JP2006143967A - Production method of aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method obtaining an aromatic polycarbonate resin composition excellent in molding thermostability and moist heat resistance. <P>SOLUTION: The production method comprises adding, into (A) an organic solvent solution of an aromatic polycarbonate resin having 10,000-50,000 viscosity-average molecular weight, (B) 0.0001-0.15 pts.wt. phosphorous-based stabilizer composition based on 100 pts.wt. aromatic polycarbonate resin, and removing the organic solvent to obtain a solid aromatic polycarbonate resin composition, wherein, phosphorous-based stabilizer has ≤100 ppm 2,4,6-tri-tert-butylphenol content and comprises a specific compound (B-1 component) having four aromatic groups substituted with tert-buthyl group, a specific compound (B-2 component) having two groups and a specific compound (B-3 component) having tree groups, and, when their total is 100 wt.%, B-1 component is 40-80 wt.%, B-2 component is 0-25 wt.% and B-3 component is 5-50 wt.%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an aromatic polycarbonate resin composition having excellent molding heat resistance and wet heat resistance in a step of obtaining a solid aromatic polycarbonate resin composition by removing an organic solvent from an organic solvent solution of an aromatic polycarbonate resin. About.

  Aromatic polycarbonate resin is a material having relatively high heat resistance among polymer materials. However, with increasing demands for higher functionality and higher performance of materials, further improvement in molding heat resistance and moist heat resistance is required. In order to improve the molding heat resistance, a method of adding a stabilizer to a solid aromatic polycarbonate resin is generally used, but it is also important that the solid aromatic polycarbonate resin itself is excellent in molding heat resistance.

  As a method for producing a solid aromatic polycarbonate resin excellent in molding heat resistance, for example, in Patent Document 1, tetrakis (2,4-) is added to an organic solvent solution of an aromatic polycarbonate resin after polymerization reaction produced by a solution method. A method in which di-tert-butylphenyl) -4,4′-biphenylenephosphonite is previously added has been proposed. Patent Document 2 focuses on the concentration of chlorine atoms and chloride ions contained in the phosphonite stabilizer, and shows that the molding heat resistance and wet heat fatigue resistance are improved by setting these concentrations within a specific range. Yes.

  These methods are effective means, but in order to further improve each performance such as molding heat resistance and moist heat resistance as polycarbonate resin products are diversified, more effective means are required. ing.

Japanese Patent Laid-Open No. 62-007725 JP 2001-0197757 A

  An object of the present invention is to provide an aromatic polycarbonate resin composition having excellent molding heat resistance and moisture and heat resistance in a step of obtaining a solid aromatic polycarbonate resin composition by removing an organic solvent from an organic solvent solution of an aromatic polycarbonate resin. It is to provide a manufacturing method to obtain.

  As a result of intensive studies to achieve the above object, the inventors of the present invention, in the step of obtaining a solid aromatic polycarbonate resin by removing the organic solvent from the organic solvent solution of the aromatic polycarbonate resin, When carrying out a method of adding a specific biphenylenephosphonite to a solvent solution in advance, paying attention to a trace component contained in the biphenylenephosphonite, 2,4,6-tri- The present inventors have found that the tert-butylphenol component has an adverse effect on both the thermal stability and wet heat resistance of the polycarbonate resin, and have reached the present invention.

That is, according to the present invention,
1. (A) To an organic solvent solution of an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 50,000, (B) a compound (B-1 component) represented by the following general formula (1), the following general formula ( 2) and a compound (B-3 component) represented by the following general formula (3), and when the total is 100% by weight, the B-1 component is 40%. Phosphorus based on ˜80 wt%, B-2 component is 0-25 wt%, B-3 component is 5-50 wt%, and 2,4,6-tri-tert-butylphenol concentration is 100 ppm or less An aromatic polycarbonate characterized in that a stabilizer composition is added in an amount of 0.0001 to 0.15 parts by weight per 100 parts by weight of an aromatic polycarbonate resin, and then an organic solvent is removed to obtain a solid aromatic polycarbonate resin composition. Method for producing a fat composition.

［式中、Ａｒ１、Ａｒ２およびＡｒ３は少なくとも１つのｔｅｒｔ−ブチル基で置換された芳香族基であって、それぞれ同一でも異なっていてもよい。］

[Wherein Ar1, Ar2 and Ar3 are aromatic groups substituted with at least one tert-butyl group, and may be the same or different. ]

2. 2. The method for producing an aromatic polycarbonate resin composition according to item 1, wherein the B-2 component is 5 to 25% by weight.
Is provided.

Hereinafter, the present invention will be described in more detail.
(About A component aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the component (A) in the present invention is obtained, for example, by reacting a dihydric phenol and a carbonate precursor by an interfacial polymerization method (solution method) or a melting method. Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, 1,4-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy -3,5-dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy) Phenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, , 2-bis {(3,5-dibromo-4-hydroxy) phenyl} propane, 2,2-bis {(3-isopropyl-4 Hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl)- 3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) Pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1 , 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxy) Enyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4- Hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4 ′ -Dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxydiphenyl ester Can be mentioned. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred.

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by reacting the dihydric phenol and the carbonate precursor by an interfacial polymerization method or a melting method, the dihydric phenol can be used alone or in combination of two or more, as necessary. Catalysts, end terminators, dihydric phenol antioxidants, and the like may also be used. The aromatic polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Moreover, the mixture of 2 or more types of aromatic polycarbonate resin may be sufficient.

  The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is about several minutes-about 5 hours.

The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and diphenyl carbonate. The dihydric phenol and diphenyl carbonate are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the phenols produced at 1.3 × 10 ² Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.

  In the polymerization reaction, monofunctional phenols can be used as a terminal terminator. In particular, in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for molecular weight control, and the resulting aromatic polycarbonate resin has a terminal that is converted to a monofunctional phenol. Since it is blocked by a base group, it is superior in thermal stability compared to those that are not. Such monofunctional phenols may be those used as a terminal stopper for polycarbonate, and are generally phenols or lower alkyl-substituted phenols, which are monofunctional phenols represented by the following general formula (4). Can show.

［式中、Ｒは水素原子または炭素数１〜９のアルキル基もしくはフェニルアルキル基であり、ｍは１〜５、好ましくは１〜３の整数を示す。］

[Wherein, R represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or a phenylalkyl group, and m represents an integer of 1 to 5, preferably 1 to 3. ]

  Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

  The molecular weight of the aromatic polycarbonate resin in the present invention is preferably 10,000 to 50,000, more preferably 14,000 to 35,000 in terms of viscosity average molecular weight (M). An aromatic polycarbonate resin having such a viscosity average molecular weight is preferable because it has a certain mechanical strength with respect to the obtained molded product while maintaining a relatively good fluidity during extrusion and molding.

The viscosity average molecular weight (M) in the present invention is obtained by inserting a specific viscosity (η _SP ) measured using a solution of 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation. It is done.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(About the phosphorus stabilizer composition of component B)
The component B phosphorus stabilizer composition used in the present invention comprises a compound represented by the following general formula (1) (component B-1) and a compound represented by the following general formula (2) (B-2). Component) and a compound represented by the following general formula (3) (component B-3), and when the total is 100% by weight, the component B-1 is 40 to 80% by weight and the component B-2 is 0. -25 wt% and B-3 component is 5-50 wt%. Preferably, the B-1 component is 40 to 80% by weight, the B-2 component is 5 to 25% by weight, and the B-3 component is 5 to 50% by weight. More preferably, the B-1 component is 55 to 80% by weight. % By weight, 5 to 25% by weight of the B-2 component, and 5 to 45% by weight of the B-3 component.

［式中、Ａｒ１、Ａｒ２およびＡｒ３は少なくとも１つのｔｅｒｔ−ブチル基で置換された芳香族基であって、それぞれ同一でも異なっていてもよい。］

[Wherein Ar1, Ar2 and Ar3 are aromatic groups substituted with at least one tert-butyl group, and may be the same or different. ]

  Specific examples of the B-1 component of the present invention include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl). ) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl)- 4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3, 3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenedi Suphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -3, 3'-biphenylene diphosphonite and the like are mentioned, tetrakis (di-tert-butylphenyl) -biphenylene diphosphonite is preferable, and tetrakis (2,4-di-tert-butylphenyl) -biphenylene diphosphonite is more preferable. . The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically tetrakis (2,4-di-tert-butylphenyl) -4,4. '-Biphenylenediphosphonite (component B-1-1), tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite (component B-1-2) and tetrakis (2 , 4-Di-tert-butylphenyl) -3,3′-biphenylenediphosphonite (component B-1-3) is more preferred. Further, the mixing ratio of this mixture is preferably in the range of 100: 37 to 64: 4 to 14 by weight of B-1-1 component, B-1-2 component and B-1-3 component, and 100: 40 The range of ˜60: 5 to 11 is more preferable.

  Specific examples of the B-2 component of the present invention include bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl)- 3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphospho Knight, bis (2,4-di-tert-butyl-5-methylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butyl-5-methylphenyl) -4-phenyl- Phenylphosphonite and the like, and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferable, and bis (2,4-di-t rt- butyl phenyl) - phenyl - phenyl phosphonite are more preferred. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- A mixture of phenyl-phenylphosphonite (B-2-1 component) and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite (B-2-2 component) is more preferable. In addition, the mixing ratio of the mixture is preferably in the range of 5: 1 to 4, more preferably in the range of 5: 2 to 3, with respect to the B-2-1 component and the B-2-2 component.

  Specific examples of the B-3 component of the present invention include tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite and the like, and tris (di-tert-butylphenyl) phosphite is more preferable, and tris (2,4-di-tert-butylphenyl) phosphite Is particularly preferred. The compound of the B-3 component may be one type or a mixture of two or more types.

  In this invention, the compounding quantity of the phosphorus stabilizer composition of B component is the range of 0.0001-0.15 weight part with respect to 100 weight part of aromatic polycarbonate resin, 0.002-0.15 A range of parts by weight is more preferred, and a range of 0.02 to 0.1 parts by weight is most preferred.

  The 2,4,6-tri-tert-butylphenol contained in the phosphorus stabilizer composition is mainly present from the raw material stage in the production process of the phosphorus stabilizer. The commercial product contains about 1000 ppm of 2,4,6-tri-tert-butylphenol.

Examples of a method for reducing 2,4,6-tri-tert-butylphenol contained in the phosphorus stabilizer composition include a method of washing the phosphorus stabilizer composition with a solvent and a method of purification by distillation. Can be mentioned. In the case of the method of washing the phosphorus stabilizer composition with a solvent, the amount of washing solvent during washing with the solvent used in the production and purification process of the phosphorus stabilizer composition is increased, or the number of washings is increased. Alternatively, a method such as using a solvent that easily dissolves 2,4,6-tri-tert-butylphenol selectively can be employed. Further, in the case of the method of purification by distillation, a method can be adopted in which the fractionator is lengthened to increase the number of distillation stages and the separation capacity is increased to obtain a raw material with reduced 2,4,6-tri-tert-butylphenol. .
2,4,6-tri-tert-butylphenol in the present invention can be measured by a pyrolysis gas chromatography method.

  The concentration of 2,4,6-tri-tert-butylphenol contained in the phosphorus-based stabilizer composition of component B used in the present invention is 100 ppm or less. Preferably it is 50 ppm or less, More preferably, it is 30 ppm or less, More preferably, it is 20 ppm or less, Especially preferably, it is 10 ppm or less, Most preferably, it is 5 ppm or less. The 2,4,6-tri-tert-butylphenol concentration is preferably zero, but it is difficult to make it completely zero. 1 ppm or more may be contained, more preferably 0.1 ppm or more, still more preferably 0.01 ppm or more, and particularly preferably 0.001 ppm or more.

(About the manufacturing method of a solid aromatic polycarbonate resin composition)
The organic solvent solution of the aromatic polycarbonate resin used in the present invention is the organic solvent solution of the aromatic polycarbonate resin after the polymerization reaction in the case of the interface polymerization method described above, and the solid solution obtained in the case of the melting method. A solution in which an aromatic polycarbonate resin is dissolved in an organic solvent is used. As the organic solvent, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene are preferably used.

  The organic solvent solution of the aromatic polycarbonate resin is agitated and washed with acidic water and / or neutral water, fixed concentration treatment, filtration treatment for the purpose of removing foreign matters, moisture removal treatment, and other manufacturing processes. Any of the above-described processes may be performed, or a plurality of processes may be performed.

  In addition, the organic solvent solution of the aromatic polycarbonate resin in the present invention may be prepared by dissolving powder, flakes, or pellets of dry aromatic polycarbonate resin prepared in advance in an organic solvent. An organic solvent solution of an aromatic polycarbonate resin obtained at the end of the reaction is preferable because of easy process control.

  In the present invention, 0.0001 to 0.15 parts by weight of the phosphorus stabilizer composition is added to 100 parts by weight of the aromatic polycarbonate resin in an organic solvent solution of the aromatic polycarbonate resin, and then the organic solvent is removed. A method for obtaining a solid aromatic polycarbonate resin composition is employed. By adopting such a method, the obtained aromatic polycarbonate resin composition is more excellent in thermal stability and moist heat resistance.

  A method of producing a solid aromatic polycarbonate resin composition by removing an organic solvent from an organic solvent solution of an aromatic polycarbonate resin is to granulate the organic solvent solution while heating and concentrating it using a known method or apparatus. The method of drying the obtained powder is shown. Examples of the granulation method include a poor solvent method, a method using a kneader, a method using a thin film evaporator, a method using a spray dryer, a method using a steam tube dryer, and a flash drying method. In addition, it was concentrated in a concentrating tank and extruded and pelletized in a heated and melted state, a method of pulverizing a solid obtained by concentrating in a concentrating tank, and concentrated and extruded in a molten state. There is a method of pulverizing pellets. Examples of the stirring system used in the poor solvent method include paddle blade stirring, helical blade stirring, homomixer stirring, and kneader stirring.

(About other additives)
In the aromatic polycarbonate resin composition obtained by the production method of the present invention, the phosphorus-based stabilizer composition represented by the component B of the present invention is used in order to highly prevent molecular weight reduction and hue deterioration during molding. In addition to the above, each component compound of the phosphorus-based stabilizer composition represented by the component B of the present invention and other heat stabilizers can be additionally used in combination. Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite. Phyto, trioctyl phosphite, trioctadecyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate , Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like. Of these, tris (2,4-di-tert-butylphenyl) phosphite, trimethyl phosphate, and dimethyl benzenephosphonate are preferably used.

  You may use these 1 type or in mixture of 2 or more types. The amount of the heat stabilizer is preferably 0.001 to 0.15 parts by weight, more preferably 0.001 to 0.10 parts by weight, and more preferably 0.001 to 0 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin. More preferred is 0.05 parts by weight.

  The aromatic polycarbonate resin composition obtained by the production method of the present invention can be blended with an antioxidant generally known for the purpose of antioxidant. Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphosphinic acid tetrakis (2 , 4-Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl}- 2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The blending amount of these antioxidants is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin.

  In the aromatic polycarbonate resin composition obtained by the production method of the present invention, in order to further improve the releasability from the mold at the time of melt molding, a release agent is blended to the extent that the object of the present invention is not impaired. can do. Examples of the release agent include higher fatty acid esters of mono- or polyhydric alcohols, polyorganosiloxane, paraffin wax, beeswax and the like. The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol. Tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2- And ethyl hexyl stearate, among others, stearic acid monoglyceride, stearic acid triglyceride, pentaerythris Tall tetrastearate are preferably used. The amount of the release agent is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin composition.

  The aromatic polycarbonate resin composition obtained by the production method of the present invention can contain an ultraviolet absorber. Specifically, the ultraviolet absorber compound is 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, in benzophenone series, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4 4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl- 4-hydroxy-2-methoxy Phenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, and the like. In the benzotriazole series, 2- (2-hydroxy-5- Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy -3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole- 2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) Nzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) Benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazin-4-one), 2- [2-hydroxy -3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole. These can be used alone or in a mixture of two or more. As for the compounding quantity of this ultraviolet absorber compound, 0.1-10 weight part is preferable with respect to 100 weight part of aromatic polycarbonate resin compositions.

  An antistatic agent can be mix | blended with the aromatic polycarbonate resin composition obtained by the manufacturing method of this invention. Examples of such antistatic agents include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride, carbon, graphite, metal powder and the like. Can be mentioned. The blending amount of the antistatic agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin composition.

  A blueing agent can be mix | blended with the aromatic polycarbonate resin composition obtained by the manufacturing method of this invention. The bluing agent is effective for eliminating the yellowishness of the resin composition. In particular, in the case of a composition imparted with weather resistance, since a certain amount of UV absorber is blended, the resin product tends to have a yellowish color due to the color of the UV absorber itself and the UV absorbing ability. In order to give natural transparency to the product, it is effective to add a bluing agent. The blending amount of the bluing agent is 0.05 to 1.5 ppm, preferably 0.1 to 1.2 ppm, based on the entire resin composition. If the amount is too large, the blueness of the resin product becomes strong and the visual transparency is lowered. Representative examples of the brewing agent include Macrolex Violet B and Polysynthrene Blue RLS from Bayer.

  A flame retardant can be mix | blended with the aromatic polycarbonate resin composition obtained by the manufacturing method of this invention. Examples of the flame retardant include a halogenated bisphenol A polycarbonate flame retardant, an organic salt flame retardant, an aromatic phosphate ester flame retardant, or a halogenated aromatic phosphate ester flame retardant. It can mix | blend above. Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A, or the like. Specifically, the organic salt flame retardants are diphenyl sulfone-3,3′-disulfonate dipotassium, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, Potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, Potassium perfluorobutane sulfonate, sodium lauryl sulfate Um or potassium hexadecyl sulfate, sodium or potassium. Specifically, the halogenated aromatic phosphate ester type flame retardant is tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, etc. is there. Specifically, aromatic phosphate ester difficult agents are triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate. , Tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4′-biphenol diphosphate, aromatic ring source is resorcin and phenol Aromatic polyphosphates that do not contain phenolic OH groups, aromatic ring sources are resorcin and phenol, aromatic polyphosphates that contain phenolic OH groups, aromatic ring sources are hydroquinone and phenol, and phenolic O Aromatic polyphosphates containing no groups, aromatic polyphosphates containing similar phenolic OH groups, aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol (hereinafter aromatic polyphosphates contain phenolic OH groups) Both aromatic polyphosphates and aromatic polyphosphates not containing phenolic OH groups), aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and phenol, aromatic ring sources resorcin and 2 , 6-xylenol aromatic polyphosphate, aromatic polyphosphates whose aromatic ring sources are hydroquinone and 2,6-xylenol, aromatic polyphosphates whose aromatic ring sources are bisphenol A and 2,6-xylenol, aromatic rings Tetrabro source Aromatic polyphosphates such as bisphenol A and 2,6-xylenol. The amount of the flame retardant blended is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin composition.

In the aromatic polycarbonate resin composition obtained by the production method of the present invention, other resins and elastomers can be blended in a small proportion as long as the object of the present invention is not impaired.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.
As for the compounding quantity of this other resin and elastomer, 1-30 weight part is preferable with respect to 100 weight part of aromatic polycarbonate resin compositions.

(About a molded article formed from the aromatic polycarbonate resin composition obtained by the production method of the present invention)
In the aromatic polycarbonate resin composition obtained by the production method of the present invention, an arbitrary method is adopted to blend the aromatic polycarbonate resin with the phosphorus stabilizer composition and other additives. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like is appropriately used. The powder and pellets of the aromatic polycarbonate resin composition thus obtained are formed as they are or in a pellet form with a melt extruder, and then molded by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method. Can be made.

  The blending of the phosphorus-based stabilizer composition and other additives may be performed in one stage, but may be performed in two or more stages. The method carried out in two steps is, for example, after pre-blending a part of the aromatic polycarbonate resin powder and the additive to be blended (that is, diluting the blended additive with the aromatic polycarbonate resin powder and This is a method of blending an aromatic polycarbonate resin and a masterbatch after a concentration additive masterbatch).

  Molded articles formed from the aromatic polycarbonate resin composition obtained by the production method of the present invention include extruded articles such as sheets, films and pipes, lighting equipment parts such as lamps and lamp covers, machine parts, Electronic parts, medical / security parts, lenses, optical disks and the like can be mentioned.

  By defining the concentration of 2,4,6-tri-tert-butylphenol contained in the phosphorus-based stabilizer composition, an aromatic polycarbonate resin excellent in both molding heat resistance and moist heat resistance is obtained, and the polycarbonate resin is used. It can be applied to various uses, and its industrial value is very high.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The evaluation was performed by the following method.
(1) Preparation of phosphorus-based heat stabilizer composition Phosphorus-based heat stabilizer composition (manufactured by Clariant; trade name P-EPQ, 2,4,6-tri-tert-butylphenol (TTBP) content 890 ppm) in 3 kg On the other hand, 10 L of dehydrated acetonitrile was added, and the mixture was heated and stirred at 40 ° C. for 6 hours under a dry nitrogen atmosphere. After stirring, the mixture was cooled to room temperature and filtered under a dry nitrogen atmosphere. The operation of adding 10 L of dehydrated acetonitrile to the obtained filtered product, heating and stirring at 40 ° C. for 6 hours under a dry nitrogen atmosphere, and filtering was further repeated three times. The obtained filtered product was dried for 12 hours under the conditions of a pressure of 133 Pa and a temperature of 40 ° C. with a vacuum dryer to obtain a phosphorus-based heat stabilizer composition. The phosphorus-based heat stabilizer composition contained the following compounds (i) to (iii) in proportions of (i) 71%, (ii) 15%, and (iii) 14%, respectively. The 2,4,6-tri-tert-butylphenol (TTBP) content in the phosphorus-based heat stabilizer composition was 2 ppm.
In Examples 1 to 3, the phosphorous heat stabilizer composition was used as it was, and in Examples 4 to 6, about 13 mg of TTBP was added to 1000 g of the phosphorous heat stabilizer composition. In Comparative Example 1, about 10 mg of TTBP was added to 10 g of the phosphorous heat stabilizer composition.
(I) B-1 stabilizer Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, Tetrakis (2,4-di-tert-butylphenyl) -4,3 ′ -Biphenylene diphosphonite and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite 100: 50: 10 (weight ratio) mixture (ii) B-2 stabilizer bis 5: 3 (weight ratio) of (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite Mixture (iii) B-3 Stabilizer Tris (2,4-di-tert-butylphenyl) phosphite

(2) 2,4,6-Tri-tert-butylphenol content in phosphorus-based heat stabilizer composition Analyzed by pyrolysis GC-MS under the following equipment and conditions, and in phosphorus-based heat stabilizer composition The 2,4,6-tri-tert-butylphenol content was determined.
Apparatus / thermal decomposition apparatus: PY-2010D (manufactured by Frontier Lab)
-GC: HP-5890 series II plus (manufactured by YOKOGAWA)
・ MS: HP-5272 (made by HEWLETT PACARD)
-Column: TC-5 (manufactured by GL Sciences)
Conditions / Pyrolysis temperature: 350 ° C
Sample amount: 0.3 mg / 5 μL sample cup GC temperature 50 ° C. to 310 ° C.

(3) Molding heat resistance The pellets obtained in the examples and comparative examples were injection molded at a cylinder temperature of 350 ° C. for 1 minute cycle to prepare a sample plate (length 70 mm × width 50 mm × thickness 2 mm). Further, the sample was retained in the cylinder for 10 minutes at a temperature of 350 ° C., and then injection molded to prepare a sample plate (length 70 mm × width 50 mm × thickness 2 mm). The color difference (ΔE) was calculated by measuring the hue of the sample plate before residence (injection molding in a 1 minute cycle) and after residence (injection molding after residence in a cylinder for 10 minutes) using a color difference meter.
Hue measurement : Measure L value, a value, and b value of thickness 2mm Color difference meter: SE-2000 (manufactured by Nippon Denshoku)
Measurement conditions: C light source reflection method, viewing angle 2 °
ΔE calculation formula ΔE = {(L1-L2) ² + (a1-a2) ² + (b1-b2) ² } ^1/2
L1, a1, b1: Sample plate color before staying L2, a2, b2: Sample plate color after staying

(4) Moisture and heat resistance Using the sample plate before residence obtained by the method of (3) above, a pressure cooker test (exposure in a steam atmosphere at a temperature of 120 ° C. for 24 hours) was conducted, and the sample plate after the pressure cooker test was Haze was measured. Haze was measured with an integrating sphere type total light transmittance measuring device NDH-2000 (C light source) manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K-6735.
H = Td / Tt × 100 (%)

[Examples 1 to 6, Comparative Example 1]
Methylene chloride solutions (about 12% weight concentration) of each aromatic polycarbonate resin having viscosity average molecular weight shown in Table 1 obtained by the interfacial polymerization method from bisphenol A, p-tert-butylphenol (terminal stopper) and phosgene. Then, the phosphorus stabilizer composition prepared with the 2,4,6-tri-tert-butylphenol content was added and mixed in the amounts shown in Table 1. This solution was poured into a kneader charged with warm water at 60 ° C. (an amount that accounts for about 10% of the internal volume of the kneader) with stirring, and methylene chloride was removed by evaporation while blowing steam to produce a polycarbonate resin composition. Grained. The methylene chloride solution was charged for 1 hour, and stirring was continued for 10 minutes after the completion of the charging to obtain an aqueous slurry of the polycarbonate resin composition powder. The resulting water slurry had a slurry concentration of about 25% by weight. The water slurry was passed through a pulverizer to crush the polycarbonate resin composition granules in the slurry, and further, polycarbonate resin composition powder was obtained by centrifugal dehydration. This polycarbonate resin composition powder was put into a dryer and dried at 120 ° C. for 7 hours to obtain a polycarbonate resin composition powder. The polycarbonate resin composition powder was dried at 120 ° C. for 5 hours, melt-extruded at 280 ° C. and pelletized. The above evaluation was performed using the obtained pellets, and the evaluation results are shown in Table 1.

Claims (2)

(A) To an organic solvent solution of an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 50,000, (B) a compound (B-1 component) represented by the following general formula (1), the following general formula ( 2) and a compound (B-3 component) represented by the following general formula (3), and when the total is 100% by weight, the B-1 component is 40%. Phosphorus based on ˜80 wt%, B-2 component is 0-25 wt%, B-3 component is 5-50 wt%, and 2,4,6-tri-tert-butylphenol concentration is 100 ppm or less An aromatic polycarbonate characterized in that a stabilizer composition is added in an amount of 0.0001 to 0.15 parts by weight per 100 parts by weight of an aromatic polycarbonate resin, and then an organic solvent is removed to obtain a solid aromatic polycarbonate resin composition. Method for producing a fat composition.

[Wherein Ar1, Ar2 and Ar3 are aromatic groups substituted with at least one tert-butyl group, and may be the same or different. ]   The method for producing an aromatic polycarbonate resin composition according to claim 1, wherein the B-2 component is 5 to 25% by weight.