JP3399803B2 - Aromatic polycarbonate composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized aromatic polycarbonate composition, and more specifically, as a first object, a composition having a good color tone and a short-term and long-term stability. Regarding Further, as a second object, the present invention relates to an aromatic polycarbonate composition having improved stability upon contact with a metal.

[0002]

2. Description of the Related Art Polycarbonate is widely used because it is excellent in mechanical properties such as impact resistance, heat resistance and transparency. As a method for producing such a polycarbonate, a method of directly reacting phosgene with an aromatic diol such as bisphenol A (interfacial polymerization method), or an aromatic diol such as bisphenol A and a diallyl carbonate such as diphenyl carbonate in a molten state Methods such as transesterification (melting method) are known.

Among these production methods, the method of transesterifying an aromatic diol and diallyl carbonate (melting method) is more advantageous than the production by the interfacial polymerization method.
It is considered promising in the future because it has the advantage of being able to produce polycarbonate inexpensively without the problem of using toxic halogen compounds such as phosgene and methylene chloride as a solvent.

In the melting method polycarbonate production method by the transesterification reaction, in order to improve the production efficiency, plastic materials course 17 Polycarbonate page 48-53
Usually ester sympathetic catalysts are used as described in the literature.

Among these transesterification catalysts, a catalyst in which a basic nitrogen compound and an alkali metal compound are used in combination has a good polycarbonate productivity, a good color tone of the obtained polycarbonate, and a small branched structure in the polymer molecule. It can be said that it is a preferable catalyst because it has good qualities such as fluidity and less generation of foreign matter such as gel.

However, the melt-polymerization polycarbonate contains an alkali metal compound used as an ester sensitizing catalyst and other metal compounds, and therefore has a problem in stability. For example, regarding short-term stability, there are problems such as coloring during heating and melt molding, molecular weight reduction, black foreign matter production, etc.
In the long term, in the high temperature environment, the mechanical properties of the molded product are deteriorated in addition to the following problems. Further, it has a problem that it is susceptible to hydrolysis under a special environment, for example, in water, especially in hot water or in a steam atmosphere.

To solve these problems, Japanese Patent Laid-Open No. 4-3
28124 and Japanese Patent Application Laid-Open No. 4-328156 propose a method of neutralizing an ester sympathetic catalyst with an acidic compound containing a sulfonic acid ester. However, in this method, a stronger acidic compound is by-produced than an acidic compound containing a sulfonic acid ester, and when the acidic compound containing a sulfonic acid ester is added by the by-product, during the subsequent processing or when using a polycarbonate, hydrolysis, etc. Deterioration occurs and the problem cannot be fully solved.

According to the method described in Japanese Patent Application Laid-Open No. 8-59975, a phosphonium sulfonate is used alone or a phosphite compound or a phenolic antioxidant is used in combination with the polycarbonate obtained by such a method. As described above, the above-mentioned stability is maintained at a sufficiently good value, but when injection molding is performed using this polymer, the stain on the mold surface of the injection molding machine is compared with the case where the interfacial polymerization polycarbonate is used. And it turned out to be great. This defect is a serious defect that causes transfer defects such as groups and pits when a precision molded product such as an optical disk is molded.

[0009]

According to the studies by the present inventors, the aromatic polycarbonate composition produced in the presence of the above-mentioned combined catalyst of the nitrogen-containing basic compound and the alkali metal compound has a short-term and long-term effect. Stability, that is, coloring during melt molding, molecular weight reduction, generation of black foreign matter, or
At the same time that the hydrolysis resistance under hot water or steam atmosphere is good, when the mold molding using the composition,
It is intended to provide an aromatic polycarbonate composition which is suitable for precision molding and has a good molding operation efficiency with less mold stains.

[0010]

Means for Solving the Problems The present inventors have conducted an ester exchange method (melt polymerization method) in the presence of a combined catalyst of a nitrogen-containing basic compound and an alkali metal compound from an aromatic diol compound and a carbonic acid diester. , Melt-polycondensed,
Short-term and long-term in a composition containing both an A component; a sulfonic acid-based compound and a B component; a phosphoric acid ester-based compound and a C component; Stability, that is, coloration during heat retention or melt molding, molecular weight reduction, generation of black foreign matter, or good hydrolysis resistance under hot water or steam atmosphere, while using the composition, The object of the present invention is to provide an aromatic polycarbonate composition which is suitable for precision molding and has a good molding operation efficiency when the molding is carried out with less stains on the mold.

The aromatic polycarbonate referred to in the present invention is an aromatic fragrance obtained by melt-polycondensing an aromatic dihydroxy compound, which is a main component, and a carbonic acid ester in the presence of an ester exchange catalyst composed of a basic nitrogen compound and an alkali metal compound. As the aromatic dihydroxy compound, a compound represented by the following general formula (1) is preferably used.

[0012]

[Chemical 6]

(R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, It is a phenyl group-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group or a sulfone group.)

Specific examples of such an aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3). -Methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5)
-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) oxide, bis (3,5)
-Dichloro-4-hydroxyphenyl) oxide,
p, p'-dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, bis (hydroxyphenyl) sulfone, resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4 -Dihydroxy-3-methylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide and the like can be mentioned, but 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

Specific examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate and bis (diphenyl).
Carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. are used. Of these, diphenyl carbonate is particularly preferable.

The polycarbonate of the present invention may contain the following components, if necessary. Aliphatic diols; eg ethylene glycol, 1,4-
Dicarboxylic acids such as butanediol, 1,4-cyclohexanedimethanol, 1,10-decanediol; for example, succinic acid, isophthalic acid,
2,6-naphthalenedicarboxylic acid, adipic acid, cyclohexanecarboxylic acid, tereflutaic acid, etc .; oxy acids such as lactic acid, P-hydroxybenzoic acid, 6-hydroxy-
The catalyst system in the production of these aromatic polycarbonates, such as 2-naphthoic acid, etc., is as described in general, the basic nitrogen compound and the alkali metal compound are used in combination, and the amount of the alkali metal compound used is bisphenol A.
By controlling the amount to be less than 10 × 10 ⁻⁶ mol per mol, the transesterification reaction can be industrially advantageously promoted, and the occurrence of a branched structure in the polycarbonate can be suppressed, whereby a polycarbonate having good fluidity and color tone can be obtained. .

Examples of the alkali metal compound used as a catalyst include alkali metal hydroxides, hydrogen carbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates and stearates. , Borohydride salts, benzoate salts, phosphohydrides, bisphenols, phenol salts and the like.

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

The alkali metal compound as a catalyst is preferably from 10 ^-8 to 1 mol of the aromatic dihydroxy compound.
It may be used in the range of 10 ^-5 mol. If it deviates from the above-mentioned range of use, there are problems that various properties of the obtained polycarbonate are adversely affected, that the transesterification reaction does not proceed sufficiently and a high molecular weight polycarbonate cannot be obtained.

As the nitrogen-containing basic compound as a catalyst, for example, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), benzyl can be used. Trimethylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH), hexadecyltrimethylammonium hydroxide, and other ammonium hydroxides having alkyl, aryl, or alkylaryl groups, triethylamine, tributylamine, dimethylbenzylamine, hexadecyl Tertiary amines such as dimethylamine, or tetramethylammonium borohydride (Me ₄ NB
H ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Me ₄ NBPh ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), and other basic salts can be given. it can.

The above-mentioned nitrogen-containing basic compound is preferably used in such a ratio that the ammonium nitrogen atom in the nitrogen-containing basic compound is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ equivalent per mol of the aromatic dihydroxy compound. A more preferable ratio is a ratio of 2 × 10 ^{−5 to} 7 × 10 ⁻⁴ equivalents based on the same standard.
A particularly desirable ratio is 5 × 10 ^{−3 to} 5 × 1 based on the same criteria.
0 is a ratio comprised ^-4 equivalents.

In the present invention, if desired, (a) an alkali metal salt of an ate complex of an element of Group 14 of the periodic table or (b) an oxo acid of an element of Group 14 of the periodic table, as an alkali metal compound of the catalyst. Alkali metal salts of can be used. Here, the elements of Group 14 of the periodic table refer to silicon, germanium, and tin.

The use of these alkali metal compounds as the polycondensation reaction catalyst has an advantage that the polycondensation reaction can be rapidly and sufficiently advanced. Further, it is possible to suppress undesired side reactions such as a branching reaction generated during the polycondensation reaction to a low level.

(A) Alkali metal salts of ate complexes of elements of Group 14 of the periodic table are those described in JP-A-7-268091, specifically, compounds of germanium (Ge); NaGe (OMe) ₅ , NaGe
(OEt) ₃ , NaGe (OPr) ₅ , NaGe (OB
u) ₅ , NaGe (OPh) ₅ , LiGe (OMe) ₅ ,
Examples thereof include LiGe (OBu) ₅ and LiGe (OPh) ₅ .

The compound of tin (Sn) is NaSn.
(OMe) ₃ , NaSn (OMe) ₂ (OEt), NaS
_{n (OPr) 3, NaSn (} O-n-C 6 H 13) 3, Na
Sn (OMe) ₅ , NaSn (OEt) ₅ , NaSn (O
Bu) ₅ , NaSn (O-n-C ₁₂ H ₂₅ ) ₅ , NaSn
(OEt), NaSn (OPh) ₅ , NaSnBu ₂ (O
Me) ₃ can be mentioned.

Examples of the alkali metal salt of oxo acid of Group 14 element of the periodic table (b) include silicic acid.
acid) alkali metal salt, stanic acid alkali metal salt, germanium (II) acid (germanous aci)
d) Alkali metal salts, germanium (IV) acid (germani
The alkali metal salt of c acid) can be mentioned as a preferable example.

The alkali metal salt of silicic acid is, for example, an acidic or neutral alkali metal salt of monosilicic acid or its condensate, and examples thereof include monosodium orthosilicate and disodium orthosilicate.
Examples include trisodium orthosilicate and tetrasodium orthosilicate.

The alkali metal salt of stannic acid is, for example, an acidic or neutral alkali metal salt of monostanic acid or its condensation product, and examples thereof include disodium monostannate (Na ₂ SnO ₃ .CH ₂ O, x = 0
~ 5), monosodium tetrasodium salt (Na ₄ Sn
O ₄ ).

Germanium (II) acid
The alkali metal salt of is, for example, an acidic or neutral alkali metal salt of monogermanic acid or a condensation product thereof,
As an example, germanic acid monosodium salt (Na
HGeO ₂ ) can be mentioned.

Germanium (IV) acid
Is an acidic or neutral alkali metal salt of monogermanium (IV) acid or its condensate, for example, orthogermanate monolithic acid (LiH ₃ GeO ₄ ) orthogermanate disodium salt. , Orthogermanic acid tetrasodium salt, digermanic acid disodium salt (Na ₂ Ge ₂ O ₅ ), tetragermanic acid disodium salt (Na ₂ Ge
₄ O ₉ ), pentagermanic acid disodium salt (Na ₂
Ge ₅ O ₁₁ ).

The polycondensation reaction catalyst as described above is preferably used when the alkali metal element in the catalyst is 1 × 10 ^{-7 to} 5 × 10 ^-5 equivalents per mol of the aromatic dihydroxy compound. A more preferable ratio is 5 × 10 ^{-7 based on the} same criteria.
It is a ratio of about 1 × 10 ⁻⁵ equivalent.

In the polycondensation reaction of the present invention, at least one selected from the group consisting of an oxo acid of Group 14 element of the periodic table and an oxide of the same, together with the above catalyst, if necessary.
A co-catalyst of the species can be present together.

By using these co-catalysts in a specific ratio, a branching reaction which is likely to occur during the polycondensation reaction without impairing the end-capping reaction and the polycondensation reaction rate, and a foreign substance in the apparatus during molding processing. It is possible to more effectively suppress undesired side reactions such as the generation and burning of the.

Examples of the oxo acid of Group 14 element of the periodic table include silicic acid, stannic acid and germanic acid. As oxides of Group 14 elements of the periodic table,
Mention may be made of silicon monoxide, silicon dioxide, tin monoxide, tin dioxide, germanium monoxide, germanium dioxide and their condensates.

The cocatalyst is allowed to be present in a proportion of 50 mol (atoms) or less of the metal element of Group 14 of the periodic table in the cocatalyst per 1 mol (atoms) of the alkali metal element in the polycondensation reaction catalyst. preferable. If the cocatalyst is used in a proportion of more than 50 moles (atoms) of the same metal element, the polycondensation reaction rate becomes slow, which is not preferable.

The cocatalyst is present in a ratio of 0.1 to 30 mol (atoms) of the metal element of Group 14 of the periodic table of the cocatalyst per 1 mol (atoms) of the alkali metal element of the polycondensation reaction catalyst. Is more preferable.

By using these catalyst systems as catalysts for the polycondensation reaction and the end-capping reaction described below, there is an advantage that the polycondensation reaction and the end-capping reaction can be rapidly and sufficiently advanced. Further, undesirable side reactions such as branching reaction generated in the polycondensation reaction system can be suppressed to a low level.

(Regarding Component A) The component A sulfonic acid compounds used in the present invention are represented by the following general formulas (II) to (V).
Is a compound represented by. When one or more of these compounds is aromatic polycarbonate in a molten state after melt polymerization, 1 is added per 100 parts by weight of the polymer.
* 10 ^{−6 to} 0.1 part by weight is added. As a result, the produced aromatic polycarbonate can be stabilized by using a transesterification catalyst, and by using it together with the components B) and C), it is possible to effectively prevent the mold from being contaminated during injection molding.

[0039]

Embedded image A ¹ — (Y ¹ —SO ₃ X ¹ ) _m (I) [wherein A ¹ is an optionally substituted m-valent hydrocarbon group, and Y ¹ Is a single bond or an oxygen atom, X
¹ is a secondary or tertiary monovalent hydrocarbon group, 1 equivalent of a metal cation, an ammonium cation or a phosphonium cation, and m is an integer of 1 to 4. However, when Y ¹ is a single bond, all of m X ¹ 's are not 1 equivalent of metal cation. ]

[0040]

Embedded image ⁺ X ² —A ² —Y ¹ —SO ₃ ^— (II) [wherein A ² is a divalent hydrocarbon group, and ⁺ X ² is 2
To quaternary ammonium cation or secondary to quaternary phosphonium cation, and Y ¹ has the same definition as above. ]

[0041]

Embedded image A ³ − ( ⁺ X ³ ) _n · (R−Y ¹ —SO ₃ ⁻ ) _n ... (III) [wherein A ³ is an n-valent hydrocarbon group and ⁺ X ³ is 2
To a quaternary ammonium cation or a secondary to quaternary phosphonium cation, R is a monovalent hydrocarbon group,
n is an integer of 2 to 4, and the definition of Y ¹ is the same as above. ]

[0042]

Embedded image ^{A 5 -Ad 1 -A 4 - (} Ad 2 -A 5) k ··· (IV) [ wherein, A ⁵ is 1 or a divalent hydrocarbon group, A
⁴ is a divalent hydrocarbon group, and Ad ¹ and Ad ² are
Same or different --SO2 --O--SO2-, --SO2
It is an acid anhydride group selected from --O--CO-- or --CO--O--SO2-, and k is 0 or 1. However, when k is 0,-(Ad ² -A ⁵ ) k represents a hydrogen atom or a bond for connecting A ⁴ and A ⁵ (in this case, A ⁵ is a divalent hydrocarbon group). Or a single bond). ] The sulfonic acid compound of formula (I)

[0043]

[Chemical Formula 11] A ^1- (Y ¹ -SO ₃ X ¹ ) _m (I)

Here, A ¹ is an m-valent hydrocarbon group which may have a substituent, Y ¹ is a single bond or an oxygen atom, and X ¹ is a secondary or tertiary monovalent monovalent group. Hydrocarbon groups, 1
An equivalent amount of metal cation, ammonium cation or phosphonium cation, and m is an integer of 1 to 4. However, when Y ¹ is a single bond, all m X ¹ 's are not 1 equivalent of metal cation.

The secondary or tertiary monovalent hydrocarbon group is, for example, the following formula (I) -d.

[0046]

[Chemical 12]

[Wherein R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁶ is a hydrogen atom, a phenyl group or an alkyl group having 1 to 5 carbon atoms, and R ¹⁶ is
¹⁷ are the same as defined in R ¹⁵ the same or different R ^15. However, two of R ¹⁵ , R ¹⁶ and R ¹⁷ are not hydrogen atoms. ] A secondary or tertiary alkyl group represented by Of these, it is more preferable that R ¹⁵ and R ¹⁷ are the same or different and each is a hydrogen atom, a methyl group, an ethyl group or a propyl group, and R ¹⁶ is a methyl group or a phenyl group.

One equivalent of metal cation is, for example, an alkali metal cation such as lithium, sodium or potassium; 1/2 of an alkaline earth metal cation such as calcium or barium or 1/3 of a trivalent metal cation such as aluminum. Etc. can be mentioned.

As the ammonium cation, for example, the following formula (I) -a can be used.

[0050]

[Chemical 13]

[Where R ¹ , R ² , R ³ and R
⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group. ] The cation represented by these can be mentioned.

In the formula (I) -a, ¹ represented by R ¹ or the like
Examples of the valent hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 10 carbon atoms.
The aralkyl group and the like are preferable.

Examples of the phosphonium cation include those represented by the following formula (I) -b

[0054]

[Chemical 14]

[Where R ⁵ , R ⁶ , R ⁷ and R
Independently of each other, ⁸ is a hydrogen atom or a monovalent hydrocarbon group. ] The cation represented by these can be mentioned.

In the formula (I) -b, 1 represented by R ⁵ or the like
As the divalent hydrocarbon group, the same monovalent carbon group as exemplified for the formula (I) -a can be mentioned.

Of these, X ¹ is of secondary or tertiary
Grade alkyl group, alkali metal cation, the above formula (I)
The cation represented by -a and the cation represented by the above formula (I) -b are preferable.

In the above formula (I), m is an integer of 1 to 4, preferably 1 or 2.

Specific examples of the compound represented by the above formula (I) include the following compounds.
That is, 2-phenyl-dodecylbenzene sulfonate
2-propyl, 2-phenyl-2-butyl dodecylbenzenesulfonate, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, dodecylbenzene Sulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrahexylphosphonium salt, dodecylbenzenesulfonic acid tetraoctylphosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate,
Dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate, decyl trimethyl ammonium hexadecyl sulfate, tetrabutyl ammonium dodecyl benzyl sulfate, Examples thereof include tetraethylammonium dodecylbenzyl sulfate and tetramethylammonium dodecylbenzyl sulfate.

Sulfonic acid compound of formula (II)

[0061]

[Of 15] ^{+ X 2 -A 2 -Y 1 -SO} 3 - ··· (II)

Here, A ² is a divalent hydrocarbon group,
⁺ X ² is a secondary to quaternary ammonium or phosphonium cation, and Y ¹ has the same definition as above. In the formula (II), the divalent hydrocarbon group divalent saturated aliphatic hydrocarbon group of A ² is preferred. The saturated aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms. ⁺ X ² is an ammonium cation or a phosphonium cation. The ammonium cation is represented by the following formula (II) -a

[0063]

[Chemical 16]

[Here, R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a monovalent hydrocarbon group. ] The cation represented by

As the monovalent hydrocarbon group such as R ^{9 and the} like, the same ones as exemplified for the above formula (I) -a can be exemplified here.

The phosphonium cation is represented by the following formula (II) -b

[0067]

[Chemical 17]

[Here, R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group. ] The cation represented by As the monovalent hydrocarbon group represented by R ^{12, the same} groups as those exemplified for the above (II) -b can be exemplified.

The following compounds may be mentioned as specific examples of the compound represented by the above formula (II).

[0070]

[Chemical 18]

And the like.

Sulfonic acid compound of formula (III)

[0073]

Embedded image A ³ − ( ⁺ X ³ ) _n · (R−Y ¹ —SO ₃ ⁻ ) _{n (III)}

Here, A ³ is an n-valent hydrocarbon group,
⁺ X ³ is an ammonium cation or a phosphonium cation, R is a monovalent hydrocarbon group, and n is 2 to 4
And the definition of Y ¹ is the same as above.

The n-valent hydrocarbon group of A ³ is preferably, for example, an n-valent saturated aliphatic hydrocarbon group, aromatic hydrocarbon group or saturated aliphatic-aromatic hydrocarbon group.

Examples of the ammonium cation and phosphonium cation for ⁺ X ³ include those represented by the above formulas (II) -a and (II) -b, respectively.

R is a monovalent hydrocarbon group, examples of which are preferably an alkyl group, an aryl group and an aralkyl group. The alkyl group preferably has 1 to 20 carbon atoms, the aryl group preferably has 6 to 20 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms.

N is 2, 3 or 4, and Y ¹ is a single bond or an oxygen atom as defined above.

The following compounds may be mentioned as specific examples of the compound represented by the above formula (III).

[0080]

[Chemical 20]

[0081]

[Chemical 21]

Sulfonic acid compound of formula (IV)

[0083]

Embedded image A ⁵ −Ad ¹ −A ⁴ − (Ad ² −A ⁵ ) _k ^{... (IV)}

Here, A ⁵ is a monovalent or divalent hydrocarbon group, A ⁴ is a divalent hydrocarbon group, and Ad ¹ and Ad ² are the same or different --SO 2 --O--SO 2
-, -SO2 -O-CO- or -CO-O-SO2-
Is an acid anhydride group selected from and k is 0 or 1. However, when k is 0,-(Ad ² -A ⁵ ) k represents a hydrogen atom or a bond for connecting A ⁴ and A ⁵ (in this case, A ⁵ is a divalent hydrocarbon group). Or a single bond).

The following compounds may be mentioned as specific examples of the compound represented by the above formula (IV).

[0086]

[Chemical formula 23]

[0087]

[Chemical formula 24]

[0088]

[Chemical 25]

And the like.

Among the sulfonic acid compounds of the above formulas (I) to (IV), the phosphonium or ammonium salt type sulfonic acid compounds themselves are particularly stable even at 200 ° C. or higher. Then, when the sulfonic acid compound is added to the polymer, the catalyst is promptly neutralized to obtain the desired polymer.

In the method of the present invention, at least one selected from the group consisting of the compounds represented by the above formulas (I) to (IV).
When a sulfonic acid compound of a kind is subjected to the end-capping reaction described below after completion of the polycondensation of the polycarbonate, or 1 * 10 ^{-6 to} 0.1 part by weight with respect to the polycarbonate produced after the end-capping reaction. , Preferably 1 * 1
0 ^{−6 to} 0.05 parts by weight, more preferably 1 * 10 ^{−6 to} 0.
It is used in a proportion of 03 parts by weight.

The sulfonic acid compound is preferably used in a proportion of 0.5 to 50 mol per mol of the transesterification catalyst, relative to the alkali metal transesterification catalyst.

The method of adding the sulfonic acid compound to the polymer after polycondensation or after end-capping is not particularly limited. For example, these may be added while the reaction product polycarbonate is in a molten state, or may be added after pelletizing the polycarbonate once and then remelting.

About Component B The component B phosphate compound in the present invention includes phosphoric acid monoester, diester, triester, and mixtures thereof.

The phosphoric acid monoester has a structure in which one of the three hydrogen atoms of phosphoric acid is substituted with a hydrocarbon group, and as an example;

[0096]

[Chemical formula 26]

It is represented by (In the formula, R ⁸ represents an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group.)

In the above formula, examples of the alkyl group in the hydrocarbon group are: methyl group, ethyl group, octyl group, cyclohexyl group, 2-ethylhexyl group, tridecyl group, lauryl group, pentaerythritol group, stearyl group and the like. Can be mentioned. Examples of the aryl group include phenyl group, biphenyl group, naphthyl group and the like. Examples of the alkylallyl group are tolyl group, pt-butylphenyl group, 2,
Examples thereof include 4-di-t-butylphenyl group and 4-dodecylphenyl group. Preferred specific examples include; monophenyl phosphate, mono-p-nonylphenyl phosphate, mono (2,4-di-t-butylphenyl) phosphate, and the like.

Phosphoric acid diester has a structure in which two hydrogen atoms of phosphoric acid are substituted with hydrocarbon groups, and as an example;

[0100]

[Chemical 27]

(In the formula, R ⁸ and R ⁹ represent an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group.) In the above formula, examples of the alkyl group include a methyl group, a propyl group, a nonyl group, and a cyclopentyl group. Group, decalyl group, 2-
Examples thereof include ethylhexyl group, decyl group, lauryl group, pentaerythritol group and steryl group. The aryl group is a phenyl group or a naphthyl group. A terphenyl group and the like can be mentioned.

The alkylaryl group is a tolyl group, p
-T-butylphenyl group, 2-t-butyl-4-methylphenyl group, 2,6-di-t-butylphenyl group, m-
A nonylphenyl group and the like can be mentioned. Further, examples of the arylalkyl group include a benzyl group and a 4-methylbenzyl group.

Preferred examples are diphenyl phosphate,
Bis (4-nanylphenyl) phosphate, dimethyl phosphate, bis (2,4-di-t-butylphenyl)
Examples thereof include phosphate and bis (pt-butylphenyl) phosphate.

Examples of the phosphoric acid diester used in the present invention include those other than those represented by the above formula, for example,

[0105]

[Chemical 28]

[0106] (R ^8, R ^{8 'is} an alkyl group, an aryl group, .R represents an alkylaryl group, or an arylalkyl group ¹⁰ is alkylene, arylene, or arylalkylene group represents a.) Phosphorus atoms such as 2 Phosphoric acid diesters containing individual can also be used. The following general formula;

[0107]

[Chemical 29]

The compounds represented by (R ⁸ and R ¹⁰ are the same as above) can also be used.

Among these phosphoric acid diesters, aromatic phosphoric acid diesters are preferred. Particularly preferred examples include: diphenyl phosphate, bis (4-nonylphenyl) phosphate, bis (2,4-di-t-butylphenyl) phosphate and the like. These phosphoric acid diesters may be used alone or in a mixture.

Phosphoric acid triester has a structure in which three hydrogen atoms of phosphoric acid are substituted with hydrocarbon groups,
For example, the general formula:

[0111]

[Chemical 30]

(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group). .

Examples of the alkyl group in the above formula include ethyl group, butyl group, octyl group, cyclohexyl group, decyl group, lauryl group, pentaerythritol group and stearyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkylaryl group include a tolyl group, pt-butylphenyl group, 2,4-di-t-butylphenyl group, p-nonylphenyl group and the like.

A preferred example is tris (2,4
-Di-t-butylphenyl) phosphate, tris (4
-Dodecylphenyl) phosphate, bis (4-nonylphenyl), phenylphosphate, triphenylphosphate and the like.

Further, the general formula:

[0116]

[Chemical 31]

(In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ may be the same or different, and an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group,
And R ²¹ represents an alkylene group, an arylene group or an arylalkylene group. The phosphoric acid triester represented by the above) can also be used. Specific examples include tetraphenylethylene glycol diphosphate, tetra (dodecyl) 4,4 '.
—Isopropylidene diphenyl diphosphate, etc. Also the general formula:

[0118]

[Chemical 32]

A phosphoric acid triester represented by the formula (R ¹⁷ and R ¹⁸ are the same as above) can also be used.

As specific examples, bis (octadecyl) pentaerythritol diphosphate, bis (nonylphenyl) pentaerythritol diphosphate, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphate, bis (2,6) -Di-t-butyl-
4-methylphenyl) pentaerythritol diphosphate, distearyl pentaerythritol diphosphate, hydrogenated bisphenol A, pentaerythritol phosphate polymer, and the like.

Further general formula:

[0122]

[Chemical 33]

(In the formula, R ¹⁷ , R ¹⁸ and R ²¹ are the same as above.)
The phosphoric acid triester represented by can also be used. Specific examples include tetraphenyltetra (tridecyl) pentaerythritol tetraphosphate and the like. These may be used alone or as a mixture.

2,4-di-t-butylphenyl group, 2,
Those having a 6-di-t-butylphenyl group are particularly preferable because they improve the hydrolysis resistance of the composition. Specific examples include tris (2,4-di-t-butylphenyl) phosphate, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphate, bis (2,6-di-t).
-Butyl-4-methylphenyl) pentaerythritol diphosphate.

The phosphoric acid ester compound of the component B referred to in the present invention is indispensable for reducing mold stains, and by using the component together with the component A, the hydrolysis resistance and long-term heat resistance of the aromatic polycarbonate composition are improved. The aging property can be further improved.

The amount of the phosphoric acid ester compound used was 0.0005 per 100 parts by weight of the aromatic polycarbonate.
On the other hand, if the amount is less than 0.01 part by weight, the effect is not exhibited. On the contrary, if the amount is more than 0.015 part by weight, black foreign matter is generated and the molecular weight is lowered during the molding process. The addition amount of the phosphate ester compound is preferably 0.
It is in the range of 0005 to 0.015 parts by weight, more preferably 0.0005 to 0.01 parts by weight, and even more preferably 0.0005 to 0.008 parts by weight. Of the above-mentioned phosphoric acid ester compounds, phosphoric acid triester compounds are preferred because of their ease of handling.

Component C As the component C phosphite compound in the present invention, phosphite monoester, diester, triester, and mixtures thereof are contained.

Phosphorous acid monoester has a structure in which one of the three hydrogen atoms of phosphorous acid is substituted with a hydrocarbon group, and as an example;

[0129]

Embedded image R ⁸ —O—P— (OH) ₂ (in the formula, R ⁸ is the same as above).

In the above formula, examples of the alkyl group in the hydrocarbon group are: methyl group, ethyl group, butyl group, octyl group, cyclohexyl group, 2-ethylhexyl group, tridecyl group, lauryl group, pentaerythritol group, stearyl group. Etc. Examples of the aryl group include a phenyl group, a biphenyl group and a naphthyl group. Examples of the alkylaryl group include a tolyl group, pt-butylphenyl group, 2,4-di-t-butylphenyl group and 4-dodecylphenyl group.

Preferred examples include; phenime dihydrogen phosphate, mono-p-nonylphenyl dihydrogen phosphite, mono (2,4-di-t-butylphenyl) dihydrogen phosphite.

Phosphorous acid diester has a structure in which two hydrogen atoms of phosphoric acid are substituted with a hydrocarbon group, and as an example;

[0133]

[Chemical 35]

(Wherein R ⁸ and R ⁹ represent an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group). In the above formula, examples of the alkyl group include a methyl group, a propyl group, a nonyl group and a cyclopentyl group. Group, decalyl group, 2-
Examples thereof include ethylhexyl group, decyl group, lauryl group, pentaerythritol group and steryl group. The aryl group is a phenyl group or a naphthyl group. A terphenyl group and the like can be mentioned.

The alkylaryl group is a tolyl group. p
-T-butylphenyl group, 2-t-butyl-4-methylphenyl group, 2,6-di-t-butylphenyl group, m-
A nonylphenyl group and the like can be mentioned. Further, examples of the arylalkyl group include a benzyl group and a 4-methylbenzyl group.

Preferred examples include diphenylhydrogenphosphite, bis (4-nonylphenyl) hydrogenphosphite, dimethylhydrogenphosphite, bis (2,4-di-t-butylphenyl) hydrogenphosphite, bis (pt). -Butylphenyl) hydrogen phosphite, dicresyl hydrogen phosphite and the like.

Examples of the phosphoric acid diester used in the present invention include those other than those represented by the above formula.

[0138]

[Chemical 36]

A phosphite diester containing two phosphorus atoms such as (R ⁸ is the same as above, R ¹⁰ represents an alkylene, arylene, or arylalkylene group) can also be used. The following general formula;

[0140]

[Chemical 37]

Those represented by (R ⁸ and R ¹⁰ are the same as above) can also be used.

Among these phosphite diesters, aromatic phosphite diesters are preferred. Particularly preferred examples are: diphenyl hydrogen phosphite, bis (4
-Nonylphenyl) hydrogen phosphite and bis (2,4-di-t-butylphenyl) hydrogen phosphite. These phosphite diesters may be used alone or in a mixture.

The phosphite triester has a structure in which three hydrogen atoms of phosphoric acid are substituted with a hydrocarbon group and has, for example, a general formula:

[0144]

[Chemical 38]

(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group). .

Examples of the alkyl group in the above formula include ethyl group, butyl group, octyl group, cyclohexyl group, 2-ethylhexyl group, decyl group, lauryl group, pentaerythritol group and stearyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkylaryl group include a tolyl group, pt-butylphenyl group, 2,4-di-t-butylphenyl group, p-nonylphenyl group and the like.

Preferred examples include tris (2,4
Examples thereof include -t-butylphenyl phosphite, tris (4-dodecylphenyl) phosphite, bis (4-nonylphenyl), phenylphosphite and triphenylphosphite.

Further, the general formula:

[0149]

[Chemical Formula 39]

(R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ may be the same or different and each represents an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group, and R ²¹ is an alkylene. Group, an arylene group, an arylalkylene group).

Specific examples include tetraphenylethylene glycol diphosphite and tetra (dodecyl) 4,4 '.
—Isopropylidene diphenyl diphosphite, and the like.

General formula

[0153]

[Chemical 40]

A phosphite triester represented by the formula (R ¹⁷ and R ¹⁸ are the same as above) can also be used.

Specific examples include bis (octadecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and bis (2 , 6-di-t-butyl-
4-Methylphenyl) pentaerythritol diphosphite, disterial pentaerythritol diphosphite, hydrogenated bisphenol A, pentaerythritol phosphite polymer, and the like.

Further general formula:

[0157]

[Chemical 41]

The phosphite triester represented by (R ¹⁷ , R ¹⁸ and R ²¹ are the same as above) can also be used.

Specific examples include tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite. These may be used alone or as a mixture.

2,4-di-t-butylphenyl group, 2,
Those having a 6-di-t-butylphenyl group are particularly preferable because they improve the hydrolysis resistance of the composition. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t).
-Butyl-4-methylphenyl) pentaerythritol diphosphite.

The organic phosphonite is obtained by substituting one of the three hydroxyl groups of phosphorous acid with a hydrocarbon group and further substituting the hydrogen atoms of the remaining two hydroxyl groups with a hydrocarbon group.
For example, the general formula

[0162]

[Chemical 42]

(In the formula, R ²² , R ²³ and R ²⁴ may be the same or different and each represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group.) Examples of the alkyl group include ethyl group, propyl group,
Nonyl group, cyclohexyl group, decyl group, tridecyl group, lauryl group, stearyl group and the like can be mentioned. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkylaryl group include a tolyl group and p-
Examples thereof include t-butylphenyl group, 2,4-di-t-butylphenyl group, p-nonylphenyl group, and 2,4-di-nonylphenyl group.

In addition to the above

[0165]

[Chemical 43]

(In the formula, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ may be the same or different and each represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. ²¹ is the same as described above) and an organic phosphonite having two phosphorus atoms. Specific examples of such a compound include tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphinate. These may be used alone or as a mixture.

The phosphite compound of the component C is used in combination with the sulfonic acid compound of the component A, when the composition is heated, melt-molded, colored or the molecular weight is lowered, black foreign matter is formed, or it is used for a long time at high temperature. A favorable effect is exhibited with respect to the coloring and the like.

The amount of the C component phosphite compound used is 0.0005 to 0.03 part by weight, preferably 0.0005 to 0.025 part by weight, per 100 parts by weight of the aromatic polycarbonate. And particularly preferably 0.0005 to 0.02 parts by weight. If the amount of the phosphite compound is less than 0.0005 parts by weight, the heat resistance is little improved, and if it exceeds 0.03 parts by weight,
It is not preferable because the degree of polymerization is greatly reduced during long-term heat resistance.
At the same time, black foreign matter is generated during heat molding, which is not preferable.

D Component Phenolic Antioxidant The D component phenolic antioxidant has the general formula;

[0170]

[Chemical 44]

[0171] (wherein ^{R 11, R '11, R "} 11 is hydrogen atom, a hydroxyl group, it gives a good hydrocarbon residue which may have a substituent such as an alkoxy group, R ^11, R ^'11, R ^"11 may be the same or different, provided that at least one of R ¹¹ , R ^'11 and R ^{" 11} represents a hydrocarbon residue which may have a substituent. " Shown.

Specifically, 2,6-di-t-butyl-p
-Cresol, 2,6-di-t-butyl-p-anisole, 2,6-di-t-butyl-p-ethylphenol,
2,2'-methylenebis (6-t-butyl-p-cresol), 2,2'-methylenebis (6-t-butyl-p)
-Butylphenol), 4,4'-methylenebis (6-
t-butyl-p-cresol), 4,4'-butylidenebis (6-t-butyl-p-cresol), tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4']
-Hydroxyphenyl) propionate] methane, 4,
4'-thiobis (6-t-butyl-m-cresol),
Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-)
4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3-
(3-t-butyl-5-methyl-4-hydroxyphenyl) propinate] and the like.

Preferred phenolic antioxidants are:
General formula:

[0174]

[Chemical formula 45]

(In the formula, R ¹² is a methyl group or a t-butyl group,
R ¹³ represents a t-butyl group, A represents a b-valent hydrocarbon or heterocyclic residue having 1 to 30 carbon atoms, a represents 1 to 4 and b represents an integer of 1 or more. ) Is represented.

Specifically, tetrakis [methylene-3-
(3 ', 5-di-t-butyl-4'-hydroxyphenyl) propionate] methane ,; (registered trademark lrganox1
010, manufactured by Ciba Geigy) Stearyl-β (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate; (registered trademark lrganox 1076, manufactured by Ciba-Geigy) triethylene glycol-bis (3-t-butyl-)
5-Methyl-4-hydroxyphenyl) propionet and the like can be mentioned.

Further, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diester; (registered trademark lrganox 1222, manufactured by Ciba-Geigy) bis (3,3)
5-Di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium; (registered trademark lrganox 1425M
L, manufactured by Ciba-Geigy) and the like. These phenolic antioxidants may be used alone or in a mixture.

In the composition obtained by adding the component A, the component B, and the component C to the above-mentioned aromatic polycarbonate and further adding the component D; the phenolic antioxidant, the heat of extension is prolonged during the melt molding. It is effective in preventing coloration and decomposition during aging. Particularly when used in combination with the component B, the individual effect becomes large, which is preferable.

The amount of component D added is 0.0005 to 0.1 part by weight, preferably 0.0005 to 0.07 part by weight, more preferably 0.001 to 0.05 part by weight, per 100 parts by weight of the aromatic polycarbonate. It is a department. If it is less than 0.0005 parts by weight, the effect of adding the phenolic antioxidant is small, and if it exceeds 0.1 parts by weight, the decomposition of the polycarbonate becomes remarkable, which is not preferable.

The components B, C and D used in the present invention can be added to the polycarbonate at a desired stage after the completion of the polycarbonate melt polycondensation.

The method of adding the agent to the polymer is not particularly limited. It can be preferably added by a conventionally known method. For example, these may be added while the reaction product polycarbonate is in a molten state, or may be added after pelletizing the polycarbonate once and then remelting.

These agents may be added one at a time, or may be added continuously or may be added as a mixture of several kinds. The stability of the polymer, which is the object of the present invention, is not significantly impaired by these addition methods.

Regarding the end capping, as described above, for example, when an aromatic polycarbonate is produced using bisphenol A (BPA) as the aromatic dihydroxy compound and diphenyl carbonate (DPC) as the carbonic acid diester, the reaction formula of the aromatic polycarbonate is ;

[0184]

[Chemical formula 46]

It is represented by PhOH (phenol) represented by the above formula is removed to the outside of the system by the operation of reduced pressure.

[0186]

[Chemical 47]

An aromatic polycarbonate represented by is produced. One end of the polycarbonate molecule represented by the above formula has an aromatic hydroxyl group.

It is known that the aromatic polycarbonate having an aromatic hydroxyl group terminal is not preferable for short-term and long-term stability.

For example, in JP-A-61-87724 and JP-A-61-87725 (GE), polymer stability is obtained by reducing the hydroxyl group terminal, that is, an aging test; intrinsic property after 15 hours at 250 ° C. temperature. It has been reported that the reduction value of viscosity can be reduced.

However, the aromatic hydroxyl group present at one end of the molecule is an essential active site in the production of the melt polymerization polycarbonate as shown in the above formula.

The inventors of the present invention maintained the required number of hydroxyl groups that were originally required during the production of the polycarbonate, and when the degree of polymerization (intrinsic viscosity) of the polycarbonate reached the desired value, the terminal hydroxyl groups of the post-polycarbonate reached the desired value. Developed a method to reduce.

That is, for example, after the intrinsic viscosity of polycarbonate reaches at least 0.3 dl / g, the following formula (V)

[0193]

[Chemical 48]

[Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group, and R ¹ is
² is an alkyl group having 1 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms, and having 1 to 30 carbon atoms. The alkyl group and the alkoxyl group having 1 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl,
It may be substituted with (o-methoxycarbonylphenyl) oxycarbonyl or (o-ethoxycarbonylphenyl) oxycarbonyl, and the aryl group having 6 to 30 carbon atoms and the aryloxy group having 6 to 30 carbon atoms are methoxycarbonyl, Ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl, (o-ethoxycarbonylphenyl) oxycarbonyl, alkyl having 1 to 30 carbons, or optionally substituted with alkoxyl having 6 to 30 carbons] Is added to produce an end-capped polycarbonate having a change in intrinsic viscosity of 0.1 dl / g or less and an amount of terminal hydroxyl groups of 0 to 30 mol% based on the intrinsic viscosity at the time of addition. This is achieved by the method for producing polycarbonate.

The compound represented by the above formula (V) used in the present invention includes carbonate and carboxylic acid ester according to the definition of R ² .

In the formula (V), R ¹ is a chlorine atom, a methoxycarbonyl group (CH3 OCO—) or an ethoxycarbonyl group (C2 H5 OCO—). Of these, a chlorine atom and a methoxycarbonyl group are preferred,
A methoxycarbonyl group is particularly preferred.

R ² is an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms.

The alkyl group having 1 to 30 carbon atoms may be linear, branched, or cyclic, and may have an unsaturated group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, n
-Butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-dodecanyl group, n-lauryl group, n-palmityl group, stearyl group and other linear alkyl groups; isopropyl Group, branched alkyl group such as t-butyl group, 4-butylnonyl group; alkyl group having an unsaturated group such as allyl group, butenyl group, pentenyl group, hexenyl group, dodecenyl group, oleyl group, that is, alkenyl group; Examples thereof include cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Among these, from the viewpoint of improving the releasability of the polymer, long-chain alkyl groups,
Specifically, a lauryl group, a stearyl group, and a dodecenyl group are particularly preferable.

Further, the alkoxyl group having 1 to 30 carbon atoms may be linear, branched or cyclic, and may have an unsaturated group. Examples of the alkoxyl group include, for example, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-octoxy group, n-nonyloxy group, n-decanyloxy group, n -Straight chain alkoxyl group such as lauryloxy group, n-palmityloxy group, stearyloxy group; iso-propyl group, t
-Butyloxy group, branched-chain alkoxyl group such as 4-butylnonyloxy group; alkoxy group having unsaturated group such as allyloxy group, butenyloxy group, pentenyloxy group, hexenyloxy group, dodecenyloxy group, oleyloxy group; cyclopentyloxy group Group, a cycloalkyloxy group such as a hexylhexyloxy group, and the like. Of these, a long-chain alkyl group such as a lauryloxy group, a stearyloxy group and a dodecenyloxy group is particularly preferable from the viewpoint of improving the releasability of the polymer.

As described above, the alkyl group having 1 to 30 carbon atoms and the alkoxyl group having 1 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl.

[0201]

[Chemical 49]

Or (o-ethoxycarbonylphenyl) oxycarbonyl

[0203]

[Chemical 50]

It may be substituted with.

Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, biphenyl and anthranyl.

Further, examples of the aryloxy group having 6 to 30 carbon atoms include phenoxy, naphthoxy, biphenyloxy, anthranyloxy and the like.

The aryl group having 6 to 30 carbon atoms and the aryloxy group having 6 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl, (o-ethoxycarbonylphenyl) oxycarbonyl, It may be substituted with alkyl having 1 to 30 carbons or alkoxyl having 1 to 30 carbons. Alkyl having 1 to 30 carbons and 1 carbon
As the alkoxyl of ˜30, the same groups as those exemplified above can be mentioned here.

The compound represented by the above formula (V) is R ²
Based on the definition of, for convenience, the following formula (V) -1

[0209]

[Chemical 51]

(Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group and R ²¹
Is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and the alkyl group having 1 to 30 carbon atoms is methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl or (o-ethoxy It may be substituted with carbonylphenyl) oxycarbonyl, and the aryl group having 6 to 30 carbon atoms is methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl, (o-ethoxycarbonylphenyl) oxycarbonyl, carbon. Number 1
It may be substituted with an alkyl having 30 to 30 or an alkoxyl having 1 to 30 carbon atoms. ) And a carbonate compound represented by the following formula (V) -2

[0211]

[Chemical 52]

(Wherein R ¹ is a chlorine atom, a methoxycarbonyl group or an ethoxycarbonyl group, and R 1
²² is an alkyl group having 1 to 30 carbon atoms or 6 to 30 carbon atoms
An aryl group of 1 to 30 carbon atoms and an alkoxyl group having 1 to 30 carbon atoms are methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl or (o-ethoxycarbonylphenyl) oxycarbonyl. It may be substituted, and an aryl group having 6 to 30 carbon atoms and 6 to 6 carbon atoms
The aryloxy group of 30 is methoxycarbonyl, ethoxycarbonyl, (o-methoxycarbonylphenyl) oxycarbonyl, (o-ethoxycarbonylphenyl)
It may be substituted with oxycarbonyl, alkyl having 1 to 30 carbons or alkoxyl having 1 to 30 carbons. ) The carboxylic acid aryl ester represented by

Examples of the carbonate compound represented by the above formula (V) -1 include 2-chlorophenyl-phenyl carbonate, 2-chlorophenyl-4'-methylphenyl carbonate, 2-chlorophenyl-4'-ethylphenyl carbonate, 2- Chlorophenyl-4'-
n-butylphenyl carbonate, 2-chlorophenyl-4'-t-butylphenyl carbonate, 2-chlorophenyl-4'-nonylphenyl carbonate, 2-chlorophenyl-4'-cumyl carbonate, 2-chlorophenyl-naphthyl carbonate, 2- Chlorophenyl-4'-methoxyphenyl carbonate, 2-chlorophenyl-4'-ethoxyphenyl carbonate, 2-chlorophenyl-4'-n-butoxyphenyl carbonate, 2-chlorophenyl-4'-t-butoxyphenyl carbonate, 2-chlorophenyl- 4'-nonyloxyphenyl carbonate, 2-chlorophenyl-4'-
t-Propyloxyphenyl carbonate, 2-chlorophenyl-2'-methoxycarbonylphenyl carbonate, 2-chlorophenyl-4'-methoxycarbonylphenyl carbonate, 2-chlorophenyl-2'-ethoxycarbonylphenyl carbonate, 2-chlorophenyl-4'- 2-Chlorophenyl-acryl such as ethoxycarbonylphenyl carbonate, 2-chlorophenyl-2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbonate, 2-chlorophenyl-2'-(o-ethoxycarbonylphenyl) oxycarbonylphenyl carbonate Carbonates; 2-chlorophenylmethyl carbonate, 2-chlorophenyl-ethyl carbonate, 2-chlorophenyl-n-butyl carbonate DOO, 2-chlorophenyl - octyl carbonate, 2-chlorophenyl -i- propyl carbonate, 2-chlorophenyl 2-methoxycarbonylethyl carbonate, 2-chlorophenyl-2-
2-Chlorophenyl-alkyl carbonates such as ethoxycarbonylethyl carbonate, 2-chlorophenyl-2- (o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; 2-methoxycarbonylphenyl-phenyl carbonate, 2-methoxycarbonylphenyl-methylphenyl carbonate 2-methoxycarbonylphenyl-ethylphenyl carbonate, 2-methoxycarbonylphenyl-propylphenyl carbonate, 2-methoxycarbonylphenyl-n
-Butylphenyl carbonate, 2-methoxycarbonylphenyl-t-butylphenyl carbonate, 2-methoxycarbonylphenyl-hexylphenyl carbonate, 2-methoxycarbonylphenyl-nonylphenyl carbonate, 2-methoxycarbonylphenyl-dodecylphenyl carbonate, 2-methoxy Carbonylphenyl-hexadecylphenyl carbonate, 2-methoxycarbonylphenyl-di-n-butylphenyl carbonate, 2-methoxycarbonylphenyl-di-t-butylphenyl carbonate, 2-methoxycarbonylphenyl-dinonylphenyl carbonate, 2-methoxycarbonylphenyl -Cyclohexyl phenyl carbonate, 2-methoxycarbonyl phenyl-naphthyl phenyl carbonate 2-methoxycarbonylphenyl -
Biphenyl carbonate, 2-methoxycarbonylphenyl-cumylphenyl carbonate, 2-methoxycarbonylphenyl-4'-methoxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-ethoxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-n -Butoxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-t-butoxyphenyl carbonate, 2-methoxycarbonylphenyl-
4'-nonyloxyphenyl carbonate, 2-methoxycarbonylphenyl-4'-cumyloxyphenyl carbonate, di (2-methoxycarbonylphenyl) carbonate, 2-methoxycarbonylphenyl-4'-
Methoxycarbonylphenyl carbonate, 2-methoxycarbonylphenyl-2'-ethoxycarbonylphenyl carbonate, 2-methoxycarbonylphenyl-
4'-ethoxycarbonylphenyl carbonate, 2-
Methoxycarbonylphenyl-2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbonate, 2-methoxycarbonylphenyl-2'-(o-
2-methoxycarbonylphenyl aryl carbonates such as ethoxycarbonylphenyl) oxycarbonylphenyl carbonate; 2-methoxycarbonylphenyl-methyl carbonate, 2-methoxycarbonylphenyl-ethyl carbonate, 2-methoxycarbonylphenyl-n-butyl carbonate, 2- Methoxycarbonylphenyl-octyl carbonate, 2-methoxycarbonylphenyl-nonyl carbonate, 2-methoxycarbonylphenyl-cetyl carbonate, 2-methoxycarbonylphenyl-lauryl carbonate, 2-
Methoxycarbonylphenyl-2-methoxycarbonylethyl carbonate, 2-methoxycarbonylphenyl-2-ethoxycarbonylethyl carbonate, 2-methoxycarbonylphenyl-2- (o-methoxycarbonylphenyl) oxycarbonylethyl carbonate,
2-methoxycarbonylphenyl-alkyl carbonates such as 2-methoxycarbonylphenyl-2- (o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate; 2-ethoxycarbonylphenyl-phenyl carbonate, 2-ethoxycarbonylphenyl-methylphenyl carbonate, 2-ethoxycarbonylphenyl-ethylphenyl carbonate, 2-ethoxycarbonylphenyl-propylphenyl carbonate, 2-ethoxycarbonylphenyl-n-butylphenyl carbonate, 2-ethoxycarbonylphenyl-
t-Butylphenyl carbonate, 2-ethoxycarbonylphenyl-hexylphenyl carbonate, 2-ethoxycarbonylphenyl-nonylphenyl carbonate, 2-ethoxycarbonylphenyl-dodecylphenyl carbonate, 2-ethoxycarbonylphenyl-hexadecylphenyl carbonate, 2-ethoxy Carbonylphenyl-di-n-butylphenyl carbonate, 2
-Ethoxycarbonylphenyl-di-t-butylphenyl carbonate, 2-ethoxycarbonylphenyl-di-t
-Butylphenyl carbonate, 2-ethoxycarbonylphenyl-dinonylphenyl carbonate, 2-ethoxycarbonylphenyl-cyclohexylphenyl carbonate, 2-ethoxycarbonylphenyl-naphthylphenyl carbonate, 2-ethoxycarbonylphenyl-biphenylcarbonate, 2-ethoxycarbonylphenyl -Cumylphenyl carbonate, 2-ethoxycarbonylphenyl-4'-methoxyphenyl carbonate, 2-ethoxycarbonylphenyl-4'-ethoxyphenyl carbonate, 2-ethoxycarbonylphenyl-4'-n-butoxyphenyl carbonate, 2-
Ethoxycarbonylphenyl-4'-t-butoxyphenyl carbonate, 2-ethoxycarbonylphenyl-
4'-nonyloxyphenyl carbonate, 2-ethoxycarbonylphenyl-4'-cumyloxyphenyl carbonate, di (2-ethoxycarbonylphenyl) carbonate, 2-ethoxycarbonylphenyl-4'-
Methoxycarbonylphenyl carbonate, 2-ethoxycarbonylphenyl-4'-ethoxycarbonylphenyl carbonate, 2-ethoxycarbonylphenyl-
2 '-(o-methoxycarbonylphenyl) oxycarbonylphenyl carbonate, 2-ethoxycarbonylphenyl-2'-(o-ethoxycarbonylphenyl)
2-Ethoxycarbonylphenyl-aryl carbonates such as oxycarbonylphenyl carbonate; 2
-Ethoxycarbonylphenyl-methyl carbonate,
2-ethoxycarbonylphenyl-ethyl carbonate, 2-ethoxycarbonylphenyl-n-butyl carbonate, 2-ethoxycarbonylphenyl-octyl carbonate, 2-ethoxycarbonylphenyl-2-
Methoxycarbonylethyl carbonate, 2-ethoxycarbonylphenyl-2-ethoxycarbonylethyl carbonate, 2-ethoxycarbonylphenyl 2- (o
-Methoxycarbonylphenyl) oxycarbonylethyl carbonate, 2-ethoxycarbonylphenyl-2
And 2-ethoxycarbonylphenyl-alkyl carbonates such as-(o-ethoxycarbonylphenyl) oxycarbonylethyl carbonate. Among these, 2-methoxycarbonylphenyl-phenyl carbonate is excellent in hydrolysis resistance (moisture temperature resistance) because the end is blocked by the phenyl group.

Further, as the carboxylic acid aryl ester represented by the above formula (V) -2, for example, benzoic acid 2-
Chlorophenyl, 4-methylbenzoic acid 2-chlorophenyl, 4-ethylbenzoic acid 2-chlorophenyl, 4-n-
Butylbenzoic acid 2-chlorophenyl, 4-t-butylbenzoic acid-2-chlorophenyl, 4-nonylbenzoic acid 2-
Chlorophenyl, 4-cumylbenzoic acid 2-chlorophenyl, naphthoic acid 2-chlorophenyl, 4-methoxybenzoic acid 2-chlorophenyl, 4-ethoxybenzoic acid 2-chlorophenyl, 4-n-butoxybenzoic acid 2-chlorophenyl, 4-t- 2-Chlorophenyl butoxybenzoate, 4-Nonyloxybenzoic acid 2-chlorophenyl, 4
-2-chlorophenyl cumyloxybenzoate, 2-chlorophenyl 2-methoxycarbonylbenzoate, 2-chlorophenyl 4-methoxycarbonylbenzoate, 2-chlorophenyl 2-ethoxycarbonylbenzoate, 2-chlorophenyl 4-ethoxycarbonylbenzoate, 2- (O
-Methoxycarbonylphenyl) oxycarbonylbenzoic acid 2-chlorophenyl, aromatic carboxylic acid 2-chlorophenyl ester such as 2- (o-ethoxycarbonylphenyl) oxycarbonylbenzoic acid 2-chlorophenyl; acetic acid 2-chlorophenyl, propionic acid 2-chlorophenyl 2-chlorophenylvalerate, 2-chlorophenylpelargolate, 2-chlorophenyl-1-methylpropionate, 2-chlorophenyl-2-methoxycarbonylpropionate, 2-chlorophenyl-2
-Ethoxycarbonyl butyrate, 2-chlorophenyl 4 '-(2-methoxycarbonylphenyl) oxycarbonyl butyrate, 2-chlorophenyl 4'-(2-methoxycarbonylphenyl) oxycarbonyl butyrate and other aliphatic carboxylic acids-2- Chlorophenyl ester, (2-methoxycarbonylphenyl) benzoate, 4-methylbenzoyl- (2'-methoxycarbonylphenyl) ester, 4-ethylbenzoyl- (2 '
-Methoxycarbonylphenyl) ester, 4-n-butylbenzoyl- (2'-methoxycarbonylphenyl) ester, 4-t-butylbenzoyl- (2'-methoxycarbonylphenyl) ester, naphthoic acid-
(2'-methoxycarbonylphenyl) ester, 4-
Nonylbenzoic acid (2'-methoxycarbonylphenyl)
Ester, 4-cumylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4-methoxybenzoic acid (2 '
-Methoxycarbonylphenyl) ester, 4-ethoxybenzoic acid (2'-methoxycarbonylphenyl) ester, 4-n-butoxybenzoic acid (2'-methoxycarbonylphenyl) ester, 4-t-butoxybenzoic acid (2'- Methoxycarbonylphenyl) ester, 4-
Cumyloxybenzoic acid (2'-methoxycarbonylphenyl) ester, 2-methoxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4-
Methoxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4-ethoxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 3
-(O-Methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester, 4- (o-methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylester) ester, 3- (o- Aromatic carboxylic acid such as ethoxycarbonylphenyl), oxycarbonylbenzoic acid (2′-methoxycarbonylphenyl) ester
(2'-methoxycarbonylphenyl) ester,

(2-Ethoxycarbonylphenyl) benzoate, 4-methylbenzoyl- (2'-ethoxycarbonylphenyl) ester, 4-ethylbenzoyl-
(2'-Ethoxycarbonylphenyl) ester, 4-
n-Butylbenzoyl (2'-ethoxycarbonylphenyl) ester, 4-t-butylbenzoyl- (2'-
Ethoxycarbonylphenyl) ester, naphthoic acid-
(2'-Ethoxycarbonylphenyl) ester, 4-
Nonylbenzoic acid (2'-ethoxycarbonylphenyl)
Ester, 4-cumylbenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-methoxybenzoic acid (2 '
-Ethoxycarbonylphenyl) ester, 4-ethoxybenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-n-butoxybenzoic acid (2'-ethoxycarbonylphenyl) ester, 4-t-butoxybenzoic acid (2'- Ethoxycarbonylphenyl) ester, 4-
Nonyloxybenzoic acid (2′-ethoxycarbonylphenyl) ester, 4-cumyloxybenzoic acid (2′-ethoxycarbonylphenyl) ester, 2-methoxycarbonylbenzoic acid (2′-ethoxycarbonylphenyl) ester, 4-ethoxycarbonylbenzoic acid (2 '
-Ethoxycarbonylphenyl) ester, 3- (o-
Methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-ethoxycarbonylphenyl) ester, 4
(O-Methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-ethoxycarbonylphenyl) ester, 3-o-methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-ethoxycarbonylphenyl)
Mention may be made of aromatic carboxylic acid- (2'-ethoxycarbonylphenyl) esters such as esters.

Examples of the compound represented by the above formula (V) include 2-methoxycarbonylphenylbenzoate, 4-cumylbenzoic acid- (2'-methoxycarbonylphenyl) ester, 2-ethoxycarbonylphenylbenzoate, 4- (o). -Methoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester is preferred.

In the method of the present invention, the compound represented by the above formula (V) is added to the polycarbonate and the reaction formula

[0218]

[Chemical 53]

As shown by, it reacts with the terminal OH (to OH) of the polycarbonate to block the end of the polycarbonate. In order to carry out the terminal blocking quickly and in a high yield, it is preferable to carry out while distilling the produced 2-substituted phenol.

The compound represented by the above formula (V) is added after the aromatic dihydroxy compound and diphenyl carbonate are melt-polycondensed and the intrinsic viscosity of the polycarbonate reaches at least 0.3 dl / g. After the addition, the end capping of the polycarbonate proceeds rapidly, so the change in the intrinsic viscosity of the polycarbonate is 0.1 dl /
It is within the range of g, and the terminal hydroxyl group concentration can be kept at a low level of 0 to 30 mol%.

The compound represented by the above formula (V) is preferably 0.1% per equivalent of the terminal hydroxyl group of the polycarbonate.
It is used in an amount of 5 to 2 mol, more preferably 0.7 to 1.5 mol, and particularly preferably 0.8 to 1.2 mol.

It is preferable that the terminal hydroxyl group concentration in the polymer is measured and confirmed every time before the addition of the agent. When the polycondensation is continuously carried out under the same polycondensation conditions, the hydroxyl group concentration obtained in the preceding polycondensation may be used as it is for convenience.

A catalyst is required to carry out the above-mentioned end-capping reaction, and the catalyst used in the polycondensation reaction is preferably used as it is.

It is preferable to carry out the end-capping reaction particularly when the polycondensation of the polycarbonate is completed and the polymer is still in the molten state. Therefore, the end-capping reaction must be performed before the addition of the component A sulfonic acid compound from the end of the polycondensation. Further, at the above-mentioned time point, the end capping reaction can be preferably carried out.

Even after the polycondensation of the polycarbonate and the addition of the component A, the end-capping can be similarly carried out by newly adding the catalyst used in the end-capping reaction to the polycarbonate.

In the present invention, at least one of before end sealing, during end sealing, and after sealing is completed,
B component, C component, D component and various other known additives can be added. For example, thioether stabilizers, hindered anine stabilizers, epoxy stabilizers, salicylic acid UV absorbers, benzotriazole UV absorber release agents, colorants, antistatic activators, antifog agents, natural oil synthesis. Oil, wax Organic permanent filler can be added.

Production of Polycarbonate Aromatic diol and diphenyl carbonate (hereinafter referred to as DPC
The polymer can be produced by a polycondensation reaction with (abbreviated)) under the same conditions as the conventionally known ordinary method.

Specifically, the reaction in the first step was carried out at 80 to 250.
C, preferably 100-230 C, more preferably 12
At a temperature of 0 to 190 ° C. for 0.5 to 5 hours, preferably 1
The aromatic diol and DPC are reacted under reduced pressure for 4 hours, more preferably 1.5 to 3 hours. Then, while increasing the degree of vacuum of the reaction system, the reaction temperature is raised to react the aromatic diol with DPC, and finally, a reduced pressure of 5 Torr or less, preferably 1 Torr or less 240 to 32.
A polycondensation exchange reaction between an aromatic diol and DPC is performed at 0 ° C.

In the present invention, the hydroxyl group terminal of the polycarbonate before the addition of the terminal blocking agent is 75 to 35 mol%, preferably 70 to 35 mol% with respect to all terminals in terms of reaction rate.
It is preferable to control to 40 mol%, more preferably 60 to 40 mol%. By doing so, the terminal hydroxyl group can be finally controlled to a low ratio, and the modifying effect of the polymer can be enhanced.

The number of moles of terminal hydroxyl groups in the polymer in a fixed amount can be determined by, for example, 1 H-NMR.
The proportion of hydroxyl groups at the ends of the polymer can also be controlled by adjusting the charge ratio of the raw material aromatic diol and DPC.

In the present invention, A component, B component, C component,
There is no particular limitation on the feeder to which the D component, the end capping agent are provided and the reactor for performing the end capping reaction.

There is no particular limitation on the method of adding the components A, B, C, D, and the end-capping agent, and they may be added as solids or after being dissolved in various solvents. Good. Further, the end-blocking agent has a polymer intrinsic viscosity of 0.3.
After reaching, the predetermined amount may be added all at once or may be added in several steps.

That is, the end-capping agent is added after the intrinsic viscosity of the polymer reaches at least 0.3 dl / g.

In the present invention, the amount of free chlorine which is not covalently bound to the polymer and is contained in the polycarbonate (prepolymer) before end-capping is kept low, preferably 50 ppm or less, more preferably 5 ppm or less. Is advantageous.

If the amount of free chlorine is larger than the above range, the catalytic activity involved in the end-capping reaction tends to be lowered, and it becomes difficult to achieve the end-capping quickly and sufficiently, which is not preferable.

Further, if the amount of chlorine is large, the hue and stability of the obtained polymer are adversely affected, which is not preferable.

Controlling the amount of chlorine contained in the prepolymer to a low level can be achieved by controlling the amount of chlorine contained in the raw material to a low level.

Further, in the present invention, the amount of iron contained in the polycarbonate before the terminal is blocked is also low, and it is advantageous to suppress it to, for example, 1 ppm or less, more preferably 0.7 ppm or less.

If the amount of iron is larger than this, the activity of the catalyst involved in the terminal reforming reaction is likely to decrease, and it becomes difficult to achieve terminal blocking quickly and sufficiently, which is not preferable. Further, a large amount of iron adversely affects the hue and stability of the obtained polymer, which is not preferable.

Controlling the amount of iron contained in the prepolymer to a low level can be achieved by suppressing the amount of iron contained in the raw material to a low level and preventing the contamination of iron throughout the manufacturing process. .

After the addition of the terminal blocking agent, reduced pressure conditions are preferable in order to remove at least the phenols produced by the reaction. Specifically, it is 50 Torr or less, more preferably 10 Torr or less. Normally 0.01-100T
It is preferable to carry out in the range of orr.

The reaction temperature after addition of the terminal blocking agent is usually 25.
It is in the range of 0 to 360 ° C., preferably 260 to 340 ° C., and at a temperature lower than this range, the polymer does not melt,
At temperatures higher than this range, the polymer will decompose and color,
Not preferable. The reaction time is usually 1 to 30 minutes, preferably 1 to 20 minutes, and 1 to 15 minutes is also possible if desired.

In the present invention, the residual phenols contained in the polymer after end-capping can be suppressed to a low level.

The concentration of residual phenols in the polymer after the end-capping reaction is 300 ppm or less, more preferably 200 ppm or less. If the amount of residual phenols is higher than this concentration, the molecular weight is likely to decrease and coloring occurs,
Not preferable.

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

In the present invention, the polycarbonate obtained is in the range of ordinary heat stability, ultraviolet absorber, mold release agent, colorant, antistatic agent, lubricant, antifogging agent, natural oil, synthetic resin, within the range not impairing the object of the present invention. Oils, waxes, organic fillers, inorganic fillers and the like may be added.

According to the research conducted by the present inventor, certain compounds including a specific compound among the compounds represented by the above formula (V) are obtained by endcapping two molecules of polycarbonate, preferably by one molecule. As a result, it has been clarified that an effect of significantly improving the degree of polymerization of polycarbonate, that is, an effect of promoting polymerization is obtained.

Therefore, according to the present invention, secondly, in a method for producing a polycarbonate by melt polycondensation of an aromatic dihydroxy compound and diphenyl carbonate, the intrinsic viscosity of the polycarbonate is at least 0.3 dl.
After reaching / g, the following formula (VI)

[0249]

[Chemical 54]

Here, R ¹ is a chlorine atom, methoxycarbonyl or ethoxycarbonyl, X is an oxygen atom or the following formula

[0251]

-R-COO- [wherein R is an alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 30 carbon atoms, and R ³ is a chlorine atom, methoxy group A compound represented by carbonyl or ethoxycarbonyl] is added to form a polycarbonate having an intrinsic viscosity of more than 0.1 higher than the intrinsic viscosity at the time of addition. A method of making polycarbonate is also provided.

The polymerization accelerator represented by the above formula (VI) is
It is added to a polycarbonate having an intrinsic viscosity of at least 0.3 dl / g, and gives a polycarbonate having an intrinsic viscosity of more than 0.1 dl / g and higher than the intrinsic viscosity of the polycarbonate when added.

The polymerization accelerator represented by the above formula (V-3) is preferably about 0.
3 to about 0.7 mole, more preferably about 0.4 to about 0.6.
Mol, particularly preferably about 0.45 to about 0.55 mol.

The polymerization accelerator is added to the polycarbonate and the reaction formula

[0255]

[Chemical 56]

Two polycarbonate molecules are coupled in reaction with the terminal OH (~ OH) of the polycarbonate, as represented by:

The reaction is as shown in the above reaction scheme.
Since two molecules of 2-substituted phenol are produced, it is preferable to distill the produced 2-substituted phenol in order to carry out the coupling quickly and in a high yield.

At the end of the coupling, a polycarbonate having an intrinsic viscosity of more than 0.4 and less than 1.0 dl / g, more preferably an intrinsic viscosity of 0.41 to 0.8 dl / g is produced.

[0259]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. In the examples, polymer physical properties were measured by the following methods.

1) Intrinsic viscosity [η]; 20 in methylene chloride
It was measured with an Ubbelohde viscometer at ° C.

2) Terminal hydroxyl group concentration: sample 0.02 g
Is dissolved in 0.4 ml of chloroform and 1H-at 20 ° C
The terminal hydroxyl group and terminal phenyl group were measured using NMR (EX-270 manufactured by JEOL Ltd.), and the terminal hydroxyl group concentration was measured by the following formula. Terminal hydroxyl group concentration (mol%) = (terminal hydroxyl group concentration / total number of terminals) × 100

3) Polymer stability; a) Short-term stability; Polymer was heated in air at 340 ° C. for 15 minutes, and evaluated by [η] reduction rate and hue change. A) Long-term stability: Polymer was evaluated by [η] reduction rate after heat aging at 150 ° C. * 500 hr, hue change, and haze value.

4) Polymer wet heat stability: Polymer 12
The [η] reduction rate of the polymer retained under 0 ° C. * 100 hr saturated water vapor was measured.

5) Staining property of mold: Sumitomo Heavy Industries DISK3 molding machine and groove depth of 19 with respect to a polymer to which a predetermined additive is added.
A 3 nm stamper CD-R disc for CD-R was molded. Cylinder temperature: 340 ° C., mold temperature: 105 ° C. Stains on the stamper during molding of 50K sheets were observed and judged. ⊚: Good stain is not recognized ○: Good stain is extremely small Δ: Bad stain is slightly observed ×: Bad stain is clearly recognized

[ Reference Example 1] [Production of polymer] Bisphenol A, 228 parts by weight, 220 parts by weight of DPC, and the catalyst of the types and amounts shown in Table 1 below were charged into a reaction vessel equipped with a stirrer, a distillation column and a decompression device. After replacing with nitrogen,
Melted at 140 ° C. After stirring for 30 minutes, the internal temperature is 180 ℃
The temperature was raised to 1, and the reaction was carried out at an internal pressure of 100 mmHg for 30 minutes, and the produced phenol was distilled off.

Then, the internal temperature was raised to 200 ° C. and the pressure was gradually reduced to react at 50 mmHg for 30 minutes while distilling phenol. Further, the temperature is gradually raised between 220 ° C. and 30 mmHg, the pressure is reduced, and the same temperature and pressure are applied for 30 minutes.
0mmHg, 260 ° C, 1mmHg, 270 ° C, 1mm
In the same procedure as above, the temperature was raised and the pressure was reduced to Hg or less to continue the reaction.

Finally, when the polymerization reaction was continued at the same temperature and the same pressure and the intrinsic viscosity of the polycarbonate became about 0.35, a part of the polymer was sampled and measured, The results are shown in Table 1.

[End capping reaction] The polycarbonate 10
Predetermined amount of end-capping agent (2-methoxycarbonylphenyl-phenyl-carbonate) per 0 parts by weight of 50 mmH
g under reduced pressure at 270 ° C. Then 270 ℃, 1m
The end-capping reaction was continued for 5 minutes at mHg or less.

[Addition of Stabilizer] Stabilizers (components A to D) shown in Table 1 were added per 100 parts by weight of the above polymer, and the mixture was stirred at the same temperature and the same pressure for 10 minutes, and was mixed with a twin-screw ruder. It was pushed out and made into chips. Table 1 below shows the short-term stability, long-term stability, polymer wet heat stability, and mold stain resistance of the obtained polycarbonate.

Reference Examples 2 to 6 and Comparative Examples 1 to 3 Polycarbonate compositions were obtained in the same manner with the catalyst amounts and the stabilizer addition amounts shown in Tables 1 to 3 below. The short-term stability, long-term stability, polymer wet heat stability, and mold stain resistance of the obtained polycarbonate are shown in Tables 1 to 3 below.

[0271]

[Table 1]

[0272]

[Table 2]

[0273]

[Table 3]

[0274]

INDUSTRIAL APPLICABILITY According to the present invention, an aromatic polycarbonate composition stabilized by an aromatic polycarbonate, a sulfonic acid compound, a phosphoric acid ester compound, and a phosphorous acid ester compound, more preferably a phenolic antioxidant. Is obtained. That is, short-term, long-term stability, that is, coloring during melt molding, molecular weight reduction, generation of black foreign matter, or hydrolysis resistance in hot water or steam atmosphere good aromatic polycarbonate composition is obtained. To be
Furthermore, an aromatic polycarbonate composition having less stains on the mold when it is molded and suitable for precision molding and having good molding operation efficiency can be obtained.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08K 5/524 C08K 5/524 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 69/00

Claims (6)

(57) [Claims] 1. An aromatic diol and a carbonic acid diester,
Aromatic polycarbonate obtained by melt polycondensation in the presence of a transesterification catalyst containing a basic nitrogen compound and an alkali metal compound, 100 parts by weight and A component; sulfonic acid compound 1 * 10 ^{-6 to} 0.1 parts by weight. Part, B component; phosphoric acid ester compound 0.0005 to 0.
015 parts by weight, and C component; phosphite compound 0.0005
A stabilized aromatic polycarbonate composition comprising 0.03 parts by weight. 2. The D component before the aromatic polycarbonate composition according to claim 1; a phenolic antioxidant 0.00
The stabilized aromatic polycarbonate composition of claim 1, further comprising 05-0.05 parts by weight. 3. The sulfonic acid compound as the component A is at least one sulfonic acid compound selected from the group consisting of compounds represented by the following formulas (I) to (IV). Or the stabilized aromatic polycarbonate composition according to any one of 2). Embedded image A ¹ — (Y ¹ —SO ₃ X ¹ ) _m (I) [wherein A ¹ is an optionally substituted m-valent hydrocarbon group, and Y ¹ Is a single bond or an oxygen atom, X
¹ is a secondary or tertiary monovalent hydrocarbon group, 1 equivalent of a metal cation, an ammonium cation or a phosphonium cation, and m is an integer of 1 to 4. However, when Y ¹ is a single bond, all of m X ¹ 's are not 1 equivalent of metal cation. ] [Chemical Formula 2] ^{+ X 2 -A 2 -Y 1 -SO} 3 - ··· (II) [ wherein, A ² is a divalent hydrocarbon group, ⁺ X ² is 2
To quaternary ammonium cation or secondary to quaternary phosphonium cation, and Y ¹ has the same definition as above. A ³ − ( ⁺ X ³ ) _n · (R—Y ¹ —SO ₃ ⁻ ) _n (III) [wherein A ³ is an n-valent hydrocarbon group, ⁺ X ³ is 2
To a quaternary ammonium cation or a secondary to quaternary phosphonium cation, R is a monovalent hydrocarbon group,
n is an integer of 2 to 4, and the definition of Y ¹ is the same as above. ] Embedded image ^{A 5 -Ad 1 -A 4 - (} Ad 2 -A 5) k ··· (IV) [ wherein, A ⁵ is 1 or a divalent hydrocarbon group, A
⁴ is a divalent hydrocarbon group, and Ad ¹ and Ad ² are
Same or different --SO ₂ --O--SO _2- , --SO _2-
It is an acid anhydride group selected from O—CO— or —CO—O—SO ₂ — and k is 0 or 1. However, k is 0
,-(Ad ² -A ⁵ ) k represents a hydrogen atom or a bond for connecting A ⁴ and A ⁵ (in this case, A ⁵ is a divalent hydrocarbon group or a single bond). ). ] 4. The method for producing an aromatic polycarbonate by melt polycondensation, wherein the amount of the transesterification catalyst used per 1 mol of the aromatic diol is 10 to 500 μmol of basic nitrogen compound and 0.01 to 10 μmol of alkali metal compound. 4. The stabilized aromatic polycarbonate composition according to any one of claims 1 to 3. 5. The aromatic polycarbonate which is end-capped with at least one compound represented by the following formula (V), wherein the aromatic polycarbonate is an aromatic polycarbonate. A stabilized aromatic polycarbonate composition. [Chemical 5] 6. The aromatic polycarbonate is mainly composed of —O—Ar (allyloxy) group at the molecular end and —Ar′—OH.
The ratio of the (Ar) -OH (hydroxy) group to all terminals is 0 to 30 m.
ol% (0; not included).
Item 6. A stabilized aromatic polycarbonate composition according to any one of items 5 to 5.