JP2003138123A - Antistatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic polycarbonate resin composition giving a molded product excellent antistatic performances, excellent persistence of the antistatic performances in a heated state, good transparency, hue, and a heat, dry heat and wet heat fatigue resistance. SOLUTION: This antistatic polycarbonate resin composition comprises (A) 100 pts.wt. of a polycarbonate resin (component a) and (B) 0.05-5 pts.wt. of a phosphonium benzenesulfonate (component b) represented by general formula (I) (wherein, R<1> denotes hydrogen atom, a 1-35C alkyl group, a 6-20C aralkyl group or a 5-15C aryl group; R<2> denotes hydrogen atom, a 1-7C alkyl group, a 6-20C aralkyl group or a 5-15C aryl group; R<3> denotes a 1-5C alkyl group; R<4> denotes a 6-16C alkyl group; m denotes an integer of 0-3; and n denotes an integer of 1-4, with the proviso that m+n is 4).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antistatic polycarbonate resin composition. More specifically, the antistatic performance and the antistatic performance are excellent in the durability in the heated state,
Furthermore, the transparency, hue, molding heat resistance, dry heat resistance of molded products,
The present invention relates to an antistatic polycarbonate resin composition having excellent resistance to moisture and heat fatigue.

[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 static electricity induced by contact or friction is hard to disappear,
Dust adhered to the surface of the molded product, discomfort due to electric shock to the human body,
Furthermore, there are problems such as generation of noise and malfunction in electronic products.

In particular, recently, there has been a problem that dust adheres to the inner surface of a transparent headlamp lens or an inner surface of an interior transparent cover for automobiles, or a resin window glass for a vehicle to deteriorate the transparency as it is used. The loss of transparency in such a part is not only a problem in appearance but also a major problem in ensuring safety during traveling.

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. Among these, the phosphonium salt of sulfonic acid has somewhat good antistatic performance and heat resistance, and is disclosed in the above-mentioned JP-A-62-23083.
In Japanese Patent Laid-Open No. 5, specifically, a sheet obtained by adding a tetrabutylphosphonium salt of benzenesulfonic acid to a polycarbonate resin and molding this composition is shown to have excellent antistatic performance and appearance.

However, such a polycarbonate resin composition has a problem that the antistatic performance of a molded product is likely to be lost with time, and the antistatic performance is lost in a short period especially in a heated state. Particularly, in the case of automobile headlamp lenses and the like, there is a problem in that when continuously lit, the inner surface of the lens becomes high in temperature and the antistatic performance is lost early.

On the other hand, for the purpose of improving the durability of the antistatic property in a heated state, it is conceivable to increase the amount of the antistatic agent added as much as possible. In addition to the properties, hues, and dry heat resistance, mechanical properties are significantly reduced.

[0007]

The object of the present invention is to provide an excellent antistatic property and durability of the antistatic property in a heated state, and to obtain transparency, hue, molding heat resistance, dry heat resistance and wet heat fatigue resistance. An object is to provide a good antistatic polycarbonate resin composition.

The present inventor has conducted extensive studies to achieve the above object, and as a result, a resin composition comprising a polycarbonate resin and a phosphonium benzenesulfonate salt has a unique combination structure as a phosphonium salt substituent. Surprisingly, the antistatic property and the antistatic property have excellent durability when heated, and the deterioration of hue, molding heat resistance, dry heat resistance is also greatly suppressed, and further, the decrease of the molecular weight during molding and deterioration of wet heat fatigue resistance. It was also clarified that the above can be suppressed, and the present invention was completed.

[0009]

That is, according to the present invention, (A) 100 parts by weight of a polycarbonate resin (a component), (B) phosphonium benzenesulfonate represented by the following general formula (I): An antistatic polycarbonate resin composition comprising 05 to 5 parts by weight (component b) is provided.

[0010]

[Chemical 2]

(In the formula, R ¹ is a hydrogen atom and has ^{1 to} 35 carbon atoms.
Is an alkyl group having 6 to 20 carbon atoms or an aryl group having 5 to 15 carbon atoms, and R ² is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an aralkyl group having 6 to 20 carbon atoms or a carbon number. 5 to 15 represents an aryl group, R ³ represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents 6 to 16 carbon atoms.
In the formula, m is an integer of 0 to 3, n is an integer of 1 to 4, and m + n = 4. 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-hydroxyphenyl) -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-
Examples thereof include hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-
Hydroxyphenyl) alkane, and bisphenol A is particularly preferable.

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

In the production of a polycarbonate resin by the interfacial polymerization method of the above dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant of the dihydric phenol and the like 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. Of these, 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.

Further, in the polymerization reaction, in order to reduce the phenolic terminal group, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl may be used at the latter stage or after the termination of the polycondensation reaction. It is preferable to add a compound such as carbonate.

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

The molecular weight of the polycarbonate resin in the present invention is 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

In the present invention, the benzenesulfonic acid phosphonium salt represented by the above general formula (I) is used as the antistatic agent as the component b.

In the above general formula (I), R ¹ represents 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. Here, the aralkyl group and the aryl group may contain a hetero atom.

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 general 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,
Aralkyl and aryl groups may contain heteroatoms.

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.

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.

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

In the above general formula (I), R ³ has 1 to 1 carbon atoms.
5 represents an alkyl group.

The alkyl group having 1 to 5 carbon atoms may be a linear or branched alkyl group. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.

Among these, R ³ has 2 to 5 carbon atoms.
Is preferable, an alkyl group having 3 to 4 carbon atoms is more preferable, and an n-butyl group is particularly preferable.

In the general formula (I), R ⁴ has 6 to 1 carbon atoms.
6 represents an alkyl group. When the carbon number is less than 6,
Alternatively, when the carbon number is more than 16, the antistatic performance after the heat treatment is insufficient, which is not preferable.

The alkyl group having 6 to 16 carbon atoms may be a linear or branched alkyl group. Examples thereof include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and hexadecyl group.

Among these, R ⁴ has 7 to 1 carbon atoms.
An alkyl group having 4 to 4 carbon atoms is preferable, and an alkyl group having 8 to 12 carbon atoms is particularly preferable.

The phosphonium benzenesulfonate salt is used in an amount of 0.0 to 100 parts by weight of the polycarbonate resin.
5 to 5.0 parts by weight, preferably 0.1 to 4.0 parts by weight,
It is more preferably used in the range of 0.5 to 3.0 parts by weight. If it is less than 0.05 parts by weight, a sufficient antistatic effect cannot be obtained, and if it exceeds 5.0 parts by weight, the mechanical properties of the polycarbonate resin molded product obtained by molding are poor, and the transparency and appearance are also deteriorated, which is preferable. Absent.

Such an antistatic agent may contain a very small amount of unreacted substances and impurities at the time of production as long as the object of the present invention is not impaired.

Furthermore, 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 the same as that of the polycarbonate resin composition 1
0.01 to 5 parts by weight is preferable with respect to 00 parts by weight.

In the present invention, a fatty acid ester compound is preferably used as the component c. By using a fatty acid ester compound to improve the compatibility, dispersibility, and mobility of the antistatic agent in the resin, the concentration distribution of the antistatic agent in the resin can be reduced and the surface of the molded article can be molded. It has the effect of improving the migration of the antistatic agent to the. Further, it also has an effect of 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 total ester of the monohydric or polyhydric alcohol and the saturated fatty acid include glycerin monostearate, glycerin distearate, glycerin tristearate, glycerin monobehenate, pentaerythritol monostearate, pentaerythritol tetrastearate. Rate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate. Examples thereof include glycerin monostearate, glycerin distearate, and glycerin tristearate, among which glycerin monostearate is preferred. Monostearate is particularly preferred. The amount of the fatty acid ester used is 0.
001 to 5.0 parts by weight is preferable, and 0.01 to 1.0 parts by weight is particularly preferable.

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.

The phosphonium benzenesulfonate salt, which is 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 pK (logarithm of the reciprocal of the dissociation constant of 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 has the possibility of forming an ester-like structure and stabilizing with a benzenesulfonic acid derivative which is considered as a decomposition by-product 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.

The antistatic polycarbonate resin composition of the present invention may further contain a phosphorus-based heat stabilizer in order to prevent a decrease in molecular weight and a deterioration in hue during molding. Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof.

Specifically, triphenyl phosphite,
Tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, 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)
Octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t
ert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite,

Tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl 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, trimethyl phosphate, 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.

These heat stabilizers may be used alone or in admixture 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 to 0.15 weight part is preferable.

In the polycarbonate resin composition of the present invention, a generally known antioxidant can be used for the purpose of preventing oxidation, particularly for preventing deterioration during dry heat treatment. Examples of such an antioxidant include pentaerythritol tetrakis (3-mercaptopropionate),
Pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3-
(3-tert-Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-]
Hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-
Butyl-4-hydroxyphenyl) propionate],
Octadecyl-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate, 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-te
rt-butyl-4-hydroxybenzyl) benzene,
N, N-hexamethylenebis (3,5-di-tert-
Butyl-4-hydroxy-hydrocinnamide), 3,
5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 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 can be mentioned. The amount of these antioxidants used is 0.001 to 100 parts by weight of the polycarbonate resin.
0.5 parts by weight is preferred.

In the polycarbonate resin composition of the present invention, a releasing agent can be used to the extent that the object of the present invention is not impaired in order to further improve the releasability from the mold during melt molding. 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 preferred, and 0.5 to 2 ppm is more preferred. 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 Blu-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.

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

Specifically, organic salt flame retardants include diphenyl sulfone-3,3'-dipotassium disulfonate, potassium diphenyl sulfone-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, potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, and sodium or potassium hexadecyl sulfate.

Specifically, halogenated aromatic phosphate ester type flame retardants include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, 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 the range not impairing 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, MBS (methyl methacrylate / sterene) which is a core-shell type elastomer. / 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, polycarbonate resin powder, antistatic agent and desired additives are added to a tumbler, a V-type blender, a super mixer,
Nauta mixer, Banbury mixer, kneading roll,
A method of mixing with an extruder or the like is appropriately used. The polycarbonate resin composition 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. 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 for use as a headlamp lens because it has less hue deterioration during molding and less deterioration in wet heat fatigue resistance and excellent antistatic performance after heat treatment.

[0076]

The present invention will be further described with reference to the following examples. Unless otherwise specified, parts in the examples are parts by weight and%
Is% by weight. The evaluation was based on the following method.

(1) Antistatic performance (surface resistance before heat treatment): The specific resistance of the surface of a molded plate having a thickness of 2.0 mm was measured with a SM-8210 polar ultra-insulator manufactured by Toa Denpa Kogyo KK The smaller the value, the better the antistatic performance.

(2) Heat-resistant antistatic performance (surface resistance after heat treatment): A molding plate having a thickness of 2.0 mm was set at a temperature of 120 ° C.
Was stored in the dryer for 100 hours, and the molded plate taken out after the storage was adjusted for 1 week at 23 ° C. and 50%, and then the surface resistance was measured by the method (1).

(3) Transparency (haze): As for transparency, the haze of a 2.0 mm-thick molded plate was measured by NDH manufactured by Nippon Denshoku Co., Ltd.
It was measured at -300A. The larger the haze value, the larger the light diffusion and the poorer the transparency.

(4) Hue (YI value): X, Y, Z measured using a color difference meter Z-1001DP type manufactured by Nippon Denshoku Co., Ltd.
Was calculated using the following formula based on ASTM-E1925. The larger the YI value, the stronger the yellow tint of the molded plate. YI = [100 (1.28X-1.06Z)] / Y

(5) Molding heat resistance (ΔE): Pellets were molded using an injection molding machine at a molding temperature of 315 ° C. for 1 minute to obtain a “flat plate for hue measurement before retention” (70 mm × 50 mm × 2).
mm). In addition, 10 cylinders of resin
After being retained for a minute, it is molded and then used as a “flat plate for measuring hue after retention”.
Got The hue of the flat plate before and after the retention is measured with a color difference meter,
The color difference ΔE was calculated by the following formula. The smaller the value (ΔE) shown in the table, the better the molding heat resistance. ΔE = ((L−L ′) ² + (a−a ′) ² + (b−b ′)
² ) ^1/2 Hue before retention: L, a, b Hue after retention: L ', a', b '

(6) Dry heat resistance (ΔYI): thickness 2.0 m
The molded plate of m was stored in a dryer having a temperature setting of 120 ° C. for 1000 hours. The ΔYI value, which is the difference between the YI value of the molded plate after storage and the value before storage, was calculated. The smaller the ΔYI value, the smaller the color change of the molded plate and the better the dry heat resistance.

(7) Moisture and heat fatigue resistance: Using the so-called C-type measurement sample shown in FIG. 1, 80 ° C., 90% RH
In a sine wave with a frequency of 1 Hz and a maximum load of 2 kg, the fatigue tester [Shimadzu Corporation Shimadzu Servo Pulser EHF-EC5] was used to measure the number of times until the measurement sample broke. It was measured. The larger the value shown in the table (number of times until breakage), the better the wet heat fatigue resistance.

[Examples 1 to 4 and Comparative Examples 1 to 4] A molecular weight of 22000 produced by an interfacial polymerization method from bisphenol A and phosgene (a ratio of 0.7 g of a polymer dissolved in 100 ml of methylene chloride and measured at 20 ° C.). Viscosity 0.4
0) 100 parts of the polycarbonate resin, B in Table 1
The components (antistatic agents) were blended in the amounts shown in Table 1, 0.01 part of acetic acid as an acidity adjusting agent, and 0.000 of Macrolex Violet B manufactured by Bayer Co., Ltd. as a bluing agent.
After 18 parts were blended and mixed in a blender, melt-kneading was performed using a vent type single-screw extruder to obtain pellets. Using an injection molding machine, the obtained pellets were heated to a cylinder temperature of 31.
A 50 mm square plate having a thickness of 2 mm and a measurement sample were molded under the condition of 5 ° C. Table 1 shows the evaluation results of the obtained molded plate. In addition, in Tables 1 to 6, the B component (antistatic agent) represented by a symbol is as follows. B-1; tributylmonooctylphosphonium dodecylbenzenesulfonate B-2; dibutyldioctylphosphonium dodecylbenzenesulfonate B-3; tetrabutylphosphonium dodecylbenzenesulfonate B-4; tributylmonooctadecylphosphonium dodecylbenzenesulfonate

Reference Example 1 Pelletization was carried out in the same manner as in Example 1 except that the B component was not added. The obtained pellet was molded by the same method as in Example 1. Table 1 shows the evaluation results of the obtained molded plate.

[0086]

[Table 1]

[Example 5 and Comparative Example 5] 100 parts of the polycarbonate resin used in Example 1 was blended with the component B (antistatic agent) shown in Table 2 in the amount shown in Table 2 to prepare an acidity adjusting agent. 0.01 part of acetic acid, and Macrolex Violet B manufactured by Bayer Co., Ltd. as a bluing agent.
00018 parts and 0.1 part of glycerin monostearate as a stabilizer were further mixed and mixed in a blender, and then melt-kneaded using a vent type single-screw extruder to obtain pellets. The obtained pellets were molded into a 50 mm square plate having a thickness of 2 mm and a sample for measurement under the conditions of a cylinder temperature of 315 ° C. using an injection molding machine. Table 2 shows the evaluation results of the obtained molded plate. Table 2 shows the evaluation results of the obtained molded plate.

[Reference Example 2] Pelletization was carried out in the same manner as in Example 5 except that the component B was not added. The obtained pellets were molded by the same method as in Example 5. Table 2 shows the evaluation results of the obtained molded plate.

[0089]

[Table 2]

[Example 6 and Comparative Example 6] 100 parts of the polycarbonate resin used in Example 1 was blended with the component B (antistatic agent) shown in Table 3 in the amount shown in Table 3 to prepare an acidity adjusting agent. 0.01 part of acetic acid, and Macrolex Violet B manufactured by Bayer Co., Ltd. as a bluing agent.
00018 parts, 0.1 part of glycerin monostearate as a stabilizer, 0.005 parts of trimethyl phosphate as a heat-resistant stabilizer for molding, and blended in a blender, and then melt-kneaded using a vented single-screw extruder. And pellets were obtained. Using an injection molding machine, the pellets thus obtained were subjected to a cylinder temperature of 315 ° C. and a thickness of 2 mm.
A 0 mm square plate and a measurement sample were molded. Table 3 shows the evaluation results of the obtained molded plate.

[Reference Example 3] Pelletization was carried out in the same manner as in Example 6 except that the component B was not added. The obtained pellet was molded by the same method as in Example 6. The evaluation results of the obtained molded plate are shown in Table 3.

[0092]

[Table 3]

[Example 7, Comparative Example 7] 100 parts of the polycarbonate resin used in Example 1 was blended with the component B (antistatic agent) shown in Table 4 in the amount shown in Table 4 to prepare an acidity adjusting agent. 0.01 part of acetic acid, and Macrolex Violet B manufactured by Bayer Co., Ltd. as a bluing agent.
00018 part, 0.1 part of glycerin monostearate as a stabilizer, tetrakis (2
4-Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite (0.035 parts) was mixed and 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 obtained are 2 m thick at a cylinder temperature of 315 ° C.
A 50 mm square plate of m and a sample for measurement were molded. Table 4 shows the evaluation results of the obtained molded plate.

[Reference Example 4] Pelletization was carried out in the same manner as in Example 7 except that the component B was not added. The obtained pellet was molded by the same method as in Example 7. The evaluation results of the obtained molded plate are shown in Table 4.

[0095]

[Table 4]

[Example 8 and Comparative Example 8] 100 parts of the polycarbonate resin used in Example 1 was blended with the component B (antistatic agent) shown in Table 5 in the amount shown in Table 5 to prepare an acidity adjusting agent. 0.01 part of acetic acid, and Macrolex Violet B manufactured by Bayer Co., Ltd. as a bluing agent.
0018 parts, 0.1 part of glycerin monostearate as a stabilizer, and further 0.05 parts of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a dry heat resistance stabilizer After mixing with a blender, melt-kneading was performed using a vent type single-screw extruder to obtain pellets. The obtained pellets were molded into a 50 mm square plate having a thickness of 2 mm and a sample for measurement under the conditions of a cylinder temperature of 315 ° C. using an injection molding machine. Table 5 shows the evaluation results of the obtained molded plate.

[Reference Example 5] Pelletization was carried out in the same manner as in Example 8 except that the B component was not added. The obtained pellets were molded by the same method as in Example 8. Table 5 shows the evaluation results of the obtained molded plate.

[0098]

[Table 5]

Example 9 and Comparative Example 9 100 parts of the polycarbonate resin used in Example 1 was blended with the component B (antistatic agent) shown in Table 6 in the amount shown in Table 6 to prepare an acidity adjustor. 0.01 part of acetic acid, and Macrolex Violet B manufactured by Bayer Co., Ltd. as a bluing agent.
00018 part, 0.1 part of glycerin monostearate as a stabilizer, 0.005 part of trimethyl phosphate as a heat-resistant stabilizer for molding, tetrakis (2,4-di-te)
0.035 parts of rt-butylphenyl) -4,4′-biphenylene diphosphonite, and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as a dry heat resistance stabilizer. After blending 05 parts and mixing with a blender, pellets were obtained by melt-kneading with a vent type single-screw extruder. Cylinder temperature of the obtained pellets is 315 ° C using an injection molding machine.
Under the conditions described above, a 50 mm square plate having a thickness of 2 mm and a sample for measurement were molded. Table 6 shows the evaluation results of the obtained molded plate.

[Reference Example 6] Pelletization was carried out in the same manner as in Example 9 except that the B component was not added. The obtained pellets were molded by the same method as in Example 9. The evaluation results of the obtained molded plate are shown in Table 6.

[0101]

[Table 6]

Further, using the pellets obtained in each of Examples 1 to 9, a headlamp lens was prepared according to a known method. These headlamp lenses had a good appearance such as antistatic performance persistence, hue and transparency, little deterioration of the resin during molding and dry heat treatment, and retained functionally sufficient mechanical properties.

[0103]

EFFECTS OF THE INVENTION The antistatic polycarbonate resin composition of the present invention is excellent in antistatic performance and durability of antistatic performance in a heated state, and also has transparency, hue, molding heat resistance and dry heat resistance of a molded product. Deterioration is significantly suppressed, and further, a decrease in molecular weight at the time of molding and deterioration of wet heat fatigue resistance can be suppressed, which is extremely useful particularly for headlamp lens applications.

[Brief description of drawings]

FIG. 1 is a front view of a so-called C-type sample used for evaluating resistance to moist heat fatigue. The thickness of the sample is 3 mm. The jig of the tester is passed through the hole indicated by reference numeral 6, and a predetermined load is applied in the vertical direction indicated by reference numeral 7 to perform the test.

[Explanation of symbols]

1 Center of C-shaped double circle 2 Radius of inner circle of double circle (20 mm) 3 Radius of outer circle of double circle (30 mm) 4 Center angle indicating the position of jig mounting hole (60 °) 5 Gap between sample end faces (13 mm) 6 Jig mounting hole (circle with a diameter of 4 mm, located at the center of the sample width)

Claims (3)

[Claims] 1. (A) 100 parts by weight of a polycarbonate resin (a component), (B) 0.05 to 5 parts by weight (b) of a benzenesulfonic acid phosphonium salt represented by the following general formula (I):
An antistatic polycarbonate resin composition consisting of (component). [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.
Represents an alkyl group of 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms or an aryl group having 5 to 15 carbon atoms, and R ³ has 1 to 5 carbon atoms.
Indicates an alkyl group, R ⁴ represents an alkyl group having 6 to 16 carbon atoms, m is an integer of 0 to 3, n is an integer from 1 to 4, a and m + n = 4. ) 2. Further, 0.001 part of the (C) fatty acid ester compound is added to 100 parts by weight of the polycarbonate resin.
The antistatic polycarbonate resin composition according to claim 1, which comprises ˜5.0 parts by weight (component c). 3. A headlamp lens formed of the antistatic polycarbonate resin composition according to claim 1 or 2.