JPH06228421A - Aromatic polycarbonate resin composition - Google Patents

Abstract

(57) [Summary] [Object] To provide an aromatic polycarbonate resin having excellent antistatic properties without impairing transparency, heat resistance, hydrolysis resistance, mechanical strength and the like. An aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin and an amine salt of a specific sulfonic acid, a metal salt, and a phosphite-based antioxidant in specific amounts.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aromatic polycarbonate resin composition. More specifically, it relates to an antistatic aromatic polycarbonate resin composition having excellent transparency, heat resistance, hydrolysis resistance, mechanical strength and the like.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc.
Widely used in machinery, automobiles, medical applications, etc. However, aromatic polycarbonate resin has high surface resistivity, static electricity induced by contact or friction is hard to disappear, dust adheres to the surface of molded products, discomfort due to electric shock to human body, and noise in electronic products. There is a problem such as occurrence of noise and malfunction. In addition, the adhesion of dust becomes a big problem in the optical disc.

Conventionally, as a method of preventing electrostatic charging of an aromatic polycarbonate resin, a method of blending an alkali metal salt of sulfonic acid and a method of blending a phosphonium salt of sulfonic acid and a phosphite ester (Japanese Patent Laid-Open No. 64-14267). ), A method of blending an amine salt of sulfonic acid and a phosphoric acid ester (Japanese Patent Laid-Open No. 3-64368), and the like. However, the aromatic polycarbonate resin obtained by these methods has problems that transparency, color tone, hydrolysis resistance and the like are deteriorated and that heat resistance during molding is lowered.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate resin having excellent antistatic properties without impairing transparency, hydrolysis resistance, heat resistance, mechanical strength and the like. .

As a result of intensive studies aimed at achieving the above object, the present inventor has used an amine salt of a specific sulfonic acid, an alkali metal or alkaline earth metal salt, and a phosphite antioxidant in combination in specific amounts. By doing so, it was clarified that the aromatic polycarbonate resin can be provided with excellent antistatic properties without impairing its excellent transparency, hydrolysis resistance, heat resistance, mechanical strength, etc., and completed the present invention. .

[0006]

The present invention provides the following general formula [1] with respect to 100 parts by weight of an aromatic polycarbonate resin.

[0007]

[Chemical 3]

[Wherein R ₁ is an alkyl group having 1 to 40 carbon atoms, an alkylaryl group or an alkyldiphenyl ether group, and A is a tertiary amine having a hydrocarbon group having 1 to 30 carbon atoms]. 0.1 to 10 parts by weight of an amine salt of sulfonic acid represented by the following general formula [2]

[0009]

[Chemical 4]

[Wherein R ₂ is an alkyl group having 1 to 40 carbon atoms, an alkylaryl group or an alkyldiphenyl ether group, B is an alkali metal or an alkaline earth metal, and n is an alkali metal, 1 is an alkaline earth metal. Metallic salt of sulfonic acid represented by 2 in case of group metal 0.001
To 0.3 parts by weight and 0.00 of a phosphite antioxidant
The present invention relates to an aromatic polycarbonate resin composition containing 1 to 1.0 part by weight.

The aromatic polycarbonate resin targeted by the present invention is an aromatic polycarbonate resin or an aromatic polycarbonate resin or an aromatic polycarbonate resin obtained by the reaction of a dihydric phenol and a carbonate precursor or a dihydric phenol, an aromatic divalent carboxylic acid and a carbonate precursor. It is a polyester carbonate resin. It is usually obtained by an interfacial polycondensation reaction using phosgene or a transesterification reaction using a carbonic acid diester.

The dihydric phenol used here is mainly 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], but some or all of it may be replaced with another dihydric phenol. Good. Other dihydric phenols include, for example, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (4-hydroxy-3-methylphenyl) propane. 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like.

In the interfacial polycondensation reaction using phosgene,
Usually, a dihydric phenol is dissolved in an aqueous solution of an acid binder and reacted in the presence of a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used, and as the solvent, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. In the reaction, a terminal stopper is usually used. As the terminal terminator, for example, a monohydric phenol such as p-tert-butylphenol is preferable, and the amount thereof used is 0.01 to 10 mol%, preferably 0.03 to 8 mol% based on the dihydric phenol.
Is. The reaction temperature is 0 to 40 ° C, preferably 20 to 30
The reaction time is about 10 minutes to 10 hours. It is preferable to maintain the pH of the reaction system at 9 or more as the reaction progresses. A catalyst may be used to accelerate the reaction, and examples of the catalyst include triethylamine and tetra-n.
Examples include tertiary amines such as butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds.
Further, an antioxidant or the like may be added if necessary.

The transesterification reaction using the carbonic acid diester is carried out by distilling the alcohol or phenol produced by stirring the dihydric phenol and the carbonic acid diester while heating in an inert gas atmosphere. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is depressurized to facilitate the distillation of the produced alcohol or phenol. Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate,
Examples thereof include diethyl carbonate and dibutyl carbonate, and among them, diphenyl carbonate is preferable. A polymerization catalyst can be used to speed up the polymerization,
Examples of the polymerization catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide,
Boron and aluminum hydroxides, alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkali metal and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts, zinc compounds, boron Examples of such catalysts include compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like, which are usually used in esterification reactions and transesterification reactions.
The catalyst may be used alone or in combination of two or more kinds. The amount of catalyst used is 0.0 with respect to the dihydric phenol used as the raw material.
001 to 1% by weight, preferably 0.0005 to 0.5% by weight.

The molecular weight of the aromatic polycarbonate resin is
Although it is not particularly limited, it is usually 10,000 or more, preferably 13,000 to 20 in terms of viscosity average molecular weight.
It is 10,000.

The amine salt of sulfonic acid used in the present invention is represented by the above general formula [1], wherein R ₁ is an alkyl group having 1 to 40 carbon atoms, an alkylaryl group or an alkyldiphenyl ether group. Examples thereof include an octyl group, a decyl group, a dodecyl group, an octadecyl group, an eicosyl group, a 2-ethylhexyl group, a nonylphenyl group, a dodecylphenyl group, a dodecylnaphthalene group, a dodecyldiphenylether group, and a 2-ethylhexyldiphenylether group. If the carbon number of R ₁ exceeds 40, the antistatic effect becomes poor. A is a tertiary amine having a hydrocarbon group having 1 to 30 carbon atoms and has the following general formula [3].

[0017]

[Chemical 5]

[Wherein R ₃ , R ₄ and R ₅ are the same or different hydrocarbon groups having 1 to 30 carbon atoms, and R ₃ and R ₄ are connected to each other to form a heterocycle with a nitrogen atom. be those represented by even or] have been, R _3, R ₄ and is, for example, methyl group as R _5, a propyl group, a hexyl group, a 2-ethylhexyl group, lauryl group, oleyl group,
Alkyl group such as stearyl group, phenyl group, nonylphenyl group, alkylphenyl group such as dodecylphenyl group,
Examples thereof include an aralkyl group such as a benzyl group and a cycloalkyl group such as a cyclohexyl group. Further, a substituent may be introduced into these hydrocarbon groups, and examples thereof include a hydroxyalkyl group, or a group obtained by blocking the end of a group obtained by adding alkylene oxide to a hydroxyalkyl group with an ether or an ester. These R ₃ , R ₄ and R ₅
If the number of carbon atoms exceeds 30, the antistatic effect will be poor.

Specific examples of the amine salt of sulfonic acid include octyldimethylamine propylsulfonate, hexyldimethylamine octylsulfonate, dodecyldipropylamine dodecylsulfonate, octyldiethylamine octadecylsulfonate, and stearyldi (methoxyethyl) nonylbenzenesulfonate. ) Amine, dodecylbenzenesulfonic acid didodecylmethylamine, dodecylnaphthalenesulfonic acid behenyldipropylamine, dodecyldiphenylethersulfonic acid dodecyldipropylamine, etc., which may be used alone or in combination of two or more. Good.

The metal salt of sulfonic acid used together with the amine salt of sulfonic acid is represented by the above general formula [2], wherein R ₂ is an alkyl group having 1 to 40 carbon atoms, an alkylaryl group or An alkyl diphenyl ether group,
The same ones as described for R _{1 in} the general formula [1] can be mentioned. B is an alkali metal or alkaline earth metal such as Li, Na, K, Mg, Ca and Ba, and Li, Na, K and Ca are particularly preferable. Specific examples of the metal salt of sulfonic acid include sodium propylsulfonate, lithium octylsulfonate, potassium dodecylsulfonate, calcium octadecylsulfonate, lithium propylbenzenesulfonate, sodium nonylbenzenesulfonate, potassium dodecylbenzenesulfonate, and dodecylnaphthalene. Examples thereof include sodium sulfonate and sodium dodecyldiphenyl ether sulfonate, which may be used alone or in combination of two or more kinds.

The compounding amount of the amine salt of sulfonic acid is
0.1 per 100 parts by weight of aromatic polycarbonate resin
10 to 10 parts by weight, preferably 0.5 to 5 parts by weight.
If it is less than 0.1 part by weight, a sufficient antistatic effect is difficult to be obtained, and if it exceeds 10 parts by weight, the mechanical properties of the obtained composition deteriorate. The compounding amount of the metal salt of sulfonic acid is 0.001 to 0.3 part by weight based on 100 parts by weight of the aromatic polycarbonate resin, and 0.005 to 0.2
Parts by weight are preferred. If it is less than 0.001 part by weight, it is difficult to obtain a sufficient effect of improving the hydrolyzability, and if it exceeds 0.3 part by weight, the transparency of the obtained composition is lowered.

The above-mentioned amine salt of sulfonic acid is obtained by neutralizing sulfonic acid with a tertiary amine by a conventional method,
The metal salt of sulfonic acid can be obtained by neutralizing sulfonic acid with a compound of an alkali metal or an alkaline earth metal by a conventional method. Both can be prepared separately and then mixed in a predetermined amount in an arbitrary order or in advance and mixed with the aromatic polycarbonate resin. Further, the sulfonic acid is first neutralized with a predetermined amount of a tertiary amine by a conventional method, and subsequently, neutralized with a predetermined amount of an alkali metal or alkaline earth metal compound by a conventional method, or the tertiary amine is used. It is also possible to mix and use a compound of an alkali metal or an alkaline earth metal in a predetermined molar ratio and then neutralize the sulfonic acid to prepare a mixture of an amine salt and a metal salt of sulfonic acid in a predetermined ratio for use.

Examples of the phosphite-based antioxidant used in combination with the sulfonate include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite. , Trioctyl phosphite, trioctadecyl phosphite, didecyl-monophenyl phosphite, dioctyl-monophenyl phosphite, diisopropyl-monophenyl phosphite, monobutyl-diphenyl phosphite, monodecyl-diphenyl phosphite, monooctyl-diphenyl phosphite , Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis ( Nirufeniru) pentaerythritol - di - phosphite, bis (2,4-di -tert
-Butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite and other triesters of phosphite, or the ester moiety is an alkyl group, These are diesters and monoesters substituted with a phenyl group, an alkylaryl group, etc. These may be used alone or in combination of two or more. Of these, trisnonylphenyl phosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite are preferable.

The amount of the phosphite-based antioxidant compounded is 0.001 to 1.0 part by weight per 100 parts by weight of the aromatic polycarbonate resin. If it is less than 0.001 part by weight, the object of the present invention is difficult to achieve, and if it exceeds 1.0 part by weight, silver may be generated or foaming may occur during molding.

The aromatic polycarbonate resin composition of the present invention may further contain other phenol-based antioxidants and / or organic sulfur-based antioxidants, which is also preferable.

The phenolic antioxidant which can be preferably blended in the resin composition of the present invention is a hindered phenolic compound having a bulky group at the ortho position with respect to the hydroxyl group of the phenolic compound, for example, 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'-hexamethylene bis (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, among which pentaerythritol-tetrakis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate is preferred.

Examples of the organic sulfur antioxidants include tetrakis [methylene-3- (hexylthio) propionate] methane, tetrakis [methylene-3- (decylthio) propionate] methane, tetrakis [methylene-].
3- (laurylthio) propionate] methane, tetrakis [methylene-3- (octylthio) propionate] methane, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3 , 3'-thiodipropionate,
Ditridecyl-3,3'-thiodipropionate, 2,
2-thio-diethylenebis [3- (3,5-di-tert-
Butyl-4-hydroxyphenyl) propionate],
2,2-thiobis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like can be mentioned, and among them, tetrakis [methylene-3- (laurylthio) propionate] methane is preferable.

Any method may be employed to produce the aromatic polycarbonate resin composition of the present invention. For example, the most convenient method is to dry-blend each component using a tumbler, a super mixer, a Nauta mixer, etc., pelletize with an extruder, and then subject it to desired molding. Further, the resin composition of the present invention can be subjected to any molding such as injection molding, extrusion molding, plow molding, compression molding and the like.

In the aromatic polycarbonate resin composition of the present invention, if necessary, other additives such as ester-based compounds,
Mold release agents such as silicone, benzotriazole, benzophenone, salicylate, cyanoacrylate, and other UV absorbers, anthraquinone and other infrared absorbers,
Halogen-based, phosphorus-based, flame retardant such as salts, heat stabilizer, glass fiber, carbon fiber, metal fiber, whiskers, carbon black, calcium carbonate, filler such as glass beads,
You may mix | blend coloring agents, such as a dye and a pigment. In addition, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone, AS resin, ABS resin,
You may mix resin, such as MBS resin.

[0030]

EXAMPLES The present invention will be further described below with reference to examples. In addition,
Parts in the examples are parts by weight, and heat resistance (heat resistance during molding), hue, transparency, hydrolysis resistance and surface resistivity were measured by the following methods.

(A) A heat-resistant flat plate having a size of 50 mm × 50 mm × 2 mm is formed by an injection molding machine [Neomat N150 / manufactured by Sumitomo Heavy Industries Ltd.].
75], cylinder temperature 280 ° C., molding cycle 3
During the molding for 5 seconds, the molding was temporarily stopped, the molding was restarted after being retained at 280 ° C. for 10 minutes, and the L value of the flat plate before and after the retention, a
The value and the b value were measured with a color difference meter manufactured by Suga Test Co., Ltd., and the color difference (ΔE) was obtained. The larger the ΔE, the worse the heat resistance.

(B) The hue is represented by the b value of the flat plate before the retention.
The larger the b value, the worse the hue. (c) As for transparency, the total light transmittance of the flat plate before retention was measured by NDH-Σ80 manufactured by Nippon Denshoku Co., Ltd. (d) Hydrolysis resistance was measured by using a PR-2 GP constant temperature / humidity machine manufactured by Tabai Espec Co.
Retention rate of molecular weight (%) after wet heat treatment at RH for 1000 hours
Indicated by.

[0033]

[Equation 1]

(E) Surface resistivity: The surface resistivity of the flat plate before dwelling was measured by SM-8210 polar ultra-insulator manufactured by Toa Denpa Co., Ltd.

[0035]

Examples 1-18 and Comparative Examples 1-6 Bisphenol A
And 100 parts of an aromatic polycarbonate resin having a viscosity average molecular weight of 23,000 produced from phosgene, the antistatic agent and the antioxidant shown in Table 1 were added in the amounts (parts) shown in the table, mixed by a super mixer, and a 30φ extruder was used. By 2
Extrude at 60 ° C to form pellets.
After hot air drying at 0 ° C. for 6 hours, an evaluation flat plate was injection molded,
evaluated. The evaluation results are shown in Table 1.

The symbols representing the antistatic agent and the antioxidant in Table 1 are as follows. A-1: Dodecylsulfonic acid dodecyldipropylamine A-2: Dodecylbenzenesulfonic acid didodecylmethylamine A-3: Dodecyldiphenylethersulfonic acid didodecylmethylamine A-4: Dodecylsulfonic acid didodecylmethylamine B-1: Potassium dodecyl sulfonate B-2: Sodium dodecylbenzene sulfonate B-3: Lithium dodecyl diphenyl ether sulfonate B-4: Sodium dodecyl sulfonate B-5: Potassium dodecyl benzene sulfonate C-1: Tetrabutylphosphonium dodecyl benzene sulfonate D-1: Trisnonylphenylphosphite D-2: Tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite D-3: Nonylphenyldiphenylphosphate E-1: Octadecyl-3 -(3,5-di tert- butyl-4-hydroxyphenyl) propionate E-2: Pentaerythritol - tetrakis [3- (3,
5-Di-tert-butyl-4-hydroxyphenyl) propionate] F-1: tetrakis [methylene-3- (laurylthio) propionate] methane

[0037]

[Table 1]

[0038]

The aromatic polycarbonate resin composition of the present invention has excellent antistatic properties without impairing the original transparency, heat resistance, hydrolysis resistance and mechanical strength of the aromatic polycarbonate resin. Since it has, it is extremely useful as a substrate material for electric disks, mechanical applications, automobile applications, medical applications, etc., and further for optical discs.

Claims (1)

[Claims] 1. A compound represented by the following general formula [1] with respect to 100 parts by weight of an aromatic polycarbonate resin. [Wherein R ₁ is an alkyl group having 1 to 40 carbon atoms, an alkylaryl group or an alkyldiphenyl ether group,
A is a tertiary amine having a hydrocarbon group of 1 to 30 carbon atoms] and an amine salt of sulfonic acid represented by 0.1 to 10
By weight, the following general formula [2] [In the formula, R ₂ is an alkyl group having 1 to 40 carbon atoms, an alkylaryl group or an alkyldiphenyl ether group,
B is an alkali metal or an alkaline earth metal, n is 1 for an alkali metal, and 2 for an alkaline earth metal] 0.001 to 0.3 parts by weight of a metal salt of sulfonic acid and phosphite An aromatic polycarbonate resin composition containing 0.001 to 1.0 part by weight of a system antioxidant.