JP2001192543A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide aromatic polycarbonate resin compositions having excellent molding heat resistance while retaining releasability. SOLUTION: The aromatic polycarbonate resin compositions comprise (A) 100 pts.wt. aromatic polycarbonate resin having a viscosity average molecular weight of 10, 000-50, 000 and (B) 0.005-1.0 pt.wt. internal release agent which has >=90 wt.% full ester to be obtained from a 3-32C monohydric or polyhydric aliphatic alcohol and a 3-32C aliphatic carboxylic acid and has an acid value of 0.6-1.6, an iodine value of 0.1-1.3, and a metallic element Sn content of 5-300 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin composition having excellent mold heat resistance while maintaining mold release properties.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are relatively high in heat resistance among polymer materials. As the demand for higher functionality and higher performance of materials has increased, various types of additives have been used.In general, when additives other than stabilizers are used, the heat resistance of the resin is reduced. It tends to decrease and becomes more remarkable as the amount of addition increases.

Many proposals have been made to improve the heat resistance of resins. As a method for improving the heat resistance of the aromatic polycarbonate resin, a method of adding a stabilizer is effective, but other than that, a method of limiting the amount of the additive itself has also been proposed. For example, as a method for suppressing a decrease in molding heat resistance due to a release agent, JP-A-5-179 describes
Although there is a method disclosed in Japanese Patent Publication No. 120, it is not applicable when it is necessary to exhibit a certain or more release performance because the addition amount of an ester compound as a release agent is limited to 0.1% or less. There is a problem.

Japanese Patent Application Laid-Open No. 2-69556 proposes the use of an ester having as small an OH group as possible and an acid value as small as possible, which is also useful for improving molding heat resistance. However, the proposed ester having an acid value of less than 0.50 has a problem that the production efficiency is low and the cost is high. Moreover,
There was no clear knowledge on the relationship between the amount of metal elements such as Sn contained as impurities in the release agent and the molding heat resistance.

[0005]

A number of additives and aromatic polycarbonate resin compositions using the same have been proposed. With the diversification of polycarbonate resin products, new additives need to be developed in the future. At the same time, regarding existing additives, especially internal mold release agents, regarding resin compositions using them, it is strongly required to improve mold heat resistance and other properties while maintaining mold release properties during molding. This is an important issue.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the object, surprisingly, the amount of a specific metal element and iodine value contained in a trace amount in the release agent have a surprising effect on molding heat resistance. It has been found that it contributes, and led to the present invention.

That is, the present invention relates to (A) 100 parts by weight of an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 50,000 and (B) a monovalent or polyvalent aliphatic having 3 to 32 carbon atoms. Alcohol and carbon number 3 ~
At least 90% by weight of at least one full ester obtained from the aliphatic carboxylic acid having an acid value of 0.6 to 1.
6, an internal mold release agent having an iodine value of 0.1 to 1.3 and a metal element Sn content of 5 to 300 ppm 0.005 to 1.
It is an aromatic polycarbonate resin composition comprising 0 parts by weight.

The monohydric or polyhydric aliphatic alcohol having 3 to 32 carbon atoms may be linear or branched, and may be iso-propanol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol,
n-undecyl alcohol, lauryl alcohol, n-
Tridecyl alcohol, tetradecyl alcohol, n-
Pentadecyl alcohol, palmityl alcohol, margaryl alcohol, stearyl alcohol, n-nonadecyl alcohol, eicosyl alcohol, ceryl alcohol, myristyl alcohol, methylpentyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, 3.5 -Dimethyl-1-hexanol,
2,2,4-trimethyl-1-pentanol, pentaerythritol, dipentaerythritol, glycerin,
Examples include diglycerin, diethylene glycol, propylene glycol and the like. Preferably, stearyl alcohol, palmityl alcohol, nonyl alcohol, glycerin and pentaerythritol are mentioned.

The aliphatic carboxylic acid having 3 to 32 carbon atoms is a monovalent carboxylic acid and includes n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid and n-hexanoic acid. -Undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, n-pentadecanoic acid, palmitic acid, 1
-Heptadecanoic acid, stearic acid, n-nonadecanoic acid,
Eicosanoic acid, 1-hexacosanoic acid, behenic acid and the like, preferably stearic acid, n-nonadecanoic acid,
Lauric acid, palmitic acid, and behenic acid, more preferably stearic acid.

[0010] The full ester in the present invention is, specifically, at least one kind obtained by combining the above-mentioned alcohol and carboxylic acid. Among them, preferred are stearyl stearate, palmityl palmitate, triglyceride stearate, triglyceride behenate, pentaerythritol tetrastearate, pentaerythritol tetranonanoate, propylene glycol distearate, dipentaerythritol hexastearate and the like. Are listed.

Among these esters, triglyceride stearate, pentaerythritol tetrastearate, and a mixture of triglyceride stearate and stearyl stearate are preferably used. The mixture of triglyceride stearate and stearyl stearate is preferably
The weight ratio is preferably in the range of 60 to 80 for the former and 20 to 40 for the latter. More preferred among these esters is pentaerythritol tetrastearate.

The acid value in the present invention can be measured by a known method, and the value is from 0.6 to 1.6, preferably from 0.6 to 1.1. If the acid value exceeds 1.6, the molding heat resistance of the resin when added to the polycarbonate resin is reduced. If the acid value is smaller than 0.6, the molding heat resistance is improved to some extent. The production of a mold is very laborious and impractical. The iodine value in the present invention can be measured by a known method. Its value is between 0.1 and 1.3,
Preferably it is 0.1-1.0. If the iodine value is high, there is a problem that the molding heat resistance is reduced, and it is extremely troublesome and impractical to produce a release agent having an iodine value smaller than 0.1.

The metal element Sn in the present invention is present in the release agent due to contamination during the production of the release agent of the present invention. It originates from impurities in the production raw materials, production catalysts, vessels, equipment and the like. The content can be determined by measuring the release agent by a known fluorescent X-ray method.

In the present invention, the content of the metal element Sn is
5 to 300 ppm, preferably 30 to 250 pp
m. When the content is increased, a problem occurs that the molding heat resistance of the polycarbonate resin to which the release agent is added is reduced,
If the content is small, it is advantageous for heat resistance during molding, but the production efficiency of the release agent itself is very poor, so that it is costly and impractical.

The internal release agent in the present invention is a compound that is incorporated into a resin composition in order to improve the releasability of a resin molded product from a mold during melt molding. Such an internal release agent contains 90% by weight or more of a full ester, preferably 95% or more, and more preferably 98% or more.

In the present invention, the amount of the internal release agent is 0.00.0 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.
0.05 to 1.0 part by weight, preferably 0.01 to 1.0 parts by weight.
0.6 parts by weight. If the amount is less than 0.005 parts by weight, there is a problem that the releasability of molding the aromatic polycarbonate resin composition becomes insufficient. In addition, problems such as a decrease in molding heat resistance occur.

The aromatic polycarbonate resin in the present invention has a viscosity average molecular weight of 10,000 to 50,
000, preferably 14,000 to 35,000. 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 relatively good fluidity during extrusion and molding.

The viscosity average molecular weight referred to in the present invention is such that 0.7 g of aromatic polycarbonate resin is added to 100 ml of methylene chloride.
Refers to M obtained by inserting the specific viscosity (η _SP ) measured using a solution in which is dissolved 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 aromatic polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polymerization method (solution method) or a melting method. Representative examples of the dihydric phenol used herein include 2,2-bis (4-hydroxyphenyl)
Propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4 -Hydroxyphenyl) ether, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, of which bisphenol A is particularly preferred.

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

In producing the aromatic polycarbonate resin by reacting the dihydric phenol with the carbonate precursor by an interfacial polymerization method or a melting method, the dihydric phenol may be used alone or in combination of two or more types. If necessary, a catalyst, a terminal terminator, an antioxidant for dihydric phenol, and the like may be used. Further, the aromatic polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Also, a mixture of two or more aromatic polycarbonate resins may be used.

The reaction by the interfacial polymerization method is usually a reaction between dihydric phenol 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. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

The reaction by the melting method is usually a transesterification reaction between dihydric phenol and diphenyl carbonate. The dihydric phenol and diphenyl carbonate are mixed in the presence of an inert gas, and the reaction is carried out under reduced pressure, usually at 120 to 350 ° C. Let it. The degree of decompression is changed step by step,
The phenols generated at a pressure of 33 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.

In the polymerization reaction, a monofunctional phenol can be used as a terminal stopper. In particular, in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminating agent for controlling the molecular weight, and the obtained aromatic polycarbonate resin is converted to monofunctional phenols at the ends. Since it is blocked by a base group, it has better thermal stability than that which is not. The monofunctional phenol may be any one used as a terminal terminator for polycarbonate, and is generally a phenol or a lower alkyl-substituted phenol, and is a monofunctional phenol represented by the following general formula (1). Can be shown.

[0025]

Embedded image

[Wherein R is a hydrogen atom or a carbon number of 1 to 9]
And m represents an integer of 1 to 5, preferably 1 to 3. Specific examples of the monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

In the aromatic 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. Examples of such a heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and specifically, tetrakis (2,4-di-tert)
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl) Phenyl)-
3,3′-biphenylenediphosphonite, bis (2,4
-Di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, tris (di-iso-propylphenyl) phosphite , Tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl)
Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, triphenyl phosphite,
Tris (nonylphenyl) 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, 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 diphosphate, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzene phosphonate, diethyl benzene phosphonate, diethyl benzene phosphonate, benzene phosphonate Dipropyl and the like. Among them, phosphorous acid, trimethyl phosphate, dimethyl benzenephosphonate, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4, 4'-biphenylenediphosphonite, tris (2,4-di-tert-butylphenyl)
Phosphite is preferably used. These may be used alone or in combination of two or more. The amount of the heat stabilizer is preferably 0.001 to 0.15 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.
0.001 to 0.10 parts by weight is more preferable,
1 to 0.05 part by weight is more preferred.

The aromatic polycarbonate resin composition of the present invention may contain a generally known antioxidant for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3
-Laurylthiopropionate), 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-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Screw (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, tetrakis (2,4-di-tert) 4,4′-biphenylenediphosphosphinate
-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 compounding amount of these antioxidants is preferably 0.001 to 0.05 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.

The aromatic polycarbonate resin composition of the present invention may contain an ultraviolet absorber. UV absorber compounds, specifically, in the benzophenone system,
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-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-
4-n-dodecyloxybensophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like. Among benzotriazoles, 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- (2H-benzotriazole-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) 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 and triazine, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy]-
Phenol, 2- (4,6-bis (2.4-dimethylphenyl) -1,3,5-triazin-2-yl) -5
[(Octyl) oxy] -phenol and the like.
Preferably, 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- (2H
-Benzotriazol-2-yl) phenol] 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-[(hexyl) oxy] -phenol, 2
-(4,6-bis (2.4-dimethylphenyl) -1,
3,5-triazin-2-yl) -5-[(octyl)
[Oxy] -phenol.

The aromatic polycarbonate resin composition of the present invention may contain an antistatic agent. Examples of such an antistatic agent include polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, monoglyceride maleic anhydride, diglyceride maleic anhydride, carbon, graphite, and metal powder. No. The amount of the antistatic agent is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin composition.

A bluing agent can be added to the aromatic 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 imparted with weather resistance, a certain amount of an ultraviolet 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 ultraviolet absorber '', and especially sheet products and The blending of a bluing agent is very effective for imparting natural transparency to lens products.

The blending amount of the bluing agent in the present invention is 0.05 to 1.5 ppm of the whole resin composition,
Preferably, it is 0.1 to 1.2 ppm. If the amount is too large, the bluish color of the resin product becomes strong and the luminous transparency decreases.

As the bluing agent, a known bluing agent can be used. Representative examples include Bayer's Macrolex Violet and Terrasol Blue.
RLS, etc., are not particularly limited.

The aromatic polycarbonate resin composition of the present invention may contain a flame retardant in an amount that does not impair the purpose of the present 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, and a halogenated aromatic phosphate ester flame retardant. The above can be blended. Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrabromobisphenol A, tetrabromobisphenol A and bisphenol A.
And a polycarbonate-type flame retardant. Specifically, the organic salt-based flame retardant is diphenylsulfone-3,3'-
Dipotassium disulfonate, potassium diphenylsulfon-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, potassium 2,4,5-trichlorobenzenesulfonate, bis (2,6-dibromo-4-cumylphenyl) phosphorus Potassium, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, potassium bis (2,4,6-tribromophenyl) phosphate, bis ( Potassium 2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, sodium hexadecyl sulfate or Potassium or the like. 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 and the like. Specifically, aromatic phosphate ester-based difficulties include 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, tetraphenyl resorcin diphosphate, tetraphenyl hydroquinone diphosphate, tetraphenyl-4,4'-biphenol diphosphate, aromatic polysaccharide having resorcin and phenol as aromatic sources and containing no phenolic OH group Phosphates, aromatic polyphosphates whose aromatic ring sources are resorcinol and phenol and contain phenolic OH groups, aromatic polyphosphates whose aromatic ring sources are hydroquinone and phenol and do not contain phenolic OH groups,
Similar aromatic polyphosphates containing phenolic OH groups, ("Aromatic polyphosphate" shown below means both aromatic polyphosphates containing phenolic OH groups and aromatic polyphosphates not containing A) aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol, aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and phenol, and aromatic polyphosphates whose aromatic ring sources are resorcinol and 2,6-xylenol An aromatic polyphosphate wherein the aromatic ring source is hydroquinone and 2,6-xylenol, and the aromatic ring source is bisphenol A and 2,2.
Aromatic polyphosphate which is 6-xylenol, aromatic polyphosphate whose aromatic ring source is tetrabromobisphenol A and 2,6-xylenol, and the like.

The aromatic 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 elastomers include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, 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 aromatic polycarbonate resin with the phosphorus-based stabilizer composition, the internal release agent, and other compounding additives in the aromatic polycarbonate resin composition of the present invention, any method is employed. For example, tumblers,
A method of mixing with 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 thus obtained blend of the aromatic polycarbonate resin composition powder and pellets is pelletized as it is or after being once pelletized by a melt extruder, and is usually obtained by injection molding, extrusion molding, compression molding, sheet extrusion, or the like. It can be formed into a molded article or sheet by the known method.

The blending of the phosphorus-based stabilizer composition, the internal release agent, and other additives may be carried out in one stage, or may be carried out in two or more stages. In a method carried out in two stages, for example, after blending a part of the aromatic polycarbonate resin powder or pellets to be blended with the blending additive, that is, diluting the blending additive with the aromatic polycarbonate resin powder There is a method in which a masterbatch of the additives is used to make a final blend using the masterbatch.

For compounding the internal mold release agent and other additives, it is also possible to employ a method in which the additives are directly added to the extruder, injected, or injected after heating and melting. In the interfacial polymerization method, a method in which a stabilizer composition, an internal mold release agent, and the like are added and dissolved in an organic solvent solution of the aromatic polycarbonate resin after the polymerization is employed.

[0041]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The evaluation was performed by the following method.

(1) Acid value of release agent A sample was dissolved in a benzene-ethanol solution, and phenolphthalein was used as an indicator, and KOH (0.1 mol / mol) was used.
l) Perform a neutralization titration with an ethanol solution. The acid value is determined by the following equation. Acid value (KOH mg / g) = A × f × N × 56.11 ° SA: Number of ml of KOH solution required for neutralization of sample f: KOH titer N: Normality of KOH S: Sample weight ( g)

(2) Iodine value of release agent 3 to 5 g of a sample was precisely weighed in a stoppered Erlenmeyer flask, 10 ml of carbon tetrachloride was added and dissolved, and 25 ml of Wies solution was added.
Seal tightly and shake gently. Leave in the dark for 30 minutes. Then, 20 ml of potassium iodide aqueous solution and 100 m of pure water
and shaken, and titrated with a 0.05 mol / l sodium thiosulfate solution. This is used as the main test. Perform titration in the same manner except that no sample is added, and use this as the blank test. Then, the iodine value is calculated by the following formula: iodine value = (AB) × f × 1.269 ° S [where A is the used amount (ml) of a 0.05 mol / l sodium thiosulfate solution in the blank test, B Is 0.05 in this test
mol / l of sodium thiosulfate solution used (m
l) and f were determined based on the titer of a 0.05 mol / l sodium thiosulfate solution, and S was determined based on the sampled amount (g).

(3) Measurement of Sn Content of Release Agent A sample was formed into a disk having a diameter of 40 mm and a thickness of 4 mm by pressure compression molding, and a fluorescent X-ray was measured. In order to determine the Sn content in the sample from the measurement results, Sn
A calibration curve prepared from a sample with a known content was used.

(4) Heat resistance during molding A pet was molded using an injection molding machine at a molding temperature of 350 ° C. for 1 minute and “a flat plate for measuring hue before staying” (70 mm × 50 mm).
mm × 2 mm). Further, after the resin was retained in the cylinder for 10 minutes, a "plate for measuring hue after retention" was obtained. The hue of the flat plate before and after the stay was measured by a color difference meter, and the color difference ΔE was determined by the following equation. Values shown in the table (△
It shows that molding heat resistance is so excellent that E) is small.

[0046]

(Equation 1) Hue before staying: L, a, b Hue after staying: L ', a', b '

(5) Release Load A cup-shaped molded piece was molded using a Sumitomo SS75 injection molding machine, and the protrusion load at the time of release was measured with a memoryizer.

The internal release agents and the like used in Examples and Comparative Examples are as follows. 1. Fatty acid ester 1 stearic acid monoglyceride (purity 97.0% by weight, S
n: 230 ppm, acid value: 0.8, iodine value: 1.4) 2. Fatty acid ester 2 A mixture of stearic acid triglyceride and stearyl stearate (the mixing ratio of the former is about 70% by weight and the purity is 9)
7% by weight, Sn: 400 ppm, acid value: 2.1, iodine value: 0.6) 3. Fatty acid ester 3 A mixture of triglyceride stearate and stearyl stearate (the mixing ratio of the former is about 70% by weight, the purity is 9
7% by weight, Sn: 220 ppm, acid value: 1.5, iodine value: 0.6) 4. Fatty acid ester 4 pentaerythritol tetrastearate (purity: 99% by weight, Sn: 700 ppm, acid value: 1.5, iodine) Price:
0.7) 5. Fatty acid ester 5 Pentaerythritol tetrastearate (purity 99% by weight, Sn: 330 ppm, acid value: 0.3, iodine value:
0.8) 6. Fatty acid ester 6 pentaerythritol tetrastearate (purity: 99% by weight, Sn: 150 ppm, acid value: 0.7, iodine value:
0.2) 7. Blueing agent 1- (4-methylphenylamino) -4-hydroxy-
9,10-anthraquinone 8. Stabilizer 1 Tris (nonylphenyl) phosphite 9. Stabilizer 2 71: 1 consisting of B-1, B-2 and B-3 shown below
5:14 mixture B-1: tetrakis (2,4-di-t
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3'-biphenylenediphosphonite and
Tetrakis (2,4-di-t-butylphenyl) -3,
100: 50: 1 of 3'-biphenylenediphosphonite
0 (weight ratio) mixture, B-2: bis (2,4-di-te)
5 of rt-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite:
3 (weight ratio) mixture, B-3: Tris (2,4-di-t)
ert-butylphenyl) phosphite (C in stabilizer
1 content 20 ppm) 10. Stabilizer 3 bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 11. Stabilizer 4 tris (2,4-di-tert-butylphenyl) Phosphite (Cl content of stabilizer 20ppm)

Examples 1 to 7 and Comparative Examples 1 to 5 Powdery and granular fragrances having a viscosity average molecular weight shown in Table 1 and obtained from bisphenol A, p-tert-butylphenol (terminal terminator) and phosgene by an interfacial polymerization method. An internal mold release agent and the like were added to and mixed with the aromatic polycarbonate resin according to the composition shown in Table 1, extruded and pelletized at 280 ° C., and the above-mentioned molding evaluation was carried out.

[0050]

[Table 1]

[0051]

In a system using an aliphatic full ester compound as an internal release agent, the amount of a specific metal element contained in the release agent, and the acid value and iodine value of the release agent are limited. Accordingly, an object of the present invention is to provide an aromatic polycarbonate resin composition having excellent molding heat resistance while maintaining the mold releasability of the aromatic polycarbonate resin composition.

Claims (2)

[Claims] (A) a viscosity average molecular weight of 10,000 to
100 parts by weight of 50,000 aromatic polycarbonate resin and (B) at least one kind obtained from a monohydric or polyhydric aliphatic alcohol having 3 to 32 carbon atoms and an aliphatic carboxylic acid having 3 to 32 carbon atoms. Is 90% by weight or more, the acid value is 0.6 to 1.6, the iodine value is 0.1 to 1.3, and the content of the metal element Sn is 5 to 300 p.
An aromatic polycarbonate resin composition comprising 0.005 to 1.0 parts by weight of an internal release agent having a pm. 2. The aromatic polycarbonate resin composition according to claim 1, wherein the full ester is pentaerythritol tetrastearate.