JP2002167501A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition exhibiting excellent demoldability and leaving little material adhered to a mold at molding, and having good heat resistance. SOLUTION: This polycarbonate resin composition comprises (A) a polycarbonate resin (component (a)) and (B) an aliphatic ester (component (b)) having a specific branched aliphatic ester group, wherein the component (b) is <0.1 pts.wt. and >=0.001 pts.wt. based on 100 pts.wt. of the component (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition which is excellent in handleability during production of a polycarbonate resin composition, has excellent mold releasability during molding, has little adhesion to a mold, and has excellent heat resistance.

[0002]

2. Description of the Related Art Generally, a releasing agent such as a fatty acid partial ester of a polyhydric alcohol is blended with a polycarbonate resin for the purpose of improving the releasability of a molded product from a mold. However, there has been a problem that these compounds generally deteriorate the thermal stability when blended with a polycarbonate resin.

[0003] From this point of view, Japanese Patent Laid-Open No. 2-69556
The publication proposes to use an ester compound having a small acid value while reducing the number of OH groups as much as possible, and shows that it is useful for improving heat resistance.

However, such a compound has a small effect of improving the releasability at the time of molding due to a large molecular skeleton.
In order to obtain sufficient releasability, a large excess must be added, which is economically problematic. Further, when a large excess is added, the amount of deposits on the mold and the adherence of the stamper increases, the defective rate increases, and the cleaning cycle is shortened, so that the productivity is remarkably deteriorated. Particularly in molding optical disc substrates such as compact discs and automobile headlamp lenses, high transfer performance and good economic performance (productivity) are essential and are problems.

Further, it has been shown that by blending a polycarbonate resin with a compound having a branched fatty acid ester group in a specific amount, a resin composition having excellent antistatic performance can be provided (WO 00/15707). Specification).

On the other hand, in a melt polymerization method which is one of the methods for producing a polycarbonate resin, as a method for adding a release agent to the molten resin at the time of production, more accurate measurement, more complete compatibility, and more uniform In order to obtain a resin composition, it is desirable to add a liquid by heating and dissolving. Usually, since the release agent is solid at normal temperature and normal pressure, it is added after being heated and dissolved at a high temperature.At this time, it is necessary to keep the temperature at a high temperature in order to completely dissolve the release agent. There is a problem that the resin composition is liable to be colored and deteriorated, and the quality of the resin composition is significantly deteriorated.

[0007]

SUMMARY OF THE INVENTION The first object of the present invention is to provide excellent mold releasability at the time of molding and to reduce the amount of deposits on a mold.
Another object of the present invention is to provide a polycarbonate resin composition having good heat resistance.

[0008] A second object of the present invention is to provide a polycarbonate resin composition which is easy to handle when added in liquid form and which is excellent in heat resistance, particularly by melt-kneading, by using a specific compound as a releasing agent. Is to do.

The present inventor has conducted intensive studies to achieve the above object. As a result, a specific amount of a fatty acid ester compound having a specific branched structure in a fatty acid portion as a mold release agent is mixed with a polycarbonate resin to form a mold. The present inventors have sought to obtain a polycarbonate resin composition which is excellent in handleability and heat resistance at the time of production, and which has little adhesion to a mold, without impairing the releasability at the time of production, and completed the present invention.

[0010]

That is, according to the present invention, there are provided (A) a polycarbonate resin (a component) and (B) a fatty acid ester compound (b component) represented by the following general formula (I): For 100 parts by weight of component a,
A polycarbonate resin composition is provided, wherein the component b is less than 0.1 part by weight and not less than 0.001 part by weight.

[0011]

Embedded image

(Wherein l, m, and n are each independently an integer of 0 to 5, and R ¹ , R ² , and R ³ are each independently a hydrogen atom, a straight-chain having 1 to 25 carbon atoms. A chain or branched aliphatic carboxylic acid residue, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and at least one of R ¹ , R ² and R ³ is a branched fatty acid; Group carboxylic acid residue.)

The polycarbonate resin used in the present invention is obtained by reacting a dihydroxy compound with a carbonate precursor by an interfacial polycondensation method or a melt polymerization method. Representative examples of the dihydroxy compound used herein include hydroquinone, resorcinol, 4,
4'-dihydroxydiphenyl, 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
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-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-hydroxyphenyl) 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'-dihydroxydiphenylketone, 4,4'-dihydroxy Examples thereof include diphenyl ether and 4,4'-dihydroxydiphenyl ester, and these can be used alone or in combination of two or more. Of these, bisphenol A is preferred.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of a dihydroxy compound.

In producing the polycarbonate resin by reacting the dihydroxy compound with the carbonate precursor by an interfacial polycondensation method or a melt polymerization method, if necessary, a catalyst, a terminal stopper, an antioxidant for the dihydroxy compound, etc. May be used. The polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound or an aliphatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid. Or a mixture of two or more of the obtained polycarbonate resins.

The reaction by the interfacial polycondensation method is usually a reaction between a dihydroxy compound and phosgene, and is carried out 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 promote the reaction, for example, triethylamine, tetra-n-
Catalysts such as tertiary amines such as butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds can also be used. At that time, the reaction temperature is usually 0 to 40.
° C, the reaction time is about 10 minutes to 5 hours, and the pH during the reaction is 9
It is preferable to keep the above.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such monofunctional phenols are generally phenol or lower alkyl-substituted phenols, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

The reaction by the melt polymerization method is usually a transesterification reaction between a dihydroxy compound and a carbonate ester. The dihydroxy compound and the carbonate ester are mixed while heating in the presence of an inert gas to produce alcohol or phenol. Is carried out by a method of distilling. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the pressure of the system is reduced to about 1300 to 13 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc. Is preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such a polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, and sodium and potassium salts of dihydroxy compounds.
Alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals , Organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds Catalysts usually used for esterification and transesterification such as manganese compounds, titanium compounds, and zirconium compounds can be used. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably 1 × 10 ^-9 to 1 mol per mol of the starting dihydroxy compound.
× 10 ⁻³ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁴
It is selected within the range of equivalents.

The polycarbonate resin has a viscosity average molecular weight (M) of preferably 10,000 to 100,000, more preferably 11,000 to 45,000, and
000 to 30,000 are particularly preferred. A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength is obtained, the melt fluidity during molding is good, and molding distortion does not occur. The viscosity average molecular weight of 0.7 g of polycarbonate resin in 100 ml of methylene chloride is 2
The specific viscosity (η _sp ) obtained from the solution dissolved at 0 ° C. was obtained by inserting it into the following equation. 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

The fatty acid ester compound which is a release agent used in the present invention is a compound represented by the above general formula (I), and particularly has a fatty acid moiety having a branched structure.

In the formula, l, m and n are each independently 0
An integer of from 0 to 5, preferably from 0 to 2, l, m,
At least one of n is preferably an integer of 1 or more, more preferably a glycerin structure in which one of l, m, and n is 0 and two is 1. R ¹ , R ² and R ³ each independently represent a hydrogen atom, a linear or branched aliphatic carboxylic acid residue having 1 to 25, preferably 10 to 20 carbon atoms, an aliphatic hydrocarbon group, An aromatic hydrocarbon group and an alicyclic hydrocarbon group, and some of these hydrogen atoms
OH group or the like, and R ¹ , R ² , R
^At least one of ³ is a branched aliphatic carboxylic acid residue. Particularly preferably, R ¹ , R ² and R ³ are all linear or branched aliphatic carboxylic acid residues, and R ¹ ,
At least one of R ² and R ³ is a branched aliphatic carboxylic acid residue. The aliphatic carboxylic acid residue is represented by -OR
¹ (, -OR ² or -OR ³⁾ is meant to be a fatty acid ester group.

Further, when the composition ratio of the fatty acid ester groups in the fatty acid ester compound is such that the total weight of triester, diester and monoester is 100% by weight, triester 0-20% by weight, diester 15-5-5%
5% by weight, preferably 30 to 70% by weight of monoester, 5 to 15% by weight of triester, 25 to 25% of diester
A ratio of 45% by weight and a monoester of 40 to 60% by weight are more preferable, and a ratio of a triester 8 to 13% by weight, a diester 30 to 40% by weight, and a monoester 45 to 55% by weight are particularly preferable.

The amount of the fatty acid ester compound used is
It is less than 0.1 part by weight and not less than 0.001 part by weight, preferably not more than 0.095 part by weight and not less than 0.005 part by weight based on 100 parts by weight of the polycarbonate resin.
If the amount is less than 0.001 part by weight, sufficient releasability cannot be obtained, which is not preferable. In addition, if such a fatty acid ester compound is a very small amount, an unreacted product (glycerin) or an impurity at the time of production may be mixed.

As the release agent, glycerin monostearate and pentaerythritol tetrastearate, which are generally used, and other fatty acid ester compounds in which all the fatty acid groups are not branched but linear are used. Is not achieved.

The fatty acid ester compound used in the present invention is characterized by having a branched structure in the fatty acid group of the fatty acid ester. When the fatty acid group is branched, the molecule becomes more difficult to crystallize, and thus has an ideal characteristic as a mold release agent for a polycarbonate resin having a low melting point and excellent volatility resistance.

Specifically, the fatty acid ester compound used in the present invention is often a transparent liquid at normal temperature and normal pressure, and particularly when the polycarbonate resin is melt-kneaded.
The liquid can be added with little or no heating. For this reason, problems such as coloring deterioration of the release agent in the present process, which has been a problem in the past, are less likely to occur. In this specification, the normal temperature and the normal pressure are based on 25 ° C. and 1013 hPa.

Further, since the fatty acid ester compound used in the present invention has a low melting point and excellent volatilization resistance, it is possible to greatly reduce the amount of deposits on a mold when molding a polycarbonate resin. Therefore, especially in the molding of optical discs and automobile headlamp lenses that require precise transferability, the number of times of mold cleaning can be reduced, productivity is improved, and the molding defect rate is reduced. Is preferably used.

[0030] The above-mentioned mold adhering matter refers to a substance which accumulates on the mold cavity or on the outer periphery of the stamper or in the gap of the gas vent portion by continuously molding the polycarbonate resin composition. In order to reduce the deposits on the mold, a method of reducing gaseous substances volatilized from the molten resin is effective. As one of the evaluation methods, there is a method of measuring the weight loss temperature in thermogravimetric analysis of each additive. The release agent used in the present invention is a compound having a 20% weight loss temperature of 300 ° C. or more, It has excellent resistance to volatilization, and the amount of deposits on the mold during molding is extremely small.

In the polycarbonate resin composition of the present invention, the above-mentioned fatty acid ester compound and other release agents may be used in combination as long as the object of the present invention is not impaired. Such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, polyorganosiloxanes,
Examples include paraffin wax and beeswax. The higher fatty acid ester is preferably a partial ester or a whole ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial or total esters of monohydric or polyhydric alcohols and saturated fatty acids include monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbitate stearate,
Behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraperargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl Biphenate, sorbitan monostearate,
2-ethylhexyl stearate and the like can be mentioned. The amount of the release agent is preferably 0.001 to 0.5 part by weight based on 100 parts by weight of the aromatic polycarbonate resin composition.

In the polycarbonate resin composition of the present invention, a heat stabilizer can be used in order to highly prevent a decrease in molecular weight and a deterioration in hue during molding. Such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and the like,
Specifically, triphenylphosphite, trisnonylphenylphosphite, 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, monooctyldiphenyl phosphite, bis (2,6-di-ter
t-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, distearylpentaerythritol diphosphite, tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate , Diphenyl monoorthoxenyl phosphate, dibutyl phosphate,
Dioctyl phosphate, diisopropyl phosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, dimethyl benzenephosphonate, diethylbenzenebenzene, dipropylbenzenephosphonate and the like can be mentioned.

Of these, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-te
(rt-butylphenyl) -4,4-diphenylenephosphonite is preferably used. These heat stabilizers are:
Species or a mixture of two or more species may be used. The compounding amount of the heat stabilizer is preferably 0.001 to 0.15 parts by weight, preferably 0.1 to 0.15 parts by weight, based on 100 parts by weight of the polycarbonate resin.
001 to 0.1 part by weight is more preferred.

The polycarbonate resin composition of the present invention may contain an antioxidant generally known for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and 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-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t
tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, tetrakis (4,4'-biphenylenediphosphosphinate) (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2
-[Β- (3-tert-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy] ethyl}-
Examples thereof include 2,4,8,10-tetraoxaspiro (5,5) undecane, and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferable. The amount of these antioxidants is 0.001 to 100 parts by weight of the polycarbonate resin.
0.1 parts by weight is preferred.

The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber compound is, specifically, benzophenone-based 2,4
-Dihydroxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5
-Sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2, 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-
4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2
-Methoxyphenyl) methane, 2-hydroxy-4-n
-Dodecyloxybensophenone, 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-benzotriazol-2-yl) phenol], 2- (2-hydroxy-
3,5-di-tert-butylphenyl) benzotriazole, 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) benzotriazo-
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) and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, among which 2- (2- Hydroxy-5-tert
(Octylphenyl) benzotriazole is preferred.
These ultraviolet absorbers can be used alone or in a mixture of two or more. The amount of the ultraviolet absorber is preferably 0.01 to 1 part by weight based on 100 parts by weight of the polycarbonate resin composition.

A bluing agent can be added to the polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. The bluing agent is effective for eliminating the yellow tint of the resin composition. In particular, in the case of a composition with weather resistance, a certain amount of UV absorber is blended, so there is a reality that the resin product tends to take on a yellow tint due to the `` action and color of the UV absorber ''. In order to impart natural transparency, the compounding of a bluing agent is very effective.

The amount of the bluing agent is preferably from 0.05 to 10% based on the polycarbonate resin composition.
1.5 ppm, more preferably 0.1 to 1.2 ppm.
ppm. If the amount is too large, the bluish tint of the resin product may increase and the luminous transparency may decrease. Typical examples of the blueing agent include Bayre's Macrolex Violet and Triazole Blue-RLS.

The polycarbonate resin composition of the present invention may contain an antistatic agent in an amount that does not impair the object of the present invention. Examples of such antistatic agents include ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, fatty acid ester compounds, carbon, graphite, and metal powder. The compounding amount of the antistatic agent is determined according to the polycarbonate resin composition 1
0.1 to 10 parts by weight with respect to 00 parts by weight is preferable,
0.1 to 5 parts by weight is more preferred.

The polycarbonate resin composition of the present invention may contain a flame retardant in an amount that does not impair the object of the present invention. As the flame retardant, a halogenated bisphenol A polycarbonate-type flame retardant, an organic salt-based flame retardant,
Aromatic phosphate ester flame retardants, halogenated aromatic phosphate ester type flame retardants and the like can be mentioned. Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrabromobisphenol A, a copolymerized polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A, and the like. Specifically, the organic salt-based flame retardant is diphenyl sulfone-
Dipotassium 3,3'-disulfonic acid, potassium diphenylsulfon-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, potassium 2,4,5-trichlorobenzenesulfonate, bis (2,6-dibromo- Potassium 4-cumylphenyl) phosphate, bis (4-
Sodium cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphoric) imide, potassium bis (2,4,6-tribromophenyl) phosphate, bis (2,4-dibromophenyl) Potassium phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, sodium or potassium hexadecyl sulfate, and the like. Specifically, halogenated aromatic phosphate ester type flame retardants include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate and the like. is there. Specifically, the aromatic phosphate ester-based flame retardant includes triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, and tetrakis (2,6-xylyl) hydroquinone diphosphate. , Tetrakis (2,6-xylyl) -4,4'-biphenol diphosphate, tetraphenylresorcinol diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4 '
Biphenol diphosphate, aromatic polyphosphate whose aromatic ring source is resorcinol and phenol and does not contain phenolic OH group, aromatic polyphosphate whose aromatic ring source is resorcinol and phenol and which contains phenolic OH group, and aromatic ring source is Aromatic polyphosphates containing hydroquinone and phenol and not containing phenolic OH groups, similar aromatic polyphosphates containing phenolic OH groups, ("aromatic polyphosphates" shown below are aromatic polyphosphates containing phenolic OH groups Aromatic polyphosphate whose aromatic ring source is bisphenol A and phenol, aromatic polyphosphate whose aromatic ring source is tetrabromobisphenol A and phenol Aromatic ring source is resorcinol and 2,
Aromatic polyphosphate which is 6-xylenol, aromatic polyphosphate whose aromatic ring source is hydroquinone and 2,6-xylenol, aromatic polyphosphate whose aromatic ring source is bisphenol A and 2,6-xylenol, aromatic ring source Are aromatic polyphosphates that are tetrabromobisphenol A and 2,6-xylenol.

The polycarbonate resin composition of the present invention may contain other resins and elastomers 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, and the like.
Polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer Resins such as a polymer (ABS resin), a polymethacrylate resin, a phenol resin, and an epoxy resin are exemplified.

Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / sterene elastomer) which is a core-shell type elastomer. / Butadiene) rubber, MA
S (methyl methacrylate / acrylonitrile / styrene) rubber and the like.

For blending the compounding agent in the polycarbonate resin of the present invention, an arbitrary method is adopted. For example, tumbler, V-type blender, super mixer,
Nauta mixer, Banbury mixer, kneading roll,
A method of mixing with an extruder or the like is appropriately used. The polycarbonate resin composition powder thus obtained is directly or pelletized by a melt extruder, and then a molded product or a molded product is obtained by a generally known method such as an injection molding method, an extrusion molding method, a compression molding method, and a sheet extrusion method. Can be a sheet.

The blending of the compounding agents may be carried out in one stage, or may be carried out in two or more stages. As a method carried out in one step, for example, in the case of the interfacial polycondensation method, in a drying step which is the final step of resin powder production, each additive is put into a drier during drying, and blended simultaneously with drying. There is a way to do it. In addition, in the case of the melt polymerization method, there is a method of adding during the extruder in the final stage of the melt polymerization. As a method performed in two stages, for example, after blending a part of the polycarbonate resin powder to be compounded and the compounding agent, that is, the compounding agent is diluted with the polycarbonate resin powder to obtain a master batch of the compounding agent Thereafter, a method of performing a final blending using this is used.

[0046]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, parts in Examples are parts by weight and% is% by weight. The evaluation was based on the following method.

(1) Observation of the state of the release agent at normal temperature and normal pressure (evaluation of handleability of the release agent) The state of each release agent in a state of being left closed for one day at a temperature of 25 ° C. and a pressure of 1013 hPa in a closed state. Was observed.

(2) Thermogravimetric Analysis of Release Agent (Evaluation of Volatility Resistance of Release Agent) Using a 951 TGA device manufactured by DuPont, a 20% weight loss was achieved in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. The temperature was measured.

(3) Measurement of Release Load (Evaluation of Release Property) Using a Sumitomo SS75 injection molding machine, a cup-shaped molded piece was molded, and the protrusion load at the time of release was measured with a memoryizer. The smaller this value is, the more excellent the releasability is.

(4) Mold Deposits Measurement Test (Evaluation of Die Deposits Generated) Injection molding machine, DISK3 M III manufactured by Sumitomo Heavy Industries, Ltd.
Attach a mold for exclusive use of CD to the mold, attach a stamper for pitted nickel CD to this mold, put the molding material into the hopper of the molding machine by automatic conveyance, cylinder temperature 340 ° C, mold temperature 65 ° C, injection speed 100mm / se
c, Under the conditions of a holding pressure of 3.9 MPa (40 kgf / cm ² ), 10,000 optical disk substrates having a diameter of 120 mm and a thickness of 1.2 mm were continuously formed. After molding 10,000 sheets continuously,
The stamper adhering matter after the molding was extracted and dried with chloroform, and the amount of the adhering matter was measured. The result of measuring the amount of deposits was evaluated according to the following criteria. Evaluation criteria for the amount of attached matter A: Amount of attached matter after forming 10,000 sheets 7 mg or less B: Amount of attached matter after forming 10,000 sheets exceeds 7 mg and 15 mg or less C: Amount of attached matter after forming 10,000 sheets exceeds 15 mg D: 10,000 pieces The deposit was transferred to the substrate before molding.

(5) Measurement Test of Heat Resistance of Polycarbonate Resin Composition (Evaluation of Heat Resistance) Using an injection molding machine, pellets of the polycarbonate resin composition were molded at a molding temperature of 330.
A molded plate having a thickness of 2.0 mm was prepared at a cycle of 1 ° C. for 1 minute. This molded plate is placed in a dryer at a temperature of 150 ° C. for 500
Stored for hours. The YI value of the molded plate before storage and the YI value of the molded plate after storage were respectively measured by a color difference meter Z-10 manufactured by Nippon Denshoku Co., Ltd.
The difference was measured with a 01DP type, and the difference (ΔYI value) was calculated. The smaller the ΔYI value, the smaller the change in hue of the molded plate, indicating that the heat resistance is excellent.

[Examples 1 and 2, Comparative Examples 1 to 6] 100 parts of a polycarbonate resin having a molecular weight of 15500, which was produced from bisphenol A and phosgene by an interfacial polycondensation method,
0.003 parts of tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite was blended as a heat stabilizer, and the release agent shown in Table 1 was blended in the amount shown in Table 1. . Then, after mixing in a blender,
The mixture was melt-kneaded using a vent-type single screw extruder to obtain pellets. Table 1 shows the evaluation results of the obtained sample pellets. The release agents represented by the symbols in the table are as follows.

A-1: Branched fatty acid ester compound ΔI
CI Chemicals & Polymers L
Atmer 801 manufactured by imitated; in the above formula (I)
Where l, m and n are integers of 1, 0 and 1, respectively, and
R structure¹, R^Two, R ^ThreeAre hydrogen atoms or
Or a linear or branched aliphatic carbon having 10 to 20 carbon atoms
A boric acid residue, R¹, R^Two, R^ThreeAt least one of the branches
Aliphatic carboxylic acid residue. Also, its composition ratio
Is glycerin triester 9%, glycerin diester
35%, glycerin monoester 52% (other
A-2; glycerin monostearate A-3; stearyl stearate A-4; pentaerythritol tetrastearate

Reference Example 1 Pellets were obtained in the same manner as in Example 1 except that no release agent was added to the polycarbonate resin used in Example 1.
The obtained pellets were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

[0055]

[Table 1]

[0056]

The polycarbonate resin composition of the present invention is excellent in handleability during production, mold release during molding, and heat resistance by using a release agent having a specific chemical structure. When manufacturing resin,
A polymer with less deterioration in quality can be obtained. In addition, since the polycarbonate resin composition of the present invention has a small amount of deposits on the mold during continuous molding, it is possible to reduce the number of times of cleaning the mold particularly when molding an optical disk substrate or molding an automobile headlamp lens. It is extremely useful not only in terms of quality but also in terms of production efficiency.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CG001 CG011 CG031 EH046 EH056 EH126 FD050 FD060 FD070 FD100 FD130 GN00 GP00 GP01

Claims (3)

[Claims] 1. A polycarbonate resin (A component)
And (B) a fatty acid ester compound (component (b)) represented by the following general formula (I), wherein component b is less than 0.1 part by weight and 0.001 part by weight or more based on 100 parts by weight of component a. A polycarbonate resin composition comprising: Embedded image (In the formula, l, m, and n are each independently an integer of 0 to 5, and R ¹ , R ² , and R ³ are each independently a hydrogen atom, a linear or branched chain having 1 to 25 carbon atoms. An aliphatic carboxylic acid residue, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, wherein at least one of R ¹ , R ² and R ³ is a branched aliphatic carboxylic acid Residue.) 2. When the fatty acid ester compound of the component b is a mixture and the composition ratio is 100% by weight of the total weight of triester, diester and monoester, 0 to 20% by weight of triester, 15% of diester 15 ~ 5
The polycarbonate resin composition according to claim 1, which is 5% by weight and 30 to 70% by weight of a monoester. 3. The fatty acid ester compound has a 20% weight loss temperature of 300 ° C. or higher in thermogravimetric analysis.
Or the polycarbonate resin composition according to claim 2.