JP2001192544A - Aromatic polycarbonate resin composition - Google Patents

Abstract

(57) [Summary] (Modifications) [Problem] An aromatic polycarbonate resin composition having excellent ultraviolet absorption performance and transparency, as well as excellent mold release properties and molding heat resistance. (A) A viscosity average molecular weight of 10,000 to
100 parts by weight of 50,000 aromatic polycarbonate resin, (B) phosphorus-based stabilizer composition 0.0001 to 0.15
(C) 90% by weight or more of one or more full esters 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. 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.
In an absorption spectrum at a chloroform solution concentration of 10 mg / L, an absorption maximum was observed at a wavelength of 320 to 400 nm using 0.005 to 1.0 parts by weight of an internal mold release agent having a pm and a (D) 10 mm layer thickness quartz cell. An aromatic polycarbonate resin composition comprising 0.005 to 1.0 parts by weight of at least one ultraviolet absorber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic polycarbonate resin composition having excellent ultraviolet absorbing performance and transparency, as well as excellent mold release properties and molding heat resistance.

[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, for each existing additive, especially for the internal release agent and ultraviolet absorber, regarding the resin composition using it,
It is strongly required to improve the molding heat resistance and other performances while maintaining the releasability during molding, and this is an important issue.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the object, surprisingly, surprisingly, a specific biphenylenephosphonite and a specific phosphite are combined as a phosphorus-based stabilizer in a specific amount. That is, limiting the concentration of chlorine atoms or chloride ions contained in the phosphorus-based stabilizer composition, and limiting the amount of a specific metal element or iodine value contained in a trace amount in the release agent is an internal release. It was discovered that it contributed to the improvement of the molding heat resistance of the polycarbonate resin to which the mold agent and the ultraviolet absorber were added.
In order to achieve a high degree of ultraviolet absorption performance and a high degree of transparency, we discovered that the contribution to the molding heat resistance of polycarbonate resin using two types of ultraviolet absorption was more remarkable,
The present invention has been reached.

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 compound represented by the following general formula (1): Component), a compound represented by the following general formula (2) (component B-2), and a compound represented by the following general formula (3) (component B-3), when the total thereof is 100% by weight. , B-1 component is 40 to 80% by weight, B-2 component is 0 to 25% by weight, and B-3 component is 5 to 50% by weight.
And the concentration of chlorine atoms and chlorine ions is 1 to 1
Phosphorus-based stabilizer composition having a concentration of 1000 ppm 0.0001
(C) 90% or more of a monohydric or polyhydric aliphatic alcohol having 3 to 32 carbon atoms and one or more full esters obtained from an aliphatic carboxylic acid having 3 to 32 carbon atoms. % 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 5.
Using 0.005 to 1.0 parts by weight of an internal release agent having a concentration of 300 ppm and (D) a quartz cell having a layer thickness of 10 mm, the absorption maximum was observed at a wavelength of 320 to 400 nm in an absorption spectrum at a chloroform solution concentration of 10 mg / liter. An aromatic polycarbonate resin composition comprising 0.005 to 1.0 parts by weight of at least one ultraviolet absorber.

[0008]

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[In the formula, Ar1 and Ar2 are aromatic groups which may have an alkyl substituent, and may be the same or different. Ar3 is a dialkyl-substituted aromatic group, which may be the same or different. ]

[0010] The phosphorus-based stabilizer composition of the present invention comprises the B-1, B-2 and B-3 components, and when the total thereof is 100% by weight, the B-1 component is 40 to 80% by weight. 0 to 25% by weight of B-2 component and 5% of B-3 component
５０50% by weight. Preferably, the B-1 component is 40 to
80% by weight, 5 to 25% by weight of B-2 component and B-3
The component is 5 to 50% by weight, more preferably B-1
55 to 80% by weight of component, 5 to 25% by weight of component B-2
And the component B-3 is 5 to 45% by weight.

Specific examples of the component B-1 of the present invention include:
Tetrakis (2,4-di-iso-propylphenyl)
-4,4'-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t
tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl) Butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,
4'-biphenylenediphosphonite, tetrakis (2,
6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert)
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
3,3'-biphenylenediphosphonite and the like,
Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and tetrakis (2,4
-Di-tert-butylphenyl) -biphenylenediphosphonite is more preferred. This 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 (B-1-1)
Component), tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite (B
-1-2 component) and tetrakis (2,4-di-te)
More preferred is a mixture of three of rt-butylphenyl) -3,3′-biphenylenediphosphonite (B-1-3 component). The mixing ratio of this mixture is such that the B-1-1 component, the B-1-2 component, and the B-1-3 component are 1 by weight.
00:37 to 64: 4 to 14 is preferable, and 10
The range of 0:40 to 60: 5 to 11 is more preferable.

Specific examples of the component B-2 of the present invention include:
Bis (2,4-di-iso-propylphenyl) -4-
Phenyl-phenylphosphonite, bis (2,4-di-
n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl)- 3-phenyl-phenylphosphonite bis (2,6-di-iso
-Propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3
-Phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite And bis (di-tert-butylphenyl) -phenyl-phenylphosphonite.
4-Di-tert-butylphenyl) -phenyl-phenylphosphonite is more preferred. This screw (2,4-
Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl)-
4-phenyl-phenylphosphonite (B-2-1 component) and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite (B-2
-2 components) are more preferred. The mixture ratio of this mixture is preferably in the range of 5: 1 to 4 by weight ratio of the B-2-1 component and the B-2-2 component, and more preferably in the range of 5: 2 to 3.

Specific examples of the component B-3 of the present invention include:
Tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-
Propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-t
tert-butylphenyl) phosphite, tris (2,
6-di-tert-butylphenyl) phosphite and the like, preferably tris (dialkyl-substituted phenyl) phosphite, more preferably tris (di-tert-butylphenyl) phosphite, and tris (2,4-di- (tert-Butylphenyl) phosphite is particularly preferred. The compound of the component B-3 may be a single compound or a mixture of two or more compounds.

The amount of the phosphorus-based stabilizer composition of the present invention is 0.0 to 100 parts by weight of the aromatic polycarbonate resin.
001 to 0.15 parts by weight, and 0.002 to
The range of 0.15 parts by weight is more preferable, and the range of 0.02 to 0.1 is preferred.
A range of 1 part by weight is most preferred.

The "chlorine atom and chlorine ion contained in the phosphorus-based stabilizer composition" in the present invention are derived from the chlorine compound contained in the phosphorus-based stabilizer composition of the present invention. The chlorine compound is, for example, one generated in the stabilizer during the production process or existing from the raw material stage, and cannot be completely removed at the time of purification.
These chlorine compounds are, specifically, chlorine-based solvents, chlorine-based catalysts, unreacted chlorine, by-produced hydrogen halides, by-product hydrogen halide ammonium salts and amines used during production (reaction, purification, etc.). Salts and the like can be mentioned.

As a method for reducing the amount of chlorine compounds contained in the phosphorus-based stabilizer composition, there is a method for enhancing purification in the production of the stabilizer. For example, in the case of purification by washing using a solvent, it is possible to increase the number of washing solvents, increase the number of washings, or use a solvent capable of selectively dissolving a chlorine compound. In the case of purification by distillation or sublimation, there is a method of increasing the number of distillation stages by lengthening the rectification column and increasing the separation ability.

In order to reduce the amount of chlorine compounds contained in the phosphorus-based stabilizer composition, it is also effective to reduce the amount of chlorine compounds immediately after completion of the synthesis reaction in the production and before purification. For example, reducing the amount of chlorine-based catalyst used, using a catalyst that does not contain chlorine, reducing the amount of chlorine-based solvent used as a reaction solvent, not using a chlorine-based solvent, and completing the reaction more completely And the like. In order to complete the reaction more completely, extend the reaction time, increase the reaction temperature, use a more active catalyst, or increase the `` molar ratio of phenolic compound to chlorine compound '' in charging the raw materials. Alternatively, when there is a dehydrochlorination reaction in the production process, a method of increasing the efficiency of trapping hydrogen chloride can be used.

When the phosphorus-based stabilizer composition contains a "reaction product of hydrogen chloride and a hydrogen chloride scavenger", in order to reduce this, in addition to the above-mentioned method, the purification step The use of a hydrogen chloride scavenger that can be easily removed as a "reaction product of hydrogen chloride and a hydrogen chloride scavenger" can be mentioned.

In the production of the phosphorus-based stabilizer, a chlorine-based catalyst is used as a catalyst. If the chlorine-based catalyst and the chlorine-based compound derived therefrom remain in the stabilizer, a method for reducing them is as follows. In addition to the methods described above, there may be mentioned a method of selecting a catalyst which can be easily removed in the purification step as a chlorine-based catalyst.

When a chlorine-based solvent is used as a solvent in the production of the phosphorus-based stabilizer, the chlorine-based solvent in the stabilizer can be reduced by a non-chlorine-based solvent in the purification step in addition to the method described above. And a method of extending the drying time.

As a method for reducing the amount of chlorine compounds contained in the phosphorus-based stabilizer, it is preferable to carry out the above-mentioned method without sacrificing the production efficiency and yield of the stabilizer. However, in order to achieve the object of the present invention,
The methods described so far may be implemented at the expense of production efficiency and yield of the stabilizer.

The “chlorine atom and chlorine ion concentration” in the present invention can be measured by any method. Examples of the method include a chemical analysis method, a fluorescent X-ray method, a combustion chlor method, a head space gas chromatography method, and a purge and trap gas chromatography method. Among them, particularly preferred is a fluorescent X-ray method, in which chlorine atoms and chlorine ions can be measured simultaneously.

The concentration of chlorine atoms and chlorine ions is 1
１11000 ppm, preferably 1-8000 p
pm, more preferably 1 to 3000 ppm.

It is industrially difficult to completely remove chlorine atoms and chlorine ions contained in the component B-1.
From an economic viewpoint, the concentration is from 1 to 13700 ppm, preferably from 1 to 10000 ppm, and more preferably from 1 to 5500 ppm.

It is industrially difficult to completely remove chlorine atoms and chlorine ions contained in the component B-2,
From an economic point of view, the concentration is 1 to 20000 ppm, preferably 1 to 14500 ppm, and more preferably 1 to 5500 ppm.

It is industrially difficult to completely remove chlorine atoms and chlorine ions contained in the component B-3,
From an economic viewpoint, the concentration is 0.1 to 50 ppm, preferably 0.1 to 40 ppm, and more preferably 10 to 40 ppm.

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.

The full ester in the present invention is specifically one or more 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.

The content of the metal element Sn in the present invention 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.

The compounding amount of the internal release agent in the present invention is 0.0 to 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 ultraviolet absorbent according to the present invention has a layer thickness of 10
Using a mm quartz cell, chloroform solution concentration 10mg
/ Liter in the absorption spectrum
One or more ultraviolet absorbers having an absorption maximum at 0 to 400 nm, and having an absorption maximum at a wavelength of 300 to 345.5 nm in an absorption spectrum obtained by using a 10-mm-thick quartz cell with a chloroform solution having a concentration of 10 mg / liter. UV absorber having a wavelength of 345.5 to
It is preferable to use two types of ultraviolet absorbers having an absorption maximum at 400 nm.

In the present invention, the amount of one or more ultraviolet absorbers having an absorption maximum at a wavelength of 300 to 400 nm is as follows:
For 100 parts of aromatic polycarbonate resin,
0.005 to 1.0 part by weight, preferably 0.0
1 to 0.6. If the amount is less than 0.005 parts by weight, the ultraviolet absorbing performance is not sufficient.

The chloroform solution 10 used in the present invention
As an ultraviolet absorber having an absorption maximum at a wavelength of 320 to 400 nm in an absorption spectrum in a quartz cell having a thickness of 10 mg / l and a layer thickness of 10 mm, specifically, a benzotriazole-based ultraviolet absorber is 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- (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, in the triazine system, 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 and the like, and these can be used alone or in a mixture of two or more.

Among these, (D-
1) In a light absorption spectrum of a chloroform cell having a thickness of 10 mg / l and a layer thickness of 10 mm, a wavelength of 320 to 34
Specific examples of the UV absorber having an absorption maximum at 5.5 nm include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5).
-Tert-octylphenyl) benzotriazole,
2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-5
-Tert-octylphenyl) benzotriazole and the like.

In the absorption spectrum of the (D-2) chloroform solution (10 mg / l, 10 mm thick quartz cell) used in the present invention, the wavelength was 345.5 to 400 nm.
As an ultraviolet absorber having an absorption maximum, for example, 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-triazin-2-yl) -5-[(hexyl)
Oxy] -phenol, 2- (4,6-bis (2.4-
Dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol, 2-
(2-hydroxy-4-octoxyphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-te
rt-butylphenyl) benzotriazole, 2- (2
-Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole and the like.

The ultraviolet absorber (D-1) and the ultraviolet absorber (D-2) can be used in combination. When both are used, (D-1) based on 100 parts by weight of the aromatic polycarbonate resin is used.
The amount of the ultraviolet absorber added is preferably 0.05 to 0.5 parts by weight, and (D-2) the amount of the ultraviolet absorber added is 0.01 to 0.5 parts by weight.
0.3 weight is preferred. The compounding ratio R represented by the following formula
Is preferably in the range of 0.05 to 0.7. R = (D-2) / (D-1) If the compounding ratio R is less than 0.05 or exceeds 0.7, the excellent ultraviolet absorption performance, heat resistance and transparency of the molded product cannot be expressed in a well-balanced manner. Particularly preferred is 0.0
6 to 0.4.

The molecular weight of the aromatic polycarbonate resin in the present invention is from 10,000 to 50, in terms of viscosity average molecular weight.
000 is preferable, and 14,000 to 35,000 is more preferable. 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.

In the present invention, the viscosity average molecular weight is such that 0.7 g of aromatic polycarbonate resin is added to 100 ml of methylene chloride.
Is measured at 20 ° C. using a specific viscosity (η
_SP ) in 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 or haloformate is used, and specific examples thereof 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 (4). Can be shown.

[0050]

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[Wherein, R represents 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 phenol and p
-Tert-butylphenol, p-cumylphenol and isooctylphenol.

The aromatic resin composition of the present invention may contain a bluing agent 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, known bluing agents can be used. Representative examples include Bayer's Macrolex Violet and Terrasol Blue.
RLS, etc., are not particularly limited.

In the aromatic polycarbonate resin composition of the present invention, any method can be employed for blending the aromatic polycarbonate resin with the phosphorus-based stabilizer composition, the internal mold release agent, and other additives. 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 example, in a one-stage blending method, a method in which a predetermined amount of B-1 to B-3 components are preliminarily mixed and blended with an aromatic polycarbonate resin powder or pellets, or a method in which a predetermined amount of B -1 component to B-
It is possible to employ a method in which the three components are separately weighed, added sequentially to the aromatic polycarbonate resin powder or pellets, and then blended.

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.

[0059]

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) Cl Content of Stabilizer Chlorine atoms and chloride ions in the stabilizer were measured by a fluorescent X-ray method.

(2) 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)

(3) Iodine value of mold 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).

(4) Measurement of Sn Content of Release Agent The 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.

(5) Absorption maximum of ultraviolet absorber The maximum absorption wavelength of 300 to 400 μm is indicated from an absorption spectrum at a chloroform solution concentration of 10 mg / liter using a quartz cell having a layer thickness of 10 mm.

(6) 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 × 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.

[0066]

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

(7) 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.

(8) Spectral Transmittance A pet was molded into a 1.5 mm thick sample plate at a molding temperature of 300 ° C. for one minute using an injection molding machine. This sample was measured in a wavelength range of 360 to 800 nm using a spectrophotometer CARY-5 manufactured by Varian Japan.

(9) Luminous transmittance The following equation is obtained from the value of the spectral transmittance.

[0070]

(Equation 2)

Where λ is the spectral transmittance, τ is the relative luminous sensitivity, and (i) is 380 to 780 nm.

The phosphorus-based stabilizer, internal release agent, ultraviolet absorber and bluing agent used in Examples and Comparative Examples are as follows. 1. B-1 stabilizer 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) -3,3'-biphenylenediphosphonite 100: 50: 10 (weight ratio) mixture 2.B-2 Stabilizer bis (2,4-di-tert-butylphenyl) -4-
Phenyl-phenylphosphonite and bis (2,4-
5: 3 (weight ratio) mixture of di-tert-butylphenyl) -3-phenyl-phenylphosphonite 3.B-3 Stabilizer Tris (2,4-di-tert-butylphenyl) phosphite (in the stabilizer) 4. TNPP stabilizer Tris (nonylphenyl) phosphite 5. Fatty acid ester 1 stearic acid monoglyceride (purity 97.0% by weight, S
n: 400 ppm, acid value: 0.8, iodine value: 1.4) 6. 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) 7. Fatty acid ester 3 A mixture of stearic acid triglyceride and stearyl stearate (the mixing ratio of the former is about 70% by weight, the purity is 70% by weight. 9
7% by weight, Sn: 220 ppm, acid value: 1.5, iodine value: 0.6) 8. Fatty acid ester 4 pentaerythritol tetrastearate (purity: 99% by weight, Sn: 700 ppm, acid value: 1.5, iodine) Price:
0.7) 9. Fatty acid ester 5 pentaerythritol tetrastearate (purity 99% by weight, Sn: 330 ppm, acid value: 0.3, iodine value:
0.8) 10. Fatty acid ester 6 pentaerythritol tetrastearate (purity: 99% by weight, Sn: 150 ppm, acid value: 0.7, iodine value:
0.2) 11. UV absorber A-1 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole (absorption maximum: 343 μm) 12. UV absorber B-1 (3-tert-butyl-) 5-Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (maximum absorption: 353 μm) 13. UV absorber B-2 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) ) -6- (2H-benzotriazole-
2-yl) phenol] (absorption maximum: 353 μm) 14. Blueing agent 1- (4-methylphenylamino) -4-hydroxy-
9,10-anthraquinone

[Examples 1 to 5, Comparative Examples 1 to 7] The powdery aromatic polycarbonate resin obtained from bisphenol A, p-tert-butylphenol (terminal terminating agent) and phosgene by an interfacial polymerization method is shown in Table 1. Such as a Cl-containing phosphorus-based stabilizer composition and an internal release agent, an ultraviolet absorber,
A bluing agent and the like were added and mixed according to the composition shown in Table 1, extruded and pelletized at 280 ° C., and the above-mentioned molding evaluation was performed.

[0074]

[Table 1]

[0075]

According to the present invention, in a system using a fatty acid ester compound as an internal release agent and a specific phosphorus-based stabilizer composition as a stabilizer, the amount of chlorine contained in the phosphorus-based stabilizer composition is limited. An object of the present invention is to provide an aromatic polycarbonate resin composition which has improved mold heat resistance, dry heat resistance and wet heat fatigue resistance while maintaining the mold releasability of the aromatic polycarbonate resin composition.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CG001 EH049 EU179 EU189 EW068 EW116 EW117 FD036 FD037 FD038 FD059 FD169 FD200

Claims (4)

[Claims] (A) a viscosity average molecular weight of 10,000 to
100 parts by weight of 50,000 aromatic polycarbonate resin, (B) a compound represented by the following general formula (1) (B-1
Component), a compound represented by the following general formula (2) (component B-2), and a compound represented by the following general formula (3) (component B-3), when the total thereof is 100% by weight. , B-
Phosphorus stable in which one component is 40 to 80% by weight, the B-2 component is 0 to 25% by weight, and the B-3 component is 5 to 50% by weight, and the concentration of chlorine atoms and chlorine ions is 1 to 11000 ppm. One or more 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. The above full ester is 90% by weight or more, the acid value is 0.6 to 1.6, and the iodine value is 0.1.
To 1.3, 0.005 to 1.0 parts by weight of an internal mold release agent having a metal element Sn content of 5 to 300 ppm, and (D)
Using a quartz cell with a layer thickness of 10 mm, in the absorption spectrum at a chloroform solution concentration of 10 mg / liter,
An aromatic polycarbonate resin composition comprising 0.005 to 1.0 parts by weight of one or more UV absorbers having an absorption maximum at a wavelength of 320 to 400 nm. Embedded image [Wherein, Ar1 and Ar2 are aromatic groups which may have an alkyl substituent, and may be the same or different. Ar3 is a dialkyl-substituted aromatic group, which may be the same or different. ] 2. The aromatic polycarbonate resin composition according to claim 1, wherein the full ester is a full ester of pentaerythritol and stearic acid. 3. An absorption spectrum obtained by using a chloroform cell having a layer thickness of 10 mm with a chloroform solution having a concentration of 10 mg / liter as an ultraviolet absorber, and having a (D-1) wavelength of 320
3. An ultraviolet absorber having an absorption maximum at a wavelength of from 34 to 345.5 nm and (D-2) an ultraviolet absorber having an absorption maximum at a wavelength of 345.5 to 400 nm.
Item 10. The aromatic polycarbonate resin composition according to item 8. 4. An ultraviolet absorbent having an absorption maximum at a wavelength of 320 to 345.5 nm is 0.05 to 0.5 parts by weight, and an ultraviolet absorber having an absorption maximum at a wavelength of 345.5 to 400 nm is 0.01 to 0. The aromatic polycarbonate resin composition according to claim 3, wherein the amount is 0.3 parts by weight.