JPH08291281A - Antistatic agent and resin composition - Google Patents

Abstract

PURPOSE: To obtain an antistatic agent capable of exhibiting high antistatic effect by adding small amount, excellent in heat resistance and a permanent antistatic effect and useful for a resin composition for automobile parts, etc., and composed of a specific compound having plural quaternary ammonium salt groups in a molecule. CONSTITUTION: This resin composition is composed of a reaction product of (A) a 4-20C dicarboxylic acid or its ester-forming derivative (e.g. adipic acid, sebacic acid or a methyl ester of one of them) and (B) a compound of the formula [R<1> is a 1-22C aliphatic hydrocarbon group; A<1> and A<2> are each a 2-3C alkylene; (m) and (n) are each one or more than one, and (m)+(n)=2-20] (e.g. N-1-18C alkyldiethanolamine) with (C) a quaternary compound-forming agent such as an alkylsulfuric acid ester. The reaction product has two or more than two ammonium salt groups in a molecule.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antistatic agent and a resin composition using the same. More specifically, the present invention relates to a cationic antistatic agent that exhibits excellent permanent antistatic properties with a small amount of addition, and a permanent antistatic resin composition using the same.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polystyrene resins and the like are lightweight, tough, inexpensive and easy to mold, and are therefore materials for plastic molded products in a wide range of fields. Is used as. However, since these plastic molded products are insulative, the surfaces of the molded products are charged by static electricity, and dust and dirt are likely to adhere to them, which makes the molded products unattractive and also used for housings of electronics-related equipment. If it is done, there is a big problem that it causes a malfunction due to static electricity.

As a method for improving these drawbacks,
A general method is to add a cationic, anionic or amphoteric ionic surfactant or a nonionic surfactant to the thermoplastic resin. However, the method of adding the activator is that the activator added over time bleeds out on the surface of the plastic molded product and is easily detached by washing with water or wiping with cloth, so that the antistatic property is very temporary. There is a major drawback that it only works.

As a method for solving this drawback, a method of adding a polymer type antistatic agent which is not easily released from the surface of a plastic molded article; for example, (meth) acrylic acid into which a hydrophilic group such as polyethylene glycol is introduced. A method for imparting antistatic properties by introducing an ester as an antistatic monomer into the plastic skeleton (JP-A-55-3623).
No. 7, etc.), a method of improving the antistatic property of a plastic molded article by using (meth) acrylamide containing a quaternary ammonium salt group or maleimide as one component and copolymerized with another vinyl monomer (special Kaihei 5-32
No. 0526) and the like are known.

[0005]

However, in the above method, since the nonionic group having a low antistatic effect is used as the antistatic property-imparting group, it is necessary to use the monomer at a high concentration, and as a result, the plastic is not used. There is a problem in that the physical properties of the resin itself inherently deteriorate. Further, as described above, even if a cationic group having a high antistatic effect is introduced randomly into the copolymer and into the side chain, the antistatic effect is small, as in the case of
Since it is necessary to use it at a high concentration, it is inevitable to affect the physical properties of plastics.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have incorporated a cationic group having an antistatic effect into the main chain of a molecule and, at a certain interval, provide cationic properties. It was found that a large antistatic effect can be obtained by repeatedly positioning the groups, and as a result, it is possible to impart excellent permanent antistatic properties to various thermoplastic resins including polyolefin with a small amount of addition,
The present invention has been reached.

That is, the present invention comprises a dicarboxylic acid having 4 to 20 carbon atoms or its ester-forming derivative (a1),
General formula

[0008]

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[Wherein R ¹ is an aliphatic hydrocarbon group having 1 to 22 carbon atoms, A ¹ and A ² are alkylene groups having 2 to 3 carbon atoms, m and n are integers of 1 or more,
m + n is 2-20. ] A cationic antistatic agent comprising a compound (A), which is a reaction product of an amine compound (a2) represented by the formula (a2) and a quaternizing agent (a3), and has two or more quaternary ammonium bases in the molecule. And a resin composition containing the antistatic agent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as the dicarboxylic acid having 4 to 20 carbon atoms in (a1), succinic acid,
Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; 1 Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid; alkali metal salts of 3-sulfoisophthalic acid such as sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate; Mixtures of two or more may be mentioned. Of these, preferred are aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and particularly preferred are adipic acid, sebacic acid, terephthalic acid and isophthalic acid.

Examples of the ester-forming derivative of a dicarboxylic acid having 4 to 20 carbon atoms in (a1) include, for example, lower alkyl esters (methyl ester, ethyl ester, etc.) of dicarboxylic acid and ester salts (exemplified above). Alkali metal salts, alkaline earth metal salts, ammonium salts, etc.) and acid anhydrides. Two or more kinds of these dicarboxylic acids or their ester-forming derivatives may be used in combination.

Specific examples of the aliphatic hydrocarbon group having 1 to 22 carbon atoms represented by R ¹ in the general formula (1) include hexyl, n-octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl,
A group such as oleyl can be mentioned. Examples of the alkylene group having 2 to 3 carbon atoms represented by A ¹ and A ² include an ethylene group and a propylene group. When the oxyalkylene group (A ¹ O) or (A ² O) is composed of plural oxyalkylene groups (m or n is 2 or more), A ¹ or A ² is composed of plural kinds of alkylene groups. May be. Further, m and n are positive integers within a range where m + n satisfies the condition of 2 to 20. Specific examples of the amine compound (a2) represented by the general formula (1) include compounds represented by the following general formulas (2) to (5).

[0013]

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[0014]

[Chemical 4]

[0015]

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[0016]

[Chemical 6]

Among the above-exemplified amine compounds, N-alkyl (C 1-18) diethanolamine is particularly preferable.

Examples of the quaternizing agent (a3) include alkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl carbonates such as dimethyl carbonate and diethyl carbonate; trimethyl phosphate, alkylbenzyl chloride, benzyl chloride, alkyl chloride and alkyl. Examples include various phosphates such as bromide or halides. Of these, preferred are alkyl sulfates, and particularly preferred are dimethyl sulfate and diethyl sulfate.

The reaction product (A) is the above (a1) and (a2).
And (a3), and a compound having two or more quaternary ammonium bases in the molecule. The (A)
There are the following two production methods depending on the order in which these components are reacted. A method in which (a1) and (a2) are subjected to a polyesterification reaction, and the reaction product is quaternized with (a3) to obtain (A). A method of obtaining (A) by performing a quaternization reaction of (a2) and (a3) and then performing a polyesterification reaction of the reaction product and (a1).

In any of the above methods, counter ion exchange may be carried out by neutralizing with an acid after the quaternization reaction. By this method, counterion exchange can be performed for perhalogenate ion, benzenesulfonate ion, alkylbenzenesulfonate ion and the like.

In any of the above methods, if necessary, an aromatic compound (toluene, xylene, etc.) may be used as a reaction solvent. The polyesterification reaction is usually carried out under reduced pressure in the temperature range of 150 to 180 ° C., and the reaction time is usually 0.5 to 20 hours. Also,
The quaternization reaction is usually performed in the temperature range of 50 to 80 ° C. under normal pressure, and the reaction time is usually 2 to 8 hours.

In the polyesterification reaction, a usual esterification catalyst may be used. There is no limitation on the esterification catalyst, for example, antimony-based catalysts such as antimony trioxide; tin-based catalysts such as monobutyltin oxide and dibutyltin oxide; titanium-based catalysts such as tetrabutyl titanate; zirconium-based catalysts such as tetrabutyl zirconate. Metal acetate catalysts such as zinc acetate; and the like.

The number average molecular weight of the compound (A) in the present invention is usually 600 to 30,000, preferably 800.
~ 20,000. If the molecular weight is less than 600, the heat resistance is greatly reduced, and the permanent antistatic effect is poor.
If it exceeds 50,000, it becomes difficult to handle because the viscosity becomes too high during melting. Further, in order to exhibit an excellent antistatic effect, the number of quaternary cation groups in (A) usually needs to be 2 or more in the molecule, and preferably 3 or more. If it is less than 2, the effect of imparting the antistatic property is remarkably inferior and the desired permanent antistatic effect cannot be obtained.

As the thermoplastic resin (B) in the resin composition of the present invention, polyolefin resins such as polypropylene and polyethylene; polyvinyl chloride resins; polystyrene resins; acrylic resins such as polymethylmethacrylate; styrene and methacryl. Two or more copolymers selected from the group consisting of methyl acid, acrylonitrile and butadiene (styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene copolymers, styrene / methyl methacrylate / acrylonitrile copolymers, etc.); Polycarbonate; polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.); polyamide resin (nylon 6, nylon 66, nylon 6/12, etc.), polyacetal resin, thermoplastic polyurethane resin, etc. That. Of these, preferred are polyolefin resins and polyvinyl chloride resins, and particularly preferred are polyolefin resins.

Examples of polyolefin resins include (co) polymers of propylene and / or ethylene, and copolymers (random or block) of propylene and / or ethylene with one or more other α-olefins. Other α-olefins include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1
-Decene, 1-dodecene and the like.

The melt flow rate (MFR) of the polyolefin resin is usually 0.5 to 150, preferably 1 to
100. Melt flow rate is JIS K67
58 (for polypropylene resin; temperature 230 ° C., load 2.16 kgf, for polyethylene resin; temperature 1
It can be measured according to 90 ° C. and a load of 2.16 kgf).

In the resin composition of the present invention, the weight ratio of (A) and (B) is usually (1 to 50) :( 99 to 5).
0), preferably (3-20) :( 97-80). If the ratio of (A) is less than 1, a good antistatic effect cannot be obtained, and if it exceeds 50, the original physical properties of the resin are impaired.

The resin composition of the present invention can be obtained by kneading (A) and (B) using various known mixers. Mixers include, for example, extruders, Brabenders, kneaders and Banbury mixers.

In the resin composition of the present invention, a modified polyolefin compatibilizer (C) may be used particularly for the purpose of improving the compatibility between the compound (A) and the polyolefin resin. Examples of the (C) include a polyolefin modified with an α, β-unsaturated carboxylic acid or an ester-forming derivative compound thereof, a modified polyolefin having at least one functional group selected from a hydroxyl group and an epoxy group, and the like. Examples of the polyolefin used for the modification include polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, and further copolymers containing a small amount of diene. Is mentioned.

Specific examples of the modified polyolefin-based compatibilizer (C) include ethylene / (meth) acrylic acid copolymer, ethylene / fumaric acid copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate. Copolymer, ethylene / glycidyl methacrylate copolymer, ethylene /
Vinyl acetate / glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, N-hydroxymaleinimide grafted polyethylene, maleic anhydride grafted polypropylene,
N-hydroxymaleinimide-grafted polypropylene, maleic anhydride-grafted ethylene / propylene copolymer, acrylic acid-grafted ethylene / propylene copolymer, maleic anhydride-grafted ethylene / propylene / diene monomer copolymer, acrylic acid-grafted ethylene /
Examples thereof include a propylene / diene monomer copolymer and an N-hydroxymaleinimide graft ethylene / propylene / diene monomer copolymer. These may be used in combination of two or more.

Particularly preferred among (C) are one or more modified polyolefins selected from the following (C1) to (C3). (C1); number average molecular weight is 800 to 25,000,
A modified low molecular weight polyolefin having an acid value of 5 to 150. (C2); number average molecular weight is 800 to 25,000,
A modified low molecular weight polyolefin having a hydroxyl value of 5 to 150. (C3); Number average molecular weight 1, in which part or all of (C1) is esterified with a polyoxyalkylene compound 1,
000-28,000 modified low molecular weight polyolefin.

(C1) is a low molecular weight polyolefin having a number average molecular weight of 700 to 20,000 obtained by a polymerization method of propylene and / or ethylene or a thermal degradation method of high molecular weight polypropylene and / or polyethylene, and α, β. -Unsaturated carboxylic acid and / or its anhydride can be obtained by reacting and modifying in the presence of an organic peroxide, if necessary, by either a solution method or a melting method. 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, by the method described in JP-A-3-62804.

Examples of the α, β-unsaturated carboxylic acid or its anhydride used for modification include (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and citraconic acid anhydride. Can be mentioned. Among these, (anhydrous) maleic acid is preferable. These amounts used during modification are usually 1 to 25% by weight, preferably 3 to 20% by weight, based on the weight of the low molecular weight polyolefin. The number average molecular weight of (C1) obtained by the above method is usually 800 to 25,000, preferably 1,000 to 20,000. Number average molecular weight is 80
If it is less than 0, the heat resistance is poor, and if it exceeds 25,000, the effect as a compatibilizer becomes poor, and the mechanical properties of the resin composition deteriorate. Also, the acid value of (C1) (mgKOH / g)
Is usually 5 to 150, preferably 10 to 100.
If the acid value is less than 5, the effect as a compatibilizer is poor, and
When it exceeds 0, the hue deteriorates, which causes coloring of the resin composition.

(C2) can be obtained by secondarily modifying the above (C1) with an alkanolamine or the like. Alkanolamines include, for example, monoethanolamine, monoisopropanolamine, diethanolamine and diisopropanolamine.
Of these, particularly preferred is monoethanolamine. The hydroxyl value (mgKOH / g) of (C1) is usually 5 to 150, preferably 10 to 100. If the hydroxyl value is less than 5, the effect of introducing the hydroxyl group is small,
If it exceeds, the hue deteriorates, which causes coloring of the resin composition.

(C3) can be obtained by esterifying a part or all of the (anhydrous) carboxylic acid unit of (C1) with a polyoxyalkylene compound.
Examples of the polyoxyalkylene compound used for esterification include compounds having a hydroxyl group at both ends, such as polyethylene glycol and polypropylene glycol, and compounds having the above hydroxyl group substituted with an amino group or an epoxy group. Furthermore, alcohols (methanol, ethanol, butanol, octanol, lauryl alcohol,
2-ethylhexyl alcohol, etc.), phenols (phenol, alkylphenol, naphthol, phenylphenol, benzylphenol, etc.) and other compounds having active hydrogen to which alkylene oxide is added, such as polyoxyalkylene compounds having a hydroxyl group at one end. To be The number average molecular weight of these polyoxyalkylene compounds is usually 300 to 5,000. The esterification rate is not particularly limited, but it is preferable that 10 to 100 mol% of the (anhydrous) carboxylic acid unit of (C1) is esterified. The number average molecular weight of (C3) is usually 1,000 to 28,000, preferably 1,200 to 2
It is 5,000. If it is less than 1,000, the heat resistance is poor,
If it exceeds 28,000, the effect as a compatibilizer becomes poor.

Two or more kinds of the modified low molecular weight polyolefins (C1) to (C3) exemplified above may be used in combination. A modified low molecular weight polyolefin having all of a carboxyl group, a hydroxyl group and a polyoxyalkylene group in the molecule may be used.

The amount of (C) in the resin composition is usually 0.5.
-15 wt%, preferably 0.5-10 wt%.
When the amount of (C) is less than 0.5% by weight, the effect as a compatibilizing agent becomes small, so that the problem of phase separation easily occurs, and when it exceeds 15% by weight, the mechanical strength of the resin decreases.

The antistatic resin composition of the present invention may be a molded product as it is or may be molded in a state of being mixed with another resin (masterbatch). Examples of other resins include polyolefin resins such as polyethylene and polypropylene.

The antistatic resin composition of the present invention also comprises
Other known additives for resins may be added according to various uses within a range that does not impair the characteristics of the resin. Examples of additives that can be added include pigments, dyes, fillers, nucleating agents, glass fibers, lubricants, plasticizers, release agents, antioxidants, flame retardants, and ultraviolet absorbers.

[0040]

EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited thereto. In the following, "part" means "part by weight" and "%" means "% by weight".

Production Example 1 A four-necked flask equipped with a stirrer, a condenser, a water separator and a thermometer was charged with N-methyldiethanolamine (MEA;
Molecular weight 119) 357 parts and dimethyl adipate (AA;
A molecular weight of 174) 348 parts and dibutyltin oxide 0.7 part as an esterification catalyst were charged and stirred at 120 ° C.
The temperature was raised to 0 and the transesterification reaction was carried out for 12 hours while distilling off methanol to obtain an intermediate (MEA-AA-MEA-AA-MEA) having hydroxyl groups at both ends of MEA: AA = 3: 2. 40 to 5 parts of 378 parts of dimethyl sulfate were added to this intermediate.
It was added dropwise at 0 ° C. over 2 hours. The temperature was further raised to 70 ° C., and the mixture was aged for 2 hours. Toluene was added to the reaction product to carry out liquid separation to remove unreacted dimethylsulfate to obtain a quaternized antistatic agent [A-1] of the present invention having hydroxyl groups at both terminals. The thermal loss onset temperature (measured by TG-DTA under air. The same applies hereinafter) was 270 ° C.

Production Example 2 A four-necked flask equipped with a stirrer, a condenser, a water separator, a dropping funnel and a thermometer was charged with 238 parts of N-methyldiethanolamine (MEA; molecular weight 119), and then 252 parts of dimethyl sulfate. It dripped at 40-50 degreeC over 2 hours. The temperature was further raised to 70 ° C., and the mixture was aged for 2 hours to obtain quaternized MEA [A-2-1]. The thermal loss onset temperature of this product was 215 ° C. To this quaternary product, 292 parts of adipic acid and 0.7 part of dibutyltin oxide as an esterification catalyst were added, and the temperature was raised to 180 ° C. with stirring, and the mixture was esterified under a nitrogen stream for 2 hours and further under reduced pressure for 10 hours. The reaction was carried out to obtain the antistatic agent [A-2] of the present invention. The thermal loss onset temperature of this product was 265 ° C.

Production Example 3 In a four-necked flask equipped with a stirrer, a condenser, a water separator and a thermometer, N-lauryldiethanolamine (LE
A; molecular weight 273) 410 parts, dimethyl adipate (A
A; 174 parts of a molecular weight of 174) and 0.6 part of dibutyltin oxide as an esterification catalyst were charged, and the mixture was stirred for 1
The temperature was raised to 20 ° C., transesterification was carried out for 12 hours while distilling off methanol, and an intermediate product of LEA: AA = 3: 2 hydroxyl groups at both terminals (LEA-AA-LEA-AA-LE) was obtained.
A) was obtained. To this intermediate, 4 parts of 189 parts of dimethylsulfate were added.
It was added dropwise at 0 to 50 ° C. over 2 hours. The temperature was further raised to 70 ° C., and the mixture was aged for 2 hours. Then, the same operation as in Production Example 1 was performed to obtain a quaternized antistatic agent [A-3] of the present invention having hydroxyl groups at both terminals. The heat loss starting temperature of this is 27
It was 0 ° C.

Production Example 4 A four-necked flask equipped with a stirrer, a condenser, a water separator, a dropping funnel and a thermometer was charged with 357 parts of N-stearyldiethanolamine (SEA; molecular weight 357), and then 126 parts of dimethyl sulfate were added. It dripped at 40-50 degreeC over 2 hours. Further raise the temperature to 70 ° C and ripen for 2 hours,
SEA [A-4-1] quaternized was obtained. The thermal loss onset temperature of this product was 220 ° C. To this quaternary product, 146 parts of adipic acid and 0.6 part of dibutyltin oxide as an esterification catalyst were added, and the temperature was raised to 180 ° C. with stirring, and the mixture was esterified under a nitrogen stream for 2 hours and further under reduced pressure for 10 hours. After the reaction, the antistatic agent of the present invention [A-4]
I got The thermal loss onset temperature of this product was 265 ° C.

Production Example 5 In a four-necked flask equipped with a stirrer, a condenser, a water separator and a thermometer, a tertiary amine (LEO4A; molecular weight 537) 4 in which 8 mol of ethylene oxide was added to laurylamine 4
83 parts, dimethyl adipate (AA; molecular weight 174) 1
04 parts and 0.7 parts of dibutyltin oxide as an esterification catalyst were charged, the temperature was raised to 120 ° C. under stirring, the transesterification reaction was carried out for 12 hours while distilling methanol, and both LEA: AA = 3: 2. Intermediate of terminal hydroxyl group (L
EA-AA-LEA-AA-LEA) was obtained. To this intermediate, 113 parts of dimethylsulfate was added dropwise at 40 to 50 ° C. over 2 hours. The temperature was further raised to 70 ° C. and aging was carried out for 2 hours. Then, the same operation as in Production Example 1 was performed to obtain a quaternized antistatic agent [A-5] of the present invention having hydroxyl groups at both terminals.
The thermal loss onset temperature of this product was 270 ° C.

Comparative Production Example 1 N-Methyldiethanolamine (MEA; MEA; was added to a four-necked flask equipped with a stirrer, a condenser, a water separator and a thermometer.
119 parts of molecular weight 119) and dimethyl adipate (AA;
Charge 348 parts of molecular weight 174) and 0.5 parts of dibutyl tin oxide as an esterification catalyst, stir and stir at 120 ° C.
The temperature was raised to 0 and the transesterification reaction was carried out for 12 hours while distilling off methanol. An intermediate (AA-MEA-AA) with MEA: AA = 1: 2 was obtained. To this intermediate, 126 parts of dimethylsulfate was added dropwise at 40 to 50 ° C over 2 hours. The temperature was further raised to 70 ° C. and aging was carried out for 2 hours. Toluene was added and liquid separation was carried out to remove unreacted dimethylsulfate to obtain a comparative antistatic agent [Q] having quaternized both terminal hydroxyl groups. The thermal loss onset temperature of this product was 230 ° C.

[Production of Modified Low Molecular Weight Polyolefin] Production Example 6 Number average molecular weight 3,000 obtained by thermal degradation method, density of 0.
38 parts of low molecular weight polyethylene 93 and maleic anhydride 2
And 60 parts of xylene were dissolved under nitrogen at 140 ° C. under reflux of xylene, and then a 50% xylene solution containing 0.3 part of ditert-butyl peroxide was dissolved in 15 parts of the solution.
The mixture was added dropwise over a period of 2 minutes, and after the reaction was carried out for 2 hours, the solvent was distilled off to obtain acid-modified low molecular weight polyethylene. This had an acid value (mgKOH / g) of 28.0 and a number average molecular weight of 3,800. This modified product is abbreviated as [C-1] below.

Production Example 7 95 parts of low molecular weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89 obtained by the thermal degradation method and 5 parts of maleic anhydride were melted under nitrogen at 180 ° C. Xylene 5 with 1.5 parts of dicumyl peroxide dissolved in
A 0% solution was added dropwise over 15 minutes, and after the reaction for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene. This product has an acid value of 25.7 and a number average molecular weight of 1.
It was 5,000. This modified product is abbreviated as [C-2] below.

Production Example 8 95 parts of [C-2] obtained in Production Example 7 was added to xylene 100.
Part under nitrogen at 120 ° C., then 5 parts of monoethanolamine was added dropwise thereto over 15 minutes, and after reacting for 1 hour, the solvent and unreacted monoethanolamine were distilled off to remove hydroxyl groups. A modified low molecular weight polypropylene having was obtained. This had a hydroxyl value of 25.2 and a number average molecular weight of 16,000. This modified product is abbreviated as [C-3] below.

Production Example 9 95 parts of [C-2] obtained in Production Example 7 and 50 parts of ethylene oxide 24 mol adduct of lauryl alcohol were melted under nitrogen at 180 ° C. and then esterified under reduced pressure of 10 mmHg for 5 hours. The reaction was carried out to obtain a 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 referred to below as [C-
4].

[Preparation of Masterbatch] Production Example 10 After blending the components (A) to (C) in the proportions shown in Table 1 for 3 minutes with a Henschel mixer, 180 ° C. with a vented twin-screw extruder ( [When using [B-1]] or 24
Master batch (M-1) to melt-kneading at 0 ° C (when using [B-2]), 100 rpm, and residence time of 5 minutes.
(M-3) was obtained.

[0052]

[Table 1]

(Note) [B-1]: Polyethylene [trade name "LEXRON J6
9 ", manufactured by Nippon Petrochemical Co., Ltd.] [B-2]: polypropylene [trade name" Ube Polypro J
609 ", manufactured by Ube Industries, Ltd.]

Examples 1 to 5 The master batches (M-1) to (M-3) and the polyolefin-based resin (B) shown in Table 2 were prepared as in Production Example 10.
Melt-kneading was carried out under the same conditions as above to obtain a resin composition of the present invention. The composition of the resin composition of the present invention via the masterbatch and the final ratio of each component are shown in Table 2.

[0055]

[Table 2]

Examples 5 to 15 and Comparative Examples 1 to 3 The ratios (A) to (C) shown in Table 3 were blended and kneaded under the same conditions as in Production Example 10 to prepare resin compositions of the present invention and comparative examples. A resin composition was obtained.

Examples 16 and 17 and Comparative Example 4 100 parts of PVC [trade name "Kanevinyl 1008", manufactured by Kanebuchi Chemical Co., Ltd.], calcium stearate 2.5
Parts, zinc stearate 1.0 part, octyl tin malate polymer 0.5 parts and polyethylene wax [trade name "Sun Wax 171-P", Sanyo Chemical Industry Co., Ltd.]
For rigid PVC compound [B-3] consisting of 0.5 parts,
The antistatic agent of the present invention ([A-2] and [A-1]) and the comparative antistatic agent ([A-2-1]) were mixed at a ratio shown in Table 3, respectively, and then 180 ° C. Extrusion molding was performed under kneading conditions for 5 minutes to obtain sheets of the resin composition of the present invention and the comparative resin composition.

[0058]

[Table 3]

Performance Test Examples Test pieces were prepared from the resin compositions of the present invention (Examples 1 to 17) and comparative resin compositions (Comparative Examples 1 to 4) using an injection molding machine or a compression molding machine, The antistatic property, resin physical properties and compatibility were evaluated. The results are shown in Table 4.
In the case of injection molding, the cylinder temperature is 180 ° C ([B-
1) was used) or 230 ° C. (when [B-2] was used), and a mold temperature was 50 ° C. to prepare a test piece. In the case of compression molding (when [B-3] is used), the mold temperature is 180 ° C,
A test piece was prepared at a pressure of 100 Kg / cm ² . The antistatic properties, resin properties and compatibility were evaluated by the following methods. (1) Antistatic property: The test piece was subjected to the following treatment and conditioning, and the surface resistivity was measured. (A) After molding, the test piece is kept at 20 ° C. and humidity 50% R
Leave in H atmosphere for 24 hours. (B) After molding, the test piece was washed with a detergent (Mama Lemon; Lion).
(Manufactured by K.K.), followed by washing with an aqueous solution, followed by thorough washing with ion-exchanged water, and after removing water on the surface by drying, at 20 ° C.
Leave for 24 hours in an atmosphere of 50% humidity RH. (2) Compatibility: The molded product was bent and the fracture surface thereof was visually observed and evaluated according to the following evaluation criteria. Evaluation Criteria ◯: Good Δ: Some delamination is observed ×: Poor compatibility, delamination

[0060]

[Table 4]

As is clear from Table 4, the thermoplastic resin compositions containing the antistatic agent of the present invention are comparative examples 1 to
Compared with No. 4, the permanent antistatic property is remarkably excellent, indicating that it has an excellent permanent antistatic property that could not be achieved in the past. In particular, the compositions via the masterbatch (Examples 1 to 4) outperform the corresponding compositions via the masterbatch (Examples 8 and 14). This indicates that a small amount of components (such as an antistatic agent) is uniformly dispersed and contributes to performance development.

[0062]

The antistatic agent of the present invention has the following effects. (1) Since the content of ionic groups is high, the effect of imparting antistatic property is high even when added in a small amount. (2) Since the ionic portion and the nonionic portion are not unevenly distributed in a specific portion but form a certain repeating structure and the ionic portion is averaged, the antistatic effect is high. (3) Since the ionic group is incorporated in the main chain instead of the side chain, the effect of imparting antistatic property is high even when added in a small amount. (4) Since a high antistatic effect is exhibited even with a small amount of addition, the original physical properties of the synthetic resin as the base are not impaired. (5) Since the ionic group concentration does not decrease even if the molecular weight is increased, the heat resistance of the antistatic agent itself can be improved without decreasing the antistatic property imparting effect.

Because of the above effects, the resin composition containing the antistatic agent of the present invention has excellent permanent antistatic properties that cannot be achieved by the conventional techniques, and has mechanical properties and molding properties. Since it has excellent properties, it is extremely useful as various molding materials that require antistatic properties such as housing products for home electric appliances and office automation equipment, various plastic containers, and automobile parts.

Claims (8)

[Claims] 1. A dicarboxylic acid having 4 to 20 carbon atoms or an ester-forming derivative (a1) thereof, and a compound represented by the general formula: [In the formula, R ¹ represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms, A ¹
And A ² are each an alkylene group having 2 to 3 carbon atoms, m
And n are each an integer of 1 or more, and m + n is 2 to
Twenty. ] And an amine compound (a2)
A cationic antistatic agent comprising a compound (A) which is a reaction product with a grading agent (a3) and has two or more quaternary ammonium bases in the molecule. 2. The counter ion constituting the quaternary ammonium salt group in the compound (A) is chlorine ion, bromine ion, perhalogenate ion, benzenesulfonate ion, alkylbenzenesulfonate ion, methylsulfate ion, ethylsulfate. The antistatic agent according to claim 1, which is one or more selected from the group consisting of ions and phosphonium ions. 3. A resin composition comprising the antistatic agent according to claim 1 or 2 and a thermoplastic resin (B). 4. The resin composition according to claim 3, wherein (B) is a polyvinyl chloride resin. 5. The resin composition according to claim 3, wherein (B) is a polyolefin resin. 6. The weight ratio of (A) and (B) is (1-5).
0): (99 to 50), The resin composition according to any one of claims 3 to 5. 7. The modified polyolefin compatibilizer (C) is further added in an amount of 0.5 based on the total weight of (A) and (B).
The resin composition according to any one of claims 4 to 6, which comprises -15% by weight. 8. The resin composition according to claim 7, wherein (C) is at least one selected from the following (C1) to (C3). (C1); number average molecular weight is 800 to 25,000,
Modified low molecular weight polyolefin (C2) having an acid value of 5 to 150; a number average molecular weight of 800 to 25,000,
Modified low molecular weight polyolefin having a hydroxyl value of 5 to 150 (C3); number average molecular weight 1, in which part or all of (C1) is esterified with a polyoxyalkylene compound 1,
000-28,000 modified low molecular weight polyolefin