JP2003176405A - Antistatic polycarbonate resin composition - Google Patents

Abstract

(57) [Problem] An object of the present invention is to provide a molded article having excellent antistatic performance and durability of antistatic performance after dry heat treatment without reducing the transparency, hue, and molding heat resistance. Is high temperature
Provided is an antistatic polycarbonate resin composition having good transparency under high humidity conditions (moisture heat treatment). SOLUTION: (A) 100 parts by weight of polycarbonate resin (component (a)), (B) 0.05 to 5 parts by weight of specific benzenesulfonic acid phosphonium salt (component (b)) and (C) metal salt of perfluoroalkanesulfonic acid 0 .001-0.
An antistatic polycarbonate resin composition comprising 8 parts by weight (component (c)).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antistatic polycarbonate resin composition. More specifically, it does not deteriorate the transparency, hue, and heat resistance of molding, and has excellent antistatic performance and durability of antistatic performance after dry heat treatment. Furthermore, under high temperature and high humidity conditions (wet heat treatment) The present invention relates to an antistatic polycarbonate resin composition having a significantly improved transparency.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used in electric, mechanical, automobile, medical and other applications because they have excellent transparency, heat resistance and mechanical strength. However, the polycarbonate resin has a large surface resistivity and is easily charged with static electricity due to contact or friction, which may cause dust on the surface of the molded product, discomfort due to electric shock to the human body, and noise or malfunction of electronic products. There are problems such as occurrence.

Particularly, in recent years, there has been a problem that dust adheres due to static electricity to impair transparency in long-term use of the inner surface of a transparent headlamp lens for automobiles, the inner surface of an interior transparent cover, and vehicle resin window glass. In addition, there is a concern that the temperature will rise when the lamp is lit. Preventing the persistence of antistatic performance and deterioration of transparency in high-temperature and high-humidity environments is not only a cosmetic problem, but also a safety factor during running. It is also a big problem in securing it.

Conventionally, as a method for preventing the electrostatic charge of a polycarbonate resin, a method of adding an alkali metal salt of sulfonic acid, a method of adding a phosphonium salt of sulfonic acid (JP-A-62-230835), and an amine salt of sulfonic acid. And phosphoric acid ester (JP-A-3-643)
No. 68) are proposed. However, the polycarbonate resin composition obtained by these methods has a problem that the antistatic performance of the molded product is lost early in a long-term heating test (dry heat treatment), and the transparency is largely lost in a wet heat treatment. there were. Therefore, particularly in automobile headlamp lens applications, since it is used under conditions of high temperature and high humidity, there has been a demand for a polycarbonate resin composition having excellent dry heat resistance and wet heat resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antistatic polycarbonate resin composition having excellent antistatic performance and excellent transparency, hue, molding heat resistance, dry heat resistance and wet heat resistance. To provide.

The present inventor has conducted extensive studies to achieve the above object, and as a result, by adding a specific perfluoroalkanesulfonic acid metal salt to a resin composition comprising a polycarbonate resin and a benzenesulfonic acid phosphonium salt, The present invention has been completed by discovering that the durability of antistatic performance by dry heat treatment and the transparency by wet heat treatment can be significantly improved without lowering the molding heat resistance.

[0007]

That is, according to the present invention, (A) 100 parts by weight of a polycarbonate resin (a component), (B) a benzenesulfonate phosphonium salt represented by the following formula (I): 0.05 ~ 5 parts by weight (component b) and (C) metal salt of perfluoroalkanesulfonic acid 0.00
An antistatic polycarbonate resin composition comprising 1 to 0.8 parts by weight (component c) is provided.

[0008]

[Chemical 2]

The polycarbonate resin used as the component a in the present invention can be obtained, for example, by reacting a dihydric phenol with a carbonate precursor by a method such as an interfacial polymerization method or a melt polymerization method. Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4
-Hydroxyphenyl) propane (abbreviation bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxy) Phenyl)
-1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) ) Pentane, α, α′-bis (4-hydroxyphenyl) -m-
Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,1
-Bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl)
Ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo-)
4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-
Examples thereof include bis (4-hydroxy-3-methylphenyl) fluorene. A preferable dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferable.

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

In producing a polycarbonate resin by the interfacial polymerization method of the above-mentioned dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, a dihydric phenol antioxidant, etc. may be used, if necessary. . Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid, It may also be a mixture of two or more of the obtained polycarbonate resins.

The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, which 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, pyridine or the like is used.

As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.

A catalyst such as a tertiary amine or a quaternary ammonium salt may be used to accelerate the reaction. As a molecular weight regulator, for example, phenol or p-ter is used.
It is preferable to use an end terminating agent such as t-butylphenol or p-cumylphenol.

It is preferable that the reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually 10 or more.

The reaction by the melt polymerization method is usually a transesterification reaction between a dihydric phenol and a carbonic acid diester, and the dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas, and usually at 120 to 350 ° C. under reduced pressure. React. The degree of pressure reduction is changed stepwise, and finally the phenols produced at 133 Pa or less are removed to the outside of the system. The reaction time is usually about 1 to 4 hours.

Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate, among which diphenyl carbonate is preferred.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, and waters of boron and aluminum. Oxides, alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal organic acid salts, zinc compounds, boron compounds, silicon compounds, Examples of the catalyst that are usually used for esterification reaction or transesterification reaction of germanium compound, organotin compound, lead compound, antimony compound, manganese compound, titanium compound, zirconium compound and the like. The catalyst may be used alone or in combination of two or more kinds.

In the polymerization reaction, in order to reduce the phenolic terminal group, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are added at the latter stage or after the completion of the polymerization reaction. It is preferable to add a compound such as

Regarding the details of reaction modes other than the above, the reaction modes well known in the books and patent publications can be adopted.

The polycarbonate resin in the present invention has a molecular weight of 10,000 to 10 in terms of viscosity average molecular weight (M).
10,000 is preferable, 12,000 to 45,000 is more preferable, 15,000 to 40,000 is further preferable, and 21,000 to 30,000 is particularly preferable.
A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength can be obtained, melt flowability at the time of molding is also good, and molding distortion does not occur. The viscosity average molecular weight is obtained by inserting the specific viscosity (η _sp ) obtained from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. into the following equation. η _sp /c=[η]+0.45×[η] ² c (however, [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

As the component b of the present invention, a benzenesulfonic acid phosphonium salt represented by the above formula (I) is used as an antistatic agent.

In the above formula (I), R ¹ is a hydrogen atom,
An alkyl group having 1 to 35 carbon atoms, an aralkyl group having 6 to 20 carbon atoms or an aryl group having 5 to 15 carbon atoms is shown. Here, the aralkyl group and the aryl group may contain a hetero atom. Further, R ¹ may be one in which some or all of the hydrogen atoms in the structure are replaced with fluorine atoms.

The alkyl group having 1 to 35 carbon atoms may be a linear or branched alkyl group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group. , Tetradecyl group, octadecyl group, eicosyl group and the like.

As the aralkyl group having 6 to 20 carbon atoms,
Examples thereof include a benzyl group, a 2,6-ditertiarybutyl-4-methylbenzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a 2-phenylisopropyl group.

Examples of the aryl group having 5 to 15 carbon atoms include phenyl group, tolyl group, naphthyl group and pyridinyl group.

Among these, R ¹ has 1 to 3 carbon atoms.
An alkyl group having 5 carbon atoms is preferable, an alkyl group having 5 to 20 carbon atoms is more preferable, and an alkyl group having 10 to 15 carbon atoms is further preferable. Particularly, a dodecyl group is preferable from the viewpoint of compatibility with a polycarbonate resin and molecular dispersibility in the resin.

In the above formula (I), R ² represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an aralkyl group having 6 to 20 carbon atoms or an aryl group having 5 to 15 carbon atoms. Here, the aralkyl group and the aryl group may contain a hetero atom. Further, R ² may be one in which some or all of the hydrogen atoms in the structure are replaced with fluorine atoms.

The alkyl group having 1 to 7 carbon atoms may be a linear or branched alkyl group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, 2-ethylbutyl group,
Hexyl group, heptyl group and the like can be mentioned.

The aralkyl group having 6 to 20 carbon atoms includes
Examples thereof include a benzyl group, a 2,6-ditertiarybutyl-4-methylbenzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a 2-phenylisopropyl group.

Examples of the aryl group having 5 to 15 carbon atoms include phenyl group, tolyl group, naphthyl group and pyridinyl group.

Of these, a hydrogen atom or an alkyl group having 1 to 7 carbon atoms is preferable as R ² , and a hydrogen atom is particularly preferable.

In the above formula (I), R ³ , R ⁴ , R ⁵ and R ⁶
Are each independently a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 6 carbon atoms.
The aryl groups of 15 are shown.

The C1-C24 alkyl group may be a linear or branched alkyl group. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples thereof include tridecyl group, tetradecyl group, pentadecyl group and hexadecyl group.

As the aralkyl group having 7 to 20 carbon atoms,
Examples thereof include a benzyl group, a 2,6-di-tert-butyl-4-methylbenzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a 2-phenylisopropyl group.

Examples of the aryl group having 6 to 15 carbon atoms include phenyl group, tolyl group and naphthyl group.

Among them, R ³ , R ⁴ , R ⁵ and R ⁶ are preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and a butyl group and an octyl group. Particularly preferred.

The phosphonium benzenesulfonate salt is added in an amount of 0.0 to 100 parts by weight of the polycarbonate resin.
It is used in the range of 5 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 0.5 to 3 parts by weight. 0.05
If it is less than 5 parts by weight, a sufficient antistatic effect cannot be obtained, and if it exceeds 5 parts by weight, the polycarbonate resin molded article obtained by molding is inferior in mechanical properties and transparency and appearance are also deteriorated.

Further, the antistatic polycarbonate resin composition of the present invention may be used in combination with an antistatic agent other than the phosphonium benzenesulfonate salt.

Examples of such other antistatic agents include lithium benzenesulfonate, sodium benzenesulfonate, potassium benzenesulfonate, calcium benzenesulfonate, magnesium benzenesulfonate, barium benzenesulfonate, fatty acid ester compounds, carbon and graphite. , Metal powder, and the like. The amount of the antistatic agent used is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

In the present invention, perfluoroalkanesulfonic acid metal salt is used as the component c. The metal salt of perfluoroalkanesulfonic acid preferably contains an alkyl group in which all hydrogen atoms of an alkyl group having 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms are substituted with fluorine atoms, The structure may be a linear structure or a branched structure, and examples of the metal include lithium, sodium, potassium, magnesium and calcium. Specific examples include potassium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, potassium perfluorooctane sulfonate, sodium perfluorooctane sulfonate, and the like. Among these, production and purification are easy and thermal stability is high. Potassium perfluorobutane sulfonate is preferably used because of its excellent properties. These perfluoroalkanesulfonic acid metal salts may be used alone or in combination of two or more.

The amount of the perfluoroalkane sulfonic acid metal salt used in the present invention is preferably 0.001 to 0.8 part by weight, more preferably 0.01 to 0.8 part by weight, based on the polycarbonate resin.
0.5 parts by weight is more preferable, and 0.02 to 0.3 parts by weight is particularly preferable. When the amount is less than 0.001 part by weight, the antistatic performance is not sufficiently improved, and when the amount is more than 0.8 part by weight, the antistatic performance of the molded product is improved but the transparency is lowered.

The benzenesulfonic acid phosphonium salt blended as an antistatic agent in the present invention is usually an unstable substance and is easily decomposed by a thermal decomposition reaction or an oxidation reaction. In addition, some of the by-products generated by the decomposition reaction are substances that cause side reactions with colored substances and polycarbonate resins, so if the product is heated and melted and molded, or if a thermal history occurs in the molded product, the discoloration of the molded product will occur. Deterioration in hue and reduction in molecular weight are likely to occur due to. In particular, in a basic atmosphere, a nucleophilic reaction to a sulfonic acid group is likely to occur, so that it is considered that the antistatic agent is easily decomposed. In order to reduce such decomposition as much as possible, a method of adding an acid to the resin composition to adjust the acidity is preferable.

As the acidity adjusting agent used for this purpose, various acidic compounds having a pK (logarithm of the reciprocal of the dissociation constant of an acid) in the weakly acidic region can be considered. Among them, the preferable pK range is from 4 to 4. 7, particularly preferably 4.5-5.
It is 5. A resin composition of 4 or more has a moderate acidity of the resin composition without being too strong, and the antistatic agent is unlikely to decompose during molding,
Further, the dissociation of the antistatic agent on the surface of the molded product is increased, and the antistatic performance is excellent, and those of 7 or less have an appropriate acidity of the resin composition without being too weak. The carbonate bond is preferred because it is less susceptible to nucleophilic attack and less susceptible to decomposition.

Specifically, among acidic compounds exhibiting weak acidity, carboxylic acid compounds and carboxylic acid anhydride compounds are preferably used. Such a carboxylic acid compound or a carboxylic acid anhydride compound not only acts to suppress the nucleophilic decomposition reaction but also forms and stabilizes an ester-like structure with a benzenesulfonic acid derivative which is considered to be a decomposition byproduct of the antistatic agent. It is considered that there is also an effect of suppressing the decomposition of polycarbonate due to a further side reaction. The above-mentioned acidic compound is 0.1% with respect to 100 parts by weight of the polycarbonate resin.
It is used in the range of 0005 to 1 part by weight, preferably 0.001 to 0.5 part by weight, more preferably 0.005 to 0.2 part by weight.

In the antistatic polycarbonate resin composition of the present invention, a phosphorus-based heat stabilizer or a hindered phenol-based stabilizer can be used in order to prevent a decrease in molecular weight and a deterioration in hue during molding. . Examples of such phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof.

Specific examples of phosphorus-based stabilizers include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophosphite. Phenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite,
Tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-)
Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert) -Butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite,

Tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-orthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate,
Diisopropyl phosphate,

Tetrakis (2,4-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4 '
-Biphenylene diphosphonite, tetrakis (2,4-
Di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-ter
t-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite,
Tetrakis (2,6-di-n-butylphenyl) -4,
4'-biphenylene diphosphonite, tetrakis (2,
6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-t)
ert-Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-). Butylphenyl)-
Phenyl-phenylphosphonite,

Examples thereof include dimethyl benzenephosphonate, diethyl benzenephosphonate and dipropyl benzenephosphonate.

Among them, tris (2,4-di-tert-
Butylphenyl) phosphite, tetrakis (2,4-
Di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-tert)
-Butylphenyl) -phenyl-phenylphosphonite is preferred.

As the hindered phenol stabilizer, for example, pentaerythritol tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-p-cresol, 4,4'-butylidenebis- (6-
tert-butyl-3-methylphenol, 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert)
-Butylphenyl) methane, thiodiethylenebis- [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,3
5-di-tert-butyl-4-hydroxyphenyl)
Propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], diethyl [[3,
5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″,
5,5 ', 5 "-hexa-tert-butyl-a,
a ', a "-(methylene-2,4,6-triyl) tri-p-cresol, hexamethylenebis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-te)
rt-Butyl-4-hydroxybenzyl) -1,3,5
-Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-
Bis (octylthio) -1,3,5-triazine-2-
Ilamino) phenol and the like.

These heat stabilizers may be used alone or in combination of two or more. The heat stabilizer is used in an amount of 0. 0 with respect to 100 parts by weight of the polycarbonate resin.
001-0.2 weight part is preferable.

In the antistatic polycarbonate resin composition of the present invention, the purpose is to improve the dispersion efficiency of the antistatic agent in the resin and reduce the concentration distribution, and the migration of the antistatic agent to the surface of the molded article during molding. The fatty acid ester compound can be used for the purpose of improving the above-mentioned properties, and for imparting releasability from the mold during molding.

Examples of such fatty acid esters include monohydric or polyhydric alcohols having 1 to 20 carbon atoms and 1 carbon atom.
Partial or total esters with 0 to 30 saturated fatty acids are preferred. Examples of the partial or whole ester of monohydric or polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol. Tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2- Examples thereof include ethylhexyl stearate, and among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythric acid. Tall tetrastearate are preferably used. The amount of the fatty acid ester used is 100
0.001 to 0.5 parts by weight is preferable with respect to parts by weight.

When such a fatty acid ester compound is used in a polycarbonate resin, a method in which a master in which an antistatic agent is uniformly dispersed in a fatty acid ester compound is prepared in advance and this is blended with a polycarbonate resin and molded is It is more desirable from the viewpoint of dispersibility in resin, uniformity of concentration, and transferability to the surface of a molded product.

A releasing agent may be used in the polycarbonate resin composition of the present invention in order to further improve the releasability from the mold during melt molding so long as the object of the present invention is not impaired. Examples of the releasing agent include the fatty acid ester, polyorganosiloxane, paraffin wax, and beeswax. The amount of the release agent used is 0.001 to 100 parts by weight of the polycarbonate resin.
0.5 parts by weight is preferred.

An ultraviolet absorber can be used in the polycarbonate resin composition of the present invention. The ultraviolet absorbent compound is specifically 2,4 in the benzophenone type.
-Dihydroxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5
-Sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride 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
-Dodecyloxybenzophenone, 2-hydroxy-4
-Methoxy-2'-carboxybenzophenone and the like can be mentioned.

In the benzotriazole type, 2- (2-hydroxy-5-methylphenyl) benzotriazole,
2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,
5-dicumylphenyl) phenylbenzotriazole,
2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,
2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole-2-
Yl) phenol], 2- (2-hydroxy-3,5-
Di-tert-butylphenyl) 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 can be mentioned, and these can be used alone or as a mixture of two or more kinds. The amount of the ultraviolet absorber used is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

In the polycarbonate resin molded article of the present invention, a bluing agent can be used within the range not impairing the object of the invention. The bluing agent is effective for eliminating the yellow tint of the polycarbonate resin molded product. In particular, in the case of molded products with weather resistance, since a certain amount of UV absorber is used, there is a reality that resin products tend to become yellowish due to "action and color of UV absorber". The use of a bluing agent is very effective for giving a molded article a natural transparency.

The amount of the bluing agent used in the present invention is 0.05 to 3 ppm with respect to the polycarbonate resin.
Is preferable, and 0.5-2.5 ppm is more preferable. If the amount used is too large, the blue tint of the resin product may be increased and the visual transparency may be reduced.

Typical examples of the blowing agent include Macrolex Violet B manufactured by Bayer and Triazol Bull-RLS manufactured by Sand Co.

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 flame retardant,
Examples thereof include aromatic phosphate ester-based flame retardants, halogenated aromatic phosphate ester-based flame retardants, and the like, and one or more of them can be used.

Concretely, the halogenated bisphenol A polycarbonate type flame retardant is a tetrabromobisphenol A polycarbonate type flame retardant, a copolymerized polycarbonate type flame retardant of tetrabromobisphenol A and bisphenol A, and the like.

Specific examples of the organic salt flame retardant include diphenylsulfone-3,3'-dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,4. 5-
Potassium trichlorobenzenesulfonate, bis (2,6
-Potassium dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, bis (p
-Toluene sulfone) imide potassium, bis (diphenylphosphoric acid) imide potassium, bis (2,4,6-tribromophenyl) phosphate potassium, bis (2,4-dibromophenyl) phosphate potassium, bis (4-bromo) Examples thereof include potassium phenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, sodium or potassium lauryl sulfate, and sodium or potassium hexadecyl sulfate.

Specific examples of the halogenated aromatic phosphate ester type flame retardant include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate and tris (4-bromophenyl). For example, phosphate.

Specific examples of the aromatic phosphate ester flame retardant include triphenyl phosphate, tris (2,6-xylyl) phosphate and tetrakis (2,6-xylyl).
Resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate, tetrakis (2,2
6-xylyl) -4,4'-biphenol diphosphate, tetraphenyl resorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4'-biphenol diphosphate, aromatic ring source is resorcin and phenol and phenolic OH Group-free aromatic polyphosphate, aromatic ring source is resorcin and phenol and aromatic polyphosphate containing phenolic OH group, aromatic ring source is hydroquinone and phenol, aromatic polyphosphate not containing phenolic OH group, Aromatic polyphosphates containing similar phenolic OH groups, (“Aromatic polyphosphate” below refers to both aromatic polyphosphates containing phenolic OH groups and aromatic polyphosphates not containing phenolic OH groups. ) Aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol, aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and phenol, aromatic polyphosphates whose aromatic ring sources are resorcin and 2,6-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, and aromatic ring source tetrabromobisphenol A and 2,6 -Aromatic polyphosphates such as xylenol.

Other resins and elastomers may be used in the polycarbonate resin composition of the present invention in a small proportion within a range that does not impair the object of the present invention.

Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins,
Polyether imide 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 polymers (ABS resins), polymethacrylate resins, phenol resins, and epoxy resins can be mentioned.

As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and core-shell type MBS (methyl methacrylate / sterene) are used. / Butadiene) rubber, MA
Examples thereof include S (methyl methacrylate / acrylonitrile / styrene) rubber and the like.

Any method may be used to produce the polycarbonate resin composition of the present invention. For example, a method of mixing a polycarbonate resin powder, an antistatic agent, a perfluoroalkanesulfonic acid metal salt and a desired additive with a tumbler, a V-type blender, a super mixer, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like. Used as appropriate. The polycarbonate resin composition thus obtained can be molded into a molded product by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method as it is or after it is once pelletized by a melt extruder.

The additive may be blended in one step, or in two or more steps. As a one-step method, there are a method of previously blending all the resin components and additives and supplying them to the extruder, and a method of directly injecting only the liquid raw material into the extruder cylinder using a liquid injecting device. The method carried out in two stages, for example, a method of previously blending the antistatic agent and the additive, and then blending with the polycarbonate resin powder, or a part of the polycarbonate resin powder to be blended and the additive first. After blending, that is, after diluting the additive with the polycarbonate resin powder to form a master batch of the additive, a method of blending the master batch with the polycarbonate resin powder can also be adopted.

The polycarbonate resin composition of the present invention is
It is suitable for headlamp lenses, lighting cover, and organic window glass (for vehicles and building materials) because of its excellent antistatic property, transparency, hue, and heat resistance. In particular, the polycarbonate resin composition of the present invention is suitable as a headlamp lens because it has little deterioration in hue during molding, deterioration in wet heat fatigue resistance, and excellent antistatic performance after dry heat treatment and transparency after wet heat treatment. Used for.

[0074]

The present invention will be further described with reference to the following examples. The evaluation was carried out by the following method. (1) Antistatic performance (surface resistance before dry heat treatment) The surface resistance of a 2.0 mm thick molded plate surface was measured by SM-8210 manufactured by Toa Denpa Kogyo Co., Ltd. The smaller the value, the better the antistatic performance. (2) Antistatic performance after dry heat treatment (surface resistance after dry heat treatment) [dry heat resistance] A molded plate having a thickness of 2.0 mm is stored for 100 hours in a dryer set at a temperature of 120 ° C, and then taken out after storage. The molded plate was adjusted at 23 ° C. and 50% for one week, and the surface resistance was measured by the method (1). (3) Transparency of molded product Using a haze meter NDH-300A manufactured by Nippon Denshoku Co., Ltd., total light transmittance and Haz of a molded plate having a thickness of 2.0 mm were measured.
e was measured. The higher the numerical value of the total light transmittance, the higher the transparency. Haze is the turbidity of the molded product,
The lower the value is, the less turbidity is. (4) Transparency after wet heat treatment [moisture and heat resistance] A molded plate having a thickness of 2.0 mm is subjected to wet heat treatment in a test machine at 120 ° C for 11 hours under pressurized steam, and Haz of the molded product after the treatment is performed.
e was measured by the same method as in (3) above.

[Examples 1 to 5, Comparative Examples 1 to 5] A molecular weight of 22000 produced by an interfacial polymerization method from bisphenol A and phosgene (a ratio of 0.7 g of polymer dissolved in 100 ml of methylene chloride and measured at 20 ° C.). Viscosity 0.4
0) Polycarbonate resin 100 parts by weight (a component)
And an antistatic agent of component b and a metal salt of perfluoroalkane sulfonic acid of component c described below are blended in the amounts shown in Tables 1 and 2, (component b) b-1; tetrabutyl dodecylbenzene sulfonate. Phosphonium b-2; dodecylbenzene sulfonic acid tributyl monooctyl phosphonium (c component) c-1; perfluorobutane sulfonic acid potassium salt Further, as another component, tetrakis (2,4-di-t)
ert-butylphenyl) -biphenylenediphosphonite 0.035 parts by weight, bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite 0.
005 parts by weight, tris (2,4-di-tert-butylphenyl) phosphite 0.005 parts by weight, and Bayer KK-made Macrolex Violet 0.0002 parts by weight were compounded.

The obtained polycarbonate resin composition was mixed in a blender and then melt-kneaded using a vent type single-screw extruder to obtain pellets. Using an injection molding machine, the pellets thus obtained have a thickness of 2 at a cylinder temperature of 315 ° C.
A 50 mm square plate of mm and a sample for measurement were molded.
The evaluation results of the obtained molded plate are shown in Tables 1 and 2. A headlamp lens was prepared according to a known method using the pellets obtained from the compositions of Examples 1 to 5. These headlamp lenses were good in appearance such as antistatic performance persistence, hue and transparency.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

INDUSTRIAL APPLICABILITY The antistatic polycarbonate resin composition of the present invention is excellent in the antistatic property and the durability of the antistatic property after dry heat treatment without deteriorating the transparency, hue and molding heat resistance of the molded product. Furthermore, since it has good transparency under high temperature and high humidity conditions (wet heat treatment), it is extremely useful especially for headlamp lens applications.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2K009 CC34 EE03                 4F071 AA50 AC14 AC15 AE16 AF30                       AF34 AF38 AF45 AH07 BA01                       BB05 BC03                 4J002 CG001 CG011 CG021 EV257                       EW176 FD050 FD060 FD090                       FD106 FD107 FD130 FD160                       GP01

Claims (2)

[Claims] 1. (A) 100 parts by weight of a polycarbonate resin (a component), (B) 0.05 to 5 parts by weight of a benzenesulfonic acid phosphonium salt represented by the following formula (I) (b component) and (C). An antistatic polycarbonate resin composition comprising 0.001 to 0.8 parts by weight (component c) of a perfluoroalkanesulfonic acid metal salt. [Chemical 1] (In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 35 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or 5 to 1 carbon atoms.
5 represents an aryl group, R ² is a hydrogen atom, and has 1 to 7 carbon atoms.
Is an alkyl group, a C6-20 aralkyl group, or a C5-15 aryl group. R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a carbon number of 1 to 24.
Is an alkyl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms. ) 2. A headlamp lens formed from the antistatic polycarbonate resin composition according to claim 1.