JPH0913014A - Antistatic agent - Google Patents

Abstract

(57) [Summary] [Purpose] It is intended to provide a novel antistatic agent. [Structure] The antistatic agent of the present invention comprises a combined use of a phenol sulfonic acid cyclic derivative or a copolymer containing a monomer unit thereof in a molecule and an alkylene oxide addition compound in a specific ratio. The antistatic agent of the present invention exhibits an excellent antistatic effect regardless of the type of substrate to be coated. In particular, since the coating film has a feature of good transparency, it is suitably used as a coating type antistatic agent for various materials requiring antistatic properties.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic agent. More specifically, a phenol sulfonic acid cyclic derivative or a copolymer containing a phenol sulfonic acid cyclic derivative unit in the molecule and an alkylene oxide adduct are contained in a specific ratio to provide excellent antistatic property and good transparency. To an antistatic agent having.

[0002]

2. Description of the Related Art Plastics, rubbers, fibers and the like have a drawback that they are easily charged with static electricity due to friction and the like, and that the electrostatic charge causes dust adhesion and electrostatic damage. In order to avoid this disadvantageous property, many methods of providing a thin surface coating of an antistatic agent on the surface of the material have been proposed.
For example, as an antistatic agent for plastic materials, it has been proposed to use anionic, cationic and amphoteric ionic surfactants or nonionic surfactants alone or in combination. Further, JP-A-3-139591 discloses a coating type antistatic agent having an excellent antistatic property by using a choline ester salt in combination with various alkylene oxide type surfactants.

[0003]

However, when the above various surfactants are used alone or in combination of two or more,
Depending on the type of plastic material used as the base material, sufficient antistatic ability may not be exhibited. Further, in this case, even a material having a low surface resistivity is about 10 ⁹ Ω, and a lower resistance value is generally required. Further, when the antistatic agent described in JP-A-3-139591 is applied, although the antistatic property is improved, the surface resistivity is about 10 ⁹ Ω, and unless the coating amount is very large, A resistance of about 10 ⁸ Ω cannot be expected. Further, a lower resistance value is required depending on the type and purpose of the base material.

In order to solve the above-mentioned drawbacks of the prior art, the present inventors have conducted extensive research on antistatic agents, and as a result, found that the compound and copolymer represented by the component A have antistatic ability. It was However, when the component A is used alone as an aqueous solution, the antistatic property is exhibited by the sulfonic acid group of the component A, but the wettability may be insufficient depending on the type of the substrate, and a uniform coating film is formed. Sometimes it is difficult to do. As a result of further studies by the present inventors in order to solve such a problem, as a result, the component A and the component B are
It has been found that when used in a specific ratio, a synergistic effect is exhibited and an antistatic agent having excellent wettability to a substrate, antistatic properties and transparency of a coating film can be obtained. More specifically, when the component B is used alone as an aqueous solution, the wettability with the substrate is good, but the antistatic property is a surface specific resistance of about 10 ⁹ Ω, and a sufficient antistatic effect is obtained. I can't.
When an aqueous solution of an anionic surfactant such as sodium dodecylbenzenesulfonate is used as the compound used in combination with the component A, the wettability is good,
Although a certain degree of antistatic effect was exhibited, no synergistic effect was observed. Furthermore, when an aqueous solution of ammonium chloride-based surfactant is used in combination, it is difficult to form a uniform coating film because a precipitate is generated in the prepared coating solution. The present invention has been made on the basis of such findings, and an antistatic agent having excellent wettability and antistatic properties for various materials such as plastic, rubber, fibers, paper, and glass, and having good coating transparency is provided. The purpose is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies made by the present inventors in view of the above problems, a phenol sulfonic acid cyclic derivative or a copolymer containing a monomer unit thereof in a molecule and an alkylene oxide addition compound are selected. When used together in a specific ratio, a synergistic effect is exhibited, each of which has an excellent antistatic effect that cannot be imagined when used alone, and the coating film formed on the substrate has good transparency. Then, the present invention was completed.

That is, the antistatic agent of the present invention contains the following components A and B, and the component B is added to 1 mol of the compound represented by the general formula (1) and / or its salt in the component A. Of 0.01 to 0.5 mol. Component A: a compound represented by the following general formula (1) and / or a salt thereof; a copolymer containing a compound represented by the following general formula (1) and / or a salt thereof as a constituent unit in the molecule; or Mixture of.

Embedded image Component B: a compound obtained by adding an alkylene oxide to a compound having a hydroxyl group, a carboxyl group or an amino group in the molecule.

Hereinafter, the present invention will be described specifically. In the present invention, the component A contains the compound represented by the general formula (1) and / or a salt thereof; or the compound represented by the general formula (1) and / or a salt thereof in the molecule as a constituent unit. It is a copolymer, and both may be used in combination. The compound represented by the general formula (1) and the salt thereof in the component A are known compounds and are disclosed in, for example, JP-A-61-83156, and prepared by the method described in the publication. You can Examples of the salt of the compound represented by the general formula (1) include inorganic salts such as alkali metal salts (eg sodium salt, potassium salt etc.) and alkaline earth metal salts (eg magnesium salt, calcium salt etc.). Examples include metal salts, ammonium salts, organic base salts (eg, trimethylamine salt, triethylamine salt, ethanolamine salt, triethanolamine salt, etc.), salts with amino acids (eg, lysine salt, arginine salt, etc.), but alkali Metal salts are preferred. It should be noted that the salt of the compound represented by the general formula (1) includes a compound in which all of the sulfonic acids of the compound represented by the general formula (1) are neutralized and a compound in which a part thereof is neutralized. Is also included. Further, the phenolic hydroxyl group in the compound represented by the general formula (1) includes both a partially neutralized compound and a partially neutralized compound.

The copolymer containing the compound represented by the general formula (1) and / or its salt as a constituent unit in the molecule of the component A is a known method (for example, JP-A-5-2091).
70, JP-A-6-212096), for example, one or two compounds represented by the general formula (1) and / or a salt thereof in the presence of a polymerization initiator. It can be obtained by polymerizing with the above polymerizable monomers. As the polymerizable monomer, for example, styrenes that may have a substituent (for example,
Styrene, α-methylstyrene, p-chlorostyrene, etc.), acrylonitrile, acrylamides that may have a substituent (eg, acrylamide, N-hydroxyethylacrylamide, etc.), vinyl acetates, acrylic acid or its salts, methacryl Acids or salts thereof, esters of acrylic acid or methacrylic acid that may have a substituent (for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid 2-hydroxyethyl ester, etc.) Can be mentioned. Examples of the salts of the above monomers include the salts exemplified as the salts of the compound represented by the above general formula (1). Moreover, you may use together a crosslinking agent monomer (For example, N, N'- methylene bis acrylamide, ethylene glycol diacrylate, etc.) as needed.

During the polymerization, the compound represented by the general formula (1) and / or its salt acts as a chain transfer agent.
As the polymerization reaction progresses, it is incorporated into the polymer by a chain transfer reaction and becomes a constituent component of the copolymer. The content of the compound represented by the general formula (1) and / or its salt in the copolymer containing the compound represented by the general formula (1) and / or its salt as a constitutional unit in the molecule is not particularly limited. But,
Preferably 50 wt% or more, more preferably 70 wt%
It is adjusted above.

In the present invention, as the component B, a compound obtained by adding alkylene oxide to a compound having a hydroxyl group, a carboxyl group or an amino group in the molecule is used, and examples thereof include fatty acid alkylene oxide adducts and alkylphenol alkylene. Oxide adduct,
Examples thereof include aliphatic alcohol alkylene oxide adducts, polyhydric alcohol alkylene oxide adducts, alkylamine alkylene oxide adducts, betaine (that is, zwitterionic compound) type alkylene oxide adducts, and the like. Good. Examples of the alkylene oxide include, but are not limited to, ethylene oxide and propylene oxide. The alkylene oxide may be added in the form of blocks of two or more kinds of alkylene oxides or in the form of random addition.

More specifically, examples of the compound of component B include the following compounds. POE (POE represents polyethylene oxide; the same applies hereinafter) Saturated or unsaturated fatty acid ester (saturated and unsaturated fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid) , Behenic acid), POE-POP (POP represents polypropylene oxide, the same applies hereinafter) saturated or unsaturated fatty acid ester (as the saturated and unsaturated fatty acids,
The above fatty acids are exemplified).

POE (mono- or di) alkylamines (Examples of alkylamines include octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, eicosylamine, behenylamine), POE -PO
P (mono or di) alkyl amine (the above alkyl amine is exemplified as the alkyl amine).

POE alkyl phenyl ether (Examples of the alkyl phenyl ether include octyl phenyl ether, nonyl phenyl ether, decyl phenyl ether and dodecyl phenyl ether), POE
-POP alkyl phenyl ether (the above alkyl phenyl ether is exemplified as the alkyl phenyl ether).

POE alkyl ether (Examples of the alkyl ether include octyl ether, decyl ether, lauryl ether, myristyl ether, palmityl ether, stearyl ether, oleyl ether, eicosyl ether, behenyl ether), POE
-POP alkyl ether (the above alkyl ether is exemplified as the alkyl ether).

POE glycerin, POE glycerin (mono or di) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids), PO
E-POP glycerin, POE-POP glycerin (mono or di) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids).

POE diglycerin, POE diglycerin (mono-, di- or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids), POE-POP diglycerin, POE-PO
P diglycerin (mono, di or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids).

POE sorbitol, POE sorbitol (mono-, di- or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids), POE-POP sorbitol, POE-PO
P sorbitol (mono, di or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids).

POE mannitol, POE mannitol (mono, di or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids), POE-POP mannitol, POE-PO.
P-mannitol (mono-, di- or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids).

POE galactitol, POE galactitol (mono, di or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids), POE-POP galactitol, POE-
POP galactitol (mono, di or tri) saturated or unsaturated fatty acid ester (as saturated and unsaturated fatty acids,
The above fatty acids can be exemplified).

POE sorbitan, POE sorbitan (mono, di or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids), POE-POP sorbitan, POE-POP sorbitan (mono, Di or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids).

POE pentaerythritol, POE pentaerythritol (mono-, di- or tri) saturated or unsaturated fatty acid ester (the above-mentioned fatty acids can be exemplified as the saturated and unsaturated fatty acids), POE-POP pentaerythritol, POE -POP pentaerythritol (mono-, di- or tri) saturated or unsaturated fatty acid ester (the saturated and unsaturated fatty acids can be exemplified by the above-mentioned fatty acids).

As the betaine-type alkylene oxide adduct, an (alkyl or alkenyl) di (2-hydroxyethyl) ammonioacetate alkylene oxide adduct represented by the following general formula (2) or the following general formula (3)
A di (alkyl or alkenyl) (2-hydroxyethyl) ammonioacetate alkylene oxide adduct represented by:

[0023]

Embedded image

In the general formula (2), R represents alkyl or alkenyl, and in the general formula (3), R and R ¹
Are the same or different and represent alkyl or alkenyl. Examples of the above alkyl include octyl, decyl, lauryl, myristyl, palmityl, stearyl, eicosyl, behenyl and the like, and examples of the alkenyl include oleyl and the like. In addition, in the general formulas (2) and (3), X represents POE or POE-POP.

In the compound of component B, the number of moles of alkylene oxide added is not particularly limited, but generally 2
˜50 mol, preferably about 3-30 mol.

In the antistatic agent of the present invention, 0.01 to 0.5 mol of the compound of component B is added to 1 mol of the compound represented by the general formula (1) in component A and / or its salt. The range of 0.03 to 0.1 mol is desirable. When the usage ratio of the component B is less than this range, the coating property is poor and it is difficult to exhibit good antistatic property. Further, when the use ratio of the component B exceeds this range, the coatability is good, but the antistatic ability is lowered.

The antistatic agent of the present invention is used for antistatic materials such as plastics, rubbers, fibers, papers and glasses, and the method of use can be the same as the conventional antistatic agents. A particularly preferable use mode is to apply the solution of the antistatic agent of the present invention to a substrate such as a plastic material for use. As the antistatic agent solution, an aqueous solution is generally used, but in applications requiring quick drying, isopropanol, lower alcohols such as ethanol, acetone, and also as a mixed solvent solution of an aqueous organic solvent such as dioxane and water. Good. Also,
Since the same property can be obtained by re-dissolving the solution after drying it up, the dried product or the concentrate may be re-dissolved before use. As the above plastic materials,
Examples include polyester, polycarbonate, polymethylmethacrylate, rigid vinyl chloride, polypropylene, polyethylene, polystyrene and the like. The form of the material is not particularly limited, and examples thereof include a sheet, a film, a molded product, or a laminated body thereof.

As a coating method for a base material such as plastic, various commonly used coating methods can be applied.
For example, a coating method such as brush coating, dipping method, roll coater, doctor blade, knife blade, applicator, or spray is used, and is appropriately selected according to the shape and physical properties of the substrate to be coated. The concentration of the antistatic agent in the above treatment liquid is appropriately determined depending on the required degree of antistatic ability, the properties of the substrate to be coated, the coating method, etc., but is usually in the range of 0.1 to 10 wt%. Is preferably used.

[0029]

The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to these examples. In addition, in the following Examples and Comparative Examples, the sodium salt of the compound represented by the general formula (1) was used. Further, in the following description, CALX- is an abbreviation for the sodium salt of the compound represented by the general formula (1).
In the compound represented by the general formula (1) using SN,
The sodium salt of the compound in which n is 4 is represented by CALX-S4, and similarly, the sodium salt of the compound in which n is 6 is represented by CALX-S6, and the sodium salt of the compound in which n is 8 is represented by CALX-S8. .

Example 1 CALX-S4 and POE (3) dihydroxyethyllaurylamine (numbers in parentheses are the number of moles of ethylene oxide added) in a molar ratio of 1: 0.1 and the total concentration was An antistatic agent solution was prepared by dissolving the antistatic agent solution in water to a concentration of 0.3 wt%. The antistatic agent (0.3 wt
%) A commercially available polyester film (manufactured by Toray, Lumirror, thickness 100 μm, abbreviated as PET hereinafter) was immersed in the solution for 3 seconds, immediately air-dried in a hanging state for 3 hours, and used as a test material. It was evaluated by. Table 1 shows the results.

Evaluation method 1. Antistatic effect The test material was temperature-controlled for 24 hours at a temperature of 23 ° C and a relative humidity of 50%, and an insulation resistance meter (SM-5 manufactured by Toa Denpa Kogyo KK) was used.
The surface resistivity was measured at E and an applied voltage of 500 V). 2. Transparency The sample material was temperature-controlled and controlled at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and a haze value was measured with a haze meter (TC-HIII manufactured by Tokyo Denshoku Co., Ltd.).

Examples 2 to 12 and Comparative Examples 1 to 24 In the same manner as in Example 1, 0.3 wt% aqueous solutions of the antistatic agents shown in Table 1 and Table 2 were prepared, and the same coating as in Example 1 was applied. The substrate was used, treated in the same manner, and evaluated in the same manner. The results are shown in Tables 1 and 2.

[0033]

[Table 1]

[0034]

[Table 2]

Example 13 The CALX-S4 of Example 1 was replaced with CALX-S4-PVAc.
(PVAc is polyvinyl acetate, CALX-S4 / PVA
c = 76.7 wt% / 23.3 wt% copolymer, the same applies hereinafter), and a 0.3 wt% aqueous solution of the antistatic agent shown in Table 3 was prepared in the same manner as in Example 1 to prepare Example 1 The same substrate to be coated was used, treated in the same manner, and evaluated in the same manner. Table 3 shows the results. In addition, CALX-S
4-PVAc was prepared by the following method. Add 8 parts of water to a reactor equipped with a stirrer, thermometer, dropping device and reflux condenser.
1 g and 2.41 g (2.82 mmol) of CALX-S4 were charged, and the temperature was raised to 82 to 84 ° C. under a nitrogen gas stream. To this solution, 7.2 g (83.7 mmol) of vinyl acetate and 5.0 g (0.2%) of a 1 wt% ammonium persulfate aqueous solution as a polymerization initiator.
(2 mmol) was simultaneously added dropwise over 14 hours. As the dropping proceeded, the polymerization reaction proceeded and the viscosity of the reaction system increased. After the dropping was completed, the polymerization reaction was aged at 82 to 84 ° C. for 1 hour to obtain a CALX-S4-PVAc aqueous solution.

Examples 14 to 17 and Comparative Examples 25 to 30 A 0.3 wt% aqueous solution of the antistatic agent shown in Table 3 was prepared in the same manner as in Example 13 and the same coated substrate as in Example 13 was prepared. Used, treated in the same way and evaluated in the same way. The results are shown in Table 3. In addition, CALX-
S6-PVAc and CALX-S8-PVAc were prepared in a manner substantially similar to CALX-S4-PVAc above.

[0037]

[Table 3]

Examples 18 to 22 and Comparative Examples 31 to 36 A 1.0 wt% aqueous solution of the antistatic agent shown in Table 4 was prepared, and a commercially available resin film or various resin molded products were dipped for 3 seconds and immediately suspended. Air-drying for 3 hours in the air in the lowered state was used as a test material, and the antistatic property was evaluated by the same method as in Example 1. Table 4 shows the results. The resins used for evaluation are as follows. PET: Polyethylene terephthalate (Toray Industries, Inc.)
100 μm thick, commercially available film PP: polypropylene (manufactured by Ube Industries, Ltd.), thickness 3 m
m compression molded product OPP: Biaxially oriented polypropylene (manufactured by Tokuyama Corp.), commercially available film with a thickness of 60 μm PE: Polyethylene (manufactured by Showa Denko KK), thickness 3 mm
High-impact polystyrene (Asahi Kasei Corp.)
Made), compression molded product with a thickness of 3 mm

[0039]

[Table 4]

From the above results, when the phenol sulfonic acid cyclic derivative of the component A or the copolymer containing the monomer unit in the molecule and the alkylene oxide addition compound of the component B are used in a specific ratio, synergistic effects of both are obtained. It is clearly recognized that, by using the conventional antistatic agent and each of them alone, an excellent antistatic effect that cannot be imagined can be obtained, and that the coating film has good transparency.

[0041]

The antistatic agent of the present invention exhibits an excellent antistatic effect regardless of the type of substrate to be coated. In particular, since the coating film has good transparency, it can be applied to various materials that require antistatic properties (eg, plastic, rubber, fiber, paper, glass, etc.). Is preferably used as.

Claims (3)

[Claims] 1. A compound containing the following components A and B, wherein the component B is 0.01 to 0.5 with respect to 1 mol of the compound represented by the general formula (1) and / or its salt. An antistatic agent characterized by containing a mole. Component A: a compound represented by the following general formula (1) and / or a salt thereof; a copolymer containing a compound represented by the following general formula (1) and / or a salt thereof as a constituent unit in the molecule; or Mixture of. Embedded image Component B: a compound obtained by adding an alkylene oxide to a compound having a hydroxyl group, a carboxyl group or an amino group in the molecule. 2. The component B is a fatty acid alkylene oxide adduct, an alkylphenol alkylene oxide adduct, an aliphatic alcohol alkylene oxide adduct,
The antistatic agent according to claim 1, which is a polyhydric alcohol alkylene oxide adduct, an alkylamine alkylene oxide adduct or a betaine alkylene oxide adduct. 3. The antistatic agent according to claim 1, which is a surface coating type antistatic agent for plastic materials.