WO2013118624A1

WO2013118624A1 - Polycarbonate resin composition

Info

Publication number: WO2013118624A1
Application number: PCT/JP2013/052099
Authority: WO
Inventors: 智子阿部; 中江　貢
Original assignee: 出光興産株式会社
Priority date: 2012-02-08
Filing date: 2013-01-30
Publication date: 2013-08-15
Also published as: CN104125985A; KR20140127208A; JP2013159755A; TW201335227A

Abstract

The present invention relates to a polycarbonate resin composition which contains 0.001-0.5 part by mass of at least one organic phosphorus compound that is selected from among phosphite compounds and phosphate compounds per 100 parts by mass of a polycarbonate that is obtained by a transesterification reaction which uses, as a polymerization catalyst, a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group.

Description

Polycarbonate resin composition

The present invention relates to a polycarbonate resin composition having excellent heat resistance and good color tone.

Polycarbonate is an engineering plastic with excellent transparency, heat resistance, and impact resistance, and is currently widely used in the electrical / electronic field, automobile field, optical part field, and other industrial fields. In general, polycarbonate is produced by a method in which an aromatic dihydroxy compound and phosgene are directly reacted (interfacial polycondensation method), or a method in which an aromatic dihydroxy compound and a carbonic acid diester are transesterified in a molten state (melt polymerization method). )It has been known. In this polycarbonate production method, the interfacial polycondensation method requires the use of toxic phosgene, corrosion of production equipment by by-produced chlorine-containing compounds such as hydrogen chloride and sodium chloride, and chlorination mixed in the resin. There are various problems such as difficulty in separating impurities such as sodium which adversely affect the physical properties of the polymer. On the other hand, the transesterification method (melt polymerization method) has the advantage that polycarbonate can be produced at a lower cost than the interfacial polycondensation method, but is usually used for a long time reaction at a high temperature of 280 to 310 ° C. , There is a great drawback that the polycarbonate obtained is inevitably colored.

As a method for solving the coloring problem of polycarbonate, it has been proposed to neutralize an inorganic base catalyst of alkali metal or alkaline earth metal with a quenching agent which is an aromatic sulfonic acid compound (for example, Patent Document 1). reference). Further, a method has been proposed in which an inorganic base catalyst of an alkali metal or alkaline earth metal is neutralized with a deactivating agent such as a sulfonic acid compound, and then a phosphite phosphorus antioxidant is added ( For example, see Patent Document 2). In addition, a method has been proposed in which a quaternary ammonium salt and a quaternary phosphonium salt are used as an organic catalyst for the transesterification catalyst, and the catalyst is removed by thermal decomposition at the final stage of the reaction without the need for a quencher. (For example, refer to Patent Document 3).

Japanese Patent Laid-Open No. 10-25409 JP 2002-241487 A Japanese Patent Laid-Open No. 10-45896

In the method of neutralizing the inorganic base catalyst proposed in Patent Documents 1 and 2 with a deactivating agent, the effect of preventing coloration is not satisfactory, while the organic salt catalyst proposed in Patent Document 3 In the method using, since the catalyst can be removed by thermal decomposition, a deactivator is unnecessary and a polycarbonate having excellent quality can be obtained, but further improvement in the color tone of the polycarbonate is desired.

An object of the present invention is to provide a polycarbonate resin composition having excellent heat resistance and good color tone using a polycarbonate produced by a transesterification reaction.

As a result of intensive studies, the present inventors have found that the above problem can be solved by mixing a specific organophosphorus compound with a polycarbonate obtained by a transesterification reaction using a specific polymerization catalyst. .
That is, the present invention relates to the following 1 to 17.

1. Phosphite compound and phosphate compound with respect to 100 parts by mass of a polycarbonate obtained by a transesterification reaction using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst A polycarbonate resin composition containing 0.001 to 0.5 parts by mass of at least one organic phosphorus compound selected from the group consisting of:
2. 2. The polycarbonate resin composition according to 1 above, wherein the contents of sodium, cesium, and potassium are each less than 0.1 ppm by mass as elements.
3. (A) The polycarbonate resin composition according to 1 or 2 above, wherein the nitrogen-containing organic basic compound is a quaternary ammonium salt.
4). (A) The polycarbonate resin composition according to the above 1 or 2, wherein the nitrogen-containing organic basic compound is a compound represented by the following general formula (I).
(NR ¹ ₄ ) ⁺ (X ¹ ) ⁻ (I)
Wherein, R ¹ represents an alkyl group, an aryl group or an alkylaryl group, four R ¹ may be the same with or different from each other, also form a two R ¹ is bonded to the ring structure Also good. X ¹ represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR ₄ (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
5. (B) The polycarbonate resin composition according to any one of the above 1 to 4, wherein the quaternary phosphonium salt containing an aryl group is a compound represented by the following general formula (II).
(PR ² ₄ ) ⁺ (X ² ) ⁻ (II)
[Wherein R ² represents an alkyl group, an aryl group or an alkylaryl group, but at least one of the four R ² is an aryl group. Further, the four R ² may be the same or different, and two R ² may be bonded to form a ring structure. X ² represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR ₄ (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
6). 6. The polycarbonate resin composition according to any one of 1 to 5 above, wherein the raw materials for the transesterification reaction are (A) a dihydroxy compound and (B) a carbonic acid diester.
7). (A) The polycarbonate resin composition as described in 6 above, wherein the dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane.
8). (B) The polycarbonate resin composition according to 6 or 7, wherein the carbonic acid diester is diphenyl carbonate.
9. (A) The nitrogen-containing organic basic compound is tetramethylammonium hydroxide, and (b) the quaternary phosphonium salt containing an aryl group is tetraphenylphosphonium tetraphenylborate. Polycarbonate resin composition.
10. The organophosphorus compound is tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis. Selected from (4,6-di-tert-butylphenyl) octyl phosphite, triphenyl phosphate, bisphenol A bis (diphenyl phosphate), and 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate The polycarbonate resin composition according to any one of the above 1 to 9, which is at least one selected from the group consisting of:
11. Using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst, a polycarbonate was obtained by a transesterification reaction. A method for producing a polycarbonate resin composition, comprising mixing 0.001 to 0.5 parts by mass of at least one organic phosphorus compound selected from a phyto compound and a phosphate compound.
12 12. The method for producing a polycarbonate resin composition according to 11 above, wherein after completion of the transesterification reaction, the reaction product is heat-treated at a temperature equal to or higher than the decomposition temperature of the polymerization catalyst to obtain a polycarbonate.
13. (A) The method for producing a polycarbonate resin composition according to the above 11 or 12, wherein the nitrogen-containing organic basic compound is a quaternary ammonium salt.
14 (A) The method for producing a polycarbonate resin composition according to the above 11 or 12, wherein the nitrogen-containing organic basic compound is a compound represented by the following general formula (I).
(NR ¹ ₄ ) ⁺ (X ¹ ) ⁻ (I)
Wherein, R ¹ represents an alkyl group, an aryl group or an alkylaryl group, four R ¹ may be the same with or different from each other, also form a two R ¹ is bonded to the ring structure Also good. X ¹ represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR ₄ (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
15. (B) The method for producing a polycarbonate resin composition according to any one of the above 11 to 14, wherein the quaternary phosphonium salt containing an aryl group is a compound represented by the following general formula (II).
(PR ² ₄ ) ⁺ (X ² ) ⁻ (II)
[Wherein R ² represents an alkyl group, an aryl group or an alkylaryl group, but at least one of the four R ² is an aryl group. Further, the four R ² may be the same or different, and two R ² may be bonded to form a ring structure. X ² represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR ₄ (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
16. 16. The method for producing a polycarbonate resin composition according to any one of 12 to 15 above, wherein the temperature at which the reaction product is heat-treated is 240 ° C. or higher and 350 ° C. or lower.
17. 17. A polycarbonate resin composition produced by the method for producing a polycarbonate resin composition according to any one of 11 to 16 above.

According to the present invention, a polycarbonate resin composition having excellent heat resistance and excellent color tone can be provided.

The polycarbonate resin composition of the present invention was obtained by using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst to obtain a polycarbonate by a transesterification reaction. It is obtained by a production method in which 0.001 to 0.5 parts by mass of at least one organic phosphorus compound selected from phosphite compounds and phosphate compounds is mixed with 100 parts by mass of polycarbonate.

[Polycarbonate]
The polycarbonate contained in the polycarbonate resin composition of the present invention is obtained by a transesterification reaction using a specific polymerization catalyst, and there are no particular restrictions on the raw materials used in this transesterification method. Various products used for production by the method are used, and for example, (A) dihydroxy compounds and (B) carbonic acid diesters are preferably used.

Examples of the (A) dihydroxy compound include an aromatic dihydroxy compound and an aliphatic dihydroxy compound, and are at least one compound selected from these.
Examples of the aromatic dihydroxy compound used as one of the components (A) include compounds represented by the following general formula (1).

In the general formula (1), R ⁴ and R ⁵ are each a halogen atom of fluorine, chlorine, bromine, iodine or an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group. N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, hebutyl group, octyl group and the like. R ⁴ and R ⁵ may be the same or different. The plurality of R ⁴ if R ⁴ is more may be the same or different, a plurality of R ⁵ if R ⁵ there are a plurality may be the same or different. m and n are each an integer of 0 to 4. Z is a single bond, an alkylene group having 1 to 20 carbon atoms, an alkylidene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group having 5 to 20 carbon atoms, or —S—, A —SO—, —SO ₂ —, —O—, —CO— bond or a bond represented by the following formulas (2) and (2 ′) is shown.

Examples of the alkylene group having 1 to 20 carbon atoms and the alkylidene group having 2 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an ethylidene group, and an isopropylidene group. Examples of the cycloalkylene group having 5 to 20 carbon atoms and the cycloalkylidene group having 5 to 20 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, and a cyclohexylidene group.

Examples of the aromatic dihydroxy compound represented by the general formula (1) include bis (4-hydroxyphenyl) methane; bis (3-methyl-4-hydroxyphenyl) methane; bis (3-chloro-4-hydroxyphenyl). ) Methane; bis (3,5-dibromo-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (2-tert-butyl-4-hydroxy-3-methyl) Phenyl) ethane; 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane; 1-phenyl-1,1-bis (3-fluoro-4-hydroxy-3-methylphenyl) Ethane; 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A); 2,2-bis (3-methyl-4-hydroxyphenyl) propyl 2,2-bis (2-methyl-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (2-t-butyl- 4-hydroxy-5-methylphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane; 2,2-bis (3-bromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxy) Phenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane; 1,1-bis (4-hydroxy-t-butylphenyl) 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 2,2-bis (4-hydroxy-3-) 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; 2,2-bis (3-bromo) -4-hydroxy-5-chlorophenyl) propane; 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; 2,2-bis (4-hydride) Loxyphenyl) butane; 2,2-bis (3-methyl-4-hydroxyphenyl) butane; 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2 -T-butyl-4-hydroxy-5-methylphenyl) butane; 1,1-bis (2-t-butyl-4-hydroxy-5-methylphenyl) isobutane; 1,1-bis (2-t-amyl) -4-hydroxy-5-methylphenyl) butane; 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane; 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane; 4,4-bis (4-hydroxyphenyl) heptane; 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane; 2,2-bis (4-hydroxyphenyl) Octane; bis (hydroxyaryl) alkanes such as 1,1- (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxyphenyl) cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane; bis (4-hydroxyphenyl) ether; bis (4, -hydroxy-3- Bis (hydroxyaryl) A such as methylphenyl) ether Bis (4-hydroxyphenyl) sulfide; bis (hydroxyaryl) sulfides such as bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide; bis (3-methyl-4 -Hydroxyphenyl) sulfoxide; bis (hydroxyaryl) sulfoxides such as bis (3-phenyl-4-hydroxyphenyl) sulfoxide; bis (4hydroxyphenyl) sulfone; bis (3-methyl-4-hydroxyphenyl) sulfone; Bis (hydroxyaryl) sulfones such as (3-phenyl-4-hydroxyphenyl) sulfone, 4,4′-dihydroxybiphenyl; 4,4′-dihydroxy-2,2′-dimethylbiphenyl; 4,4′-dihydroxy -3,3'-dimethyl Biphenyl; 4,4'-dihydroxy-3, 3'-dicyclohexylbiphenyl; and dihydroxybiphenyls such as 3,3'-difluoro-4,4'-dihydroxybiphenyl.

Examples of aromatic dihydroxy compounds other than the general formula (1) include dihydroxybenzenes, halogen and alkyl-substituted dihydroxybenzenes.
For example, resorcin, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin; 2,3,4,6- Tetrafluororesorcin; 2,3,4,6-tetrabromoresorcin; catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenyl Hydroquinone, 3-cumylhydroquinone; 2,5-dichlorohydroquinone; 2,3,5,6-tetramethylhydroquinone; 2,3,4,6-tetra-t-butylhydroquinone; 2,3,5,6- Tetrafluorohydroquinone; 2, 3, 5, - tetrabromo hydroquinone, and dihydric alcohol or ethoxylated or propoxylated products of phenols, such as bis (oxyethyl) bisphenol A, and bis (oxyethyl) tetrachloro bisphenol A or bis (oxyethyl) tetrachlorohydroquinone the like.

Examples of the aliphatic dihydroxy compound used as one of the components (A) include butane-1,4-diol; 2,2-dimethylpropane-1,3-diol; hexane-1,6-diol; Diethylene glycol; triethylene glycol; tetraethylene glycol; octaethylene glycol; dipropylene glycol; N, N-methyldiethanolamine; cyclohexane-1,3-diol; cyclohexane-1,4-diol; 1,4-dimethylolcyclohexane P-xylylene glycol; 2,2-bis (4-hydroxycyclohexyl) -propane, isosorbide; adamantanediol; adamantanedimethanol; 1,4-cyclohexanedimethanol and the like.

In the present invention, as the dihydroxy compound of component (A), one or more of the above compounds are appropriately selected and used, and among these, bisphenol A, which is an aromatic dihydroxy compound, is preferably used.

(B) The carbonic acid diester is at least one compound selected from a diaryl carbonate compound, a dialkyl carbonate compound or an alkylaryl carbonate compound.
The diaryl carbonate compound used as one of the component (B) has the following general formula (3): [wherein Ar ¹ and Ar ² each represent an aryl group, and they may be the same or different. Or a compound represented by the following general formula (4): wherein Ar ³ and Ar ⁴ each represents an aryl group, which may be the same or different, and D ¹ represents the aromatic dihydroxy compound. The residue which remove | excluded two hydroxyl groups from is shown. It is a compound represented by this.

Further, the dialkyl carbonate compound has the following general formula (5): wherein R ⁶ and R ⁷ each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and they are identical to each other. But it can be different. Or a compound represented by the following general formula (6): wherein R ⁸ and R ⁹ each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, D ² may be the same or different, and D ² represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound. It is a compound represented by this.

The alkylaryl carbonate compound is represented by the following general formula (7): wherein Ar ⁵ represents an aryl group, R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. Or a compound represented by the following general formula (8): wherein Ar ⁶ is an aryl group, R ¹¹ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and D ³ is the above-mentioned A residue obtained by removing two hydroxyl groups from an aromatic dihydroxy compound is shown. It is a compound represented by this.

Here, examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bisphenol A bisphenyl carbonate, and the like.
Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like.
Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate.
In the present invention, as the carbonic acid diester of the component (B), one or more of the above compounds are appropriately selected and used. Among these, diphenyl carbonate is preferably used.

In the present invention, raw materials other than the above (A) dihydroxy compound and (B) carbonic acid diester may be used.
Examples of diesters of dihydroxy compounds include bisphenol A diacetate, bisphenol A dipropionate, bisphenol A dibutyrate, and bisphenol A dibenzoate.
Examples of dicarbonates of dihydroxy compounds include bismethyl carbonate of bisphenol A, bisethyl carbonate of bisphenol A, and bisphenyl carbonate of bisphenol A.
Examples of monohydroxy esters of dihydroxy compounds include bisphenol A monomethyl carbonate, bisphenol A monoethyl carbonate, bisphenol A monopropyl carbonate, and bisphenol A monophenyl carbonate.

Further, in the production of polycarbonate, a terminal terminator can be used as necessary. Examples of the terminal terminator include on-butylphenol; mn-butylphenol; pn-butylphenol; o-isobutylphenol; m-isobutylphenol; p-isobutylphenol; ot-butylphenol; tert-butylphenol; pt-butylphenol; on-pentylphenol; mn-pentylphenol; pn-pentylphenol; on-hexylphenol; mn-hexylphenol; pn-hexyl O-cyclohexylphenol; m-cyclohexylphenol; p-cyclohexylphenol; o-phenylphenol; m-phenylphenol; p-phenylphenol; on-nonylphenol; mn-nonylphenol; O-cumylphenol; m-cumylphenol; p-cumylphenol; o-naphthylphenol; m-naphthylphenol; p-naphthylphenol; 2,6-di-t-butylphenol; Di-t-butylphenol; 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; ,

Examples thereof include monohydric phenols such as chroman derivatives represented by the following formula.

Among these phenols, although not particularly limited in the present invention, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferable.
Moreover, the compound etc. which are represented by a following formula can also be used.

Furthermore, in the present invention, as necessary, phloroglucin; trimellitic acid; 1,1,1-tris (4-hydroxyphenyl) ethane; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; isatin bis ( o-cresol) and the like can also be used as a branching agent.

As a specific polymerization catalyst in the transesterification reaction, a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group is used.
There is no restriction | limiting in particular as a nitrogen-containing organic basic compound of (a) component, There exist various things. For example, aliphatic tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, dimethylbenzylamine; aromatic tertiary amine compounds such as triphenylamine; N, N -Dimethyl-4-aminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, imidazole , Nitrogen-containing heterocycles such as 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-mercaptoimidazole, aminoquinoline, diazabicyclooctane (DABCO) Compounds, and the like.

Furthermore, examples of the nitrogen-containing organic basic compound of component (a) include quaternary ammonium salts represented by the following general formula (I).
(NR ¹ ₄ ) ⁺ (X ¹ ) ⁻ (I)
In the above general formula (I), R ¹ is alkyl group, aryl group or alkyl group aryl, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, cyclohexyl group, etc. An aryl group having 6 to 20 carbon atoms or an alkylaryl group, such as an alkyl group or cycloalkyl group having ˜6, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, or a benzyl group; The four R ^{1 s} may be the same or different, and two R ^{1 s} may combine to form a ring structure.
X ¹ represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR ₄ (R represents a hydrogen atom, an alkyl group or an aryl group, and four R May be the same or different).

Examples of such quaternary ammonium salts include alkyl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; ammonium hydroxides having an aryl group, an aryl group, and the like. And basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate and tetramethylammonium tetraphenylborate.

Among these (a) nitrogen-containing organic basic compounds, quaternary ammonium represented by the above general formula (I) from the viewpoints of high catalytic activity, easy thermal decomposition and hardly remaining in the polymer. Salts, specifically tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium borohydride and tetrabutylammonium borohydride are preferred, and tetramethylammonium hydroxide is particularly preferred. One (a) nitrogen-containing organic basic compound may be used, or two or more may be used in combination.

On the other hand, examples of the quaternary phosphonium salt of the component (b) include compounds represented by the following general formula (II).
(PR ² ₄ ) ⁺ (X ² ) ⁻ (II)
In the general formula (II), R ² represents an alkyl group, an aryl group or an alkylaryl group, and these may be the same as those exemplified in the description of R ¹ in the general formula (I). At least one of the four R ² is an aryl group. Further, the four R ^{2 s} may be the same or different, and two R ² may be bonded to form a ring structure.
X ² represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO ₃ or BR ₄ (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different.

Examples of such quaternary phosphonium salts include tetraarylphosphonium hydroxides such as tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra (chlorophenyl) phosphonium hydroxide, tetra (biphenyl) phosphonium hydroxide, and tetratolylphosphonium hydroxide. Methyl triphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, propyltriphenylphosphonium hydroxide, butyltriphenylphosphonium hydroxide, amyltriphenylphosphonium hydroxide, heptyltriphenylphosphonium hydroxide, hexyltriphenylphosphonium hydroxy Octyltriphenylphosphonium hydroxide, Radecyltriphenylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, ethoxybenzyltriphenylphosphonium hydroxide, methoxymethyltriphenylphosphonium hydroxide, acetoxymethyltriphenylphosphonium hydroxide, phenacyltriphenylphosphonium hydroxide, chloromethyltriphenyl Phenylphosphonium hydroxide, bromomethyltriphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, naphthyltriphenylphosphonium hydroxide, chlorophenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, Acetoki Mono (aryl or alkyl) triphenylphosphonium hydroxides such as phenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide; phenyltrimethylphosphonium hydroxide, biphenyltrimethylphosphonium hydroxide, phenyltrihexylphosphonium hydroxide, biphenyltriphe Monoaryltrialkylphosphonium hydroxides such as xylphosphonium hydroxide; di (aryl or diphenylphosphonium hydroxide, di (naphthyl) diphenylphosphonium hydroxide, di (biphenyl) diphenylphosphonium hydroxide, etc. Alkyl) diarylphosphonium hydroxy Tetraarylphosphonium tetraphenyl such as tetraphenylphosphonium tetraphenylborate, tetranaphthylphosphonium tetraphenylborate, tetra (chlorophenyl) phosphonium tetraphenylborate, tetra (biphenyl) phosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate Borates: methyltriphenylphosphonium tetraphenylborate, ethyltriphenylphosphonium tetraphenylborate, propyltriphenylphosphonium tetraphenylborate, butyltriphenylphosphonium tetraphenylborate, octyltriphenylphosphonium tetraphenylborate, tetradecyltriphenylphosphonium tetraphenyl Borate Benzyltriphenylphosphonium tetraphenylborate, ethoxybenzyltriphenylphosphonium tetraphenylborate, methoxymethyltriphenylphosphonium tetraphenylborate, acetoxymethyltriphenylphosphonium tetraphenylborate, phenacyltriphenylphosphonium tetraphenylborate, chloromethyltriphenylphosphonium tetra Phenyl borate, bromomethyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, naphthyltriphenylphosphonium tetraphenylborate, chlorophenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate Mono (aryl or alkyl) triphenylphosphonium tetraphenylborates such as acetoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate; phenyltrimethylphosphonium tetraphenylborate, biphenyltrimethylphosphonium tetraphenylborate, methyltrihexyl Mono, such as phosphonium tetraphenylborate, ethyltrihexylphosphonium tetraphenylborate, octyltrihexylphosphonium tetraphenylborate, stearyltrihexylphosphonium tetraphenylborate, phenyltrihexylphosphonium tetraphenylborate, biphenyltrihexylphosphonium tetraphenylborate Aryl trialkylphosphonium tetraphenylborate; Di (aryl or alkyl) such as dimethyldiphenylphosphonium tetraphenylborate, diethyldiphenylphosphonium tetraphenylborate, di (naphthyl) diphenylphosphonium tetraphenylborate, di (biphenyl) diphenylphosphonium tetraphenylborate And diarylphosphonium tetraphenylborate.
In addition to the above compounds, allyl triphenyl phosphonium hydroxide, cinamyl triphenyl phosphonium hydroxide, and the like can be given.

Furthermore, as a counter anion, instead of the above hydroxides and tetraphenylborates, aryloxy groups such as phenoxide; alkyloxy groups such as methoxide and ethoxide; alkylcarbonyloxy groups such as acetate; arylcarbonyloxy groups such as benzoate A quaternary phosphonium salt using a halogen atom such as chloride or bromide.

More preferably, in the production of polycarbonate, as a polymerization catalyst in the transesterification reaction, (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group represented by the following general formula (II-1) It is desirable to use in combination with a compound represented by

In the general formula (II-1), R ³ represents an organic group, which may be the same or different, and X ³ represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an aryl group. A carbonyloxy group, HCO ₃ or BR ₄ (wherein R represents a hydrogen atom or a hydrocarbon group, four Rs may be the same or different from each other), and n represents an integer of 0 to 4.

Specific examples of such quaternary phosphonium compounds include, for example, tetraphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, and naphthylphenyltriphenylphosphonium hydroxide. , Tetraphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, methoxyphenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium phenoxide, biphenyltri Phenylphosphonium phenoxide, methoxyphenyltriphenylphosphonium phenoxide, phenoxyphenyltriphenylphosphonium phenoxide, naphthylphenyltriphenylphosphonium phenoxide, tetraphenylphosphonium chloride, biphenyltriphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, Examples thereof include naphthylphenyltriphenylphosphonium chloride.

Among the above (b) quaternary phosphonium salts, tetraarylphosphonium tetraphenylborate, tetraarylphosphonium phenoxide, monoaryltriphenylphosphonium borate from the viewpoint of the balance between the activity due to thermal stability during the reaction and the quality of the obtained polycarbonate. And monoaryltriphenylphosphonium phenoxide are preferable, and tetraphenylphosphonium tetraphenylborate is particularly preferable.
That is, as the component (b), a quaternary phosphonium salt that does not contain an alkyl group is excellent in thermal stability, and is effective for increasing the molecular weight in the late reaction. This (b) quaternary phosphonium salt may be used singly or in combination of two or more.

The (a) nitrogen-containing organic basic compound and (b) the quaternary phosphonium salt containing an aryl group preferably each have a metal impurity content of 50 ppm by mass or less, and an alkali metal and alkaline earth metal compound. Is more preferably 30 mass ppm or less, and particularly preferably 10 mass ppm or less.
Furthermore, it is preferable that the total amount of each metal impurity in the component (a) and the component (b) is 50 mass ppm or less with respect to the total amount of the component (a) and the component (b). The total content of alkali metal and alkaline earth metal compound in component (b) and component (b) is more preferably 30 ppm by mass or less, based on the total amount of component (a) and component (b), Particularly preferred is 10 ppm by mass or less.

In the present invention, as the polymerization catalyst, the nitrogen-containing organic basic compound of the component (a) is 10 ⁻¹ to 10 ⁻⁸ mol, preferably 10 ⁻² to 10 ⁻⁷ mol, relative to the raw material such as a dihydroxy compound. Mol, more preferably 10 ⁻³ to 10 ⁻⁶ mol, and (b) the quaternary phosphonium salt containing the aryl group of 10 ⁻¹ to 10 ⁻⁸ mol, preferably 10 ⁻² to 10 ⁻⁷ mol, It is desirable to use 10 ⁻³ to 10 ⁻⁶ mol.
If the amount of component (a) used is less than 10 ⁻⁸ mol, the catalytic activity at the initial ^stage of the reaction becomes insufficient, and if it exceeds 10 ⁻¹ mol, the cost increases, which is not preferable. On the other hand, if the amount of component (b) used is less than 10 ⁻⁸ mol, the catalytic activity in the late stage of the reaction becomes insufficient, and if it exceeds 10 ⁻¹ mol, the cost increases, which is not preferable.

In addition, the polymerization catalyst has a total amount of (a) component and (b) component of usually 2 × 10 ⁻¹ to 2 × 10 ⁻ to 1 mol of the dihydroxy compound of component (A) as a raw material. ⁸ mol, preferably 2 × 10 ⁻² to 2 × 10 ⁻⁷ mol, more preferably 2 × 10 ⁻³ to 2 × 10 ⁻⁶ mol. If the amount of the catalyst added is less than 2 × 10 ⁻⁸ mol, the catalytic effect may not be exhibited. Moreover, if it exceeds 2 × 10 ⁻¹ mol, the physical properties of the final polycarbonate, especially heat resistance and hydrolysis resistance, may be reduced, and it will lead to cost increase, and it will be added beyond this. Never do.
In the production of polycarbonate, the polymerization activity can be increased by using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst. In the final polycarbonate obtained, it is preferable to minimize the number of metals that adversely affect hydrolysis resistance and colorability. That is, in the production of the polycarbonate in the present invention, it is substantially unnecessary to use a metal catalyst that has been used in the late stage of the reaction due to component (b).

In the present invention, in the production of the polycarbonate, raw materials used for the production of the polycarbonate by the ordinary transesterification method are used. Preferably, the component (A) is a dihydroxy compound and the component (B) is a carbonic acid diester, and if necessary. A transesterification reaction is performed using a terminal terminator or a branching agent to obtain a polycarbonate. Specifically, the reaction may proceed according to a known transesterification method. Below, the procedure and conditions of the preferable manufacturing method of this invention are shown concretely.

First, the (A) component dihydroxy compound and the (B) component carbonic acid diester are subjected to a transesterification reaction in such a ratio that the carbonic acid diester is 0.9 to 1.5 times the mole of the dihydroxy compound. Depending on the situation, 0.98 to 1.20 times mol is preferable.
In the transesterification reaction, it is obtained when the amount of the terminal terminator composed of the monohydric phenol or the like is in the range of 0.05 to 10 mol% with respect to the dihydroxy compound as the component (A). Since the hydroxyl end of the polycarbonate is sealed, a polycarbonate having excellent heat resistance and water resistance can be obtained. Such a terminal terminator made of monohydric phenol or the like may be added to the reaction system in advance, or partly added to the reaction system in advance and the remainder added as the reaction proceeds. May be. Furthermore, depending on the case, after the transesterification reaction of the dihydroxy compound of the component (A) and the carbonic acid diester of the component (B) partially proceeds, the whole amount may be added to the reaction system.

In carrying out the transesterification reaction, the reaction temperature is not particularly limited and is usually selected in the range of 100 to 330 ° C., preferably in the range of 180 to 300 ° C. More preferably, the reaction temperature gradually becomes 180 to 300 as the reaction proceeds. A method of raising the temperature to ℃ is good. If the temperature of the transesterification reaction is less than 100 ° C., the reaction rate becomes slow. On the other hand, if it exceeds 330 ° C., side reactions occur or the resulting polycarbonate is colored, which is not preferable.
The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. This should just be set so that reaction may be performed efficiently, and is not limited. Usually, in the initial stage of the reaction, an atmospheric pressure (normal pressure) or a pressurized state of 1 to 50 atm (760 to 38,000 torr) is set, and in the latter stage of the reaction, a reduced pressure state, preferably 0.01 is finally used. In many cases, it is set to ~ 100 torr.
Furthermore, the reaction time may be carried out until the target molecular weight is reached, and is usually about 0.2 to 10 hours.

The transesterification reaction is usually carried out in the absence of an inert solvent, but it may be carried out in the presence of 1 to 150% by mass of an inert solvent of the obtained polycarbonate, if necessary. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; cycloalkanes such as tricyclo (5,2,10) decane, cyclooctane, and cyclodecane. Is mentioned.
Further, it may be performed in an inert gas atmosphere as necessary. Examples of the inert gas include gases such as argon, carbon dioxide, dinitrogen monoxide and nitrogen, alkanes such as chlorofluorohydrocarbon, ethane and propane. And various types of alkene such as ethylene and propylene.

Further, in the production of polycarbonate, in order to improve the quality (coloring) of the obtained polycarbonate after completion of the above-described transesterification reaction, it is at least the decomposition temperature of the catalyst, preferably around 300 ° C., more preferably at least 240 ° C. It is preferable that the reaction product is heat-treated at 350 ° C. or lower, more preferably 260 ° C. or higher and 330 ° C. or lower, particularly preferably 270 ° C. or higher and 310 ° C. or lower, to thermally decompose and remove the catalyst.

[Organic phosphorus compounds]
The organophosphorus compound contained in the polycarbonate resin composition of the present invention is at least one selected from phosphite compounds and phosphate compounds.
The inventors of the present invention analyzed that the active species of the polymerization catalyst (organic basic catalyst) used in the production of the polycarbonate described above remained in the obtained polycarbonate in a very small amount, and determined the active species as described above. It has been found that by neutralizing and deactivating with an organic phosphorus compound, a polycarbonate resin composition having an extremely good color tone can be obtained.

For example, when tetraphenylphosphonium tetraphenylborate (TPTB) is used as an organic basic catalyst, tetraphenylphosphonium phenoxide, in which bisphenol A (BPA) is activated by TPTB, is neutralized with phosphite compounds and phosphate compounds. It is considered to be activated and stabilized, and the effect of making the color tone of the resin composition extremely excellent can be expressed. On the other hand, when sodium hydroxide, which is a strong base, is used as the inorganic basic catalyst, sodium phenoxide whose BPA has been activated by sodium hydroxide cannot be neutralized with the phosphite compound and phosphate compound. Therefore, it is considered that it works in polycarbonate as weakly basic, and the effect of improving the color tone of the resin composition cannot be exhibited.

Examples of the phosphite compound include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphospha And bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and the like.
Among these, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and 2,2′-methylenebis (4,6-Di-tert-butylphenyl) octyl phosphite is preferred. One phosphite compound may be used, or two or more phosphite compounds may be used in combination.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, tri (2-ethylhexyl) phosphate, diisopropylphenyl phosphate, trixylenyl phosphate, triphenyl Phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate Bisphenol A bis (diphenyl phosphate), hydroquinone bisphosphate, resorcinol bisphosphate, resorcinol - diphenyl phosphate, trioxybenzene phosphate, 1,3-phenylene - tetrakis (2,6-dimethylphenyl) phosphoric acid ester.
Of these, triphenyl phosphate, bisphenol A bis (diphenyl phosphate) and 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate are preferred. A phosphate compound may be used alone or in combination of two or more.

In the polycarbonate resin composition of the present invention, the content of at least one organic phosphorus compound selected from a phosphite compound and a phosphate compound is 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate, preferably Is 0.003 to 0.2 parts by mass, and more preferably 0.003 to 0.1 parts by mass. When the content is less than 0.001 part by mass, the effect of improving the color tone of the resin composition cannot be expressed, and when it exceeds 0.5 part by mass, the function deterioration such as inferior moisture resistance of the resin composition occurs.
Moreover, although a phosphite compound and a phosphate compound may each be used independently and may be used together, the said content at the time of using together represents the total amount of a phosphite compound and a phosphate compound.

[Polycarbonate resin composition]
The organophosphorus compound may be introduced into the reactor at the end of the transesterification reaction in the production of polycarbonate, or may be introduced into a twin screw extruder or the like during granulation of the polycarbonate and kneaded.
The polycarbonate resin composition of the present invention is blended with known additives such as plasticizers, pigments, lubricants, mold release agents, stabilizers, inorganic fillers, etc., in addition to the polycarbonate and the organic phosphorus compound. These can be blended and melt kneaded to obtain the polycarbonate resin composition of the present invention.
For compounding and kneading, a method that is usually used, for example, a method that uses a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder, etc. Can be performed. The heating temperature for melt kneading is usually selected in the range of 220 to 260 ° C.

In addition, since the polycarbonate resin composition of the present invention uses the polymerization catalyst (organic basic catalyst) described above during the production of the polycarbonate, unlike the case of using an inorganic base catalyst, sodium and cesium that cause coloring of the resin composition. And the content of potassium can be less than 0.1 ppm by mass, respectively.
Therefore, the polycarbonate resin composition of the present invention has excellent heat resistance and extremely good color tone.

The following examples further illustrate the present invention, but the present invention is not limited to these examples.
Quality evaluation in the examples and comparative examples was performed by the following methods.

(1) Quantitative analysis of metal amount (Na, Cs and K) The obtained polycarbonate pellet was dissolved in N-methylpyrrolidone (NMP) to prepare a 1% by mass solution, and this was prepared using Agilent ICP-MS 7500cs. Then, Na, Cs and K were quantified by the indium internal standard method.
(2) Color tone (absorbance measurement)
Using the obtained polycarbonate pellets, a thermal stability test was performed at 360 ° C. for 1 hour under a nitrogen atmosphere, and the obtained sample was dissolved in methylene chloride to prepare a 5% by mass solution. The solution was put into a quartz cell of No. 4 and absorbance at a wavelength of 420 nm was measured using UV-2450 manufactured by Shimadzu Corporation. The color tone was evaluated by the difference in absorbance before and after the thermal stability test (Δabs ₄₂₀ ).
(3) Mv (viscosity average molecular weight)
Using an Ubbelohde viscometer, the viscosity of the methylene chloride solution at 20 ° C. was measured, and the intrinsic viscosity [η] was determined from this, and the viscosity average molecular weight was calculated by the equation [η] = 1.23 × 10 ⁻⁵ Mv ^0.83 (Mv) was calculated.

[Examples 1 to 6]
To a 200 mL Ni steel flask with an internal volume of 22.8 g (0.10 mol) of bisphenol A (BPA), 23.5 g (0.11 mol) of diphenyl carbonate, and the type and amount of catalyst shown in Table 1, After 5 N ₂ substitutions, the mixture was heated to 180 ° C. and reacted at normal pressure for 30 minutes. Next, the temperature was raised to 210 ° C., the degree of vacuum was raised to 100 mmHg, and the reaction was performed for 30 minutes. Next, the temperature was raised to 240 ° C., the degree of vacuum was raised to 10 mmHg, and the reaction was performed for 30 minutes. Next, the temperature was raised to 270 ° C., the degree of vacuum was raised to 2 mmHg, and the reaction was performed for 30 minutes, and then the degree of vacuum was raised to 0.5 mmHg and the reaction was further continued for 30 minutes. At this point, the polycarbonate was sampled and Mv (viscosity average molecular weight) was measured.
Thereafter, the organophosphorus compound in the amount shown in the table was made into a toluene solution, added to the reaction system, kneaded for 5 minutes to obtain a polycarbonate resin composition, and pelletized with an extruder. Table 1 shows the metal amount, color tone, and Mv measured by the above method.

[Comparative Example 1]
It implemented like Example 1 except not adding an organophosphorus compound. Table 1 shows the metal amount, color tone, and Mv measured by the above method.

[Comparative Examples 2 to 5]
(B) TPTB used as a catalyst in Example 1 was reacted with sodium hydroxide (NaOH) except that it was reacted at the same temperature and pressure as in Example 1, and the obtained polycarbonate was sampled to measure Mv. .
Next, a deactivation agent (p-TsOBu: p-toluenesulfonate butyl) in the amount shown in the table was added to the reaction system as a toluene solution and kneaded for 15 minutes. Thereafter, the organophosphorus compound in the amount shown in the table was made into a toluene solution, added to the reaction system, kneaded for 5 minutes to obtain a polycarbonate resin composition, and pelletized with an extruder. Table 1 shows the metal amount, color tone, and Mv measured by the above method.

[Comparative Examples 6 to 8]
Comparison was made except that NaOH used as a catalyst in Comparative Example 2 was replaced with cesium carbonate (Cs ₂ CO ₃ ), and the amount of deactivating agent (p-TsOBu) shown in the table and an organic phosphorus compound were added. Performed as in Example 2. Table 1 shows the metal amount, color tone, and Mv measured by the above method.

From Comparative Examples 2 and 6, it was found that when an inorganic basic catalyst such as NaOH or Cs ₂ CO ₃ was used and a deactivator was added, the color tone of the resin composition was inferior to that of Examples, Comparative Examples 3 to 5, From 7 and 8, it can be seen that the effect of improving the color tone is not exhibited even when an inorganic basic catalyst and an organic phosphorus compound which is a phosphite and a phosphate compound are combined.
Further, from the comparison between Comparative Example 1 and Examples 1 to 6, it can be seen that the effect of drastically improving the color tone is exhibited by mixing the organic phosphorus compound.

The polycarbonate resin composition of the present invention is excellent in heat resistance and has a very good color tone, and thus is useful in the electrical / electronic field, the automotive field, the optical part field, and other wide industrial fields.

Claims

Phosphite compound and phosphate compound with respect to 100 parts by mass of a polycarbonate obtained by a transesterification reaction using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst A polycarbonate resin composition containing 0.001 to 0.5 parts by mass of at least one organic phosphorus compound selected from the group consisting of:
The polycarbonate resin composition according to claim 1, wherein the contents of sodium, cesium, and potassium are each less than 0.1 ppm by mass as elements.
The polycarbonate resin composition according to claim 1 or 2, wherein (a) the nitrogen-containing organic basic compound is a quaternary ammonium salt.
(A) The polycarbonate resin composition according to claim 1 or 2, wherein the nitrogen-containing organic basic compound is a compound represented by the following general formula (I).
(NR 1 4 ) + (X 1 ) − (I)
Wherein, R 1 represents an alkyl group, an aryl group or an alkylaryl group, four R 1 may be the same with or different from each other, also form a two R 1 is bonded to the ring structure Also good. X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
5. The polycarbonate resin composition according to claim 1, wherein (b) the quaternary phosphonium salt containing an aryl group is a compound represented by the following general formula (II).
(PR 2 4 ) + (X 2 ) − (II)
[Wherein R 2 represents an alkyl group, an aryl group or an alkylaryl group, but at least one of the four R 2 is an aryl group. Further, the four R 2 may be the same or different, and two R 2 may be bonded to form a ring structure. X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
The polycarbonate resin composition according to any one of claims 1 to 5, wherein the raw materials for the transesterification reaction are (A) a dihydroxy compound and (B) a carbonic acid diester.
The polycarbonate resin composition according to claim 6, wherein the (A) dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane.
(B) The polycarbonate resin composition according to claim 6 or 7, wherein the carbonic acid diester is diphenyl carbonate.
9. The method according to claim 1, wherein (a) the nitrogen-containing organic basic compound is tetramethylammonium hydroxide, and (b) the quaternary phosphonium salt containing an aryl group is tetraphenylphosphonium tetraphenylborate. Polycarbonate resin composition.
The organophosphorus compound is tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis. Selected from (4,6-di-tert-butylphenyl) octyl phosphite, triphenyl phosphate, bisphenol A bis (diphenyl phosphate), and 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition is at least one selected from the group consisting of:
Using a combination of (a) a nitrogen-containing organic basic compound and (b) a quaternary phosphonium salt containing an aryl group as a polymerization catalyst, a polycarbonate was obtained by a transesterification reaction. A method for producing a polycarbonate resin composition, comprising mixing 0.001 to 0.5 parts by mass of at least one organic phosphorus compound selected from a phyto compound and a phosphate compound.
The method for producing a polycarbonate resin composition according to claim 11, wherein after completion of the transesterification reaction, the reaction product is heat-treated at a temperature equal to or higher than the decomposition temperature of the polymerization catalyst to obtain a polycarbonate.
(A) The method for producing a polycarbonate resin composition according to claim 11 or 12, wherein the nitrogen-containing organic basic compound is a quaternary ammonium salt.
(A) The method for producing a polycarbonate resin composition according to claim 11 or 12, wherein the nitrogen-containing organic basic compound is a compound represented by the following general formula (I).
(NR 1 4 ) + (X 1 ) − (I)
Wherein, R 1 represents an alkyl group, an aryl group or an alkylaryl group, four R 1 may be the same with or different from each other, also form a two R 1 is bonded to the ring structure Also good. X 1 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
The method for producing a polycarbonate resin composition according to any one of claims 11 to 14, wherein (b) the quaternary phosphonium salt containing an aryl group is a compound represented by the following general formula (II).
(PR 2 4 ) + (X 2 ) − (II)
[Wherein R 2 represents an alkyl group, an aryl group or an alkylaryl group, but at least one of the four R 2 is an aryl group. Further, the four R 2 may be the same or different, and two R 2 may be bonded to form a ring structure. X 2 represents a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, HCO 3 or BR 4 (R represents a hydrogen atom, an alkyl group or an aryl group, and four Rs are May be the same or different. ]
The method for producing a polycarbonate resin composition according to any one of claims 12 to 15, wherein a temperature at which the reaction product is heat-treated is 240 ° C or higher and 350 ° C or lower.
A polycarbonate resin composition produced by the method for producing a polycarbonate resin composition according to any one of claims 11 to 16.