JP2561598B2 - Antistatic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic resin composition. More specifically, it relates to a resin composition having excellent permanent antistatic properties.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting antistatic properties to polyolefin resins, (1) a surfactant having antistatic properties (polyhydric alcohol fatty acid ester, low molecular weight carbobetaine type compound, etc.) is used as a polyolefin. (2) A method of grafting a radical-reactive antistatic monomer having a double bond onto polyethylene or polypropylene (for example, JP-B-46-30293, JP-B-49-26955, etc.) Alternatively, (3) a method of blending and dispersing a rubber trunk polymer having a polyoxyalkylene chain as it is or by graft-polymerizing a vinyl-based monomer or the like into a thermoplastic resin (for example, JP-A-55-36237, JP-A-56-118446, etc.) is known.

[0003]

However, in the method described in (1) above, since the surfactant is not chemically bound to the polyolefin resin, the antistatic property can be easily obtained by washing with water or rubbing. It has the drawback of disappearing, and if a large amount of a surfactant is added and kneaded in order to maintain antistatic properties, not only will the mechanical properties of the resin be impaired, but the surfactant will also easily bleed out on the resin surface, making it sticky. However, there is a drawback that dust and the like are more likely to occur and the appearance is impaired. According to the method described in (2), the grafting rate is extremely small, and it is difficult to impart substantially permanent antistatic property. In addition, although the method according to (3) certainly exhibits the effect of permanent antistatic property, a polymer having antistatic property is produced by emulsion polymerization, suspension polymerization, or the like, and then a resin such as polyolefin. Since it is a method of obtaining an antistatic resin by adding to the above, a very complicated process is required.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by blending polyethylene or polypropylene with a rubbery polymer,
The present invention has been accomplished by finding a method in which an antistatic resin can be easily introduced into a composite resin of polyethylene or polypropylene without requiring complicated steps.

That is, the present invention comprises the following (A), (B) and (C), where (A) / (B) is (5)
0-95) / (50-5), and (C) / [(A) +
(B)] is an antistatic resin composition obtained by melt-kneading a compounding component of (1 to 30) / 100 and performing a radical reaction. (A): Polyethylene or polypropylene. (B): A rubbery polymer having a glass transition temperature of 0 ° C. or lower. (C): Mono (meth) acrylate of polyoxyalkylene ether of monohydric alcohol or phenol having at least 8 carbon atoms.

In the present invention, polyethylene or polypropylene (A) includes low-medium density polyethylene, high-density polyethylene and copolymers of ethylene with one or more other α-olefins, propylene homopolymers and propylene and other α. -Copolymers with one or more olefins. Examples of other α-olefins include ethylene (excluding polyethylene), propylene (excluding polypropylene), 1-butene, and 4-methyl-olefin.
Examples include 1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene. The melt flow rate (MFR) of (A) is usually 0.5 to 250, preferably 1 to 200. The melt flow rate is, for example, JIS K6758 (temperature 230 ° C, load 2.16 kgf) for polypropylene, and JIS K6760 (temperature 190 ° C, load 2. for polyethylene).
16 kgf) can be measured.

In the present invention, as the rubbery polymer (B) having a glass transition temperature of 0 ° C. or less, a butadiene rubbery polymer (for example, butadiene homopolymer rubber, styrene / butadiene copolymer rubber, butadiene / ( (Meth) acrylic ester copolymer rubber, acrylonitrile / butadiene copolymer rubber), chloroprene rubber polymer, isoprene rubber polymer, natural rubber, ethylene / propylene copolymer rubber polymer, ethylene / propylene / diene monomer Examples thereof include a copolymer rubbery polymer and a cycloolefin rubbery polymer. Two or more of these may be used in combination. Of these, preferred are a butadiene rubber polymer, an ethylene / propylene copolymer rubber polymer, and an ethylene / propylene / diene monomer copolymer rubber polymer. The molecular weight of the rubber-like polymer (B) is not particularly limited, but usually the number average molecular weight is 1,000 to 100,000.
Is.

The weight ratio (A) / (B) of (A) and (B) in the present invention is usually 50 to 95/50 to 5, preferably 50.
~ 90/50 ~ 10. When (A) is less than 50, the resin characteristics of (A) cannot be exhibited, and when it exceeds 95, the effect of permanent antistatic property becomes small.

(C) is a monohydric alcohol having at least 8 carbon atoms (octyl alcohol, lauryl alcohol, 2-ethylhexyl alcohol, etc.) or phenols (phenol, alkylphenol, naphthol,
Phenylphenol, benzylphenol, etc.) polyoxyalkylene ether obtained by polyaddition of alkylene oxide (ethylene oxide, propylene oxide, butene oxide or a mixture thereof),
It can be obtained by an esterification reaction with (meth) acrylic acid.

Preferred as (C) are mono (meth) acrylates of ethylene oxide polyadducts of the above alcohols or phenols, and particularly preferred are monooxy of polyoxyethylene alkyl (having at least 8 carbon atoms) ether. It is a (meth) acrylate.

The number average molecular weight of (C) is usually from 500 to
It is 6,000, preferably 800 to 5,000. 5
When it is less than 00, the effect of antistatic property is small and 6,000
If it exceeds, the grafting ratio is lowered, and thus the substantial permanent antistatic property is lowered.

The amount of (C) used is usually 1 to 30% by weight, preferably 3 to 20% by weight, based on the total weight of the above (A) and (B). If (C) is less than 1% by weight, the antistatic effect is poor, and if it exceeds 30% by weight, the physical properties of the resin deteriorate.

When melt-kneading the compounding components consisting of (A), (B) and (C) to cause a radical reaction, a sulfonate-containing monomer (D) copolymerizable with (C) may be used. preferable.

Examples of (D) include aromatic hydrocarbon vinyl sulfonates, sulfonate-containing (meth) acrylamides, sulfonate-containing (meth) acrylates, and aliphatic hydrocarbon vinyl sulfonates.

Specific examples of (D) include p- and o-.
Styrene sulfonate, styrene disulfonate, α-
Aromatic hydrocarbon vinyl sulfonates such as methyl styrene sulfonate and vinyl phenyl methane sulfonate;
2- (meth) acrylamide-2-methylpropanesulfonate, 3- (meth) acrylamidepropane-1-
Sulfonate, 2- (meth) acrylamidoethyl-1
Sulfonate-containing (meth) acrylamides such as sulfonates, 3- (meth) acrylamide-2-hydroxypropane sulfonate, p- (meth) acrylamidomethylbenzene sulfonate; 3- (meth) acryloyloxy Propane-1-sulfonate, 4- (meth) acryloyloxybutane-1-sulfonate, 4- (meth)
Acryloyloxybutane-2-sulfonate, 2- (meth) acryloyloxyethyl-1-sulfonate, 3-
Examples thereof include sulfonate-containing (meth) acrylates such as (meth) acryloyloxy-2-hydroxypropanesulfonate; and aliphatic hydrocarbon vinylsulfonates such as vinylsulfonate and (meth) allylsulfonate. Of these, preferred are aromatic hydrocarbon vinyl sulfonates, sulfonate-containing (meth) acrylamides and aliphatic hydrocarbon vinyl sulfonates,
Particularly preferred are p- and o-styrene sulfonates, 2- (meth) acrylamido-2-methylpropane sulfonate and (meth) allylsulfonate.

As the cation component constituting the sulfonate of (D), alkali metals such as sodium, potassium and lithium, alkaline earth metals such as calcium and magnesium, ammonia, ethanolamine, diethylethanolamine and monomethyl. Examples include amines such as amine and trimethylamine. Preferred among these are sodium, potassium and ammonia. Two or more kinds of the sulfonate-containing monomer (D) and the cation component exemplified above may be mixed and used.

The amount of (D) used is usually 0.5 to 15% by weight, preferably 1 to 10% by weight, based on the total weight of (A) and (B). If it is less than 0.5% by weight, the antistatic effect is poor, and if it exceeds 15% by weight, the physical properties of the resin deteriorate.

Further, when the blended components are melted and kneaded to cause a radical reaction, it is preferable to use a radical initiator (E). Examples of the (E) include organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide and dicumyl peroxide, 2,2'-azobis (isobutyronitrile), 2,2'-azobis ( Examples thereof include azonitriles such as 2,4-dimethylvaleronitrile) and 4,4'-azobis (4-cyanovaleric acid). Two or more of these may be used in combination. The usage is
It is usually 1 to 30% by weight, preferably 1 to 15% by weight, based on the total weight of (C) and (D).

In the radical reaction, a chain transfer agent known as a molecular weight modifier can be used if necessary. As the chain transfer agent, n-butyl mercaptan, ter
Aliphatic mercaptans such as t-butyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, ethers such as phenyl ether, phenylethyl ether, isopropylphenyl ether, dibenzyl ether, and cumene, alcohols, phenols, Examples thereof include halogenated hydrocarbons and the like, and the amount used is usually 15% by weight or less based on the total weight of (C) and (D).

The radical reaction temperature is usually 150 to 300 ° C., preferably 160 to 280 ° C., and the reaction time is usually 2 to 30 minutes, preferably 3 to 15 minutes. After the reaction, the unreacted volatile matter and the like are usually degassed and removed while maintaining the temperature to obtain the antistatic resin composition of the present invention. Decompression degree is usually 0.1 to 20 mmHg.

The reactor is not particularly limited, but generally known mixers can be used. Examples of the mixer include an extruder, a Brabender, a kneader and a Banbury mixer.

In the present invention, the modified polyolefin-based dispersant (F) may be further contained in the compounding ingredients.
Among (F), the following (F ₁ )
(F ₃ ) can be raised. (F ₁ ); number average molecular weight 800 to 25,000, acid value 5 to 150
Acid-modified low-molecular-weight polyolefin (F ₂ ) having a number average molecular weight of 800 to 25,000 and a hydroxyl value of 5
~ 150 hydroxyl group modified low molecular weight polyolefin. (F ₃ ); A polyoxyalkylene-modified low-molecular-weight polyolefin having a number average molecular weight of 1,000 to 28,000 in which part or all of the (anhydrous) carboxylic acid unit of (F ₁ ) is esterified with a polyoxyalkylene compound.

The (F ₁ ) is a number average molecular weight of 70 obtained by a polymerization method or a thermal degradation method of a high molecular weight polyolefin.
By modifying a low molecular weight polyolefin having a molecular weight of 0 to 20,000 with α, β-unsaturated carboxylic acid and / or anhydride thereof in the presence of an organic peroxide, if necessary, by a solution method or a melting method. Obtainable. A low molecular weight polyolefin obtained by a thermal degradation method is preferable because it is easily modified. The low molecular weight polyolefin obtained by the thermal degradation method can be obtained, for example, according to the method described in JP-A-3-62804.

The α, β-unsaturated carboxylic acid and / or its anhydride used for modification include (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and citraconic anhydride. Can be given. Among these, (anhydrous) maleic acid is preferable. The modification degree is usually 1-2 based on the weight of the low molecular weight polyolefin.
It is 5% by weight, preferably 3 to 20% by weight. The number average molecular weight of (F ₁ ) obtained by the above method is 800 to 25,00.
It is 0, preferably 1,000 to 20,000. Less than 800 or 25,
If it exceeds 000, the effect as a dispersant decreases. The acid value of (F ₁ ) is 5 to 150, preferably 10 to 100.
If it is less than 5, the effect as a dispersant is poor, and if it exceeds 150, the hue is deteriorated, which causes coloring of the resin composition.

The (F ₂ ) can be obtained by secondarily modifying the above (F ₁ ) with an alkanolamine. Alkanolamines include, for example, monoethanolamine, monoisopropanolamine, diethanolamine and diisopropanolamine. Of these, particularly preferred is monoethanolamine. The hydroxyl value of (F ₂ ) is 5 to 150, preferably 10 to 100. If it is less than 5, the effect of introducing a hydroxyl group is small, and if it exceeds 150, the hue is deteriorated, which causes coloring of the resin composition.

Further, the (F ₃ ) can be obtained by esterifying a part or all of the (anhydrous) carboxylic acid unit of the above (F ₁ ) with a polyoxyalkylene compound. Examples of the polyoxyalkylene compound used for esterification include compounds having hydroxyl groups at both ends such as polyethylene glycol and polypropylene glycol, and compounds in which the above hydroxyl groups are replaced with amino groups or epoxy groups. Further, compounds having active hydrogen such as alcohols (methanol, ethanol, butanol, octanol, lauryl alcohol, 2-ethylhexyl alcohol, etc.) and phenols (phenol, alkylphenol, naphthol, phenylphenol, benzylphenol, etc.) have alkylene oxides. A polyalkylene compound which is added and basically has a hydroxyl group at one end is given. The esterification rate is not particularly limited, but is 10 to 100 mol% of the (anhydrous) carboxylic acid unit of (F ₁ ).
Is preferably esterified. The number average molecular weight of (F ₃ ) is 1,000 to 28,000, preferably 1,200 to 250,000.
00. If it is less than 1,000 or more than 28,000, the effect as a dispersant decreases.

Examples of the modified polyolefin dispersant (F) other than those exemplified above are copolymers of olefin and α, β-unsaturated monomer, for example, ethylene / (meth) acrylic acid copolymer, ethylene / fumar. Examples thereof include acid copolymers, ethylene / ethyl acrylate copolymers, ethylene / vinyl acetate copolymers, ethylene / glycidyl methacrylate copolymers, ethylene / vinyl acetate / glycidyl methacrylate copolymers. Two or more of these may be used in combination.

The amount of (F) used is the same as in (A),
Usually 0.5 to 30 relative to the total weight of (B) and (C)
%, Preferably 1 to 20% by weight. If it is less than 0.5% by weight, the effect as a dispersant is small, and if it exceeds 30% by weight, the resin physical properties of the composition deteriorate.

In addition, for the purpose of further improving the antistatic effect, the compounding component may contain a metal salt (G) consisting of a halide of an alkali metal and / or an alkaline earth metal. Examples of (G) include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide and the like. Particularly preferred of these are sodium chloride and potassium chloride. The amount of (G) used is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the total weight of (A), (B), (C) and (D). If it is less than 0.01% by weight, the effect is not exhibited, and if it exceeds 5% by weight, it deposits on the resin surface and impairs the appearance of the resin.

The antistatic resin composition obtained by the method of the present invention is particularly suitable as a material for molding as it is, but it may be used in a state of being mixed with another resin (masterbatch). Examples of other resins include polyolefin resins such as polyethylene and polypropylene.

In addition, the antistatic resin composition of the present invention may be optionally added with other resin additives within a range that does not impair the characteristics of the composition according to various uses. As the additive, pigment, dye, filler, nucleating agent, glass fiber,
Lubricants, plasticizers, release agents, antioxidants, flame retardants, UV absorbers and the like can be mentioned.

[0032]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples indicate parts by weight. In addition, the measurement of the surface resistivity in the examples uses a square test piece having a thickness of 2 mm formed by a pressure press, and a super insulation meter (manufactured by Advantest) at 20 ° C. and a humidity of 65.
It was measured under a% RH atmosphere.

[(Meth) of polyoxyalkylene compound
Production of Acrylic Ester] Production Example 1 3 L 4-necked Kolben equipped with a nitrogen inlet tube, a thermometer, a temperature controller, a condenser, and a stirring rod is added with 40 mol of ethylene oxide of lauryl alcohol 96 moles.
5 g, toluene 600 g, acrylic acid 54 g, sulfuric acid 10 g and pyrogallol 8 g as a polymerization inhibitor were charged under a nitrogen atmosphere. Thereafter, nitrogen was continuously aerated in the Kolben until the reaction was completed. Heat with a mantle heater, raise the temperature and stir 11
After the temperature was raised to 5 ° C, the esterification reaction was carried out for 8 hours while maintaining this temperature. Water by-produced in the esterification reaction was distilled off while azeotropically distilling with toluene. Next, the temperature was cooled to 40 ° C., 100 g of 20% aqueous sodium hydroxide solution was added, and the mixture was stirred at high speed for 5 minutes. After that, stirring was stopped, and the mixture was allowed to stand and separated into three layers, and then the lower layer and the intermediate layer were removed. Toluene (300 g) was added to the upper layer reaction solution remaining in the Kolben and sufficiently mixed, and then the solution was suction-filtered using a filter aid to remove by-product salts. Then, the filtered solution was transferred into the same Kolben as above, and toluene was removed under reduced pressure at a temperature of
It was distilled off at 110-115 ° C. The obtained compound was a white solid at room temperature, and the acid value and the hydroxyl value were each 0.5 or less. From analysis by NMR, it was confirmed that this compound was the target CH ₂ ═CH—COO (CH ₂ CH ₂ O) ₄₀ —C ₁₂ H ₂₅ . This compound is abbreviated as (C-1) below.

Production Example 2 The same operation as in Production Example 1 was carried out except that 415 g of a compound obtained by adding 15 mol of ethylene oxide to lauryl alcohol was used. The obtained compound was a white solid at room temperature, and the acid value and the hydroxyl value were each 0.5 or less. From the analysis by NMR, this compound was identified as C
It was confirmed that H ₂ = a _{CH-COO (CH 2 CH 2} O) 15 -C 12 H 25. This compound is abbreviated as (C-2) below.

[Production of Modified Polyolefin Dispersant] Production Example 3 95 parts of low molecular weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89 obtained by thermal degradation and 5 parts of maleic anhydride were melted at 180 ° C. under nitrogen. Then, a 50% solution of xylene in which 1.5 parts of dicumyl peroxide was dissolved was added dropwise over 15 minutes, and after reacting for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene. The acid value of this product is 2
5.7, the number average molecular weight was 15,000. This modified product is abbreviated as (F-1) below.

Production Example 4 95 parts of the acid-modified low-molecular-weight polypropylene obtained in Production Example 3 was dissolved in 100 parts of xylene under nitrogen at 120 ° C., and then 5 parts of monoethanolamine was added dropwise over 15 minutes. After reacting for 1 hour, the solvent and unreacted monoethanolamine were distilled off to obtain a modified low molecular weight polypropylene having a hydroxyl group. The hydroxyl value of this product is 25.2.
The number average molecular weight was 16,000. This modified product is described below (F
-2) is abbreviated.

Production Example 5 95 parts of the acid-modified low-molecular-weight polypropylene obtained in Production Example 3 and 50 parts of ethylene oxide 24 mol adduct of lauryl alcohol were melted under nitrogen at 180 ° C., then under reduced pressure of 10 mmHg.
The esterification reaction was carried out for a time to obtain the intended polyoxyalkylene-modified low-molecular-weight polypropylene. This product had a hydroxyl value of 0.5 and a number average molecular weight of 18,000. In addition, NMR analysis confirmed that the esterification reaction was performed quantitatively. This modified product is abbreviated as (F-3) below.

Production Example 6 95 parts of low molecular weight polyethylene having a number average molecular weight of 5,000 and a density of 0.92 obtained by thermal degradation and 5 parts of maleic anhydride were dissolved in 100 parts of xylene under nitrogen at 140 ° C. 15% xylene 50% solution containing 1.5 parts of mill peroxide
The mixture was added dropwise over a period of 1 minute, and after the reaction was carried out for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polyethylene. This had an acid value of 27.4 and a number average molecular weight of 7,000. This modified product is abbreviated as (F-4) below.

Examples 1 to 7, Comparative Examples 1 to 3 Polypropylene (A) shown in Table 1, rubbery polymer (B) having a glass transition temperature of 0 ° C. or lower, polyoxyalkylene-containing compound (C), sulfone A predetermined amount of the acid salt-containing monomer (D), the dispersant (F) and the metal salt (G) were mixed in a ratio shown in Table 1, and Laboplast mill (volume: 60 m
l, manufactured by Toyo Seiki Co., Ltd., and melt-kneaded at 200 ° C. and 60 rpm for 5 minutes. Subsequently, the radical initiator (E) was added at a ratio shown in Table 1 and melt-kneaded for 5 minutes to prepare an antistatic resin composition. Then, using a pressure molding machine, hot pressing is performed for 1 minute at a temperature of 170 ° C. and a pressure of 100 Kg / cm ² , and then a temperature of 40 ° C. and a cooling press of 100 Kg / cm ² are used for cooling to a thickness of 2 mm. Square test pieces were prepared and subjected to the following treatments and conditionings to measure the surface specific resistance (measurement results are shown in Table 3). (1) After molding, the square test piece is left as it is in an atmosphere of 20 ° C. and a humidity of 65% RH for 24 hours. (2) After molding, the square test piece is washed with a detergent (Mama Lemon; Lion)
After washing with an aqueous solution (manufactured by K.K. Co., Ltd.) and then thoroughly washing with ion-exchanged water, the surface water is dried and removed, and then left in an atmosphere of 20 ° C. and a humidity of 65% RH for 24 hours.

[0040]

[Table 1]

* 1: Dicumyl peroxide is used. * 2: Polypropylene (Product name "Ube Poly Pro J60
9 ", propylene / ethylene (94/6) block copolymer, MFR = 9 (230 ° C, 2.16 kgf), manufactured by Ube Industries, Ltd.). * 3: Ethylene-propylene-ethylidene norbornene copolymer (trade name "JSR EP43", propylene content 43%, iodine value = 6.3, Mooney viscosity = 48 (1
00 ° C, ML1 + 4), manufactured by Nippon Synthetic Rubber Co., Ltd.). * 4: Obtained in Production Example 1 (C-1). * 5: Obtained in Production Example 2 (C-2). * 6: Sodium styrene sulfonate monomer is used. * 7: Allyl-type sulfonate-containing monomer having the following structural formula is used. * 8: Obtained in Production Example 3 (F-1). * 9: Obtained in Production Example 4 (F-2). * 10: Obtained in Production Example 5 (F-3). * 11: Potassium chloride is used as the alkali metal salt. * 12: N, N-dihydroxyethyl-carboxymethyl-lauryl betaine, which is a commercially available antistatic agent for kneaded polyolefin, is used.

Examples 8-14, Comparative Examples 4-6 Polypropylene or polyethylene (A) shown in Table 2,
A rubbery polymer (B) having a glass transition temperature of 0 ° C. or lower, a polyoxyalkylene-containing compound (C), a sulfonate-containing monomer (D), a radical initiator (E),
The dispersant (F) and the metal salt (G) were blended in a predetermined amount at the ratios shown in Table 2, blended for 3 minutes with a Henschel mixer, and the resulting blended components were mixed with a vented twin-screw extruder to 200 Melt kneading under conditions of ℃, 30 rpm, residence time 5 minutes,
An antistatic resin composition was prepared. Then, using a pressure molding machine, hot pressing is performed for 1 minute at a temperature of 170 ° C. and a pressure of 100 Kg / cm ² , and then a temperature of 40 ° C. and a cooling press of 100 Kg / cm ² are used for cooling to a thickness of 2 mm. Square test pieces were prepared, and the surface specific resistance after unwashed and washed with water was measured (measurement results are shown in Table 3).

[0043]

[Table 2]

* 1: Dicumyl peroxide is used. * 2: Polypropylene ["Ube Polypro J385", propylene / ethylene (98/2) random copolymer, M
FR = 9 (230 ° C., 2.16 Kg · f); Ube Industries, Ltd.). * 3: Low density polyethylene ["Ube polyethylene J10
19 ", low density polyethylene, density = 0.919, MF
R = 10 (190 ° C., 2.16 Kg · f), manufactured by Ube Industries, Ltd.]. * 4: Ethylene-propylene copolymer [“JSR EP
11 ", propylene content 49% by weight, Mooney viscosity = 4
0 (100 ° C, ML1 + 4), Japan Synthetic Rubber Co., Ltd.
Made). * 5: Obtained in Production Example 1 (C-1). * 6: Obtained in Production Example 2 (C-2). * 7: The same sulfonate-containing monomer as * 7 in Table 1 above. * 8: An acrylamide-type sulfonate-containing monomer having the following structural formula is used. CH ₂ = CH-CONH-C
_{(CH 3) 2 -CH 2 -SO} 3 Na * 9: obtained in Production Example 5 (F-3). * 10: Obtained in Production Example 3 (F-1). * 11: Obtained in Production Example 6 (F-4). * 12: Sodium chloride is used as the alkali metal. * 13: The same N * N-dihydroxyethyl-carboxymethyl-lauryl betaine as * 12 in Table 1 above was used.

[0045]

[Table 3]

[0046]

According to the method of the present invention, since it has excellent permanent antistatic property and the antistatic group is chemically bonded to the resin skeleton, the resin can be treated like a conventional kneading type antistatic agent. It is possible to easily obtain an antistatic resin composition that is less sticky on the surface and less deteriorates the physical properties of the resin. Furthermore, by containing a rubber component, it is possible to impart mechanical properties (such as impact resistance) to polyethylene or polypropylene in addition to excellent physical properties (such as processability and chemical resistance). Since it has the above effects, the antistatic resin composition obtained by the method of the present invention is used as a molding material that requires various antistatic properties such as housing products for home electric appliances and OA equipment, various plastic containers and automobile parts. It can be used preferably.

Claims (10)

(57) [Claims] 1. The following (A), (B) and (C), wherein (A) / (B) is (50-95) / (5) on a weight basis.
0-5), and (C) / [(A) + (B)] is (1-
30) / 100 is an antistatic resin composition obtained by melt-kneading the compounding ingredients and radically reacting. (A): Polyethylene or polypropylene. (B): A rubbery polymer having a glass transition temperature of 0 ° C. or lower. (C): Monovalent alcohols having at least 8 carbon atoms
Of phenolic polyoxyalkylene ethers
No (meth) acrylate. 2. (C) is an alkyl group having a small number of carbon atoms.
At least 8 polyoxyethylene alkyl ether mono
The resin composition according to claim 1, which is a (meth) acrylate . 3. The number average molecular weight of (C) is from 500 to
The resin composition according to claim 1 or 2, which is 6,000. 4. A sulfonate-containing monomer (D) copolymerizable with (C) is contained in the compounding component in an amount of 0.5 to 15% by weight based on the total weight of (A) and (B). The resin composition according to claim 1. 5. The method according to claim 1, wherein (D) is at least one selected from aromatic hydrocarbon vinyl sulfonate, sulfonate-containing (meth) acrylamide, and aliphatic hydrocarbon vinyl sulfonate. Or the resin composition as described above. 6. (B) is a butadiene rubber polymer,
The resin composition according to claim 1, which is at least one selected from an ethylene / propylene copolymer rubbery polymer and an ethylene / propylene / diene monomer copolymer rubbery polymer. 7. A radical reaction initiator (E) is added to (C) and (D) when radically reacting the blending components.
0.5 to 30% by weight based on the total weight of
6. The resin composition according to any one of 6. 8. The modified polyolefin-based dispersant (F) is further contained in the compounding components in an amount of 0.5 to 15% by weight based on the total weight of (A), (B), (C) and (D). Item 8. A resin composition according to any one of items 1 to 7. 9. The dispersant (F) comprises the following (F ₁ )
The resin composition according to claim 1, wherein the resin composition is at least one selected from (F ₃ ). (F ₁ ); number average molecular weight 800 to 25,000, acid value 5 to 150
Acid-modified low molecular weight polyolefin. (F ₂ ); number average molecular weight is 800 to 25,000 and hydroxyl value is 5
~ 150 hydroxyl group modified low molecular weight polyolefin. (F ₃ ); A polyoxyalkylene-modified low-molecular-weight polyolefin having a number average molecular weight of 1,000 to 28,000 in which part or all of the (anhydrous) carboxylic acid unit of (F ₁ ) is esterified with a polyoxyalkylene compound. 10. A metal salt (G) comprising a halide of an alkali metal and / or an alkaline earth metal is added in an amount of 0.01 to 5 parts by weight based on the total weight of (A), (B), (C) and (D). % Of the resin composition according to any one of claims 1 to 9.