WO2018212352A1 - Coating-type antistatic agent and polymer material coated with same - Google Patents

Abstract

Provided is a coating-type antistatic agent which makes it difficult for a coating solution to foam, maintains transparency after coating and drying, and is capable of obtaining an excellent antistatic performance. The coating-type antistatic agent is characterized by comprising: at least one ion-bonding salt represented by chemical formula (1) or chemical formula (2); and an organic solvent. (R1, A, and R2 are various organic groups. Q1+ and Q2+ are secondary or tertiary ammonium ions.)

Description

Coating type antistatic agent and polymer material coated with the same

The present invention relates to a coating-type antistatic agent used on the surface of a polymer material and a polymer material coated with the coating-type antistatic agent.

Polymer materials are widely used in industrial materials and food packaging materials because of their light and strong features. However, since it is difficult to conduct electricity, it is easily charged with static electricity, causing various troubles such as malfunction of electrical equipment, discomfort to the human body, and reduction in commercial value due to the adsorption of dust. As a means for preventing such troubles caused by static electricity, a method of applying a surfactant to the surface of a polymer material and using it as an antistatic agent is known.

However, when a surfactant is used alone, the antistatic film on the surface is weak, and there is a risk that the performance may be reduced by contact or friction. In order to solve these problems, improvements are made by blending a plurality of types of surfactants, but the performance is insufficient. In addition, turbidity occurs due to insufficient compatibility of these constituent materials, the film cannot be maintained, and the antistatic agent becomes innumerable droplets on the resin surface and becomes cloudy and transparent. Decreasing is a problem.

In view of the above circumstances, Patent Document 1 describes a film having a surfactant layer composed of a specific anionic surfactant mixed with a specific ratio and a specific nonionic surfactant. The surface resistivity is still not satisfactory.

In addition, a coating-type antistatic agent is usually used at a dilute concentration, for example, a concentration of about 1 to 2% by weight at the time of coating, but this concentration is most easily foamed with an aqueous antistatic agent. The workability at the time of coating work is significantly reduced. Furthermore, this foam causes uneven coating when the object to be treated is dried at a high temperature, deteriorates the appearance, and reduces the antistatic performance. In addition, the surfactant has poor storage stability with time in a dilute aqueous solution as described above, and the antistatic performance is greatly impaired.

In view of the above circumstances, Patent Document 2 describes a film using an ionic conductive agent as a film-forming component, but the surface resistivity is still not satisfactory.

JP 2002-012687 A JP 2007-320093 A

Accordingly, an object of the present invention is to provide a coating-type antistatic agent that hardly foams the coating solution, maintains transparency after coating and drying, and provides excellent antistatic performance.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, surprisingly, when an ion-binding salt dissolved in an organic solvent is applied to the surface of the polymer material, excellent antistatic performance can be obtained regardless of the type of the polymer material, and the coating solution Therefore, the present invention has been completed by finding a coating-type antistatic agent that is excellent in workability because it does not foam and can impart transparency after coating and drying.

That is, the present invention is a coating type antistatic agent characterized by comprising at least one ion-binding salt represented by the following chemical formula (1) or the following chemical formula (2) and an organic solvent.

In the chemical formula (1), R ¹ is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 An aryl group having ˜30, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
A is a linear or branched alkylene group having 2 to 4 carbon atoms,
n is an integer from 0 to 50,
Q1 ⁺ is a secondary ammonium ion or a tertiary ammonium ion.

In the chemical formula (2), R ² is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 An aryl group having ˜30, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
Q2 ⁺ is a secondary ammonium ion or a tertiary ammonium ion.

According to the present invention, it is possible to provide a coating-type antistatic agent that hardly foams the coating solution, imparts transparency after coating and drying, and provides excellent antistatic performance.

Embodiments of the present invention will be specifically described below, but the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited to the following embodiments.

The antistatic effect obtained by the coating type antistatic agent of the present invention is considered to be obtained, for example, by the high ion conductivity or electrical conductivity of the ion-binding salt contained in the antistatic agent.

In the present specification, the “ion-binding salt” is a free combination of a cation and an anion, and various physical properties such as melting point and solubility in water or an organic solvent can be adjusted. A stable salt.

[Ion-binding salt]
One embodiment of the present invention is a coating-type antistatic agent containing an ion-binding salt represented by the following chemical formula (1) or the following chemical formula (2) and an organic solvent. In this embodiment, as the ion-binding salt, one of the chemical formula (1) may be used alone, two or more kinds may be used in combination, or one of the chemical formula (2) may be used alone. Alternatively, two or more of them may be used in combination, or one or more of those represented by chemical formula (1) may be used in combination with one or more of those represented by chemical formula (2). However, it is preferable to use at least one ion-binding salt represented by the chemical formula (2). In addition, the ion binding salt represented by the chemical formula (2) composed of the sulfonic acid anion is more heat resistant than the ion binding salt represented by the chemical formula (1) composed of the sulfate ester anion. It is preferable because it is excellent.

In the chemical formulas (1) and (2), R ¹ and R ² are each independently a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms.

Examples of substituted or unsubstituted linear, branched, or cyclic alkyl groups having 1 to 30 carbon atoms used as R ¹ and R ^{2 in the} chemical formulas (1) and (2) Are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, tert-pentyl, neopentyl Group, n-hexyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentan-2-yl group, 1,3-dimethylbutyl Group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, -Methylhexyl group, 1-ethylpentyl group, 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3 -Trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-methylhexane-2-yl group, 2,4-dimethylpentan-3-yl group, 1,1-dimethylpentane -1-yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5-dimethylhexane-3 -Yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group, 2-methylheptane - 2-yl group, 3-methylheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propylpentyl group 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl-4-methylpentyl group 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl group, n-nonyl group 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n-propyl) pentyl group, 1,5, -Trimethylhexyl group, 1,1,5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloctyl group, 1- (n-butyl) hexyl group 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 1-methyl Tridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 1,2-bis (2-ethylhexyloxycarbonyl) ethyl group, cyclo A propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc. are mentioned. From the viewpoint of antistatic performance, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms is preferable. A 2-ethylhexyl group, dodecyl group, tridecyl group, 1,2-bis ( 2-ethylhexyloxycarbonyl) ethyl group is more preferable, and 2-ethylhexyl group is particularly preferable.

Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms used as R ¹ and R ^{2 in the} chemical formulas (1) and (2) include, for example, a phenyl group, a dimethylphenyl group ( 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, etc.), isopropylphenyl group (2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group), dodecyl Phenyl group (2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group), biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, -Terphenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl, phenalenyl, fluorenyl, anthryl Group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, playadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group Group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, ruvicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group And the like, and the like, and the ovalenyl group. From the viewpoint of antistatic performance, a substituted or unsubstituted aryl group having 8 to 18 carbon atoms is preferable, and a dimethylphenyl group (2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4- Dimethylphenyl group, etc.), isopropylphenyl group (2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group),
A dodecylphenyl group (2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group) is more preferable, and an isopropylphenyl group is particularly preferable.

Examples of the substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms used as R ¹ and R ^{2 in the} chemical formulas (1) and (2) include, for example, benzyl group, phenylethyl group 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 3- (1-naphthyl) propyl group, or And 3- (2-naphthyl) propyl group.

Preferable examples of the group used as R ¹ in the chemical formula (1) include the following chemical formula (3
) To (6).

Further, preferable examples of the group used as R ² in the chemical formula (2) include those having the chemical structures of the following chemical formulas (7) to (10), and among them, the following chemical formulas (9) and (10) Those having the following chemical structure are preferred.

In the chemical formula (1), A is a linear or branched alkylene group having 2 to 4 carbon atoms. Examples of the linear or branched alkylene group having 2 to 4 carbon atoms used as A in the chemical formula (1) include an ethylene group, a propylene group, a butylene group, and the like. From the viewpoint of availability, an ethylene group and a propylene group are particularly preferable.

The linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms, or the arylalkyl group having 7 to 31 carbon atoms, and the straight chain having 2 to 4 carbon atoms. The hydrogen atom in the chain or branched alkylene group may be substituted with another substituent.

Examples of such substituents include halogens such as fluorine, chlorine, bromine and iodine, alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group, phenyl group, p-tolyl group, xylyl group, Aryl groups such as cumenyl group, naphthyl group, anthryl group, phenanthryl group, alkoxy groups such as methoxy group, ethoxy group, tert-butoxy group, aryloxy groups such as phenoxy group, p-tolyloxy group, methoxycarbonyl group, butoxycarbonyl Groups, alkoxycarbonyl groups such as 2-ethylhexyloxycarbonyl group and phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxy group An acyl group such as a ryl group, an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group, an alkylamino group such as a methylamino group and a cyclohexylamino group, In addition to dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, Examples include mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, and phosphono group.

N in the chemical formula (1) is an integer of 0 to 50. From the viewpoint of easy handling due to a decrease in viscosity or the like, or from the viewpoint of interface characteristics, n is preferably an integer of 1 to 50, more preferably an integer of 1 to 30, and particularly preferably an integer of 1 to 10.

In the chemical formulas (1) and (2), Q1 ⁺ and Q2 ⁺ are each independently a secondary ammonium ion or a tertiary ammonium ion. Here, the secondary ammonium ion and the tertiary ammonium ion representing Q1 ⁺ and Q2 ⁺ can be collectively represented by the following chemical formula.

In the formula, R ³ is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. R ⁴ and R ⁵ are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may be substituted with a hydroxy group. Here, when R ³ is a hydrogen atom, the ammonium ion represented by the chemical formula is secondary, and when R ³ is the predetermined alkyl group, the ammonium ion represented by the chemical formula is a third ion. Class. Among these, R ³ is preferably a hydrogen atom (that is, Q1 ⁺ and Q2 ⁺ are secondary ammonium ions). In addition, it is preferable that only one of R ⁴ and R ^{5 is} a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms substituted with a hydroxy group. The substituted alkyl group is particularly preferably a hydroxyethyl group. As specific examples of “a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms”, those listed above can be used in the same manner, and detailed description thereof is omitted here. .

As specific examples of Q1 ⁺ and Q2 ⁺ as described above, secondary ammonium ions (R ³ = hydrogen atom) include dimethylamine, diethylamine, di-1-propylamine, di-2-propylamine, Di-n-butylamine, di-2-butylamine, di-1-pentylamine, di-2-pentylamine, di-3-pentylamine, dineopentylamine, dicyclopentylamine, di-1-hexylamine, di Examples include ions of protonated -2-hexylamine, di-3-hexylamine, dicyclohexylamine, methylethanolamine, and ethylethanolamine. Tertiary ammonium ions (R ³ = alkyl group) include trimethylamine, triethylamine, tri-1-propylamine, tri-2-propylamine, tri-n-butylamine, tri-2-butylamine, tri-1-pentyl. Amine, tri-2-pentylamine, tri-3-pentylamine, trineopentylamine, tricyclopentylamine, tri-1-hexylamine, tri-2-hexylamine, tri-3-hexylamine, tricyclohexylamine, Examples thereof include ions obtained by protonating dimethylethanolamine, ethylmethylethanolamine, diethylethanolamine, lauryldiethanolamine, and bis (2-methoxyethyl) methylamine. Among them, methylethanolamine, ethylethanolamine, diethylethanolamine, or lauryldiethanolamine is more preferably a protonated ion, and methylethanolamine, ethylethanolamine, or lauryldiethanolamine is a protonated ion. More preferably, methylethanolamine or ethylethanolamine is particularly preferably a protonated ion, and ethylethanolamine is most preferably a protonated ion.

More preferable compounds of the ion-binding salt represented by the chemical formula (1) include ion-binding salts represented by the following chemical formulas (11) to (18). Of these, the ion-binding salts represented by the following chemical formulas (11) and (13) are particularly preferable in terms of high antistatic performance, and the ion-binding salts represented by the following chemical formulas (11) and (17) are more preferable. preferable.

Further, more preferable compounds of the ion-binding salt represented by the chemical formula (2) include ion-binding salts represented by the following chemical formulas (19) to (26). Of these, ionic bond salts represented by the following chemical formulas (22) to (26) are particularly preferred because of their high antistatic performance, and ionic bonds represented by the following chemical formulas (22), (23) or (24). Salt is most preferred.

The production method of the ion-binding salt is not particularly limited, and examples thereof include an anion exchange method, a neutralization method, and an acid ester method. In addition, a deammonia method in which an ammonium salt of a sulfate ester or an ammonium salt of a sulfonate ester and a nitrogen-containing compound are reacted to distill off ammonia to obtain an ion-binding salt is also preferably used. In addition, C described in the chemical formulas (4), (6), (7) and (10) and the chemical formulas (15), (16), (18), (19), (25) and (26). ₈ H _17- , C ₁₂ H ₂₅ -and C ₁₃ H ₂₇ -may each be linear or branched. For example, C ₈ H ₁₇ — can be 2-ethylhexyl.

[Organic solvent]
The organic solvent is not particularly limited as long as it dissolves an ion-binding salt. For example, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated fatty acid hydrocarbons (methane derivatives, ethane derivatives, ethylene, etc.) Derivatives), alcohols, esters, ethers, ketones, glycol ethers (cellosolves), dialkyl glycol ethers, alicyclic hydrocarbons, aliphatic hydrocarbons and the like. These organic solvents can be used alone or in combination of two or more.

Specific examples of aromatic hydrocarbons include toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, cumene, styrene, naphthalene, anthracene, phenanthrene, cresol and the like.

Specific examples of chlorinated aromatic hydrocarbons include chlorobenzene and o-dichlorobenzene.

Specific examples of chlorinated fatty acid hydrocarbons (methane derivatives, ethane derivatives, ethylene derivatives) include, for example, chloromethane, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1. , 1-trichloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, trichloroethylene and the like.

Specific examples of alcohols include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, n-pentyl alcohol, isopentyl alcohol, n-hexyl alcohol, cyclohexanol, methyl And cyclohexanol.

Specific examples of esters include, for example, methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, normal butyl acetate, isobutyl acetate, normal pentyl acetate, and isopentyl acetate.

Specific examples of ethers include dimethyl ether, ethyl methyl ether, diethyl ether, diphenyl ether, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, furan, benzofuran, dibenzofuran, dioxane, and the like.

Specific examples of ketones include, for example, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl normal butyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, methyl cyclohexanone, isophorone, acetophenone, benzophenone, and the like. It is done.

Specific examples of glycol ethers (cellosolves) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol Mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl Ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, diethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol Ethylene glycol monobutyl ether, triethylene glycol monoisobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono 2-ethylhexyl ether, triethylene glycol monoallyl ether, triethylene glycol monophenyl ether, triethylene glycol monoben Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol mono n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monohexyl ether, propylene glycol mono 2-ethylhexyl Ether, propylene glycol monoallyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipro Lenglycol mono n-butyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono 2-ethylhexyl ether, dipropylene glycol monoallyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monobenzyl ether , Tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monoisobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono 2-ethylhexyl ether, Tripropylene glycol Examples include monoallyl ether, tripropylene glycol monophenyl ether, and tripropylene glycol monobenzyl ether.

Specific examples of dialkyl glycol ethers include, for example, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene. Glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol diethyl ether, propylene glycol di Chill ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc. Is mentioned.

Specific examples of the alicyclic hydrocarbons include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclopropene, cyclobutene, cyclopropene, cyclohexene, Examples include cycloheptene, cyclooctene, bicycloundecane, decahydronaphthalene, norbornene, norbornadiene, and the like.

Specific examples of aliphatic hydrocarbons include normal hexane, heptane, cyclohexane, mineral spirit, methylcyclohexane, and the like.

From the viewpoint of drying workability after coating, a solvent having a boiling point of 200 ° C. or less is suitable, preferably a polar solvent, and more preferably a protic polar solvent.
Moreover, as an organic solvent, glycol ethers are preferable from the viewpoint of drying workability after application and antistatic performance. As the glycol ether, any of those mentioned as the above-mentioned specific examples may be used, among them, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monopropyl ether, Diethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether , Ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, polyoxyethylene monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether Particularly preferred are ethoxylate glycol ethers such as polyoxyethylene monophenyl ether, ethylene glycol monobenzyl ether and diethylene glycol monobenzyl ether.

The content of the ion-binding salt in the coating solution as the coating-type antistatic agent is preferably from 100 parts by weight of the diluent solvent from the viewpoint of the aesthetics of the coated polymer material and the antistatic performance. 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 1 to 5 parts by mass.

As a component constituting the coating type antistatic agent of the present invention, additives other than the ion-binding salt and the organic solvent described above may be added as long as the effects of the present invention are not impaired. Although there is no restriction | limiting in particular in an additive, For example, antioxidant, a ultraviolet absorber, a plasticizer, a pigment, dye, a light stabilizer, etc. are mentioned.

The polymer material to which the coating type antistatic agent of the present invention can be used includes resins such as thermoplastic resins and thermosetting resins in addition to rubber and fibers. The resin is preferably a thermoplastic resin and / or a thermosetting resin, and more preferably a thermoplastic resin. Hereinafter, each resin will be described. In the present specification, the term “resin” includes monomers, oligomers, prepolymers and polymers.

[Thermoplastic resin]
The thermoplastic resin used in the present invention is not particularly limited. For example, (meth) acrylic resin, styrene resin, olefin resin (including cyclic olefin resin), polyester resin, polycarbonate resin, polyamide resin, polyphenylene ether resin, polyphenylene Sulfide resins, halogen-containing resins (polyvinyl chloride, polyvinylidene chloride, fluorine resins, etc.), polysulfone resins (polyethersulfone, polysulfone, etc.), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (Polydimethylsiloxane, polymethylphenylsiloxane, etc.), polyvinyl ester resins such as polyvinyl acetate, polyvinyl alcohol resins and their derivative resins, rubber or elastomers Tomah (polybutadiene, diene rubbers such as polyisoprene, styrene - butadiene copolymer, acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.) and the like. The above thermoplastic resins can be used alone or in combination of two or more.

Specific examples of (meth) acrylic resins include monofunctional (meth) acrylic monomers and their homopolymers or copolymers, polyfunctional (meth) acrylic monomers and their homopolymers or copolymers, monofunctional or polyfunctional Copolymers of (meth) acrylic monomers and other monomers are exemplified.

Specific examples of monofunctional (meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, ( (Meth) acrylic acid esters having 1 to 10 carbon atoms such as 2-ethylhexyl (meth) acrylate, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile Etc.

Specific examples of the polyfunctional (meth) acrylic monomer include polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate. Examples include acrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

Specific examples of the homopolymer or copolymer of the (meth) acrylic monomer include, for example, poly (meth) acrylic acid ester, acrylic acid ester-methacrylic acid ester copolymer, polyacrylonitrile and the like. Specific examples of the copolymer of the (meth) acrylic monomer and other monomers include, for example, a (meth) acrylic acid-styrene copolymer, a (meth) acrylic acid ester-styrene copolymer, and a (meth) acrylic. Acid ester- (meth) acrylic acid-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer, acrylonitrile-styrene- (meth) acrylic acid ester copolymer, acrylonitrile- Acrylic ester-styrene copolymer (AAS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and the like.

Specific examples of the styrene resin include, for example, polystyrene, poly-α-methylstyrene, α-methylstyrene-acrylonitrile copolymer, styrene-N-phenylmaleimide copolymer, and styrene-N-phenylmaleimide-acrylonitrile copolymer. And rubber reinforced polystyrene resin (HIPS resin).

Examples of the olefin resin include a homopolymer of an olefin monomer, a copolymer of an olefin monomer, and a copolymer of an olefin monomer and another copolymerizable monomer. Specific examples of the olefin monomer include, for example, chain olefin [carbon such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, etc. [Alpha] -olefin having 2 to 20], cyclic olefin [for example, cycloalkene having 4 to 10 carbon atoms such as cyclopentene; cycloalkadiene having 4 to 10 carbon atoms such as cyclopentadiene; 7 carbon atoms such as norbornene and norbornadiene -20 bicycloalkene or C7-20 bicycloalkadiene; dihydrodicyclopentadiene, dicyclopentadiene, etc., C10-25 tricycloalkene or tricycloalkadiene, etc.]. These olefin monomers can be used alone or in combination of two or more. Of the olefin monomers, chain olefins such as α-olefins having 2 to 4 carbon atoms such as ethylene, propylene, and 1-butene are preferable.

Specific examples of the other copolymerizable monomer copolymerizable with the olefin monomer include, for example, fatty acid vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic acid, alkyl (meth) acrylate, glycidyl (meth) (Meth) acrylic monomers such as acrylates; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and maleic anhydride or anhydrides thereof; vinyl esters of carboxylic acids (for example, vinyl acetate, vinyl propionate, etc.)]; norbornene And cyclic olefins such as cyclopentadiene; and dienes such as butadiene and isoprene. These copolymerizable monomers can be used singly or in combination of two or more.

More specific examples of the olefin resin include, for example, polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, etc.), polypropylene (homopolypropylene, block polypropylene, random polypropylene, etc.), Examples thereof include (co) polymers of chain olefins (particularly α-olefins having 2 to 4 carbon atoms) such as ethylene-propylene copolymers and ethylene-propylene-butene terpolymers. Specific examples of copolymers of olefin monomers and other copolymerizable monomers include, for example, chain olefins (particularly α-olefins having 2 to 4 carbon atoms such as ethylene and propylene) and fatty acid vinyl ester monomers. Copolymer (eg, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, etc.); copolymer of chain olefin and (meth) acryl monomer [chain olefin (particularly 2 carbon atoms) A copolymer of (meth) acrylic acid (for example, ethylene- (meth) acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, ionomer, etc.); chain olefin (Especially an α-olefin having 2 to 4 carbon atoms) and an alkyl (meth) acrylate copolymer (for example, ethylene-alkyl (meth) acrylate) A copolymer of a chain olefin (particularly an α-olefin having 2 to 4 carbon atoms) and a diene (for example, ethylene-butadiene copolymer); an epoxy-modified polyolefin (for example, Ethylene-glycidyl (meth) acrylate copolymer), carboxy-modified polyolefin (eg, ethylene-maleic anhydride copolymer), epoxy and carboxy-modified polyolefin (eg, ethylene-maleic anhydride-glycidyl (meth) acrylate copolymer) Modified polyolefins such as olefins; olefin elastomers (such as ethylene-propylene rubber).

Specific examples of the polyester resin include, for example, (a) at least one selected from the group consisting of a dicarboxylic acid or a derivative thereof and a diol or a derivative thereof, (b) a hydroxycarboxylic acid or a derivative thereof, and (c) a lactone. Examples thereof include a polymer or copolymer obtained by polycondensation.

Examples of the dicarboxylic acid or derivatives thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4 , 4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid and other aromatic dicarboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid And aliphatic dicarboxylic acids such as glutaric acid and dimer acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. Examples of the diol or derivative include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1,6-hexanediol. , Decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol and the like, or long chain glycols having a molecular weight of 200 to 100,000, that is, aromatic dioxy compounds such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, That is, 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and derivatives thereof And the like. Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Derivatives and the like. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one and the like. The polyester resin also includes a polyester elastomer.

Specific examples of the polycarbonate resin include a thermoplastic resin obtained by reacting a divalent or higher valent phenol compound with a carbonic acid diester compound such as phosgene or diphenyl carbonate.

Examples of the divalent or higher phenol compound include 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4- Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1-phenyl-1,1-bis (4-hydroxyphenyl) Ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2-methyl-1,1-bi (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis ( 3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2 , 2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4 Methyl-2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy) Phenyl) nonane, 1,10-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl)- Dihydroxydiarylalkanes such as 1,1,1,3,3,3-hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclodecane and other dihydroxydiarylcycloalka Dihydroxydiaryl sulfones such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4- Dihydroxyaryl ethers such as hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone, 3,3 ′, 5,5′-tetramethyl-4,4 Dihydroxy diaryl ketones such as' -dihydroxybenzophenone, dihydroxy such as bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide Diaryl sulfide Dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl, dihydroxyaryl fluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene, and the like It is done. In addition to the above dihydric phenol compounds, dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene can be used as the divalent phenol compound. .

These divalent or higher valent phenol compounds may be used alone or in combination of two or more. Moreover, you may use linear aliphatic divalent carboxylic acid, such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, as a copolymerization component.

Specific examples of the polyamide resin include aliphatic polyamides such as polyamide 46, polyamide 5, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 6/66, polyamide 6/11; Cycloaliphatic polyamides such as 1,4-norbornene terephthalamide, poly-1,4-cyclohexane terephthalamide poly-1,4-cyclohexane-1,4-cyclohexaneamide; fragrances such as polyamide 6T, polyamide 9T, polyamide MXD Group polyamides; copolyamides formed by at least two different polyamide-forming components among these polyamides. The polyamide resin includes a polyamide elastomer.

Specific examples of the polyphenylene ether resin include poly (2,5-dimethyl-1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether), and poly (2-methyl-6). -Ethyl-1,4-phenylene ether), poly (2,6-di-n-propyl-1,4-phenylene ether), poly (2-methyl-6-chloroethyl-1,4-phenylene ether), etc. Examples include homopolymers, modified polyphenylene ether copolymers based on these homopolymers, polyphenylene ether homopolymers or modified graft copolymers in which a styrene polymer is grafted on the copolymer. .

Specific examples of the polyphenylene sulfide resin include polyphenylene sulfide, polyphenylene sulfide ketone, polybiphenylene sulfide, and polyphenylene sulfide sulfone.

The above thermoplastic resin may be a synthetic product or a commercially available product. In the case of synthetic products, resins (resin polymers) are synthesized using known methods such as high-pressure radical polymerization, medium-low pressure polymerization, solution polymerization, slurry polymerization, bulk polymerization, emulsion polymerization, and gas phase polymerization. However, it may be applied to a resin composition. At that time, the above-mentioned thermal polymerization initiator or photopolymerization initiator may be used.

Note that the form of the copolymer when the thermoplastic resin is a copolymer may be any of a block copolymer, a random copolymer, a graft copolymer, and an alternating copolymer.

The thermoplastic resin preferably contains at least one selected from the group consisting of (meth) acrylic resins, styrene resins, olefin resins and polyester resins, and more preferably contains (meth) acrylic resins.

[Thermosetting resin]
The thermosetting resin used in the present invention is not particularly limited, and examples thereof include phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyurethane resin, polyimide resin, diallyl phthalate resin and the like. It is done. As the thermosetting resin, a synthetic product or a commercially available product may be used.

The form of the polymer material in which the coating type antistatic agent of the present invention is used is not particularly limited, and examples thereof include various forms such as a film, a sheet, a hollow molded article, an injection molded article, a woven fabric, and a nonwoven fabric. . In particular, by applying the coating type antistatic agent of the present invention as a form of a molded article including a hollow molded article or an injection molded article with a polymer material, a molded article having excellent antistatic properties, specifically, It can be used for housings such as home appliances, bumpers such as automobiles and motorcycles, and cowls.

In addition, as a method of applying the coating solution to the polymer material having antistatic properties, a known coating method can be used as appropriate, for example, spin coating, roll coating, gravure coating, reverse coating, spray coating. Methods such as air knife coating, curtain coating, roll brushing, and impregnation can be used.

(Aspect 1) In the present invention, at least one ion-binding salt represented by the following chemical formula (1) or the following chemical formula (2):

In the chemical formula (1), R ¹ is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 An aryl group having ˜30, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
A is a linear or branched alkylene group having 2 to 4 carbon atoms,
n is an integer from 0 to 50,
Q1 ⁺ is a secondary ammonium ion or a tertiary ammonium ion.

In the chemical formula (2), R ² is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 An aryl group having ˜30, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
Q2 ⁺ is a secondary ammonium ion or a tertiary ammonium ion.
And a coating-type antistatic agent containing an organic solvent can be implemented as various preferred embodiments, or a combination thereof.

(Aspect 2) In the aspect 1, the present invention preferably includes an ion-binding salt represented by the chemical formula (2).

(Aspect 3) In the aspect 1 or 2, the present invention is preferably that in the chemical formula (2), R ² is a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms.

(Aspect 4) According to the present invention, in any one of the above aspects 1 to 3, Q1 ⁺ and Q2 ⁺ are preferably secondary ammonium ions.

(Aspect 5) In the present invention, in any one of Aspects 1 to 4, it is preferable that Q1 ⁺ and Q2 ⁺ have a hydroxy group.

(Aspect 6) In the aspect 5 according to the present invention, Q1 ⁺ and Q2 ⁺ preferably have a structure in which a hydroxyethyl group is bonded to a nitrogen atom.

(Aspect 7) In the present invention according to any one of Aspects 1 to 6, the organic solvent is preferably a polar solvent.

(Embodiment 8) In the present invention, in any one of Embodiments 1 to 6, the organic solvent is preferably a protic polar solvent.

(Aspect 9) According to the present invention, in any of the aspects 1 to 6, the organic solvent is preferably a glycol ether.

(Aspect 10) In the aspect 10, the anion forming the ion-binding salt represented by the chemical formula (2) in the aspect 1 or 2 is cumene sulfonate anion, xylene sulfonate anion, dodecylbenzene sulfonate anion, paratoluene sulfonate. An anion or a dioctyl sulfosuccinate anion is preferable.

(Aspect 11) The present invention provides the method according to any one of Aspects 1 to 6, wherein Q1 ⁺ and Q2 ⁺ are N, N-diethyl-N-hydroxyethylammonium cation, N-methyl-N-hydroxyethylammonium cation, N Preferred is -ethyl-N-hydroxyethylammonium or N, N-bishydroxyethyl-N-methylammonium cation.

(Aspect 12) The present invention provides the aspect 9, wherein the glycol ether is selected from ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, Ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol Monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, polyoxyethylene monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, poly One or more ethoxylate glycol ethers selected from the group consisting of oxyethylene monophenyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether are preferred.

(Aspect 13) According to the present invention, in any one of the above aspects 1 to 12, the coating type antistatic agent is a coating liquid, and the content of the ion-binding salt in the coating liquid is 100 masses of the organic solvent. The amount is preferably 0.1 to 20 parts by mass with respect to parts.

(Aspect 14) The present invention also provides various preferred methods for producing an antistatic polymer material, including the step of applying the coating type antistatic agent according to any one of Aspects 1 to 13 onto the surface of the polymer material. It can be implemented as an aspect or a combination thereof.

(Aspect 15) According to the present invention, in the aspect 14, the polymer material is preferably a thermoplastic resin.

(Aspect 16) According to the present invention, in the aspect 14, the polymer material is preferably an ABS resin.

(Aspect 17) In the present invention, the antistatic polymer material coated with the coating-type antistatic agent according to any one of the above aspects 1 to 13 may be implemented as various preferable aspects or a combination thereof. it can.

(Aspect 18) According to the present invention, in the aspect 17, the polymer material is preferably a thermoplastic resin molded article.

(Aspect 19) In the aspect 17 according to the present invention, the polymer material is preferably an ABS resin molded product.

(Aspect 20) The present invention is preferably any one of the above aspects 17 to 19, wherein the polymer material is a molded polymer material having a specific surface resistivity (Ω / sq.) Of 1 × 10 ¹⁰ or less. . Surface specific resistivity (Ω / sq.), For example, is a target using a high resistivity meter Hirester UP and URS probe manufactured by Mitsubishi Chemical Analytech Co., Ltd. under a room temperature of 25 ° C. and a humidity of 50% RH. Measurement can be performed by applying an applied voltage of 500 V to the molded article of the polymer material.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following description, “part” or “%” may be used, but “part by mass” or “% by mass” is indicated unless otherwise specified. In addition, the evaluation items in Examples and the like were measured as follows.

Example A
Example 1
An ion-binding salt ([MEM] [EHDG-S]) represented by the following chemical formula (chemical formula (11) in the specification) was prepared.

(Example 2)
An ion-binding salt ([MEM] [Cum-SO3]) represented by the following chemical formula (chemical formula (22) in the specification) was prepared.

(Example 3)
An ion-binding salt ([2A] [EHDG-S]) represented by the following chemical formula (chemical formula (17) in the specification) was prepared.

Example 4
An ion-binding salt ([2A] [Cum-SO3]) represented by the following chemical formula (chemical formula (23) in the specification) was prepared.

(Examples 5 to 7)
In addition to the above examples, ion-binding salts of Examples 5 to 7 shown in Table 1 were prepared. In addition, the following description in Table 1 represents the following substances, respectively.
[MEM]: N-ethyl-N-hydroxyethylammonium cation [2A]: N, N-diethyl-N-hydroxyethylammonium cation [Xyl-SO3]: xylenesulfonate anion [DB-SO3]: dodecylbenzenesulfonate anion [ DOSS]: Dioctylsulfosuccinate anion [1305-S]: Polyoxyethylene tridecyl ether sulfate anion

(Comparative Example 1)
In Comparative Example 1, tri-n-butylmethylammonium bis (trifluoromethanesulfonyl) imide ([N _4,4,4,1 ] [TFSI]; 3M ^TM ionic liquid type antistatic agent FC-4400; manufactured by 3M Company ) Was prepared.

(Comparative Example 2)
In Comparative Example 2, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([Bmim] [TFSI]; reagent; manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared.

(Comparative Example 3)
In Comparative Example 3, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide ([MPPyr] [TFSI]; reagent; manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared.

(Comparative Example 4)
In Comparative Example 4, polyoxyethylene tridecyl ether sulfate ammonium salt (N-1305-SF; Newcor (registered trademark) 1305-SF; manufactured by Nippon Emulsifier Co., Ltd.), which is an anionic surfactant, was prepared.

(Comparative Example 5)
In Comparative Example 5, a nonionic surfactant polyoxyethylene tridecyl ether (N-1305; New Coal (registered trademark) 1305; manufactured by Nippon Emulsifier Co., Ltd.) was prepared.

[Diluted solvent]
As an organic solvent for diluting the ion binding salt to prepare a coating type antistatic agent, ethylene glycol monomethyl ether (MG; manufactured by Nippon Emulsifier Co., Ltd.), propylene glycol monomethyl ether (MFG; manufactured by Nippon Emulsifier Co., Ltd.) ), Methanol (reagent; manufactured by Wako Pure Chemical Industries, Ltd.), toluene (reagent; manufactured by Wako Pure Chemical Industries, Ltd.), and methyl ethyl ketone (abbreviation: MEK; reagent; manufactured by Wako Pure Chemical Industries, Ltd.).

[Create specimen]
Coating-type charging in which the ion-binding salts prepared in Examples 1 to 7 and Comparative Examples 1 to 5 are adjusted to the respective solution concentrations (1.0% by weight with respect to the dilution solvent) with each dilution solvent. A sample of inhibitor was obtained. Also, using ABS resin as the base material, a vertically-split base material (length 7.5 cm, width 3.5 cm) diluted with each solvent, a commercially available spray bottle was placed 20 cm away from the base material surface. Used and sprayed once. Then, it dried for 1 minute with a 110 degreeC dryer, and the ABS test piece was obtained.

[Antistatic test (surface resistivity)]
Surface resistivity after preparation of test piece The surface resistivity (Ω / sq.) Of the test piece after preparation was measured at room temperature 25 using a high resistance resistivity meter Hirester UP and URS probe manufactured by Mitsubishi Chemical Analytech Co., Ltd. The measurement was performed at an applied voltage of 500 V against an ABS test piece at a temperature of 50 ° C. and a humidity of 50% RH.

Table 1 shows the measurement results of evaluating the antistatic properties of the test pieces prepared above. In the table, “over” means 1 × 10 ¹³ or more, and “−” indicates that the evaluation item is not evaluated.

In Table 1 above, any of the coating solutions can be applied to the substrate surface without foaming. In Examples 1 to 7, most of the numerical values are better than those of the comparative examples when compared according to the type of organic solvent used. Overall, it was 1 × 10 ¹⁰ or less. On the other hand, in Comparative Examples 1 to 5, most of them showed 1 × 10 ¹⁰ to over, and most of them showed abnormal values as compared with Examples. In addition, at the said solution density | concentration, the stickiness was not seen on the base-material surface after application | coating, but transparency by visual observation was maintained.

Example B
The ion-binding salts of Examples 8 to 10 shown in Table 2 were prepared together with Examples 1, 2, 5, 6 and Comparative Examples 1 to 5 used in Example A above.
Propylene glycol monomethyl ether (MFG; manufactured by Nippon Emulsifier Co., Ltd.) was used as a diluent solvent, and for each of the examples and comparative examples, the solution concentrations were 0.1, 0.5, 1.0, 5.0, 10.0 and A sample of a coating type antistatic agent was prepared so as to be 20.0% (weight ratio with respect to the diluent solvent).
Using an ABS resin as a base material, an ABS test piece was obtained using the above-mentioned coating type antistatic agent sample in the same manner as in Example A, and an antistatic property test (surface resistivity) was applied at an applied voltage of 500V. Rate).

Table 2 shows the measurement results for evaluating the antistatic properties of the test pieces prepared above. In Table 2, [PT-SO3] represents a paratoluenesulfonate anion. The meanings of “over” and “−” are the same as those in Table 1.

As is apparent from the results in Table 2 above, at a solution concentration of 0.1% to 20.0%, any coating solution can be applied to the substrate surface without foaming. , 6, 8, 9 and ¹⁰ were all better than the comparative example when compared according to the concentration used, and most of them showed 1 × 10 ¹⁰ or less, but most of the comparative examples 1 to 5 1 × 10 ¹⁰ to over, all showing a malfunctioning numerical value compared to the example. In addition, the base-material surface after application | coating maintained transparency by visual observation in all the Examples.

Example C
Along with Examples 1 to 10 and Comparative Examples 1 to 5 used in Examples A and B above, ion-binding salts of Examples 11 to 18 shown in Table 3 were prepared. In addition, the following description in Table 3 represents the following substances, respectively.
[LDEA]: N, N-bishydroxyethyl-N-laurylammonium cation [MMA]: N-methyl-N-hydroxyethylammonium cation [MDA]: N, N-bishydroxyethyl-N-methylammonium cation

Using a propylene glycol monomethyl ether (MFG; manufactured by Nippon Emulsifier Co., Ltd.) as a diluting solvent, for each of the examples and comparative examples, a coating type antistatic agent so that the solution concentration is 0.1% (weight ratio with respect to the diluting solvent). Samples were prepared.
Using an ABS resin as a base material and using the above-mentioned coating-type antistatic agent sample as in Example A, an ABS test piece was obtained, and an antistatic property test (surface-specificity) was applied at an applied voltage of 500 V, respectively. Resistivity).

Table 3 shows the measurement results for evaluating the antistatic properties of the test pieces prepared above.

As is apparent from the results in Table 3 above, it can be seen that any of the coating-type antistatic agents of Examples 1 to 18 is superior in antistatic performance to the comparative example.
Therefore, it was shown that a coating-type antistatic agent having excellent antistatic properties can be provided by using the ion-binding salts represented by the chemical formulas (1) and (2).

From the above, it has been shown that by using an ion-binding salt, a coating-type antistatic agent can be obtained in which the coating solution is difficult to foam, maintains transparency after coating and drying, and provides excellent antistatic performance.

The coating type antistatic agent of the present invention provides excellent antistatic performance while maintaining transparency with respect to a polymer material, and can be used, for example, for purposes aimed at improving aesthetic appearance.

Claims (20)

1. At least one ion-binding salt represented by the following chemical formula (1) or the following chemical formula (2):
   

   

   In the chemical formula (1), R ¹ is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 An aryl group having ˜30, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
   A is a linear or branched alkylene group having 2 to 4 carbon atoms,
   n is an integer from 0 to 50,
   Q1 ⁺ is a secondary ammonium ion or a tertiary ammonium ion.
   

   

   In the chemical formula (2), R ² is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number of 6 An aryl group having ˜30, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms,
   Q2 ⁺ is a secondary ammonium ion or a tertiary ammonium ion.
   And a coating-type antistatic agent comprising an organic solvent.
2. The coating type antistatic agent according to claim 1, comprising an ion-binding salt represented by the chemical formula (2).
3. The coating type antistatic agent according to claim 2, wherein R ² in the chemical formula (2) is a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms.
4. The coating-type antistatic agent according to claim 1, wherein Q1 ⁺ and Q2 ⁺ are secondary ammonium ions.
5. The coating type antistatic agent according to claim 1, wherein Q1 ⁺ and Q2 ⁺ have a hydroxy group.
6. The coating type antistatic agent according to claim 5, wherein Q1 ⁺ and Q2 ⁺ have a structure in which a hydroxyethyl group is bonded to a nitrogen atom.
7. The coating type antistatic agent according to claim 1, wherein the organic solvent is a polar solvent.
8. The coating type antistatic agent according to claim 1, wherein the organic solvent is a protic polar solvent.
9. The coating type antistatic agent according to claim 1, wherein the organic solvent is a glycol ether.
10. The anion forming the ion-binding salt represented by the chemical formula (2) is cumene sulfonate anion, xylene sulfonate anion, dodecylbenzene sulfonate anion, paratoluene sulfonate anion, or dioctyl sulfosuccinate anion. The coating type antistatic agent as described.
11. Q1 ⁺ and Q2 ⁺ are N, N-diethyl-N-hydroxyethylammonium cation, N-methyl-N-hydroxyethylammonium cation, N-ethyl-N-hydroxyethylammonium or N, N-bishydroxyethyl-N The coating type antistatic agent according to claim 6, which is a methylammonium cation.
12. The glycol ethers include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol. Monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol Monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, diethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, polyoxyethylene monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, polyoxyethylene monophenyl ether The coating type antistatic agent according to claim 9, which is one or more ethoxylate glycol ethers selected from the group consisting of ethylene glycol monobenzyl ether and diethylene glycol monobenzyl ether.
13. The coating type antistatic agent is a coating solution, and the content of the ion-binding salt in the coating solution is 0.1 to 20 parts by mass with respect to 100 parts by mass of the organic solvent. The coating type antistatic agent as described.
14. A method for producing an antistatic polymer material, comprising a step of applying the coating type antistatic agent according to any one of claims 1 to 13 to the surface of the polymer material.
15. The method for producing an antistatic polymer material according to claim 14, wherein the polymer material is a thermoplastic resin.
16. The method for producing an antistatic polymer material according to claim 14, wherein the polymer material is an ABS resin.
17. An antistatic polymer material, wherein the coating type antistatic agent according to any one of claims 1 to 13 is applied.
18. The antistatic polymer material according to claim 17, wherein the polymer material is a thermoplastic resin molded product.
19. The antistatic polymer material according to claim 17, wherein the polymer material is an ABS resin molded product.
20. The antistatic polymer material according to claim 17, wherein the polymer material is a molded polymer material having a surface resistivity (Ω / sq.) Of 1 × 10 ¹⁰ or less.