JP2811433B2 - Antistatic agent and resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 exhibiting 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, and polystyrene resins are lightweight, tough, and inexpensive and easy to mold. Has been used as However, since these plastic molded products are insulative, the surface of the molded product is charged by static electricity and the like, and dust and dirt easily adhere to the molded product, and the appearance of the molded product deteriorates. In such a case, there is a major problem that a malfunction is caused by static electricity.

[0003] As a method for improving these disadvantages,
It is common to add a cationic, anionic, amphoteric, or other ionic surfactant or a nonionic surfactant to a thermoplastic resin. However, the method of adding the activator is such that the activator added over time bleeds out to the surface of the plastic molded product and is easily detached by washing with water or wiping with a cloth. There is a major drawback that only works.

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

[0005]

However, in the above-mentioned method, since a nonionic group having a low antistatic effect is used as an antistatic imparting group, it is necessary to use a monomer at a high concentration, and as a result, plastic There is a problem that the physical properties of the resin inherently deteriorate significantly. Further, as described above, even when a cationic group having a high antistatic effect is introduced randomly and into a side chain in the copolymer, the antistatic effect is small, as in the case of
Since it is necessary to use a high concentration, it is unavoidable to affect the resin properties of the plastic.

[0006]

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

That is, the present invention provides a dicarboxylic acid having 4 to 20 carbon atoms or an ester-forming derivative (a1) thereof,
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 each an alkylene group having 2 to 3 carbon atoms, m and n are each an integer of 1 or more, m + n is 2-20. A cationic antistatic agent comprising a compound (A) which is a reaction product of the amine compound (a2) represented by the formula (1) with a quaternizing agent (a3), and which has two or more quaternary ammonium bases in the molecule. , A thermoplastic resin (B) and a modified polyolefin compatibilizer (C), wherein the weight ratio of (A) and (B) is (1-50) :( 9
9 to 50), wherein the amount of (C) is 0.5 to 15% by weight based on the total weight of (A) and (B); a dicarboxylic acid having 4 to 20 carbon atoms or an ester thereof. Forming derivative (a1) and a compound of the general formula Wherein R ¹ is 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
-20. An amine compound (a2) represented by the formula:
A reaction product with a quaternizing agent (a3) selected from an alkyl sulfate quaternizing agent, an alkyl carbonate quaternizing agent, a phosphate quaternizing agent, and a halide quaternizing agent, and A cationic antistatic agent comprising a compound (A) having two or more quaternary ammonium bases therein; and a resin composition comprising the antistatic agent and a thermoplastic resin (B).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the dicarboxylic acid having 4 to 20 carbon atoms in (a1) includes succinic acid,
Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandic acid, dodecandic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid; Alicyclic dicarboxylic acids such as 1,4-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 are mentioned. Among these, preferred are aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and particularly preferred are adipic acid, sebacic acid, terephthalic acid and isophthalic acid.

The ester-forming derivatives of dicarboxylic acids having 4 to 20 carbon atoms in (a1) include, for example, lower alkyl esters (eg, methyl ester and ethyl ester) of the above-mentioned dicarboxylic acids, and ester salts ( Alkali metal salts, alkaline earth metal salts, ammonium salts and the like) and acid anhydrides. Two or more of these dicarboxylic acids or ester-forming derivatives thereof may be used in combination.

In the general formula (1), specific examples of the aliphatic hydrocarbon group having 1 to 22 carbon atoms represented by R ¹ include hexyl, n-octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl,
Groups such as oleyl can be given. 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 a plurality of oxyalkylene groups (m or n is 2 or more), A ¹ or A ² is composed of a plurality of types of alkylene groups. You may. 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, for example, compounds represented by the following general formulas (2) to (5).

[0013]

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[0014]

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[0015]

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[0016]

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Among the amine compounds exemplified above, particularly preferred is N-alkyl (C1-18) diethanolamine.

As the quaternizing agent (a3), 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, alkyl chloride 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 reactant (A) is obtained by reacting the above (a1) and (a2)
And a compound having two or more quaternary ammonium bases in the molecule. (A)
The following two methods can be used 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 for obtaining (A) by subjecting (a2) and (a3) to a quaternization reaction and then subjecting the reaction product to (a1) for a polyesterification reaction.

In any of the above methods, after the quaternization reaction, counterion exchange may be performed by neutralizing with an acid. By this method, counter ion exchange can be performed with perhalate ion, benzene sulfonate ion, alkylbenzene sulfonate 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 performed under reduced pressure in a 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 at a temperature 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 catalysts such as antimony trioxide; tin catalysts such as monobutyltin oxide and dibutyltin oxide; titanium catalysts such as tetrabutyl titanate; zirconium catalysts such as tetrabutylzirconate A metal acetate-based catalyst such as zinc acetate;

The number average molecular weight of the compound (A) in the present invention is usually from 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 000, the viscosity becomes too high at the time of melting, so that handling becomes difficult. 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 the number is less than 2, the effect of imparting antistatic properties is extremely poor, and the desired permanent antistatic effect cannot be obtained.

In the resin composition of the present invention, the thermoplastic resin (B) includes polyolefin resins such as polypropylene and polyethylene; polyvinyl chloride resins; polystyrene resins; acrylic resins such as polymethyl methacrylate; styrene and methacrylic. Two or more copolymers selected from the group consisting of methyl acrylate, acrylonitrile, and butadiene (styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, styrene / methyl methacrylate / acrylonitrile copolymer, 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-based resins and polyvinyl chloride-based resins, and particularly preferred are polyolefin-based resins.

Examples of the polyolefin resin 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,
-Decene, 1-dodecene and the like.

The polyolefin resin has a melt flow rate (MFR) of usually from 0.5 to 150, preferably from 1 to 150.
100. Melt flow rate is JIS K67
58 (in the case of a polypropylene resin; temperature 230 ° C., load 2.16 kgf; in the case of a 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) to (B) is usually (1 to 50): (99 to 5).
0), preferably (3-20): (97-80). If the ratio of (A) is less than 1, no good antistatic effect can be obtained, and if it exceeds 50, the intrinsic physical properties of the resin are impaired.

The resin composition of the present invention can be obtained by kneading the components (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 (C) include a polyolefin modified with an α, β-unsaturated carboxylic acid or an ester-forming derivative compound thereof, and a modified polyolefin having at least one functional group selected from a hydroxyl group and an epoxy group. Examples of the polyolefin used for the modification include polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, and copolymers containing a small amount of diene. Is mentioned.

Specific examples of the modified polyolefin 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-hydroxymaleimide grafted polyethylene, maleic anhydride grafted polypropylene,
N-hydroxymaleimide 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 include a propylene / diene monomer copolymer and an N-hydroxymaleimide grafted 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); a number average molecular weight of 800 to 25,000,
Modified low molecular weight polyolefin having an acid value of 5-150. (C2): a number average molecular weight of 800 to 25,000,
A modified low molecular weight polyolefin having a hydroxyl value of 5 to 150. (C3); a part or all of (C1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polyolefins.

(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 -It can be obtained by reacting an unsaturated carboxylic acid and / or an anhydride thereof, if necessary, in the presence of an organic peroxide by a solution method or a melting method to modify. From the viewpoint of easy modification, a low molecular weight polyolefin obtained by a thermal degradation method is preferable. 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 the modification include (meth) acrylic acid, (maleic anhydride), maleic acid, fumaric acid, (anhydrous) itaconic acid and citraconic anhydride. No. Among these, maleic acid (anhydride) is preferred. These amounts used during the 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 from 800 to 25,000, preferably from 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 is poor, and the mechanical properties of the resin composition deteriorate. The acid value of (C1) (mgKOH / g)
Is usually 5 to 150, preferably 10 to 100.
When the acid value is less than 5, the effect as a compatibilizer is poor, and
If it exceeds 0, the hue deteriorates, which causes coloring of the resin composition.

(C2) can be obtained by secondary 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. When the hydroxyl value is less than 5, the effect of introducing the hydroxyl group is small,
If the ratio exceeds the above range, the hue deteriorates, which causes coloring of the resin composition.

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

The modified low molecular weight polyolefins (C1) to (C3) exemplified above may be used in combination of two or more. 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% by weight, preferably 0.5-10% by weight.
When the amount of (C) is less than 0.5% by weight, the effect as a compatibilizer is reduced, so that a problem of phase separation is likely to occur. When the amount exceeds 15% by weight, the mechanical strength of the resin is reduced.

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

Further, the antistatic resin composition of the present invention comprises:
According to various uses, other known additives for resins may be added as long as the properties of the resin are not impaired. Examples of additives that can be blended 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 more specifically with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In the following, “part” indicates “part by weight” and “%” indicates “% by weight”.

Production Example 1 In a four-necked flask equipped with a stirrer, a condenser, a water separator and a thermometer, N-methyldiethanolamine (MEA;
(Molecular weight 119) 357 parts and dimethyl adipate (AA;
348 parts of molecular weight 174) and 0.7 part of dibutyltin oxide as an esterification catalyst were charged and stirred at 120 ° C.
Then, transesterification was carried out for 12 hours while methanol was distilled off to obtain an intermediate (MEA-AA-MEA-AA-MEA) having MEA: AA = 3: 2 at both terminal hydroxyl groups. To this intermediate, 378 parts of dimethyl sulfate was added to 40 to 5 parts.
It was added dropwise at 0 ° C. over 2 hours. The temperature was further raised to 70 ° C., and aging was performed for 2 hours. Toluene was added to the reaction product, and the mixture was separated to remove unreacted dimethyl sulfate. Thus, a quaternized antistatic agent [A-1] having hydroxyl groups at both ends of the present invention was obtained. The heat loss starting temperature (measured by TG-DTA in air; the same applies hereinafter) of this product 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 was added dropwise at 40-50 ° C. 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 heat loss starting temperature of this product was 215 ° C. To this quaternized product, 292 parts of adipic acid and 0.7 part of dibutyltin oxide as an esterification catalyst are added, and the mixture is heated to 180 ° C. with stirring, and is subjected to esterification for 2 hours in a nitrogen stream and further for 10 hours under reduced pressure. The reaction was carried out to obtain an antistatic agent [A-2] of the present invention. The heat loss starting temperature of this product was 265 ° C.

Production Example 3 N-lauryldiethanolamine (LE) was placed in a four-necked flask equipped with a stirrer, condenser, water separator and thermometer.
A; 410 parts of molecular weight 273), 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 1 part was stirred.
The temperature was raised to 20 ° C., and transesterification was carried out for 12 hours while distilling off methanol, and an intermediate of both terminal hydroxyl groups of LEA: AA = 3: 2 (LEA-AA-LEA-AA-LE).
A) was obtained. To this intermediate was added 189 parts of dimethyl sulfate.
It was added dropwise at 0 to 50 ° C over 2 hours. The temperature was further raised to 70 ° C., and aging was performed for 2 hours. The same operation as in Production Example 1 was carried out to obtain a quaternized antistatic agent [A-3] having hydroxyl groups at both ends of the present invention. The heat loss onset 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. It was added dropwise at 40-50 ° C. over 2 hours. The temperature was further raised to 70 ° C and aged for 2 hours.
A quaternized SEA [A-4-1] was obtained. The heat loss starting temperature of this product was 220 ° C. To this quaternized product, 146 parts of adipic acid and 0.6 part of dibutyltin oxide as an esterification catalyst are added, and the mixture is heated to 180 ° C. with stirring, and is esterified for 2 hours under a nitrogen stream, and further for 10 hours under reduced pressure. After the reaction, the antistatic agent of the present invention [A-4]
I got The heat loss starting temperature of this product was 265 ° C.

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

Comparative Production Example 1 A four-necked flask equipped with a stirrer, condenser, water separator and thermometer was charged with N-methyldiethanolamine (MEA;
119 parts of molecular weight 119) and dimethyl adipate (AA;
348 parts of molecular weight 174) and 0.5 part of dibutyltin oxide as an esterification catalyst were charged and stirred at 120 ° C.
The ester exchange reaction was carried out for 12 hours while distilling off methanol. An intermediate of MEA: AA = 1: 2 (AA-MEA-AA) was obtained. To this intermediate, 126 parts of dimethyl sulfuric acid was added dropwise at 40 to 50 ° C over 2 hours. The temperature was further raised to 70 ° C. and aging was performed for 2 hours. Toluene was added and the layers were separated to remove unreacted dimethyl sulfate, thereby obtaining a quaternized antistatic agent [Q] for comparison of both terminal hydroxyl groups. The heat loss starting temperature of this product was 230 ° C.

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

Production Example 7 95 parts of a low-molecular-weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89, obtained by a thermal degradation method, and 5 parts of maleic anhydride were melted at 180 ° C. under nitrogen. Xylene in which 1.5 parts of dicumyl peroxide are dissolved
A 0% solution was added dropwise over 15 minutes, and after the reaction was carried out for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene. It 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 replaced with xylene 100
Was dissolved under nitrogen at 120 ° C., and then 5 parts of monoethanolamine was added dropwise over 15 minutes, and the mixture was reacted for 1 hour. Thereafter, the solvent and unreacted monoethanolamine were distilled off to remove hydroxyl groups. To obtain a modified low molecular weight polypropylene. 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 an adduct of 24 mol of lauryl alcohol with ethylene oxide were melted at 180 ° C. under nitrogen, and then esterified under reduced pressure of 10 mmHg for 5 hours. The reaction was performed to obtain a polyoxyalkylene-modified low molecular weight polypropylene. This 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 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 using a Henschel mixer, the mixture was mixed at 180 ° C. with a vented twin-screw extruder. [B-1] use) or 24
0 ° C (when using [B-2]), melt kneading under the conditions of 100 rpm, residence time of 5 minutes, and master batch (M-1)-
(M-3) was obtained.

[0052]

[Table 1]

(Note) [B-1]: Polyethylene [trade name “Lexlon 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 masterbatches (M-1) to (M-3) and the polyolefin resin (B) shown in Table 2 were prepared in Production Example 10 respectively.
The mixture was melt-kneaded under the same conditions as described above to obtain the resin composition of the present invention. Table 2 shows the composition of the resin composition of the present invention via the masterbatch and the final ratio of each component.

[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 obtain a resin composition of the present invention and a comparative sample. A resin composition was obtained.

Examples 16 and 17 and Comparative Example 4 100 parts of PVC (trade name "Kanevinyl 1008", manufactured by Kaneka Corporation), calcium stearate 2.5
Part, zinc stearate 1.0 part, octyltin malate polymer 0.5 part and polyethylene wax [trade name "Sunwax 171-P", manufactured by Sanyo Chemical Industries, Ltd.]
For a 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 the ratios shown in Table 3, respectively, and then mixed at 180 ° C. Extrusion was performed under kneading conditions of 5 minutes to obtain sheets of the resin composition of the present invention and a 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 properties, resin properties and compatibility were evaluated. Table 4 shows the results.
In the case of injection molding, the cylinder temperature is 180 ° C ([B-
1) When used, or 230 ° C. (when using [B-2]), a test piece was prepared at a mold temperature of 50 ° C. In the case of compression molding (when using [B-3]), the mold temperature is 180 ° C.
A test piece was prepared at a pressure of 100 kg / cm ² . In addition, evaluation of antistatic property, resin physical property, and compatibility was performed by the following methods. (1) Antistatic property: The test piece was subjected to the treatment and conditioning described below, and the surface resistivity was measured. (A) After molding, the test piece is kept at 20 ° C. and humidity 50% R
Leave for 24 hours under H atmosphere. (B) After molding, test specimens were washed with detergent (mama lemon; lion
After washing with an aqueous solution and then sufficiently washing with ion-exchanged water, the water on the surface was dried and removed, and then at 20 ° C.
Left in a 50% RH atmosphere for 24 hours. (2) Compatibility: The molded product was bent and its fracture surface was visually observed and evaluated according to the following evaluation criteria. Evaluation criteria ○: good △: slight 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 were prepared in Comparative Examples 1 to
In comparison with No. 4, permanent antistatic properties were remarkably excellent, indicating that the composition had excellent permanent antistatic properties which could not be achieved conventionally. In particular, the composition via the masterbatch (Examples 1 to 4) is superior to the corresponding composition without the masterbatch (Examples 8 and 14). This indicates that a small amount of components (such as an antistatic agent) are uniformly dispersed and contribute to the performance.

[0062]

The antistatic agent of the present invention has the following effects. (1) Since the content of the ionic group is high, the effect of imparting the antistatic property is high even if a small amount is added. (2) Since the ionic portion and the non-ionic portion are not localized in a specific portion but form a certain repeating structure and the ionic portions are averaged, the antistatic effect is high. (3) Since the ionic group is incorporated not in the side chain but in the main chain, the effect of imparting the antistatic property is high even with a small amount of addition. (4) Since a high antistatic effect is exhibited even with a small amount of addition, the original physical properties of the synthetic resin as a 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 lowering the effect of imparting antistatic properties.

Because of the above-mentioned effects, the resin composition containing the antistatic agent of the present invention has excellent permanent antistatic properties which cannot be achieved by the prior art, and has excellent mechanical properties and molding properties. It is also very useful as various molding materials that require antistatic properties for housing products for home appliances and OA equipment, various plastic containers, automobile parts, and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 101/00 C08L 101/00 (56) References JP-A-1-153721 (JP, A) JP-A-62-220600 (JP, A) JP-A-3-163049 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09K 3/16 C08G 63/685 C08K 5/17 C08L 23/00 C08L 27/06 C08L 101 / 00 WPI / L (QUESTEL)

Claims (8)

(57) [Claims] 1. A dicarboxylic acid having 4 to 20 carbon atoms or an ester-forming derivative thereof (a1), and a compound represented by the general formula: [Wherein, R ¹ is 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
-20. An amine compound (a2) represented by the formula:
Cationic antistatic agent comprising a compound (A) which is a reaction product with a quaternizing agent (a3) and has two or more quaternary ammonium bases in the molecule, a thermoplastic resin (B), and a modified polyolefin-based (A) consisting of a compatibilizer (C)
And the weight ratio of (B) is (1 to 50): (99 to 50), and the amount of (C) is 0.5 to 15% by weight based on the total weight of (A) and (B). An antistatic resin composition comprising: 2. The resin composition according to claim 1, wherein (C) is at least one modified polyolefin selected from the following (C1) to (C3). (C1); a number average molecular weight of 800 to 25,000,
A modified low molecular weight polyolefin having an acid value of 5 to 150 (C2); a number average molecular weight of 800 to 25,000,
A modified low molecular weight polyolefin having a hydroxyl value of 5 to 150 (C3); a part or all of (C1) is esterified with a polyoxyalkylene compound;
2,000 to 28,000 modified low molecular weight polyolefin 3. A dicarboxylic acid having 4 to 20 carbon atoms or an ester-forming derivative thereof (a1), and a compound represented by the general formula: Wherein R ¹ is 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
-20. An amine compound (a2) represented by the formula:
A reaction product with a quaternizing agent (a3) selected from an alkyl sulfate quaternizing agent, an alkyl carbonate quaternizing agent, a phosphate quaternizing agent, and a halide quaternizing agent, and A cationic antistatic agent comprising a compound (A) having two or more quaternary ammonium bases therein. 4. A counter ion constituting a quaternary ammonium base in the compound (A) is chlorine ion, bromine ion, perhalogenate ion, benzenesulfonic acid ion, alkylbenzenesulfonic acid ion, methyl sulfate ion, ethyl sulfate. The antistatic agent according to claim 3, which is at least one member selected from the group consisting of an ion and a phosphonium ion. 5. A resin composition comprising the antistatic agent according to claim 4 and a thermoplastic resin (B). 6. The weight ratio of (A) and (B) is (1-5)
0): The resin composition according to claim 5, which is (99 to 50). 7. The resin composition according to claim 5, wherein (B) is a polyvinyl chloride resin. 8. The resin composition according to claim 1, wherein (B) is a polyolefin resin.