JPH11189746A - Antistatic treating agent, its utilization and article coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for utilizing an antistatic treating agent comprising a self-dope type electroconductive polymer, capable of improving normal temperature stability of antistatic treatment and utilizing the effect and obtain an article coated with the antistatic treating agent. SOLUTION: A new antistatic treating solution capable of preventing lowering of pH in a solution and lowering of conductivity (raising of resistance of a coating film prepared from the solution) is produced by adding a mixture containing at least carboxylic acid derivative and an amine derivative and having pH buffering action to a solution of a self dope type conductive polymer having an aromatic sulfonic acid group in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic treatment agent which contains a self-doping type conductive polymer component and is extremely stable even when stored at room temperature for a long time, a method of using the same, and a coated article.

[0002]

2. Description of the Related Art Polymers having a π-electron conjugated system have attracted industrial attention because of their unique physical properties such as a change in state at the metal / semiconductor transition as well as conductivity, and many studies have been made. In particular, many conductive polymers such as polyacetylene, polythiophene, polypyrrole, and polyparaphenylene are insoluble and infusible due to a rigid main chain skeleton (Skotheim
Author, "Handbook of Conducting Polymers", Mercer D
ekker Co., Ltd., 1986), but a polymer having a substituent such as an alkyl group introduced into its side chain becomes soluble and has attracted industrial attention because of its easy processability.

As a specific example, a polymer which is soluble in an organic solvent by introducing a long-chain alkyl group into a side chain of a polythiophene ring (K. Jen et al., Journal of Chemical Society, Che.
mical Communication, p. 1346, 1986), and water-soluble polymers with sulfoalkyl groups (AOPatil et al.,
Journal of American Chemical Society, Volume 109, 18
58, 1987). The latter example is known as a water-soluble self-doped polymer, in which Bronsted acid groups are generally covalently bonded directly to the main chain of a π-electron conjugated polymer or indirectly via a spacer,
It has also been noted that it exhibits a conductive state without the contribution of extraneous dopants. Other reports of such cases include the EE
Havinga's polythiophene derivative (Polymer Bulletin
Journal, Vol. 18, p. 277, 1987), polythiophene derivatives and polypyrrole derivatives of Aldissi (US Pat. No. 4,880,508), and polymers in which a carboxyl group is covalently bonded as a substituent to a polyaniline aromatic ring (Japanese Patent Application Laid-Open No. 1-500835). Publication), a polymer in which a sulfopropyl group is substituted at the N-position of pyrrole (Journal of Chemical Society, Chemical Commun
ication magazine, p. 621, 1987), polyaniline polymer substituted with a sulfopropyl group at the N-position (Journal of Chemica
l Society, Chemical Communication, 180, 1990
Year, and Synthetic Metal, 31, 369, 1989
Year), a polyaniline derivative in which an aromatic ring is directly substituted with a sulfonic acid group (Journal of American Chemical Society,
112, 2800, 1990), and isothianaphthene polymers substituted with a sulfonic acid group (JP-A-6-49183 and JP-A-7-48436), as well as the production method. These have many industrial advantages because they are water-soluble, exhibit good conductivity without the contribution of foreign dopants, and can be easily formed into thin films.

[0004] However, among self-doping conductive polymers, self-doping in which aromatic ring is directly substituted with sulfonic acid is used.
It has been known that, when stored in a solution at room temperature, the conductive polymer has a change in physical properties such as a decrease in the pH of the solution and an increase in the resistance value (decrease in conductivity) of a coating film formed from the solution. Such a change in physical properties is described in, for example, JP-A-4-328.
As described in JP-A-48-48, when used for the purpose of preventing a charging phenomenon in a step of irradiating a charged particle beam, the effect is extremely large, and improvement is required. Usually, in order to prevent such a charging phenomenon, the surface resistance is required to be 5 × 10 ⁷ Ω / □ or less (Electronic Materials Magazine, December 1990, pp. 48-54).

[0005] As a method of improving the change in physical properties,
Japanese Patent Application Laid-Open No. Hei 8-259573 discloses a method for removing oxygen from a solution. However, this deoxygenation treatment or the like requires special measures in terms of the production process and storage in a container, and requires stabilization of the antistatic treatment agent itself. In addition, chemically amplified resist materials have recently been used as photosensitive materials in the process of irradiating a charged particle beam in semiconductor manufacturing in semiconductor manufacturing, and antistatic treatment agents with small pH fluctuations are required. On the other hand, although not using an antistatic agent, Japanese Patent Publication No. Hei 6-511283 discloses a pH buffer solution for controlling the polymerizability of the precursor monomer when producing a conductive polymer such as polypyrrole. Is disclosed, but an example using a pH buffer solution for imparting stability to the conductive polymer has not been known so far.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antistatic treatment agent containing a self-doping type conductive polymer which is excellent in stability when left at room temperature, a method of using the same, and a coated article. . Specifically, it includes a self-doping type conductive polymer having a specific fused heteropolycyclic compound skeleton or iminophenylene skeleton, and has excellent long-term stability at room temperature, and its use, An object of the present invention is to provide a coated article manufactured by using them.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by using a mixture having a pH buffering action (including a compound) together, a self-doping type conductive compound having an aromatic sulfonic acid group can be obtained. The present inventors have found that a polymer-containing antistatic treatment agent can specifically suppress a decrease in the conductivity of a coating film of the polymer without causing a change (de-doping or oxidation) in characteristics such as a self-doping state. Invented the invention. The self-doped conductive polymer having an aromatic sulfonic acid group in the present invention is a π-electron conjugated polymer in which an aromatic ring is directly substituted with a sulfonic acid group, and the sulfonic acid group Any self-doped conductive polymer having a zwitterion structure formed between it and the π-electron conjugated main chain may be used, and the primary structure of the chemical structure is not particularly limited. Specific examples of the repeating structural unit include the chemical structure of each divalent group of a sulfonic acid-substituted product and a anilinesulfonic acid-substituted derivative of a condensed heteropolycyclic compound having a specific structure or various salts of the above-mentioned structure. That is, the polymer form is a polymer (homopolymer) having the above-mentioned repeating structure or a copolymer (copolymer) containing the structure. The divalent group other than the repeating structure in the copolymer may be anything that can form a π-electron conjugated structure in the polymer main chain structure,
For example, divalent groups such as phenylene, pyrrolylene, thienylene, vinylene, acetylene, iminophenylene, isothianaphthenylene, furylene, and carbazolylene are exemplified, and isothianaphthenylene and iminophenylene groups are preferably selected.

Hereinafter, the present invention will be described in detail. As the divalent group of the sulfonic acid-substituted product of the fused heteropolycyclic compound having the specific structure used in the present invention, the following general formula (1)

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently H, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms; 1 or 2
0 linear or branched saturated or unsaturated alkoxy, hydroxyl, halogen, nitro, cyano,
Trihalomethyl groups such as chloromethyl, phenyl group and substituted phenyl group or a SO ₃ ^- represents a monovalent group such as M ¹ group, M
¹ is H ⁺ , an alkali metal ion, or N (R ⁷ )
(R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ (quaternary ammonium ion), P (R ⁷ ) (R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ , As
^{(R 7) (R 8)} (R 9) (R 10) + in represented by Vb
Represents a quaternary cation of a group III element. R ⁷ , R ⁸ , R ⁹ , R
¹⁰ independently represents H, a linear or branched substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group, and is an alkoxy group, a hydroxyl group, an oxyalkylene group, It may be an alkyl group or an aryl group including a group containing an element other than carbon and hydrogen such as an alkylene group, an azo group, an azobenzene group, and a p-diphenyleneoxy group. R ¹ , R
^When the substituents adjacent to each other among the substituents of ² , R ³ , R ⁴ and R ⁵ are hydrocarbon groups, the hydrocarbon chains are bonded to each other at any position and are substituted by such groups. With at least one carbon atom, at least one or more divalent chains forming at least one or more saturated or unsaturated 3- to 7-membered cyclic structure may be formed. L represents the number of a fused 6-membered ring sandwiched between a fused 5-membered ring having X as a member and a fused 6-membered ring separated from the 5-membered ring, and is an integer of 0 to 3. X represents a heteroatom; S, O, Se, Te or N
R ⁶ . R ⁶ represents H, a linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms. R above
^In the chain of the alkyl group, alkoxy group or alkyl ester group of ¹ , R ² , R ³ , R ⁴ and R ⁵ , a carbonyl bond, an ether bond, an ester bond, a sulfonic ester bond, an amide bond, a sulfonamide bond, It may optionally contain a sulfide bond, a sulfinyl bond, a sulfonyl bond, an imino bond, and a thioether bond. ),

Or a divalent group of an anilinesulfonic acid-substituted derivative represented by the following general formula (2):

Embedded image (In the formula, R ¹¹ , R ¹² and R ¹³ are each independently H, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear chain having 1 to 20 carbon atoms. Jo or branched, saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group such as chloromethyl, phenyl group and substituted phenyl group or a SO ₃ ^- monovalent radical such as M ² group And R ¹⁴ independently represents H or a monovalent group of a group consisting of a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group. .M ² is,
H ⁺ , alkali metal ion, or N (R ⁷ ) (R ⁸ )
(R ⁹ ) (R ¹⁰ ) ⁺ (quaternary ammonium ion), P
^{(R 7) (R 8)} (R 9) (R 10) +, As (R 7)
A quaternary cation of a group Vb element represented by (R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ . R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent H, a linear or branched, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group; Group, hydroxyl group, oxyalkylene group, thioalkylene group,
It may be an alkyl group or an aryl group including a group containing an element other than carbon and hydrogen such as an azo group, an azobenzene group, and a p-diphenyleneoxy group. In addition, R ¹¹ ,
A carbonyl bond, an ether bond, an ester bond, a sulfonic acid ester bond, an amide bond, a sulfonamide bond, a sulfide bond, a sulfinyl bond are present in the chain of the alkyl group, alkoxy group or alkyl ester group of R ¹² , R ¹³ and R ^14. , A sulfonyl bond, an imino bond, and a thioether bond. ).

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
Particularly useful examples of R ¹¹ , R ¹² and R ¹³ include H
(Hydrogen), alkyl groups, alkoxy groups, alkyl ester groups, phenyl and substituted phenyl groups, and sulfonic acid groups. Illustrating these substituents in more detail,
Examples of the alkyl group include methyl, ethyl, propyl, allyl, isopropyl, butyl, 1-butenyl, pentyl,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, ethoxyethyl, methoxyethyl, methoxyethoxyethyl, acetonyl, phenacyl, etc., and alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy , Hexyloxy, octyloxy, dodecyloxy, methoxyethoxy, methoxyethoxyethoxy and the like, alkyl ester groups, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like alkoxycarbonyl group, acetoxy, butoxyloxy and the like acyloxy group, substituted phenyl group Represents a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a methylphenyl group, a methoxyphenyl group or the like. In the chain of the alkyl group or alkoxy group of R ¹ , R ² , R ³ , R ⁴ , and R ⁵ , a carbonyl bond, an ether bond, an ester bond, a sulfonic acid ester bond, an amide bond, a sulfonamide bond, and a sulfide It may optionally contain a bond, a sulfinyl bond, a sulfonyl bond, an imino bond, and a thioether bond.

In the general formula (1), R ¹ , R ² , R ³ , R
^In R ⁴ , R ⁵ , R ¹¹ , R ¹² and R ¹³ , among the above-mentioned substituents, H, a linear or branched alkyl group or an alkoxy group having 1 to 20 carbon atoms is preferable. A linear or branched alkoxy group of the formulas 1 to 20 is particularly desirable. Also, adjacent R ¹ , R ² ,
The substituents selected from R ³ , R ⁴ , and R ⁵ are bonded to each other at an arbitrary substitution position to form a saturated or unsaturated cyclic structure (eg, a hydrocarbon) or a heterocyclic structure containing an atom substituted by the substituent. A divalent group forming a ring may be formed,
Examples of such divalent groups include butylene, pentylene, hexylene, butadienylene, substituted butadienylene, methylenedioxy, ethylenedioxy and the like.

R ⁶ in the general formula (1) and R ¹⁴ in the general formula (2) each independently represent H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, A monovalent group selected from the group consisting of a phenyl group and a substituted phenyl group is preferred.
Same as ¹ , R ² , R ³ , R ⁴ and R ⁵ .

In the general formulas (1) and (2), M ¹ and M ² are H ⁺ , N (R ⁷ ) (R ⁸ ) (R
⁹ ) a quaternary ammonium cation represented by (R ¹⁰ ) ⁺ , P (R ⁷ ) (R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ , As
^{(R 7) (R 8)} (R 9) (R 10) + in represented by Vb
Quaternary cation of group element, or Na ⁺ , Li ⁺ , K
^Represents an alkali metal ion such as ⁺ , and M ¹ and M ² may be a mixture containing one or more kinds of the cations.
R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently H, having 1 carbon atom.
Represents from 30 to 30 linear or branched substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups, and includes an alkoxy group, a hydroxyl group, an oxyalkylene group, a thioalkylene group, an azo group, an azobenzene group, p And an alkyl group or an aryl group including a group containing an element other than carbon and hydrogen such as a diphenyleneoxy group.

Such N (R ⁷ ) (R ⁸ ) (R ⁹ )
Examples of the quaternary ammonium cation represented by (R ¹⁰ ) ⁺ include NH ₄ ⁺ , NH (CH ₃ ) ₃ ⁺ , and NH (C
^{_{6 H 5) 3 +, N}} (CH 3) 2 (CH 2 OH) (CH 2
-Z) ^{+ and} other unsubstituted or alkyl-substituted or aryl-substituted cations (Z represents an arbitrary substituent having a chemical formula of 600 or less, for example, phenoxy, p-diphenyleneoxy, p-alkoxydi Substituents such as phenyleneoxy group and p-alkoxyphenylazophenoxy group), and quaternary cations of a heterocyclic amine (pyridinium ion, piperidinium ion).
P (R ⁷ ) (R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ , As
^{(R 7) (R 8)} (R 9) (R 10) + in represented by Vb
Examples of quaternary cations of group elements include PH ₄ ⁺ , PH
(CH ₃ ) ₃ ⁺ , PH (C ₆ H ₅ ) ₃ ⁺ , AsH ₄ ⁺ , AsH
Unsubstituted or alkyl-substituted or aryl-substituted cations such as (CH ₃ ) ₃ ⁺ and AsH (C ₆ H ₅ ) ₃ ⁺ are used. In order to convert to a specific cation, an ordinary ion exchange resin may be used.

In the chain of the alkyl group of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , a carbonyl bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a sulfinyl bond,
It may optionally contain a sulfonyl bond, an imino bond and the like.
In the general formula (1), a desirable example of M ⁺ is H
⁺ And ^{N (R 7) (R 8} ) (R 9) (R 10) + with a quaternary ammonium ion represented, and Na ^+, an alkali metal ion Li ⁺ or K ⁺ and the like, especially N (R ⁷ )
(R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ is desirable.

The divalent group of the condensed heteropolycyclic compound represented by the general formula (1) used in the present invention is, for example, 5-sulfoisothianaphthene-1,3-diyl, 4-sulfoisothianaphthene -1,3-diyl, 4-methyl-5-sulfoisothianaphthene-1,3-diyl, 6-methyl-5
-Sulfoisothianaphthene-1,3-diyl, 6-methyl-4-sulfoisothianaphthene-1,3-diyl, 5
-Methyl-4-sulfoisothianaphthene-1,3-diyl, 6-ethyl-5-sulfoisothianaphthene-1,3
-Diyl, 6-propyl-5-sulfoisothianaphthene-1,3-diyl, 6-butyl-5-sulfoisothianaphthene-1,3-diyl, 6-hexyl-5-sulfoisothianaphthene-1, 3-diyl, 6-decyl-5-sulfoisothianaphthene-1,3-diyl, 6-methoxy-5-sulfoisothianaphthene-1,3-diyl, 6-
Ethoxy-5-sulfoisothianaphthene-1,3-diyl, 6-chloro-5-sulfoisothianaphthene-1,3
-Diyl, 6-bromo-5-sulfoisothianaphthene-
1,3-diyl, 6-trifluoromethyl-5-sulfoisothianaphthene-1,3-diyl, 5-sulfoisobenzofuran-1,3-diyl, 5-sulfoisoindole-1,3-diyl, 6 -Sulfonaphtho [2,3-c]
Acid type compounds such as thiophene-1,3-diyl and the like, lithium salts, sodium salts, ammonium salts, methyl ammonium salts, ethyl ammonium salts, dimethyl ammonium salts, diethyl ammonium salts, trimethyl ammonium salts, triethyl ammonium salts, tetramethyl Ammonium salts, tetraethylammonium salts and the like can be mentioned.

Preferred specific examples of the chemical structure represented by the general formula (2) include 2-sulfo-1,4-iminophenylene, 3-methyl-2-sulfo-1,4-iminophenylene, 5-methyl -2-sulfo-1,4-iminophenylene, 6-methyl-2-sulfo-1,4-iminophenylene, 5-ethyl-2-sulfo-1,4-iminophenylene, 5-hexyl-2-sulfo- 1,4-iminophenylene, 3-methoxy-2-sulfo-1,4-iminophenylene, 5-methoxy-2-sulfo-1,4-iminophenylene, 6-methoxy-2-sulfo-1,4-imino Phenylene, 5-ethoxy-2-sulfo-1,4-iminophenylene, 2-sulfo-N-methyl-1,4-iminophenylene, 2-sulfo-N-ethyl-1,4-iminophenylene and the like Acid type compounds, or lithium salts, sodium salts, ammonium salts, methyl ammonium salts, ethyl ammonium salts, dimethyl ammonium salts, diethyl ammonium salts, trimethyl ammonium salts, triethyl ammonium salts, tetramethyl ammonium salts, tetraethyl ammonium salts thereof, and the like. be able to.

The repeating chemical structure of the self-doping type conductive polymer represented by the general formula (1) or (2) usually has 100 repeating units in all the repeating units of the polymer.
Mol% to 50 mol%, preferably 100 mol% to 80 mol%, and 2 to 5 mol% as a copolymer component.
It may be a copolymer composition comprising different kinds of repeating units. The copolymer is not limited to a block copolymer containing a repeating unit or a continuous unit, and may be an irregular copolymer such as a random copolymer.

The molecular weight of the self-doping type conductive polymer used in the present invention cannot be specified unconditionally because it differs depending on the chemical structure of the constituent repeating unit. Not limited. Usually, when represented by the number of repeating units (degree of polymerization) constituting the main chain, it is usually in the range of 5 to 2,000, preferably 10 to 2,000.
It is in the range of 1000.

Particularly preferred specific examples of the self-doping type conductive polymer having a sulfonic acid group used in the present invention include: i) In the general formula (1), as an example of a chemical structure represented by L = 0, 5 -Sulfoisothianaphthene-1,3-diyl polymer acid structure and its lithium salt, sodium salt, ammonium salt, triethylammonium salt, ii) random containing at least 80 mol% of the chemical structure described in i) above. Copolymers, i.e. poly (5-sulfoisothianaphthene-1,3-diyl-co-isothianaphthene-
Examples of the acid structure of 1,3-diyl) and its lithium salt, sodium salt, ammonium salt, triethylammonium salt, and iii) an example of the chemical structure represented by the general formula (2):
Acid structure of random copolymer containing 2-sulfo-1,4-iminophenylene in an amount of 50 mol% or more, that is, poly (2-sulfo-1,4-iminophenylene-co-1,4-iminophenylene), and lithium thereof Salts, sodium salts, ammonium salts, and triethylammonium salts.

The weak acid mixed into the antistatic treatment agent of the present invention is not particularly limited as long as it exhibits a pH buffering action when formed into a mixture with a base. Further, the base is not limited either. Examples of the weak acid include a carboxylic acid derivative, a phosphoric acid derivative, a boric acid derivative, and the like. Among them, a carboxylic acid derivative is preferable.
Specific examples of the weak acid include carbonic acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, cyclohexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, and tridecane. Linear and branched aliphatic saturated or unsaturated monocarboxylic acids such as acids, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, methacrylic acid, acrylic acid, crotonic acid, and oleic acid Or oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aliphatic saturated dicarboxylic acids such as sebacic acid, or maleic acid, fumaric acid, mesaconic acid, citraconic acid, etc. Aliphatic unsaturated dicarboxylic acids, furthermore benzoic acid, phenylacetic acid, phthalic acid Isophthalic acid, terephthalic acid, and aromatic carboxylic acids and their substituted derivatives such as naphthalene carboxylic acid. Similarly, phosphoric acid, phosphorous acid,
Examples include polyphosphoric acid and boric acid. In the present invention, preferably acetic acid, propionic acid, butanoic acid, pentanoic acid,
Linear and branched monocarboxylic acids such as hexanoic acid, cyclohexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid.

On the other hand, as the base, in addition to ammonia, a saturated or unsaturated aliphatic amino compound, aromatic amino compound and nitrogen-containing heterocyclic compound are preferable. Specific examples of such an aliphatic amino compound include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, aniline, methylaniline, benzylamine, monoethanolamine, diethanolamine,
Examples thereof include triethanolamine, morpholine, pyridine, piperidine, cyclohexylamine, and 1,4-butanediamine.

Specific examples of aromatic amino compounds include aniline, 4-methylaniline, 4-methoxyaniline, 4-chloroaniline, 4-nitroaniline, and 4-nitroaniline.
Examples thereof include cyanoaniline, N-methylaniline, N-ethylaniline, diphenylamine, triphenylamine, benzylamine, naphthylamine, and naphthalenediamine. Specific examples of the nitrogen-containing heterocyclic compound include pyrrole, tetrahydropyrrole, thiazole, oxazole, triazole, pyridine, piperazine, pyrazine, pyrimidine, pyridazine, triazine, indole, isoindole, indolizine, purine, quinoline, isoquinoline, quinoxaline, and phenazine. And the like.

The solvent used in the antistatic treatment agent of the present invention is not particularly limited as long as it is a solvent that dissolves a polymer containing a structural unit represented by the general formula (1) or (2) and a weak acid or base. It is not something to be done. For example, specifically, water or a solvent system miscible with water is preferred. Specific examples of the solvent include ethers such as 1,4-dioxane and tetrahydrofuran, dimethyl carbonate, diethyl carbonate, ethylene carbonate, carbonates such as propylene carbonate, nitriles such as acetonitrile and benzonitrile, methanol, ethanol, and propanol. , Alcohols such as isopropanol, N,
N-dimethylformamide, dimethylsulfoxide, N
An aprotic polar solvent such as -methyl-2-pyrrolidone can be used.

The concentration of the compound represented by the general formula (1) or the general formula (2), the weak acid and the base used as the antistatic treatment agent of the present invention is 0.001 g / L to 500 g, respectively, as the component concentration. / L is preferred, and more preferably 0.01 g / L to 50 g / L.

The antistatic treatment agent of the present invention may contain at least one surfactant in addition to the self-doping type conductive polymer compound, weak acid and base. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a silicone-based surfactant, a fluorine-based surfactant, and an amphoteric surfactant. When such a surfactant is used, the weight ratio is 0.001 to 95 times, preferably 0.005 to 20 times, more preferably 0.01 to 100 times the weight of the self-doping type conductive polymer compound. Use 5 times the amount. The amount of surfactant is 0.001
If the amount is less than twice, the effect of adding the surfactant may be lost. If the amount is more than 95 times, good electron conductivity may not be secured.

The antistatic treatment agent of the present invention can be added to any p-acid in an acidic to alkaline range by changing the mixing ratio of a weak acid and a base and the amount of addition contained in the antistatic treatment agent.
It can be set to the H value. It is also possible to independently mix one or more kinds of weak acids and bases. The antistatic treatment agent can also be used to coat an article surface as a conductive film by coating or the like. As a method of application or the like, specifically, an aqueous solution of the antistatic treatment agent is applied to an article, or the article is dipped (immersed) in the aqueous solution or sprayed on the article, for example, for the purpose of the article or specification. Various methods may be used depending on the case. Further, when the composition is applied on an article, an aqueous solution containing at least one kind of the above-mentioned surfactants can be used in order to improve the application performance.

The article to be prevented from being charged by the antistatic treatment agent is not particularly limited as long as it is an article required to be prevented from being charged. Specific examples of the base article include fiber, non-woven cloth, cardboard paper and the like. Paper such as high-quality paper and recycled paper, polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethyl methacrylate, polymethacrylate, polyacrylate, polyvinyl alcohol,
Polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyacetals, polysulfones, polyethersulfones, polyetheretherketones, polycarbonates, polyethers, polyimides, polyamideimides, polyurethane plastics, diene plastics, natural Films and molded products such as rubber-based plastics, cellulose-based plastics, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, and fluororesins, and films and molded products that have been hydrophilized by surface modification of the plastics, Water-absorbing polymers such as acrylic acid / vinyl alcohol copolymers, acrylic acid / acrylamide copolymers and their films and molded products, silicone resins, liquid crystals and liquid crystal polymers, semiconductors Photomask used in the manufacture,
Pellicle, phase shifter material, silicon having a resist layer on the surface, silicon oxide film, metal oxide such as magnesium oxide, oxide single crystal such as LiNbO ₃ , compound semiconductor such as AsGa or InP, quartz glass and soft glass, CRT Substrates and the like are included. The antistatic treatment agent used for these articles can be removed by a method such as washing with water, if necessary.

[0029]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the following examples do not limit the scope of the present invention. Hydrogen ion concentration (pH) of aqueous solution
Was measured with a glass electrode type hydrogen ion concentration meter (manufactured by HORIBA, Ltd., pH METER F-13). Further, the surface resistance of the coating film was measured by using a spinner (1H-III type manufactured by Kyoei Semiconductor Co., Ltd.) to spin-coat the aqueous solution on a glass substrate at 1500 rpm, and measure the surface resistance of the coating film produced by a surface resistance measuring instrument Megaresta. (Model HT-301, manufactured by Shisido Electrostatic Co., Ltd.). In addition, bar coating is performed by dripping the coating liquid on the substrate and sliding the bar coater (a rod with a groove like a screw) along the surface of the substrate, or rolling the coating liquid to evenly coat the coating liquid. Is a method of applying the composition to a substrate. ETO & CO. Was used.

(Example 1) In the general formula (1), R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and M ¹ are each H, X =
A method for producing an antistatic treatment agent which is a self-doping conductive polymer compound containing a chemical structure of a repeating structural unit represented by S and L = 0, wherein acetic acid is a weak acid and ammonia is a base. An acid-type polymer of poly (5-sulfoisothianaphthene-1,3-diyl) synthesized with reference to the method disclosed in JP-A-7-48436, 0.6 (w /
w) 1N- containing 5.6 ml of acetic acid in 100 ml of a% aqueous solution
By adding 15 ml of aqueous ammonia and mixing with stirring, an intended antistatic treatment agent was obtained. The hydrogen ion concentration (pH value) immediately after the preparation of the antistatic treatment agent was 3.6. Further, after spin-coating 3 ml of the antistatic treatment agent on a glass substrate and drying, a thin film of the antistatic treatment agent was formed on the glass surface, and the surface resistance was measured. The result was 5.4 × 10 ⁵ Ω. / □. The antistatic treatment agent was left at room temperature, sampled with time, and its pH value was measured, and a glass coating film was prepared in the same manner as above to examine the surface resistance value (Rs).
3.5, Rs = 2.9 × 10 ⁶ Ω / □, p after 2 months
H = 3.2, Rs = 2.7 × 10 ⁷ Ω / □, pH = 3.1 after 3 months, Rs = 4.7 × 10 ⁷ Ω / □.

Example 2 An acid-type polymer of poly (5-sulfoisothianaphthene-1,3-diyl) synthesized in the same manner as in Example 1, a 0.6 (w / w)% aqueous solution 100
1N-ammonia water containing 5.4 ml of acetic acid per ml 14.
4 ml and 0.1 g of dodecylbenzenesulfonic acid were added and mixed with stirring to obtain a desired antistatic treatment agent. The hydrogen ion concentration (p
H value) was 3.6. Also, 3 ml of the antistatic treatment agent was spin-coated on a glass substrate and dried to form a thin film of the antistatic treatment agent on the glass surface, and the surface resistance was measured. The result was 5.0 × 10 ⁵ Ω. / □
Met. The antistatic treatment agent was allowed to stand at room temperature, sampled with time, and its pH value, and a glass coating film was prepared in the same manner as above to examine its surface resistance value. 5, Rs = 2.9 × 10 ⁶ Ω /
□ After 2 months, pH = 3.2, Rs = 2.3 × 10 ⁷
Ω / □, pH = 3.1 after 3 months, Rs = 4.3 × 1
0 ⁷ Ω / □.

Example 3 Acidic polymer of poly (5-sulfoisothianaphthene-1,3-diyl) synthesized in the same manner as in Example 1, 0.8 (w / w)% aqueous solution 100
15 ml of 1N ammonia water containing 3.5 ml of acetic acid in ml
1 and 0.1 g of dodecylbenzenesulfonic acid were added and mixed by stirring to obtain the desired antistatic treatment agent. The hydrogen ion concentration (pH
Value) was 4.1. Also, 3 ml of the antistatic treatment agent was spin-coated on a glass substrate and dried to form a thin film of the antistatic treatment agent on the glass surface, and the surface resistance was measured. The result was 2.7 × 10 ⁵ Ω. / □. The antistatic treatment agent was allowed to stand at room temperature, sampled with time, and its pH value, and a glass coating film was prepared in the same manner as above to examine its surface resistance value. 0, Rs = 2.6 × 10 ⁶ Ω / □,
After 2 months, pH = 3.9, Rs = 3.3 × 10 ⁷ Ω /
□ After 3 months, pH = 3.8, Rs = 4.6 × 10 ⁷
Ω / □.

Example 4 Poly (5-sulfoisothianaphthene-1,3-diyl) acid-type polymer synthesized in the same manner as in Example 1, 0.8 (w / w)% aqueous solution 100
1N-aqueous ammonia containing 1.7 ml of butyric acid in 7.5 ml
Then, the desired antistatic treatment agent was obtained by adding and mixing with stirring. The hydrogen ion concentration (pH value) immediately after the preparation of this charge treating agent was 4.3. Also, 3 ml of the antistatic treatment agent was spin-coated on a glass substrate and dried to form a thin film of the antistatic treatment agent on the glass surface, and the surface resistance was measured.
0 ⁵ Ω / □. The antistatic treatment agent was allowed to stand at room temperature, sampled with time, and its pH value, and a glass coating film was prepared in the same manner as above to examine its surface resistance value. 2, Rs = 2.0 × 1
0 ⁶ Ω / □, in the two months after pH = 4. 1, Rs = 2. 6
× 10 ⁷ Ω / □, pH = 4.0 after 3 months, Rs =
It was 4.0 × 10 ⁷ Ω / □.

(Example 5) Poly (5-) synthesized by referring to the method disclosed in JP-A-7-48436.
Acid type polymer of sulfoisothianaphthene-1,3-diyl-co-isothianaphthene (80 mol%: 20 mol%), acetic acid in 100 ml of a 0.6 (w / w)% aqueous solution.
18 ml of 1N-ammonia water containing 8 ml was added and mixed by stirring to obtain a desired antistatic treatment agent. The hydrogen ion concentration (pH
Value) was 3.7. Further, 3 ml of the antistatic treatment agent was spin-coated on a glass substrate and dried to form a thin film of the antistatic treatment agent on the glass surface, and the surface resistance was measured. The result was 5.5 × 10 ⁵ Ω. / □. The antistatic treatment agent was allowed to stand at room temperature, sampled with time, and its pH value, and a glass coating film was prepared in the same manner as above to examine its surface resistance value. 6, Rs = 2.3 × 10 ⁶ Ω / □,
After 2 months, pH = 3.5, Rs = 2.9 × 10 ⁷ Ω /
□ After 3 months, pH = 3.5, Rs = 3.9 × 10 ⁷
Ω / □.

Example 6 R ¹ in the general formula (1),
R ² , R ³ , R ⁴ , R ⁵ and M ¹ are each H, X =
A method for producing an antistatic treatment agent which is a self-doping conductive polymer compound containing a chemical structure of a repeating structural unit represented by S and L = 1, wherein acetic acid is a weak acid and ammonia is a base. As a polymer having the title chemical structure, poly (naphtho [2,
3-c] thiophene-6-sulfonic acid) and synthesized with reference to the method described in JP-A-8-188777.
A 0.6 (w / w)% aqueous solution was prepared. This embodiment is the same as the embodiment 1 except that the poly (5-sulfoisothianaphthene-1,3-diyl) acid type polymer described in the above embodiment 1 is changed. To obtain the desired antistatic treatment agent. Then, the following characteristics were confirmed. The hydrogen ion concentration (pH value) immediately after the preparation of this antistatic treatment agent was 3.6, and the surface resistance value of the thin film formed on the glass surface was 5.9 × 10 ⁵ Ω / □. As in Example 1, the antistatic treatment agent was allowed to stand at room temperature and sampled over time to examine its pH value and surface resistance value (Rs).
3.5, Rs = 2.2 × 10 ⁶ Ω / □, p after 2 months
H = 3.2, Rs = 2.5 × 10 ⁷ Ω / □, pH = 3.1 after 3 months, Rs = 4.2 × 10 ⁷ Ω / □.

Example 7 R ¹ in the general formula (1),
R ² , R ³ , R ⁴ , R ⁵ and M ¹ are each H, X =
A method for producing an antistatic treatment agent comprising NCH ₃ , a self-doping conductive polymer compound having a chemical structure of a repeating structural unit represented by L = 0, wherein the weak acid is acetic acid and the base is ammonia. Poly (N-methyl-5-sulfoisoindole-1,3-diyl) was selected as the polymer having the title chemical structure, and was synthesized with reference to the method described in JP-A-6-49183 to obtain 0.6 ( A w / w)% aqueous solution was prepared. This embodiment is the same as the embodiment 1 except that the poly (5-sulfoisothianaphthene-1,3-diyl) acid type polymer described in the above embodiment 1 is changed. To obtain the desired antistatic treatment agent. Then, the following characteristics were confirmed. The hydrogen ion concentration (pH value) immediately after the preparation of the present antistatic treatment agent was 3.6, and the surface resistance of the thin film formed on the glass surface was 7.2 × 10 ⁵ Ω / □.
Met. As in Example 1, the antistatic treatment agent was allowed to stand at room temperature and sampled over time to examine its pH value and surface resistance value (Rs).
H = 3.5, Rs = 4.0 × 10 ⁶ Ω / □, pH = 3.2 after 2 months, Rs = 1.8 × 10 ⁷ Ω / □, pH = 3.1 after 3 months, Rs = 2.8 × 10 ⁷ Ω / □.

(Embodiment 8) In the general formula (1), R ¹ =
C ₁₀ O—, R ² , R ³ and M ¹ are each H, X =
A method for producing an antistatic treatment agent which is a self-doping conductive polymer compound containing a chemical structure of a repeating structural unit represented by S and L = 0, wherein acetic acid is a weak acid and ammonia is a base. Poly (5-decyloxy-6-sulfoisothianaphthene-1,3-diyl) as a polymer having the title chemical structure
Was synthesized with reference to the method described in JP-A-8-259873 to prepare a 0.6 (w / w)% aqueous solution.
This embodiment is the same as the embodiment 1 except that the poly (5-sulfoisothianaphthene-1,3-diyl) acid type polymer described in the above embodiment 1 is changed. To obtain the desired antistatic treatment agent. Then, the following characteristics were confirmed. The hydrogen ion concentration (pH value) immediately after the preparation of this antistatic treatment agent was 3.6, and the surface resistance of the thin film formed on the glass surface was 2.3 × 10 3
It was ⁶ Ω / □. As in Example 1, the antistatic treatment agent was allowed to stand at room temperature and sampled over time to examine its pH value and surface resistance value (Rs). Rs = 4.6 × 10 ⁶ Ω / □, 2
After months, pH = 3.2, Rs = 1.6 × 10 ⁷ Ω /
□ After 3 months, pH = 3.1, Rs = 4.3 × 10 ⁷
Ω / □.

(Example 9) The self-doping conductivity including the chemical structure of a repeating structural unit in which R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and M ² in the general formula (2) are each represented by H. A method for producing an antistatic treatment agent comprising a polymer compound, acetic acid as a weak acid and ammonia as a base. Macromolecu
Les Magazine, Vol. 29, pp. 3950-3955 (1996)
Year)), an acid-type polymer of poly (2-sulfo-1,4-iminophenylene-co-1,4-iminophenylene) (50 mol%: 50 mol%) synthesized by referring to the method described in 3.0). Acetic acid 6.8 in 100 ml of (w / w)% aqueous solution
The desired antistatic treatment agent was obtained by adding 18 ml of 1N aqueous ammonia containing water and stirring and mixing. The hydrogen ion concentration (pH value) immediately after the preparation of this charging agent is
3.7. Further, 3 ml of the above antistatic treatment agent was spin-coated on a glass substrate and dried to form a thin film of the antistatic treatment agent on the glass surface, and the surface resistance was measured. As a result, 2.1 × 10 ⁶ Ω / It was □. The antistatic treatment agent was allowed to stand at room temperature, and its pH value was sampled over time, and a glass coating film was prepared in the same manner as above to examine the surface resistance value.
H = 3.6, Rs = 8.9 × 10 ⁶ Ω / □, pH = 3.5 after 2 months, Rs = 2.1 × 10 ⁷ Ω / □, pH = 3.4 after 3 months, Rs = 4.3 × 10 ⁷ Ω / □.

Example 10 3 ml of the antistatic treatment agent prepared in Example 2 was applied onto a positive electron beam resist coating film composed of novolak and diazonaphthoquinone at 1500 rpm.
To form an antistatic coating having a thickness of 0.02 μm. Journal of VacuumScien
According to the method described in ce Technology magazine, volume B7, p. 1519 (1989), electron beam irradiation was performed, and the displacement after development was measured. The displacement was 0.05 μm.
m or less, and no effect due to charging was observed. When no conductive film was used, the displacement due to charging was 2 μm or more. The antistatic film could be peeled and removed at the same time as the development.

Example 11 A negative-type chemically amplified electron beam resist composed of a novolak type resist, a photosensitizer and an acid generator having a bromomethyl group as a resist using 3 ml of the antistatic treatment agent produced in Example 3 as a resist (Shipley Co., Ltd.) Except for using SAL601) (product name), the resist was spin-coated on the resist in exactly the same manner as in Example 10 to measure the displacement. The amount of displacement was 0.05 μm or less, and the antistatic effect was the same as in Example 10. The bake treatment after irradiating the resist on which the antistatic film is formed with an electron beam is performed before the antistatic film is peeled and removed, and the antistatic film can be completely removed by washing with water or developed during development. It was possible to remove and remove with a liquid.

(Example 12) One bencot (a gauze made by Asahi Kasei, size 150 mm x 150 mm) was immersed in 0.5 ml of the antistatic treatment agent produced in the same manner as in Example 3 for 1 minute, washed with water and dried. An antistatic treatment material was obtained in which an antistatic treatment agent was carried on the surface of the blue fiber to obtain a material. The surface resistance of this material was 8.4 × 10 ⁷ Ω / □.

Example 13 8 ml of an antistatic treatment agent produced in the same manner as in Example 3 was spray-coated on the surface of a commercially available paper cardboard box (size 60 cm × 40 cm × 40 cm) and dried. The surface resistance of the material whose charge was prevented was 2.4 × 10 ⁷ Ω / □.

Example 14 1 ml of an antistatic treatment agent produced in the same manner as in Example 2 was applied to a polyethylene terephthalate film (size: 10
(cm × 10 cm × 100 μm) with a bar coater No.8. The surface resistance of the dried antistatic material was 1.5 × 10 ⁵ Ω / □.

(Example 15) 1 ml of an antistatic treatment agent produced in the same manner as in Example 2 was applied to a polyvinyl chloride film (size: 10 cm × 10 c
m × 100 μm) using a bar coater No. 8 to apply a bar coat. The surface resistance of the dried antistatic material was 1.6 × 10 ⁵ Ω / □.

Example 16 1 ml of an antistatic treatment prepared in the same manner as in Example 2 was applied to a polyacrylate plate (size: 10 cm × 10 cm ×
5 mm) using a bar coater No. 8. The surface resistance of the dried antistatic material was 1.4 × 10 ⁵ Ω / □.

Comparative Example A comparative example using no pH buffer is shown below. Poly (5) synthesized in the same manner as in Example 1
-Sulfoisothianaphthene-1,3-diyl) acid solution, a 0.6% (w / w)% aqueous solution, was adjusted to pH 5.0 by adding 3.2 ml of 1N aqueous ammonia. The antistatic treatment agent was left at room temperature, sampled with time, and a pH value and a glass coating film were prepared in the same manner as in Example 1, and the surface resistance value was examined.
5 × 10 ⁵ Ω / □, pH = 4.2 after one month, Rs =
4.7 × 10 ⁷ Ω / □, pH = 3.8 after 3 months, R
s = 5.0 × 10 ⁸ Ω / □. When the aqueous solution obtained here was allowed to stand in an aqueous solution state at normal temperature, the pH was greatly reduced and the surface resistance of the glass coating film was increased. According to Electronic Materials Magazine (1990, December, pp. 48-54), in order to prevent the charging phenomenon in the step of irradiating the charged particle beam, the surface resistance of the coating film is 5 × 10 ⁷ Ω / □. Since the following is required, it can be seen that the effect of the aqueous solution having a pH of 5.0 is not sufficient after one month at room temperature.

[0047]

According to the present invention, a compound having a pH buffering action (for example, a mixture containing a weak acid and a base) is contained in an aqueous solution of a self-doping conductive high molecular compound having an aromatic sulfonic acid group in a molecule, whereby the air It has been found for the first time that the pH of the aqueous solution can be prevented from lowering even at room temperature, and as a result, the increase in the surface resistance of the coating film can be extremely suppressed. ADVANTAGE OF THE INVENTION The antistatic treatment agent excellent in stability of this invention can provide the excellent antistatic effect and the method for various uses which need industrial antistatic by a simple method, such as a coating method. Also,
The antistatic treatment agent of the present invention can provide not only a coated article requiring antistatic in a semiconductor manufacturing process, but also an electrode which is required to be workable as a conductive material, a humidity sensor,
It can be widely used for an electrode active material used for a biosensor, an electronic display element such as an ECD, and an optical material such as a nonlinear optical element material.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI G01T 1/28 G01T 1/28 H01L 21/027 H01L 21/30 528 (72) Inventor Yoshio Kinoshita Daito Higashi Nagahara, Kawato-cho, Kawanuma-gun, Fukushima Prefecture Haseji 111 Showa Denko Co., Ltd.

Claims (14)

[Claims] 1. An antistatic treatment agent comprising at least a mixture having a self-doping type conductive polymer having an aromatic sulfonic acid group in a molecule and a pH buffering action. 2. The antistatic treatment agent according to claim 1, wherein the mixture having a pH buffering action comprises a weak acid and a base. 3. An antistatic treatment agent, wherein the mixture comprising a weak acid and a base according to claim 2 contains at least a carboxylic acid derivative and an amine derivative. 4. The antistatic treatment agent according to claim 2, wherein the base or the amine derivative is ammonia. 5. A self-doping type conductive polymer having an aromatic sulfonic acid group in a molecule is represented by the following general formula (1). (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently H, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms; 1 or 2
0 linear or branched saturated or unsaturated alkoxy, hydroxyl, halogen, nitro, cyano,
Trihalomethyl groups such as chloromethyl, phenyl group and substituted phenyl group or a SO ₃ ^- represents a monovalent group such as M ¹ group, M
¹ is H ⁺ , an alkali metal ion, or N (R ⁷ )
(R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ (quaternary ammonium ion), P (R ⁷ ) (R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ , As
^{(R 7) (R 8)} (R 9) (R 10) + in represented by Vb
Represents a quaternary cation of a group III element. R ⁷ , R ⁸ , R ⁹ , R
¹⁰ independently represents H, a linear or branched substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group, and is an alkoxy group, a hydroxyl group, an oxyalkylene group, It may be an alkyl group or an aryl group including a group containing an element other than carbon and hydrogen such as an alkylene group, an azo group, an azobenzene group, and a p-diphenyleneoxy group. R ¹ , R
^When the substituents adjacent to each other among the substituents of ² , R ³ , R ⁴ and R ⁵ are hydrocarbon groups, the hydrocarbon chains are bonded to each other at any position and are substituted by such groups. With at least one carbon atom, at least one or more divalent chains forming at least one or more saturated or unsaturated 3- to 7-membered cyclic structure may be formed. L represents the number of a fused 6-membered ring sandwiched between a fused 5-membered ring having X as a member and a fused 6-membered ring separated from the 5-membered ring, and is an integer of 0 to 3. X represents a heteroatom; S, O, Se, Te or N
R ⁶ . R ⁶ represents H, a linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms. R above
^In the chain of the alkyl group, alkoxy group or alkyl ester group of ¹ , R ² , R ³ , R ⁴ and R ⁵ , a carbonyl bond, an ether bond, an ester bond, a sulfonic ester bond, an amide bond, a sulfonamide bond, It may optionally contain a sulfide bond, a sulfinyl bond, a sulfonyl bond, an imino bond, and a thioether bond. ) Or the general formula (2) (In the formula, R ¹¹ , R ¹² and R ¹³ are each independently H, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear chain having 1 to 20 carbon atoms. Jo or branched, saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group such as chloromethyl, phenyl group and substituted phenyl group or a SO ₃ ^- monovalent radical such as M ² group And R ¹⁴ independently represents H or a monovalent group of a group consisting of a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group. .M ² is,
H ⁺ , alkali metal ion, or N (R ⁷ ) (R ⁸ )
(R ⁹ ) (R ¹⁰ ) ⁺ (quaternary ammonium ion), P
^{(R 7) (R 8)} (R 9) (R 10) +, As (R 7)
A quaternary cation of a group Vb element represented by (R ⁸ ) (R ⁹ ) (R ¹⁰ ) ⁺ . R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent H, a linear or branched, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group; Group, hydroxyl group, oxyalkylene group, thioalkylene group,
It may be an alkyl group or an aryl group including a group containing an element other than carbon and hydrogen such as an azo group, an azobenzene group, and a p-diphenyleneoxy group. In addition, R ¹¹ ,
A carbonyl bond, an ether bond, an ester bond, a sulfonic acid ester bond, an amide bond, a sulfonamide bond, a sulfide bond, a sulfinyl bond are present in the chain of the alkyl group, alkoxy group or alkyl ester group of R ¹² , R ¹³ and R ^14. , A sulfonyl bond, an imino bond, and a thioether bond. The antistatic treatment agent according to any one of claims 1 to 4, further comprising: 6. The antistatic treatment agent according to claim 1, further comprising a surfactant as a third component in addition to the antistatic treatment agent component according to claim 1. 7. The antistatic treatment agent according to claim 1, wherein the antistatic treatment agent according to claim 1 is an aqueous solution. 8. An article coated with a conductive polymer, wherein the antistatic treatment agent according to claim 1 is formed on a substrate. 9. A conductive polymer-coated article, wherein the substrate according to claim 8 is a polymer substrate. 10. A conductive polymer-coated article, wherein the substrate according to claim 8 is a phase shift mask on which a phase shifter pattern is formed by irradiation with a charged particle beam. 11. A conductive polymer-coated article, wherein the substrate according to claim 8 is a phase shift reticle on which a phase shifter pattern is formed by irradiation with a charged particle beam. 12. A conductive polymer-coated article, wherein the substrate according to claim 8 contains a resist material which is sensitive to charged particle beam irradiation. 13. A method for irradiating a charged particle beam, comprising a step of forming the antistatic treatment agent according to claim 1 on a substrate and a step of irradiating the substrate with a charged particle beam. 14. The substrate according to claim 13, wherein the substrate is a sample to be observed or measured, and further comprising a step of detecting backscattered electrons due to the irradiation of the charged particle beam or radiation emitted from the sample to be observed or measured. A detection method characterized by using a charged particle beam irradiation method.