem that various properties of the obtained aromatic polycarbonate are adversely affected, and the transesterification reaction does not easily proceed sufficiently, and it becomes difficult to obtain a high molecular weight aromatic polycarbonate. Absent.

Examples of the catalyst AMC include hydroxides of alkali metals and alkaline earth metals, hydrocarbon compounds, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearate salts. , Borohydride,
Benzoates, hydrogen phosphates, bisphenols, salts of phenols are mentioned.

Specific examples include sodium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, lithium carbonate, cesium carbonate, sodium acetate, lithium acetate, sodium nitrate, rubidium nitrate, sodium nitrite, and nitrite. Rubidium, potassium sulfite, sodium cyanate, potassium cyanate, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, cesium thiocyanate, sodium stearate, lithium stearate, cesium stearate, sodium borohydride, lithium borohydride , Sodium borohydride, sodium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium salt, dilithium salt, monolithium salt, sodium potassium of bisphenol A Unsalted, sodium lithium salt, sodium salt of phenol, potassium salt.

Further, as the alkali metal compound,
It is possible to use (a) an alkali metal salt of an ate complex of an element of Group 14 of the periodic table or (a) an alkali metal salt of an oxo acid of an element of Group 14 of the periodic table. Here, Periodic Table 1
Group 4 elements refer to silicon, germanium, and tin.

The use of such an alkali metal compound as a catalyst for the polycondensation reaction has the advantage that the polycondensation reaction can be promptly and sufficiently proceeded as described above.
Also, undesirable side reactions such as a branching reaction that proceeds during the polycondensation reaction can be suppressed to a low level.

The alkali metal salt of the ate complex of the Group 14 element of the Periodic Table (A) is described in JP-A-7-2680.
No. 91, specifically, NaGe
(OMe) ₅ , NaGe (OPh) ₅ , LiGe (OP
h) ₅ , NaSn (OMe) ₃ , NaSn (OMe) ₅ ,
NaSn (OPh) ₅ can be mentioned.

The alkali metal salts of oxo acids of Group 14 elements of the periodic table include, for example, silicic acid, stannic acid,
Preferred examples include germanium (II) acid and alkali metal salts of germanium (IV) acid.

Specific examples thereof include disodium orthosilicate, tetrasodium orthosilicate, disodium monostannate, monosodium germanate (II) (NaHGeO ₂ ), disodium orthogermanate (IV), digermanium (IV) Disodium acid), (N
a ₂ Ge ₂ O ₅ ).

In the polycondensation reaction of the present invention, at least one member selected from the group consisting of oxo acids and oxides of Group 14 elements of the periodic table and alkoxides and phenoxides of the same elements, if necessary, together with the above catalyst. Can coexist as a co-catalyst. By using these cocatalysts in a specific ratio, the terminal blocking reaction, the branching reaction which is easily generated during the polycondensation reaction without impairing the polycondensation reaction rate,
It is preferable because undesired phenomena such as a main chain cleavage reaction, generation of foreign matter in the apparatus during molding, and burning can be more effectively suppressed.

The oxo acids of Group 14 of the periodic table include, for example, silicic acid, stannic acid and germanic acid.

Examples of the oxides of Group 14 of the periodic table include silicon dioxide, tin dioxide, germanium dioxide, silicon tetrabutoxide, silicon tetraphenoxide, tetraethoxytin, tetraphenoxytin, tetramethoxygermanium, tetrabutoxygermanium and tetraphenoxy. Mention may be made of germanium and condensates thereof.

It is preferred that the cocatalyst be present in such a proportion that the element of Group 14 of the periodic table becomes 50 mole atoms or less per mole atom of the alkali metal element in the polycondensation reaction catalyst. Use of a co-catalyst in a proportion of more than 50 mole atoms of the same metal element is not preferred because the rate of the polycondensation reaction is reduced.

The cocatalyst is more preferably present in an amount such that the element of Group 14 of the periodic table as a cocatalyst is 0.1 to 30 mole atoms per mole atom of the alkali metal element of the polycondensation reaction catalyst.

Since the sodium compound has less influence on the durability of the aromatic polycarbonate produced as compared with the compounds of alkali metals and alkaline earth metals other than sodium, the aromatic compound having excellent durability in the present invention is used. In order to obtain polycarbonate, it is preferable to use a sodium compound as a catalyst.

When AMC is used as a polymerization catalyst, as described above, it is preferably used in an amount of 0.05 to 5 μ chemical equivalent to 1 mol of BPA. More preferably, 0.07 to 3 µ chemical equivalent, particularly preferably 0.07 to
2μ chemical equivalent.

When a sodium compound is used as a catalyst, sodium derived from the catalyst is added in addition to sodium mixed in from the raw material into the polymer, so that the total content of sodium metal elements in the polymer exceeds the specified amount in the present invention. It will be appreciated that sodium compound catalysts must be used to the extent that they do not.

In the present invention, in order to obtain an aromatic polycarbonate which is unlikely to cause a decrease in molecular weight or coloration, attention is paid to the viscosity stability (defined below) of the molten polymer. It is necessary to. When this value is large, hydrolysis degradation of the aromatic polycarbonate is promoted. In order to secure practical hydrolysis stability, it is sufficient to set this value to 0.5% or less.
For this purpose, it is particularly preferable to stabilize the melt viscosity using a melt viscosity stabilizer after polymerization. The melt viscosity stability was measured under a nitrogen stream at a shear rate of 1 rad / sec.
It is evaluated by the absolute value of the change in melt viscosity measured at 00 ° C. for 30 minutes, and expressed as a change rate per minute.

The melt viscosity stabilizer in the present invention has an action to deactivate a part or all of the activity of the polymerization catalyst used in producing the aromatic polycarbonate.

The melt viscosity stabilizer may be added, for example, while the polymer is in a molten state after the polymerization, or may be added after the polycarbonate is once pelletized and then redissolved. In the former, the melt viscosity stabilizer may be added while the polycarbonate, which is a reaction product in the reaction tank or the extruder, is in a molten state, or the polycarbonate obtained after the polymerization may be extruded from the reaction tank or the extruder. The melt viscosity stabilizer can be added and kneaded while pelletizing through.

Known agents can be used as the melt viscosity stabilizer. Sulfonic acid compounds such as organic sulfonic acid salts, organic sulfonic acid esters, organic sulfonic acid anhydrides, and organic sulfonic acid betaines, because of their great effect on improving the physical properties such as the hue, heat resistance and boiling water resistance of the obtained polymer. Among them, it is preferable to use a phosphonium salt of sulfonic acid and / or an ammonium salt of sulfonic acid. Among them, particularly preferred are tetrabutylphosphonium dodecylbenzenesulfonate and tetrabutylammonium p-toluenesulfonate.

The polymer of the present invention can be obtained by the above-mentioned method. In the case of molding various molded articles using the polymer, conventionally known processing stabilizers, heat stabilizers, antioxidants, and ultraviolet absorbers are used depending on the use. Agents, antistatic agents, flame retardants, release agents, and the like may be added.

Further, a heat stabilizer can be added to the aromatic polycarbonate of the present invention in order to prevent a decrease in the molecular weight and a deterioration in hue. Such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (4,4′-biphenylenediphosphosphinate) 4-Di-t-butylphenyl), trimethyl phosphate and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more. The amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 1 part by weight, per 100 parts by weight of the aromatic polycarbonate.
0.5 parts by weight is more preferable, and 0.001 to 0.1 parts by weight is further preferable.

Further, in order to further improve the releasability from the mold at the time of melt molding, a releasing agent can be added to the aromatic polycarbonate of the present invention as long as the object of the present invention is not impaired. It is. Examples of the release agent include an olefin wax, an olefin wax containing a carboxyl group and / or a carboxylic anhydride group, silicone oil, organopolysiloxane, a higher fatty acid ester of a monohydric or polyhydric alcohol, paraffin wax, beeswax. Is mentioned. The amount of the release agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate.

The higher fatty acid esters include monohydric or polyhydric alcohols having 1 to 20 carbon atoms and
Preference is given to partial or full esters with up to 30 saturated or unsaturated fatty acids. As such a partial ester or a whole ester of a monohydric or polyhydric alcohol and a saturated or unsaturated fatty acid, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used. The amount of the release agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate.

Further, inorganic and organic fillers can be added to the aromatic polycarbonate of the present invention in order to improve rigidity and the like within a range not to impair the object of the present invention. Such inorganic fillers include, for example, talc, mica, glass flake, glass beads, calcium carbonate,
Plate or granular inorganic filler such as titanium oxide; fibrous filler such as glass fiber, glass milled fiber, wollastonite, carbon fiber, aramid fiber, metallic conductive fiber and crosslinked acrylic particles, crosslinked silicone particles Such organic particles can be mentioned. The compounding amount of these inorganic and organic fillers is preferably 1 to 150 parts by weight based on 100 parts by weight of the aromatic polycarbonate.
-100 parts by weight is more preferred.

The inorganic filler usable in the present invention may be surface-treated with a silane coupling agent or the like. By this surface treatment, good results such as suppression of decomposition of the aromatic polycarbonate can be obtained.

The aromatic polycarbonate of the present invention may contain other resins as long as the object of the present invention is not impaired.

Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins,
Polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, amorphous polyarylate resin, polystyrene resin, acrylonitrile /
Examples include a styrene copolymer (AS resin), an acrylonitrile / butadiene / styrene copolymer (ABS resin), a polymethacrylate resin, a phenol resin, and an epoxy resin.

The aromatic polycarbonate of the present invention is excellent in durability, particularly, the effect of maintaining long-term durability under severe temperature and humidity conditions. Therefore, compact disks (CDs), CD-ROMs,
CD-R, CD-RW, magnet optical disc (MO), digital versatile disc (DVD
-ROM, DVD-Video, DVD-Audio,
A substrate for a high-density optical disk represented by a DVD-R, a DVD-RAM, or the like has high reliability over a long period of time. In particular, it is useful for a high-density optical disk such as a digital versatile disk.

The sheet made of the aromatic polycarbonate of the present invention has excellent adhesiveness and printability. Therefore, it is widely used for electric parts, building material parts, automobile parts, etc. by utilizing its characteristics. Specifically, various window materials, such as general houses, gymnasiums, baseball domes, vehicles (construction machinery, automobiles, buses, bullet trains, train cars, etc.) Glazing products such as window materials, etc., as well as various side wall boards (sky dome, top light, arcade, condominium lumbar boards, road side wall boards), window materials for vehicles, etc.
Liquid crystal cell, phase difference correction by combination with display of OA equipment, touch panel, membrane switch, photo cover, polycarbonate resin laminate for water tank, front panel of projection television or plasma display, Fresnel lens, optical card, optical disk or polarizing plate Useful for optical applications such as plates. Although the thickness of the aromatic polycarbonate sheet is not particularly limited, it is usually 0.1 to 10 mm,
Preferably, it is 0.2 to 8 mm, particularly preferably 0.2 to 3 mm. In addition, in such an aromatic polycarbonate sheet,
Various types of processing to add new functions (various lamination to improve weather resistance, abrasion resistance improvement to improve surface hardness, surface graining, semi- and opacity processing, etc.) may be performed. .

For blending each of the above components with the aromatic polycarbonate of the present invention, an arbitrary method is adopted. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, and an extruder is appropriately used. The aromatic polycarbonate resin composition thus obtained can be formed into a sheet by a melt extrusion method as it is or after being once pelletized by a melt extruder.

From the aromatic polycarbonate of the present invention, a molded article having good durability and stability can be obtained by a molding method such as an injection molding method.

The aromatic polycarbonate of the present invention may be used for any purpose. As described above, for example, electronic and communication equipment, OA equipment, lenses, prisms, optical disc substrates, optical components such as optical fibers, home appliances, Lighting materials, electronic and electrical materials such as heavy electrical materials, vehicle interior and exterior,
Precision machinery, mechanical materials such as insulating materials, medical materials, security and protection materials, sports and leisure goods, household goods and other miscellaneous materials, containers and packaging materials, display and decoration materials, etc., and other resins and organic and inorganic materials Can be suitably used as a composite material.

In particular, the aromatic polycarbonate of the present invention can be particularly preferably used for an optical disk substrate because of its excellent durability and stability.

[0108]

As described in the present invention, by controlling the content of the above-mentioned specific impurities in the aromatic polycarbonate to a specific value or less, the durability of the polymer, especially the long-term durability under severe temperature and humidity conditions, is improved. And the effect of maintaining good color tone, transparency and mechanical strength is obtained.

Further, by polymerizing DPCs and BPAs having a specific metal element content of a specific value or less as a raw material, an aromatic polycarbonate resin having good stability can be produced.

[0110]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.
In addition, the test method of the aromatic polycarbonate manufactured by the Example was based on the following method.

1) Viscosity average molecular weight (Mw): The viscosity average molecular weight (Mw) was determined from the intrinsic viscosity ([η]) measured with an Ubbelohde viscometer at 20 ° C. in methylene chloride by the following equation. [Η] = 1.23 × 10 ⁻⁴ Mw ^0.83

2) Method for Quantifying Content of Metal Impurities The content of metal in the polymer was determined by using a solution prepared by dissolving 0.5 g of the polymer in 25 g of NMP for electronics industry using ICP-MS, SPQ9000 manufactured by Seiko Instruments Inc. Was prepared and quantitatively measured.

3) High-performance liquid chromatographic analysis of BPA; Column: Inertsyl ODS manufactured by GL Sciences Co., Ltd. in which 15% (as carbon content) octadecyl group is bonded to high-purity spherical silica gel having a pore size of 100 Å.
-3 type adsorbent filled inner diameter 4.6mm and length 250
The column temperature was maintained at 40 ± 0.1 ° C. using a mm column. Elution conditions: 0.1% phosphoric acid aqueous solution was used as eluent A, and acetonitrile was used as eluent B. From the start of measurement, the ratio of eluent A: eluent B was 1: 1 and eluent A was 5 minutes. And the total flow rate of eluent B is 0.9 ml / min
With the total flow rate kept constant, the ratio of eluent B was continuously increased from 5 minutes after the start of the measurement, and the ratio of eluent A: eluent B by 55 minutes after the start of the measurement. Is performed to increase the ratio of the eluent B so that the ratio becomes 0: 1. 0.1% phosphoric acid aqueous solution; JI
Phosphoric acid of S reagent special grade or higher is diluted to 0.1 ± 0.0001% with distilled water for high performance liquid chromatography, and eluent B; acetonitrile for high performance liquid chromatography is used. Chromatograph device; LC-10A detector manufactured by Shimadzu Corporation; UV detector having a wavelength of 254 nm a) Analyzing method of compound group A: 25.5 g of BPA was dissolved in 3 ml of acetonitrile and analyzed.
The total of the absorption peak areas of the compounds eluted up to the minute was measured as a ratio to the BPA absorption peak area.
If BPA having this value of 2.0 × 10 ⁻³ or less is used, a polycarbonate having a good level of hue can be produced. A) Compound group B analysis method: 2 g of BPA was dissolved in 3 ml of acetonitrile, and the total absorption peak area of the compound eluted between 22 and 24 minutes when analyzed was measured as a ratio to the absorption peak area of BPA. . If BPA having this value of 50 ppm or less is used, a polycarbonate having a good level of hue can be produced.

4) Melt Viscosity Stability The melt viscosity stability of the polymer was evaluated. Under a nitrogen stream using a rheometrics RAA flow analyzer,
The absolute value of the change in the melt viscosity measured at a shear rate of 1 rad / sec and 300 ° C. was measured for 30 minutes, and the rate of change per minute was determined. For the long-term stability of the aromatic polycarbonate to be good, this value must not exceed 0.5%.

5) Aromatic polycarbonate temperature / humidity deterioration test In order to test the durability of the aromatic polycarbonate under severe conditions of high temperature and high humidity for a long time, the aromatic polycarbonate was subjected to a temperature of 90 ° C. and a relative humidity of 90%. Hold for 1,000 hours. Ten samples were prepared for each polymer, the following measurements were performed, and the polymer was evaluated by the average value.

5-1) Hue deterioration: The hue of the polymer chip was measured with a Z-1001DP color difference meter manufactured by Nippon Denshoku Co., Ltd. The higher the L value, the higher the lightness, and the lower the b value, the less yellow coloring is preferable, and if the decrease in the L value and the increase in the b value (Δb value in the table) are 1.0 or less, the temperature is severe. It was evaluated that the desired hue stability was maintained even after prolonged use under wet conditions.

5-2) Transparency: A flat plate of 50 × 50 × 5 mm was molded at a cylinder temperature of 280 ° C. using a Neomat N150 / 75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., at a molding cycle of 3.5.
Secondly, the total light transmittance of the flat plate was measured by Nippon Denshoku Co., Ltd.
It was measured by DH- # 80. The higher the total light transmittance, the better the transparency. If the retention of the total light transmittance after the deterioration test is 90% or more, the desired transparency is maintained even when used for a long time under severe temperature and humidity conditions. We evaluated that we did.

5-3) Wet heat stability of impact resistance: Evaluated by Izod impact strength ASTM D-256 (notched). After the polymer was dried at 120 ° C. under a high vacuum for 12 hours, an injection molded plate having a thickness of 3.2 mm was prepared using a mold. The retention rate of the Izod impact strength before and after the wet heat treatment was determined. When the retention was 90% or more, it was determined that the desired strength was maintained under long-term wet heat conditions.

6) Determination of terminal hydroxyl group concentration and the number of aryloxy terminals 0.02 g of a polymer sample was dissolved in 0.4 ml of deuterated chloroform, and subjected to 1H-NMR (EX-270 manufactured by JEOL Ltd.) at 20 ° C. The OH terminal concentration was measured. The number of aryloxy terminal groups is determined by the total number of terminals determined by the following formula and OH
It was calculated as the difference in terminal numbers. Total number of terminals = 56.54 / [η] ^1.4338

7) Melted Hazen Color Number (APHA) Based on the color number test method shown in JIS K-4101, a flat bottom Pyrex (registered trademark) colorimetric tube having a diameter of 23 mm and a wall pressure of 1.5 mm was used. Liquid depth 140mm
Was compared with the Hazen standard colorimetric liquid. Measurement method: Bisphenol A (54 g), 2 mg of tetramethylammonium hydroxide were charged, and 175 in air.
The melted Hazen color number in a molten state at ℃ and the melted Hazen color number after holding at 175 ° C for 2 hours were measured. Measuring method: Diphenyl carbonate (54 g), 2 mg of tetramethylammonium hydroxide were charged, and the melted Hazen color number in a molten state at 250 ° C. in the atmosphere, and 25
The melted Hazen color number after holding at 0 ° C. for 2 hours was measured.

With bisphenol A, it is the limit of whether or not the number of melted Hazen color No. 20 or less at 175 ° C. after holding at 175 ° C. for 2 hours can be used as a polycarbonate raw material.

With diphenyl carbonate, the melting hazen color number no. 10 or less at 250 ° C. and the melting hazen color number no. 20 or less after holding at 250 ° C. for 2 hours are the limits of whether or not the polycarbonate raw material can be used.

[Raw material purification method] As a raw material for aromatic polycarbonate, bisphenol A purified as follows
(BPA) and diphenyl carbonate (DPC) were used.

1) Purification of BPA 1) -1 Sublimation purification method Commercially available BPA was charged into a glass sublimation purification apparatus, and a pressure of 13 Pa (0.1%) was applied using a decompression apparatus under a nitrogen atmosphere.
(Torr), 140 ° C., sublimation purification was performed slowly for 5 hours to obtain purified BPA. Sublimation purification as needed
A purified sample was prepared by repeating four times. Obtained purified BPA
Aa * 1 twice, sublimated purified product; Aa * 2, Aa * 2, sublimated and purified three or four more times, and further repeated n times, Aa * 3, Aa * 4,.・ ・ 、
Aa * n.

1) -2 Washing Purification Aa * 1 of the sublimation purified BPA was rinsed with acetone or methanol and dried. Each sample name is A-
Rac and A-Rme.

1) -3 Recrystallization Purification Commercial BPA was recrystallized from acetone and dried in vacuum. One recrystallized product was named Ab * 1, and two recrystallized products were named Ab * 2.

Separately, sublimated purified product A is used as a raw material.
Recrystallization was performed once using a * 1, and the recrystallized product was again sublimated and purified to prepare a recrystallized and purified bisphenol sample, Aab * 2.

1) -4 Crystallization and Purification Commercial BPA was dissolved in 5 times the amount of phenol, and adduct crystals of bisphenol and phenol were obtained at 40 ° C. The obtained adduct crystal was 5.33 kPa (40 Torr), 1
The phenol was removed at 80 ° C. until the phenol concentration in the BPA reached 3%, and the phenol was removed by steam stripping. Samples subjected to crystallization purification were named Ac * 1 and Ac * 2 according to the number of crystallizations.

2) Production of DPC Raw material 1 (Dg): DPC produced according to the method described in Plastic Materials Course 17, polycarbonate, Shoichi Sakajiri et al., Pp. 45-46. Raw material 2: DP which was produced by purifying DPC produced according to the method described in Example 1 of the Japanese Patent Laid-Open Publication No. Hei 7-188116 (Bayer), Plastic Materials Course 17, Polycarbonate, Shoichi Sakajiri et al.
C. Raw material 3: using commercially available dimethyl carbonate;
No.-091230 (Asahi Kasei) Following the description method of Example 1, except that Ti (OBu) 4 was used as a catalyst and DPC was performed.
Was prepared and purified according to the method described above. APHA (melt Hazen color number) of the raw materials 2 and 3 was very poor due to impurities, and it was judged that it was difficult to use.

3) Purification of DPC 3) -1 Sublimation Purification The same apparatus as that used for sublimation purification of BPA was used even in DPC under a nitrogen atmosphere under a pressure of 30 Pa (0.3 Ton).
rr), sublimation purification at 77 ° C. for 4 hours was repeated n times,
Purified DPC was obtained. 1 time sublimation product; Da * 1, 2 times sublimation product; Da *
2. Samples obtained by repeating the sublimation purification three or four times and further n times were named Da * 3, Da * 4,..., Da * n.

3) -2 Washing + Distillation + Sublimation Refining Separately, the raw material DPC was replaced with hot water (50%) according to the method described on page 45 of “Plastic Materials Course 17 Polycarbonate Author Tachikawa Toshihisa et al. (Nikkan Kogyo Shimbun)”.
℃) Washing was repeated 3 times, and after drying, distillation under reduced pressure was carried out.
A fraction of １６168 ° C./2.000 kPa (15 mmHg) was collected, and further subjected to the above-mentioned sublimation purification to obtain a purified product of diphenyl carbonate Dc.

3) -3 Ion exchange purification The raw material DPC was dissolved in 10 times the amount of acetone,
After passing through an anion mixed ion exchange resin column, the solvent is
The above distillation under reduced pressure and sublimation purification were performed to obtain a purified product Dd of diphenyl carbonate.

The impurities contained in the purified bisphenol A and diphenyl carbonate were measured by the above method, and the results are shown in Tables 1 to 3 below.

[0134]

[Table 1]

[0135]

[Table 2]

[0136]

[Table 3]

[Comparative Example 1] Production of an aromatic polycarbonate was carried out as follows. As a raw material, 137 parts by weight of commercially available BPA (Ag) and 135 parts of purified DPC (Da * 1)
Parts by weight, 8.2 × 10 ⁻⁶ parts by weight of disodium salt of bisphenol A and 5.5 × 10 ⁻³ parts by weight of tetramethylammonium hydroxide (hereinafter abbreviated to TMAH) as a polymerization catalyst, and charged at 180 ° C. under a nitrogen atmosphere. Melted.

Under stirring, the inside of the reaction tank was kept at 13.33 kPa (1
The pressure was reduced to 00 mmHg, and the reaction was carried out for 20 minutes while distilling off the generated phenol. Next, after the temperature was raised to 200 ° C., the pressure was gradually reduced to 4.00 while phenol was distilled off.
The reaction was performed at 0 kPa (30 mmHg) for 20 minutes. Further, the temperature was gradually raised and reacted at 220 ° C. for 20 minutes, 240 ° C. for 20 minutes, and 260 ° C. for 20 minutes. Thereafter, the pressure was gradually reduced at 260 ° C. and 10 minutes at 2.666 kPa (20 mmHg).
The reaction was continued at 1.333 kPa (10 mmHg) for 5 minutes, and finally 260 ° C./66.7 Pa (0.5 m
(mHg) until the viscosity average molecular weight reached 15,300.

Thereafter, 3.6 × 10 ^-4 parts by weight of tetrabutylphosphonium dodecylbenzenesulfonate (hereinafter abbreviated as DBSP) was added to each, and 260 ° C./66.7.
The mixture was stirred at Pa (0.5 mmHg) for 10 minutes. Finally, the viscosity average molecular weight was 15,300 and the terminal hydroxyl group concentration was 8
5, the phenoxy end group concentration was 154 (eq / ton-polycarbonate), and the melt viscosity stability was 0.

[Comparative Example 2] In Comparative Example 1, tetrabutylphosphonium hydroxide (hereinafter referred to as TBP) was used instead of TMAH.
H) (1.7.times.10.sup.- ² parts by weight) and the polymerization was carried out in the same manner. Finally, the viscosity average molecular weight is 15,300, the terminal hydroxyl group concentration is 87, and the phenoxy terminal group concentration is 152 (eq.
/ Ton-polycarbonate), and the melt viscosity stability was 0.

Example 1 The aromatic poly obtained in Comparative Example 1
Carbonate for electronic industry NMP1.5 × 10 ^ThreeParts by weight
After dissolving in methanol for electronic industry 1.1 × 10^Four
1 part by weight, and the precipitated polymer was separated by filtration.
Pa (0.1 mmHg), dried at 100 ° C for 24 hours
I let you. The resulting aromatic polycarbonate has a viscosity average
Particle size 15,300, terminal hydroxyl group concentration 85, phenoxy powder
End group concentration 154 (eq / ton-polycarbonate),
The melt viscosity stability was 0.

Example 2 At the time when the polycarbonate was produced in Comparative Example 1, when the viscosity average molecular weight reached 15,300,
8.0 parts by weight of 2-methoxycarbonylphenylphenyl carbonate (hereinafter abbreviated as SAM) per part by weight of the polymer.
× 10 ^-3 parts by weight, 260 ° C, 133.3 Pa (1 m
mHg) for 10 minutes, then DBSP was 2.3 ×
10 ^-6 parts by weight, 260 ° C., 66.7 Pa (0.5
(mmHg) for 10 minutes.

After dissolving the obtained aromatic polycarbonate in 1.5 × 10 ³ parts by weight of NMP for electronics industry, 1.1 × 10 ⁴ parts by weight of methanol for electronics industry was added, and the precipitated polymer was separated by filtration. 13.3 Pa (0.1 mmH
g) and dried at 100 ° C. for 24 hours. The obtained aromatic polycarbonate had a viscosity average molecular weight of 15,300,
Terminal hydroxyl group concentration 60, phenoxy terminal group concentration 179 (e
q / ton-polycarbonate), and the melt viscosity stability was 0.

Example 3 In Example 2, 17.6 × 10 ^-3 parts by weight of SAM was used per 1 part by weight of the polymer, and the same treatment was carried out. The resulting aromatic polycarbonate had a viscosity average molecular weight of 15,300 and a terminal hydroxyl group concentration of 3
0, phenoxy terminal group concentration 209 (eq / ton-polycarbonate), and melt viscosity stability were 0.

Example 4 In Comparative Example 1, BPA and DP
As C, purified BPA (Ac * 1) and purified DPC
Using (Da * 1), melt polymerization was performed. After polymerization, SAM and DBSP were used in the same manner as in Example 3, and the aromatic polycarbonate finally obtained had a viscosity average molecular weight of 15,
300, terminal hydroxyl group concentration 30, phenoxy terminal group concentration 2
09 (eq / ton-polycarbonate) and melt viscosity stability was 0.

Example 5 The aromatic poly obtained in Comparative Example 1
Carbonate for electronic industry NMP1.5 × 10 ^ThreeParts by weight
Dissolved in water and treated with activated charcoal.
Methanol for child industry 1.1 × 10^Four1 x 10 parts by weight^TwoHeavy
The precipitated polymer was separated by filtration.
Was. This reprecipitation operation was repeated twice, and the resulting polymer
At 13.3 Pa (0.1 mmHg) and 100 ° C.
Dry for 4 hours. The resulting polycarbonate has a viscosity
Average molecular weight 15,300, terminal hydroxyl group concentration 85, terminal
Enoxy group concentration 154 (eq / ton-polycarbonate)
G), the melt viscosity stability was 0.

Example 6 In Comparative Example 1, BPA and DP
As C, purified BPA (Ab * 2) and purified DPC
Using (Dc), melt polymerization was performed. After the polymerization, SAM and DBSP were used in the same manner as in Example 3, and the finally obtained aromatic polycarbonate had a viscosity average molecular weight of 1
5,300, terminal hydroxyl group concentration 30, phenoxy terminal group concentration 209 (eq / ton-polycarbonate), and melt viscosity stability were 0.

Example 7 The same operation as in Example 6 was carried out except that the amount of TMAH was 5.5 × 10 ^-2 parts by weight. The aromatic polycarbonate finally obtained had a viscosity average molecular weight of 15,300, a terminal hydroxyl group concentration of 30, a phenoxy terminal group concentration of 209 (eq / ton-polycarbonate), and a melt viscosity stability of 0.

Example 8 The aromatic poly obtained in Comparative Example 1
Carbonate for electronic industry NMP1.5 × 10 ^ThreeParts by weight
And treated with a mixed ion-exchange resin column.
While stirring the liquid, methanol for electronic industry 1.1 × 10^Four
1 x 10 parts by weight^TwoIt was dropped at parts by weight / min to precipitate
The polymer was filtered off. Repeat this reprecipitation operation twice
And the obtained polymer was 13.3 Pa (0.1 mmH
g) and dried at 100 ° C. for 24 hours. Finally got
The aromatic polycarbonate obtained has a viscosity average molecular weight of 15,
300, terminal hydroxyl group concentration 85, terminal phenoxy group concentration 1
54 (eq / ton-polycarbonate), low melt viscosity
The qualitative value was 0.

Example 9 In Comparative Example 1, BPA and DP
As C, purified BPA (Aab * 2) and purified DPC
Using (Dd), melt polymerization was performed. After the polymerization, SAM and DBSP were used in the same manner as in Example 3, and the aromatic polycarbonate finally obtained had a viscosity average molecular weight of 1
5,300, terminal hydroxyl group concentration 30, phenoxy terminal group concentration 209 (eq / ton-polycarbonate), and melt viscosity stability were 0.

Comparative Example 3 Raw materials were charged into a reaction vessel equipped with a stirrer, a rectification tower and a decompression device in the same manner as in Comparative Example 1, except that a disodium salt of bisphenol A 8.2 × 10 8 was used as a polymerization catalyst. ^-5 parts by weight, TMAH 5.5 × 10 ^-3
A part by weight was melted at 180 ° C. in a nitrogen atmosphere.

Under stirring, the inside of the reactor was kept at 13.33 kPa (1
The pressure was reduced to 00 mmHg, and the reaction was carried out for 20 minutes while distilling off the generated phenol. Next, after the temperature was raised to 200 ° C., the pressure was gradually reduced to 4.00 while phenol was distilled off.
The reaction was performed at 0 kPa (30 mmHg) for 20 minutes. Further, the temperature was gradually raised and reacted at 220 ° C. for 20 minutes, 240 ° C. for 20 minutes, and 260 ° C. for 20 minutes. Thereafter, the pressure was gradually reduced at 260 ° C. and 10 minutes at 2.666 kPa (20 mmHg).
The reaction was continued for 5 minutes at 1.333 kPa (10 mmHg) for 5 minutes, and finally at 280 ° C. and 66.7 Pa (0.5 mHg).
(mHg) until the viscosity average molecular weight reached 15,300.

Thereafter, 1.3 × 10 ⁻³ parts by weight of DBSP was added, and 1 part was added at 280 ° C. and 66.7 Pa (0.5 mmHg).
The mixture was stirred for 0 minutes to obtain an aromatic polycarbonate. The resulting aromatic polycarbonate had a viscosity average molecular weight of 15,3.
00, terminal hydroxyl group concentration 85, terminal phenoxy group concentration 15
4 (eq / ton-polycarbonate), melt viscosity stability was 0.

Comparative Example 4 (Example of Mw = 22,500) In Comparative Example 1, the polymerization of the aromatic polycarbonate was further continued to finally produce a polycarbonate having a viscosity average molecular weight of 22,500. The resulting aromatic polycarbonate had a viscosity average molecular weight of 22,500, a terminal hydroxyl group concentration of 73, a terminal phenoxy group concentration of 77 (eq / ton-polycarbonate), and a melt viscosity stability of 0.

[Examples 10 and 11] The aromatic polycarbonate obtained in Comparative Example 4 was used in Examples 1 and 8
Each treatment was performed in the same manner as described above. The obtained polycarbonate had a viscosity average molecular weight of 22,500, a terminal hydroxyl group concentration of 73, and a terminal phenoxy group concentration of 77 (eq / ton).
-Polycarbonate), and the melt viscosity stability was 0.

[Comparative Example 5] A raw material bisphenol A, 502.8 g (2.21 mol), 7.2% was placed in a 5 L capacity reaction tank equipped with a phosgene blowing tube, a thermometer and a stirrer.
An aqueous sodium hydroxide solution, 2.21 L (sodium hydroxide 4.19 mol) and sodium hydrosulfite, 0.98 g (0.0056 mol) were charged and dissolved, and methylene chloride, 1.27 L and 48 were stirred under stirring. .5
% Aqueous sodium hydroxide solution, 80.70 g (sodium hydroxide, 0.98 mol) was added.
0.80 g (0.253 mol) was added at 25 ° C. over 180 minutes to carry out a phosgenation reaction.

After completion of the phosgenation, p-tert-butylphenol, 17.51 g (0.117 mol), and 4
8.5% sodium hydroxide aqueous solution, 80.40 g (0.4%)
97 mol) and triethylamine as catalyst, 1.8
1 ml (0.013 mol) was added, and the mixture was maintained at 33 ° C. and stirred for 2 hours to complete the reaction. The methylene chloride layer was separated from the reaction mixture and purified by repeating washing with water five times. The viscosity average molecular weight was 15,300, the terminal hydroxyl group concentration was 15, the terminal phenoxy group concentration was 224 (eq / ton-polycarbonate), and the melt viscosity was stable. A polycarbonate resin of 0.1 was obtained.

Example 12 The polymer of Comparative Example 5 was treated in the same manner as in Example 1. Finally, viscosity average molecular weight 1
A polycarbonate resin having 5,300, a terminal hydroxyl group concentration of 15, a terminal phenoxy group concentration of 224 (eq / ton-polycarbonate) and a melt viscosity stability of 0 was obtained.

The impurities contained in the aromatic polycarbonates obtained in Examples 1 to 12 and Comparative Examples 1 to 5 (unit: p
pb, ppm) are shown in Table 4 below.

[0160]

[Table 4]

The physical properties of the aromatic polycarbonates obtained by the production methods of Examples 1 to 12 and Comparative Examples 1 to 5 are shown in Table 5 below.
Shown in

[0162]

[Table 5]

[Examples 13 and 14 and Comparative Example 6] Tris (2,4-di-t-butylphenyl) phosphite was added to the aromatic polycarbonates of Examples 8 and 9 and Comparative Example 3 in an amount of 0.01%. % By weight, and 0.08% by weight of stearic acid monoglyceride were added. Next, the composition was vented to a twin-screw extruder (KTX-4 manufactured by Kobe Steel Ltd.).
The mixture was melt-kneaded while degassing at a cylinder temperature of 240 ° C. according to 6) to obtain pellets. DVD using this pellet
(DVD-Video) A disc substrate heat / humidity deterioration test was performed.

Injection molding machine, DISK3 manufactured by Sumitomo Heavy Industries, Ltd.
A mold dedicated to DVD is attached to M III, and a nickel DV containing information such as address signals is attached to the mold.
A stamper for D was mounted, and the pellets were put into a hopper of a molding machine by automatic conveyance. The cylinder temperature was 380 ° C, the mold temperature was 115 ° C, the injection speed was 200 mm / sec, and the holding pressure was 3,432 kPa (35 kgf / cm ² ). A DVD disk substrate having a diameter of 120 mm and a wall thickness of 0.6 mm was formed under the conditions described above.

In order to test the reliability of the optical disk under severe temperature and humidity conditions for a long time, the aromatic polycarbonate optical disk substrate was kept at a temperature of 80 ° C. and a relative humidity of 85% for 1,000 hours, and then the following measurement was performed. The substrate was evaluated by:

Number of white spots: The number of white spots having a size of 20 μm or more was counted by observing the optical disk substrate after the heat and humidity deterioration test using a polarizing microscope. This is performed for 25 optical disc substrates (120 mm in diameter), and the average value is obtained.
This was defined as the number of white spots.

As a result, the number of white spots in Examples 13, 14 and Comparative Example 6 was 0.2, 0.1 and 3.5, respectively.

[Example 15] [0168] After the aromatic polycarbonate of Example 10 was melted, a fixed amount was supplied by a gear pump.
It was sent to the T die of the molding machine. 0.003% by weight of trisnonylphenyl phosphite was added from just before the gear pump,
It was melt-extruded into a sheet having a thickness of 2 mm or 0.2 mm and a width of 800 mm by pinching or single-sided touch between the mirror-surface cooling roll and the mirror-surface roll.

A visible light curable plastic adhesive (BENEFIX PC manufactured by Adel Co., Ltd.) was applied to one side of the obtained aromatic polycarbonate sheet (2 mm thick), and the same sheet was extruded to one side to prevent air bubbles from entering. 5,000 mJ / cm ² by a light curing device equipped with a metal halide type dedicated to visible light
JIS K
As a result of measuring in accordance with-6852 (test method for compressive shear bond strength of adhesive), the bond strength was 10.4 MPa (1
06 Kgf / cm ² ).

On the other hand, an aromatic polycarbonate sheet having a thickness of 0.2 mm was coated with ink (Natsuda 70-9132: color).
136D smoke) and a solvent (isophorone / cyclohexane / isobutanol = 40/40/20 (wt.
%)), Mixed, printed with a silk screen printer, and dried at 100 ° C. for 60 minutes. There was no transfer failure on the printed ink surface and the printing was good.

Separately, a polycarbonate resin obtained by subjecting 1,1-bis (4-hydroxyphenyl) cyclohexane and phosgene to an ordinary interfacial polycondensation reaction (having a specific viscosity of 0.1%).
895, Tg 175 ° C) 30 parts, Plast as a dye
A sheet (0.2 mm thick) printed with a printing ink obtained by mixing 15 parts of Red 8370 (manufactured by Arimoto Chemical Industries) and 130 parts of dioxane as a solvent was mounted in an injection molding die, and polycarbonate resin pellets (panlite) were mounted. L-
1225 Insert molding was performed at a molding temperature of 310 ° C. using Teijin Chemicals Ltd. An insert molded product having a good printed portion appearance was obtained without any abnormality such as bleeding or blurring in the printed portion pattern of the molded product after the insert molding.

[Examples 16 to 22] 0.003% by weight of trisnonylphenyl phosphite and 0.1% of trimethyl phosphate were added to the aromatic polycarbonate of Example 10 described above.
The resulting mixture was added so as to be 0.05% by weight to obtain an aromatic polycarbonate powder which was uniformly mixed. This powder and each component shown in Tables 6 and 7 (each component indicated by the symbol shown below) were uniformly mixed using a tumbler, and then mixed.
Twin screw extruder with 0mmφ vent (KT made by Kobe Steel Co., Ltd.)
X-30), cylinder temperature 260 ° C, 1.33
After degassing at a degree of vacuum of kPa (10 mmHg) and pelletizing, and drying the obtained pellet at 120 ° C. for 5 hours,
Injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.)
Using a cylinder temperature of 270 ° C and a mold temperature of 80 ° C
A molded piece for measurement was prepared under the following conditions, and the following evaluation was performed. The results are shown in Tables 6 and 7. -1 ABS: styrene-butadiene-acrylonitrile copolymer; Santac UT-61; Mitsui Chemicals, Inc.
-2 AS: styrene-acrylonitrile copolymer;
Styrac-AS 767 R27; manufactured by Asahi Kasei Corporation-3 PET: polyethylene terephthalate; TR-
8580; Teijin Limited, intrinsic viscosity 0.8-4 PBT: polybutylene terephthalate; TRB
-H: Teijin Limited, intrinsic viscosity 1.07 -1 MBS: Methyl (meth) acrylate-butadiene-styrene copolymer; Kaneace B-56; Kanebuchi Chemical Industry Co., Ltd. -2E-1: Butadiene-alkyl acrylate-
Alkyl methacrylate copolymer; Paraloid EXL
-2602; manufactured by Kureha Chemical Industry Co., Ltd. -3E-2: Composite rubber in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component have an interpenetrating network structure; Metablen S-200
1: Mitsubishi Rayon Co., Ltd. -1 T: Talc; HS-T0.8; Hayashi Kasei Co., Ltd.
, Average particle diameter L = 5 measured by laser diffraction method
μm, L / D = 8 −2 G: glass fiber; chopped strand ECS
-03T-511; manufactured by Nippon Electric Glass Co., Ltd., urethane focusing treatment, fiber diameter 13 μm −3 W: wollastonite; Psycatek NN-4;
Tomoe Kogyo Co., Ltd., number-average average fiber diameter D = 1.5 μm, average fiber length 17 μm determined by electron microscope observation,
Aspect ratio L / D = 20 WAX: Olefin wax obtained by copolymerization of α-olefin and maleic anhydride; DIAKARNA-P3
0; manufactured by Mitsubishi Kasei Corporation (maleic anhydride content = 10w)
t%)

(A) Flexural modulus The flexural modulus was measured according to ASTM D790. (B) Notched Impact Value According to ASTM D256, a 3.2 mm thick test piece was used to impact a weight from the notch side, and the impact value was measured. (C) Fluidity Cylinder temperature 250 ° C, mold temperature 80 ° C, injection pressure 9
The fluidity was measured at 8.1 MPa by Archimedes-type spiral flow (thickness 2 mm, width 8 mm). (D) Chemical Resistance A 1% strain was applied to a tensile test piece used according to ASTM D638, and the test piece was immersed in Esso regular gasoline at 30 ° C. for 3 minutes, and then the tensile strength was measured to calculate the retention.
The retention was calculated by the following equation. Retention (%) = (strength of treated sample / strength of untreated sample) × 100

[0174]

[Table 6]

[0175]

[Table 7]

[0176]

As described in the present invention, by controlling the content of the above-mentioned specific impurities in the aromatic polycarbonate to a specific value or less, the durability of the polymer, especially the long-term durability under severe temperature and humidity conditions, is improved. And the effect of maintaining good color tone, transparency and mechanical strength is obtained. As a raw material, DPC having a specific metal element content of a specific value or less is used.
Aromatic polycarbonate resin having good stability can be produced by polymerizing the compound using a compound of formula (I) or BPA.

 ──────────────────────────────────────────────────の Continuation of the front page (31) Priority claim number Japanese Patent Application No. 11-344727 (32) Priority date December 3, 1999 (12.3 December 1999) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 11-344728 (32) Priority date December 3, 1999 (Dec. 23, 1999) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application 2000-277 (P2000-277) (32) Priority Date January 5, 2000 (2000.1.5) (33) Priority Country Japan (JP) (72) Inventor Yuichi Kageyama Iwakuni, Yamaguchi Prefecture 2-1, Hinode-cho, Teikoku, Japan Teijin Co., Ltd. Iwakuni Research Center (72) Inventor Katsuji Sasaki 2-1, Hinodecho, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. 1-2-2 Teijin Chemicals Co., Ltd. (72) Inventor Koji Ishihata Higashi 1-2-2 Uchisaiwaicho, Chiyoda-ku, Kyoto Teijin Chemicals Co., Ltd. (72) Koji Maeda 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo F-term in Teijin Chemicals Co., Ltd. 4F071 AA50 AH12 BB05 BC07 4J029 AA09 AB05 AC01 AD10 AE02 AE04 AE05 AE06 AE18 BB12A BB12B BB13A BD09A BG08X BH02 DB11 DB13 HA01 HC04A HC05A JA091 JA121 JA161 JA201 JA251 JA301 JB171 JB191 JC031 JC091 JC1F02 J031J031

Claims (26)

[Claims] The main repeating unit is represented by the following formula (1): (R ₁ and R ₂ in the formula each independently have 1 to 1 carbon atoms.
20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms or aryloxy having 6 to 20 carbon atoms M and n
Are each independently an integer from 0 to 4, X is a single bond,
Oxygen atom, carbonyl group, alkylene group having 1 to 20 carbon atoms, alkylidene group having 2 to 20 carbon atoms, 6 to 20 carbon atoms
A cycloalkylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylene arylene alkylene group having 6 to 20 carbon atoms. Wherein the terminal group consists essentially of an aryloxy group (A) and a phenolic hydroxyl group (B), and their molar ratio (A) / (B) is 95/5 to 40/60; The melt viscosity stability is 0.5% or less, the content of sodium metal element is 100 ppb or less, and N
An aromatic polycarbonate, wherein the content of the first element of each of i, Pb, Cr, Mn and Fe is 70 ppb or less. 2. The content of each of the first elements is 40 p.
The aromatic polycarbonate according to claim 1, which is not more than pb. 3. The content weight of the sodium metal element is 70 p.
pb or less and the content weight of each of the first elements is 2
2. The aromatic polycarbonate according to claim 1, wherein the content is 0 ppb or less. 4. The content of sodium metal element is 20 p.
pb or less and the content weight of each of the first elements is 1
2. The aromatic polycarbonate according to claim 1, wherein the content is 0 ppb or less. 5. The concentration of terminal hydroxyl group (H) (eq / ton-
Polycarbonate) is the sum of the weights of the first elements divided by the first
2. The aromatic polycarbonate according to claim 1, wherein a relationship of (H) ≦ Σfirst element is satisfied with respect to the element (ppb). 3. 6. The concentration of terminal hydroxyl group (H) (eq / ton-
Polycarbonate) is the sum of the weights of the first elements divided by the first
2. The aromatic polycarbonate according to claim 1, wherein the relation (H) ≦ 0.5 × (Σfirst element) is satisfied with respect to the element (ppb). 3. 7. Cu, Zn, Pd, In, Si and A
2. The aromatic polycarbonate according to claim 1, wherein the content weight of each second element of l is 20 ppb or less. 8. The content of Ti as a third element is 1 pp.
2. The aromatic polycarbonate according to claim 1, wherein the content of the fourth element of each of P, N, S, Cl and Br is 1 ppm or less. 9. A molded article of the aromatic polycarbonate according to any one of claims 1, 7 and 8. 10. The molded article according to claim 9, which is an optical disk substrate. 11. An aromatic dihydroxy compound and a carbonic acid diester are added to the aromatic dihydroxy compound per mole.
A) at least one basic compound 10 selected from the group consisting of nitrogen-containing basic compounds and phosphorus-containing basic compounds;
A) at least one selected from the group consisting of an alkali metal compound and an alkaline earth metal compound per mole of an aromatic dihydroxy compound.
A method for producing a polycarbonate by polycondensation in the presence of a catalyst containing 0.05 to 5 μequivalents of the following compounds: 1) Na metal element content is 52 ppb or less, and 2) Fe, Cr, Mn , Ni and Pb, each containing an aromatic dihydroxy compound and a carbonic acid diester having a weight of 40 ppb or less. 3) The amount of the basic compound used per mole of the aromatic dihydroxy compound was A method for producing an aromatic polycarbonate, wherein the amount does not exceed 20 × Fe ^* + 200 based on the total weight of Fe ^* (ppb) contained in the compound and the carbonic acid diester. 12. The aromatic dihydroxy compound and the carbonic acid diester each contain 1) a Na metal element at 35 ppb or less and 2) a first element at 23 ppb or less.
The method of claim 1. 13. An aromatic dihydroxy compound and a carbonic acid diester each comprising: 1) a Na metal element at a weight of 6 ppb or less, and 2) a first element at a weight of 6 ppb or less.
The described method. 14. An aromatic dihydroxy compound and a carbonic acid diester each comprising Cu, Zn, In, Pd, Si
The method according to claim 11, wherein the second element of each of Al and Al is contained in an amount of not more than 10 ppb by weight. 15. Each of the aromatic dihydroxy compound and the carbonic acid diester contains 1 weight% of Ti as the third element.
12. The method of claim 11, containing less than 1 pb and less than 1 ppm by weight of each of the fourth elements of P, N, S, Cl, and Br. 16. The method according to claim 11, wherein the aromatic dihydroxy compound is bisphenol A. 17. High performance liquid chromatographic analysis of bisphenol A (having an inner diameter of 4.6 mm filled with an adsorbent in which 15% (as carbon content) octadecyl group is bonded to high-purity spherical silica gel having a pore diameter of 100 Å). A high-performance liquid chromatograph holding a column having a length of 250 mm at 40 ° C.
% Phosphoric acid aqueous solution and acetonitrile as eluent B, and the ratio of eluent A: eluent B was 1: 1 and the total flow rate of eluent A and eluent B was 0 until 5 minutes from the start of measurement. The measurement was performed so as to be 0.9 ml / min, and the ratio of the eluent B was continuously increased from 5 minutes after the start of the measurement while keeping the total flow rate constant. A gradient operation is performed to increase the ratio of the eluent B so that the ratio of the solution B becomes 0: 1, and the wavelength 254 n
m analysis of BPAs)
17. The method according to claim 16, wherein the sum of the absorption peak areas of the compounds eluted from 15.5 minutes to 24 minutes is 2.0 × 10 ⁻³ or less as a ratio to the absorption peak area of bisphenol A. 18. The method according to claim 17, wherein the total absorption peak area of the eluted compound is 1.0 × 10 ⁻³ or less with respect to the absorption peak area of bisphenol A. 19. The total absorption peak area of a compound in which bisphenol A is eluted between 22 minutes and 24 minutes by high performance liquid chromatography is 5 × 10 ⁻⁵ or less as a proportion of the absorption peak area of bisphenol A. The method according to claim 17. 20. Bisphenol A is a high performance liquid chromatograph.
Elution between 22 and 24 minutes by graphical analysis
And the absorption peak of a compound having a molecular weight of 307 to 309.
The total of the surface area corresponds to the absorption peak area of bisphenol A.
Then 2 × 10 ^-Five20. The method of claim 19, wherein: 21. Bisphenol A is represented by the following formula (2): (Wherein R ₃ and R ₄ are each independently a methyl, ethyl, n-propyl, isopropyl group or an isopropenyl group). 2 x 10 parts by weight
18. The method according to claim 17, wherein the amount is not more than ^-4 parts by weight. 22. The method according to claim 21, wherein the content of 1-naphthols is 1 × 10 ⁻⁴ parts by weight or less based on 1 part by weight of bisphenol A. 23. Bisphenol A is represented by the following formula (3): (In the formula, R _{5 to} R ₇ are each independently an alkyl group having 1 to 4 carbon atoms, and R ₈ and R ₉ are each independently an alkyl group having 1 carbon atom.
To 4 alkyl groups, and p and q are each independently an integer of 0 to 4. ) Is 5 × 1 with respect to 1 part by weight of bisphenol A.
0 ^-5 or less parts by weight, and the following general formula (4) ## STR4 ## (Wherein, R _{10 to} R ₁₂ are each independently an alkyl group having 1 to 4 carbon atoms, R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 4 carbon atoms, and s and t are Is independently an integer of 0 to 4).) The method according to claim 17, wherein the content of the codimer derivative is 5 × 10 ⁻⁵ parts by weight or less based on 1 part by weight of bisphenol A. 24. Bisphenol A is represented by the following formula (5):(Where R_Fifteen~ R₁₇Are each independently an alkyl group having 1 to 4 carbon atoms.
A alkyl group;₁₈Are each independently a hydrogen atom or carbon
A is an alkyl group of 1 to 4;
It is an integer of 0-4. Chromene compound represented by)
Is 1 × 10 5 parts by weight of bisphenol A.
^-FiveParts by weight or less, and the following formula (6):(Where R₁₉And R₂₀Are each independently 1 to 4 carbon atoms
Is an alkyl group of _{twenty one}And R_{twenty two}Are independently
An alkyl group having 1 to 4 carbon atoms and b and c are
Each is independently an integer of 0 to 4. )
1 × 1 parts by weight of bisphenol A
0^-FiveClaims using bisphenol A which is not more than parts by weight
Item 18. The method for producing an aromatic polycarbonate according to Item 17. 25. Use of the aromatic polycarbonate according to claim 1 as a raw material for producing a molded article. 26. The use according to claim 25, wherein the molded article is an optical disk substrate.