JPH0693176A - Antistatic polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in impact resistance, surface appearance and delamination resistance by mixing a polycarbonate resin with a specified antistatic agent, a rubber-reinforced styrene resin and a specified epoxy olefin copolymer. CONSTITUTION:The composition comprises 100 pts.wt. polycarbonate resin, 0.1-10 pts.wt. antistatic agent comprising an alkylbenzenesulfonate of formula I, 0.5-20 pts.wt. rubber-reinforced styrene resin and 0.1-15 pts.wt. epoxy olefin copolymer comprising an epoxy compound and an olefin or comprising an epoxy compound, an olefin and an ethylenically unsaturated compound. In the formulas, R1 and R2 are each 8-22C linear or branched alkyl; and M is an alkali metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic polycarbonate resin composition which is excellent in impact resistance and surface appearance and prevents delamination.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate resins are excellent in impact resistance, heat resistance and the like, and are widely used in various fields such as the vehicle field, light electric power, medical care, food, etc. Static electricity is easily charged and may cause various troubles and disasters. For this reason, conductive carbon black or carbon fiber is kneaded, but the color tone is limited to black and cannot be colored in any other color, so the range of use is also limited. .

On the other hand, various methods of incorporating a surfactant as an antistatic agent have been proposed. This method is advantageous in terms of easiness of processing steps and economical efficiency. However, it is difficult to disperse it uniformly because it has poor compatibility with polycarbonate resin, and it easily decomposes when heated, which deteriorates the appearance of the molded product and at the same time causes delamination, and also reduces the physical properties of the polycarbonate resin. There is a problem that it invites.

[0004] In order to improve the dispersibility of such a surfactant, MBS resin, ABS resin and the like have been blended, but they are still insufficient in terms of the surface appearance and delamination of the molded product. , Improvement was desired.

[0005]

[Means for Solving the Problems] As a result of earnest studies on the above problems, the present inventors have found that an alkyl sulfonate and /
Further, they have found that the above problems can be solved by using an alkylbenzene sulfonate and further compounding a rubber-reinforced styrene-based resin and a specific copolymer, and arrived at the present invention.

That is, in the present invention, the alkyl sulfonate represented by the following general formula [I] and / or the following general formula [II] is used as the antistatic agent (B) per 100 parts by weight of the polycarbonate resin (A). 0.1 to 10 parts by weight of alkylbenzene sulfonate, 0.5 to 20 parts by weight of rubber-reinforced styrene resin (C), and epoxy group-containing compound and olefin are epoxy group-containing olefin consisting of them and ethylenically unsaturated compound. Polymer (D) 0.1-15
The present invention provides an antistatic polycarbonate resin composition characterized by being mixed in parts by weight.

[0007]

[Chemical 3]

[Chemical 4]

(In the formula, R ₁ and R ₂ have 8 to 22 carbon atoms.
Is a linear or branched alkyl group, and M is an alkali metal. )

The present invention will be described in detail below. The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene or a transesterification method in which dihydroxydiaryl compounds are reacted with a carbonic acid ester such as diphenyl carbonate. A typical example is a polycarbonate produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

As the dihydroxydiaryl compound, in addition to bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxy diaryl ethers such as 3,3′-dimethyldiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-
Examples thereof include dihydroxydiaryl sulfoxides such as 3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, and dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone. To be

These may be used alone or in admixture of two or more, but in addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be mixed and used.

Further, the above-mentioned dihydroxyaryl compound and a phenol compound having a valence of 3 or more as shown below may be mixed and used.

Examples of trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4,6-dimethyl-2,4,6-tri. -(4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4,4-
(4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

The viscosity average molecular weight of polycarbonate is usually
It is 10,000 to 100,000, preferably 15,000 to 35,000.
In producing such a polycarbonate, a molecular weight modifier, a catalyst and the like can be used if necessary.

In the present invention, the alkyl sulfonate and the alkylbenzene sulfonate used as the antistatic agent (B) are represented by the following general formulas [I] and [II], respectively.

[0017]

[Chemical 5]

[0018]

[Chemical 6]

(In the formula, R ₁ and R ₂ have 8 to 22 carbon atoms.
Is a linear or branched alkyl group, and M is an alkali metal. )

The amount of the above-mentioned alkyl sulfonate and / or alkylbenzene sulfonate used as the antistatic agent (B) is the same as that of the polycarbonate resin (A) 1
It is 0.1 to 10 parts by weight per 00 parts by weight. If it is less than 0.1 part by weight, the antistatic property is inferior, and if it exceeds 10 parts by weight, the impact resistance and the surface appearance are inferior and delamination occurs, which is not preferable. It is preferably 0.1 to 8 parts by weight.

As the rubber-reinforced styrene resin (C) in the present invention, ABS resin, diene rubber-reinforced styrene resin represented by MBS resin, AES resin, A
Non-diene rubber reinforced styrene resins represented by AS resins and ACS resins are mentioned. A diene rubber-reinforced styrene resin is particularly preferable.

The amount of the rubber-reinforced styrene resin (C) used is 0.1 parts by weight per 100 parts by weight of the polycarbonate resin (A).
5 to 20 parts by weight. When it is less than 0.5 parts by weight, delamination occurs and the surface appearance is inferior, and when it exceeds 20 parts by weight, fluidity and rigidity are deteriorated, which is not preferable.

It is preferably 0.5 to 10 parts by weight.

The epoxy group-containing olefin copolymer (D) used in the present invention is an unsaturated epoxy compound and an olefin, or a copolymer of these and an ethylenically unsaturated compound. The composition ratio of the epoxy group-containing olefin copolymer is not particularly limited, but the unsaturated epoxy compound is preferably 0.05 to 95% by weight.

The unsaturated epoxy compound is a compound having an unsaturated group capable of copolymerizing with an olefin and an ethylenically unsaturated compound, and an epoxy group in the molecule.

For example, unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, P-
It is an unsaturated epoxy compound such as glycidyl styrenes.

Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butenecarboxylic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-P-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,
4-epoxy-1-pentene, 3,4-epoxy-3-
Methyl pentene, 5,6-epoxy-1-hexene, vinyl cyclohexene monoxide, P-glycidyl styrene and the like can be mentioned, and one kind or two or more kinds can be used. Glycidyl acrylate or glycidyl methacrylate is particularly preferable.

Examples of the olefin include ethylene, propylene, butene, pentene and the like, and one or more kinds can be used. Particularly, ethylene and propylene are preferable.

The ethylenically unsaturated compounds include vinyl esters containing C _{2 to} C ₆ in the saturated carboxylic acid component, acrylic acid and methacrylic acid esters containing C _{1 to} C ₈ in the saturated alcohol component, and maleic acid ester. And vinyl halides.

When the unsaturated epoxy compound and the olefin are copolymerized, these ethylenically unsaturated compounds are copolymerized in an amount of 50% by weight or less, particularly 0.1 to 45% by weight, based on all the compounds.

Epoxy group-containing olefin copolymer (D)
Is a copolymerization of an unsaturated epoxy compound with an olefin and optionally an ethylenically unsaturated compound, or a grafting of an unsaturated epoxy compound in the presence of an olefin polymer or a copolymer of an olefin and an ethylenically unsaturated compound. It is manufactured by copolymerization.

Epoxy group-containing olefin copolymer (D)
Preferred examples of ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl methacrylate-glycidyl methacrylate copolymer, and polyethylene, polypropylene, poly-1-butene, poly-4
-Methyl-pentene-1, ethylene-propylene copolymers, ethylene-propylene-diene copolymers and the like copolymers obtained by graft reaction of glycidyl methacrylate in the presence of olefin polymers.

Epoxy group-containing olefin copolymer (D)
As a method for producing the above, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method or a polymerization method combining these methods is used.

The amount of the epoxy group-containing olefin copolymer (D) used is 100% of the polycarbonate resin (A).
It is 0.1 to 15 parts by weight per part by weight. When it is less than 0.1 part by weight, delamination occurs and the surface appearance is inferior, and when it exceeds 15 parts by weight, fluidity and rigidity are deteriorated, which is not preferable. It is preferably 0.1 to 10 parts by weight.

There is no particular limitation on the mixing method and mixing order of the above components (A), (B), (C) and (D), and they are mixed by a known mixer such as a tumbler, a ribo blender or a high speed mixer. However, it can be performed by melt-kneading. It is also possible to simultaneously mix the above-mentioned four components or to mix only the specific components and then add and mix the remaining components.

Further, at the time of mixing, known additives such as antistatic agents other than the component (B), release agents, antioxidants, ultraviolet absorbers, flame retardants, dyes and pigments may be added, if necessary. You can

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example] Polycarbonate resin (A),
The antistatic agent (B), the rubber-reinforced styrene resin (C), and the epoxy group-containing olefin copolymer (D) were mixed in a tumbler based on the compounding ratio shown in Table 1, and then melt-kneaded in an extruder. , Pellets were obtained. Using a 4 ounce injection molding machine from the pellets obtained, set the cylinder temperature to 2
Various test pieces were prepared at 80 ° C. and subjected to the test. The test results are shown in Table 1.

The materials obtained in this example are as follows.

P C: Aromatic polycarbonate composed of bisphenol A and phosgene and having a viscosity average molecular weight of 25,000. B-1: Alkane sulfonate Lion Co., Ltd. Rheostat P-200 B-2: Alkylbenzene sulfonate Lion Co., Ltd. FD-3015 b-1: Conductive carbon fiber Toho Rayon Co., Ltd. Besfight HTA-C6-SR C -1: MBS resin Kureha Scientific Co., Ltd. KCA-102 C-2: ABS resin Sumitomo Nogatak Co., Ltd. MH MC-4 D-1: Ethylene-glycidyl methacrylate-vinyl acetate copolymer Sumitomo Chemical Co., Ltd. Made Bond First 2B

Various test methods are as follows.

O Impact Strength ASTM D-256 1/8
", Notched Izod, 23 ℃

O Fluidity (melt flow index) A
STM D-1238 300 ℃, 1.2kg

Flexural Modulus ASTM D-790 2
3 ° C

O A flat plate having a surface resistance value of 90 × 40 × 3 mm was molded and measured under the following conditions. After conditioning the test piece for 24 hours under the conditions of 23 ° C. and 55% relative humidity, using a surface high resistance meter SM-10E (manufactured by Toa Denpa Kogyo Co., Ltd.), a measurement voltage of 100 V and a sampling time of 30 seconds were used. The surface resistance value was measured.

O Surface appearance A 90 × 40 × 3 mm flat plate was molded and the state of pearly luster on the surface was visually evaluated. ○: None △: Somewhat Yes ×: Yes

O Layered Peeling After the test piece shown in the drawing is prepared, it is bent at the film gate portion to confirm the presence or absence of layered peeling at the molded product portion when the sprue portion is removed.

[0048]

[Table 1]

[Brief description of drawings]

FIG. 1 is a plan view of a test piece used to evaluate the presence or absence of delamination.

FIG. 2 is a sectional view of a test piece.

[Explanation of symbols] Gate Film gate Molded product Sprue A Bending direction

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[Procedure amendment]

[Submission date] September 6, 1993

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a plan view of a test piece used to evaluate the presence or absence of delamination.

FIG. 2 is a sectional view of a test piece.

[Explanation of symbols] Gate Film gate Molded product Sprue A Bending direction

Claims (1)

[Claims] 1. An alkyl sulfonate represented by the following general formula [I] and / or an alkylbenzene sulfonic acid represented by the following general formula [II] as an antistatic agent (B) per 100 parts by weight of a polycarbonate resin (A). Salt 0.1-
10 parts by weight, rubber-reinforced styrene resin (C) 0.5-20
An antistatic polycarbonate resin, characterized in that 0.1 to 15 parts by weight of an epoxy group-containing olefin copolymer (D) consisting of 1 part by weight and an epoxy group-containing compound and an olefin or an ethylenically unsaturated compound thereof are blended. Composition. [Chemical 1] [Chemical 2] (In the formula, R ₁ and R ₂ represent a linear or branched alkyl group having 8 to 22 carbon atoms, and M represents an alkali metal.)