WO2005056686A1 - Radiation curing conductive composition - Google Patents

Abstract

Disclosed is a radiation curing conductive composition which contains an organic conductive polymer such as a polythiophene, a polyaniline or a derivative of those; a water-soluble or aqueous emulsion-forming compound; a water-soluble or aqueous emulsion-forming epoxy or oxethane compound; a cationic photopolymerization photosensitizer and/or a radical polymerization photosensitizer; and if necessary a water-soluble or water-dispersible resin water, water or a water-soluble organic solvent.

Description

 Radiation curable conductive composition

 Technical field

 The present invention is excellent in adhesion to plastics, glass surfaces, etc., film formation, and transparency

The present invention relates to a radiation-curable conductive composition containing an organic conductive polymer, which can form a heat-resistant, abrasion-resistant, scratch-resistant conductive film.

 Background art

Conventionally, since synthetic resins are generally hydrophobic, static electricity is generated on the surface of the structure-forming body made of synthetic resins, and dust etc. easily adheres to the surface, causing various problems. I'm waking up. For example, when a polyester film is used to obtain a magnetic tape, static electricity is generated on the magnetic tape, the tape clings up and works poorly, or the magnetic tape becomes dusty and prone to contamination, and the signal dropout is accompanied accordingly. Problems such as increase will occur. Also, when handling semiconductor elements, etc., if the packaging material etc. is not provided with an antistatic function, the semiconductor may be destroyed by static electricity. As a countermeasure, an antistatic agent is added or applied to the packaging material of the magnetic tape and the semiconductor element. As the method, there are a method of kneading a conductive substance such as a surfactant, a carbon powder, a metal powder and the like into an insulating base material such as a polyester film, a method of blending the above-mentioned conductive substance into an adhesive; It is common practice to coat the back of the tape with a surfactant or other antistatic agent, or to apply an antistatic layer consisting of an ion conductive polymer between the substrate and the adhesive layer. ing. However, if it is attempted to impart sufficient antistatic properties by kneading the conductive material such as carbon powder or metal powder into the substrate, or by blending them, the transparency of the substrate is impaired. There is a drawback. For this reason, a surfactant is generally used as an antistatic agent for films, packaging materials, etc. However, the surfactant has a surface resistance (10 ^Ω Ω) that is sufficient to suppress adhesion of dust and dirt. Not only is it possible to obtain the following, but also the antistatic ability is susceptible to change due to the influence of ambient moisture and moisture. In particular, there is a disadvantage that the surface resistance of the film lowered by the surfactant, and the increase in the low humidity, the desired antistatic ability can not be obtained. As a result, film, packaging material surface The adhesion of dust on the skin causes various problems. Nowadays more advanced technology, films without electrostatic interference under low humidity environment are being sought, and for that purpose, the emergence of antistatic agents that give surface resistance values of 10 ^Ω Ω or less under low humidity is desired. .

[0003] Various materials have been proposed as materials for providing such low surface resistance, and one of them is an organic conductive polymer. As these organic conductive polymers, polyaline or polyaline derivatives, polythiophene, polythiophen derivatives, polypyrrole, polyacetylene, polyparaphenylene, polyphenylene bilene, etc. are known (for example, JP-A No. 6-73270). Publication No. 2001-81413). However, since these organic conductive polymers are generally brittle and infusible and insoluble in aqueous solvents and organic solvents, they have a problem of inferior moldability. On the other hand, the solubility in such an aqueous solvent is improved by using a poly- or poly- or poly-phosphor derivative and a dopant, and further, if necessary, a water-soluble resin or polymer emulsion, to form a conductive film. Methods have been proposed (see, for example, JP-A-7-330901, JP-A-8-41321, JP-A-8-100060 and JP-A-2000-256617).

[0004] Further, in the case of poly-arrin, a method has been proposed in which a conductive film is formed by bonding a sulfonic acid group to an aromatic ring and mixing a water-soluble or water-dispersible resin. For example, refer to JP-A-8-325432 and JP-A-9-279025). However, there is a problem that the membrane surface becomes clouded if a mixture of sulfone polyarrin and incompatible resin is used, and on the other hand, good compatibility, resin is used, and in the case of using resin, the predetermined surface resistance value is obtained. The problem arises that Also, although a surfactant is conventionally added to improve the wettability, there has been a problem such as the secondary processing property being bad. Furthermore, when a water-soluble resin is used, the mechanical properties are also inferior, so that the antistatic film formed of these conductive polymers has problems such as scratches and abrasion on the surface. On the other hand, when the conductive polymer is a polythiophen or a polythiophen derivative, it mixes well with a water-soluble polymer which is particularly compatible with the water-soluble polymer, but generally the water-soluble polymer is inferior in abrasion resistance 'hardness etc. It was difficult to obtain good mechanical properties and antistatic films.

[0005] On the other hand, electrical conductivity with improved resistance to pulling by combining a polythiophen preparation with a composition that cures with ion irradiation (eg UV light or electron beam) (See, for example, JP-A-9-12968), there is also a tendency that white turbidity of the formed film tends to occur when this composition is used. It is required to obtain a conductive film using an organic conductive material which is excellent in transparency, resistance to abrasion and scratch resistance as well as in heat resistance and abrasion resistance.

An object of the present invention is to provide a conductive composition using a base organic conductive polymer which does not have the above problems, and more specifically, a water-soluble or water-soluble organic solvent Using an aqueous solution of an aqueous soluble polymer material or an aqueous emulsion and an organic conductive polymer, the composition does not separate so the formed film is transparent, and the heat resistance 'abrasion resistance' It is an object of the present invention to provide a radiation curable conductive composition capable of forming a conductive film which is hard to stick.

 Disclosure of the invention

 Means to solve the problem

The present invention relates to the following radiation-curable conductive compositions, and the above-mentioned object can be achieved by the compositions of the present invention.

(1) Organic conductive polymer, water-soluble or aqueous emulsion-forming compound, water-soluble or aqueous emulsion-forming epoxy or oxetane compound, photosensitizer, and water and Z or water-soluble organic solvent A radiation curable conductive composition comprising:

 (2) The radiation-curable conductive material according to the above (1), characterized in that the water-soluble, water-based emulsion-forming compound is a urethane atalylate-ion compound. Sex composition

(3) The radiation curing as described in (2) above, characterized in that the above-mentioned urethane atalylate copolymer is a water-soluble or water-soluble emulsion-forming multifunctional acrylic copolymer having an acrylic group. Type conductive composition.

(4) The force of the above urethane atalylate complex compound (A) hydroxyl group-containing acrylic ester, (B) organic polyisocyanates, (C) polyethylene having at least one hydroxyl group in the molecule (E) Polyamide which is a neutralized salt of the reaction product obtained by neutralizing the reaction product consisting of glycols and (D) fatty acid containing at least one hydroxyl group in the molecule with (E) tertiary amine The radiation-curable conductive composition as described in (2) above, which is a retaatarilate.

 (5) The radiation-curable conductive composition as described in (1) above, wherein the water-soluble, water-based emulsion-forming compound is an epoxy atalylate-ion compound.

 (6) The above epoxyallylaryate compound compound general formula (I):

[Chem. 5]

 — (I)

(Wherein, R represents a hydrogen atom or a methyl group, X represents CH 2 CH 2 O—, — [CH 2 CH 2 (CH 2) 2]

 2 2 2 3

0 CH CH (OH) CH O

 k 2 2 m

または [Chemical 6]

Or

 [Chem. 7]

を表し、 kおよび mは 1一 4の整数を表す。）

And k and m represent integers of 1 to 4. )

 A radiation curable conductive composition according to the above (5), which is a compound represented by

 (7) The epoxy atallylate i compound represented by the above general formula (I) has the general formula (Π):

[Formula 8] CH ₂ = CH-C-0-CH ₂ -CH-CH ₂ -0-CH ₂ -CH ₂ -CH ₂ -0-CH ₂ -CH-CH ₂ -0-C-CH = CH ₂

 O OH OH OH O

 -A radiation curable conductive composition as described in the above (6), which is a compound represented by-()).

 (8) The radiation-curable conductive composition according to the above (1), wherein the water-soluble, water-based emulsion-forming compound is a vinyl ether group-containing acrylic compound.

 (9) The organic conductive polymer according to any one of (1) to (8) above, which is at least one selected from the group consisting of polyaniline, polyaniline derivatives, polythiophen and polithiophen derivatives. The radiation-curable conductive composition as described in any one of the above.

 (10) The radiation curable conductive composition according to any one of the above (1) to (8), characterized in that the organic conductive polymer, the polythiophen or the polythiophen derivative, and the polystyrene sulfonic acid are used. object.

 (11) Water-soluble or polythiolin or sulfonated polyarrin by a polyester resin in which a sulfonic acid group and Z or its alkali metal base are bound, or polythiophen or polythiophen derivative in the presence of polyanion The radiation curable conductive composition according to any one of the above (1) to (8), which is an organic conductive polymer dispersed in water or water.

 (12) The photosensitizer described above is a radical polymerization photosensitizer and Z or a photopower thione polymerization photosensitizer. Radiation curable conductive composition according to any one of the claims

(13) The radiation-curable conductive composition according to any one of (1) to (12) above, wherein the water-soluble or aqueous dispersion-forming epoxy compound contains a polyfunctional glycidyl compound. .

The radiation-curable conductive composition of the present invention is produced, for example, as follows. That is, for example, for polyarylated polymers such as polyarylin and Z or sulfonic acid polyarylin, a polyester resin bonded with a sulfonic acid group and Z or its alkali metal base, or polythiophen. Against an aqueous solution or aqueous emulsion of an organic conductive polymer, which is made water soluble or dispersible in a poly anion, water soluble or water soluble It is mixed with a water-soluble or aqueous emulsion-forming compound dissolved or dispersed in an organic solvent to form a solution. The water-soluble or aqueous dispersion-forming compound may be a radiation-curable monomer, oligomer or polymer compound, or may be a polymer compound which is not cured by radiation. Hereinafter, these radiation-curable monomers, oligomer and polymer compounds, and polymer compounds which are not cured by radiation, may be referred to as “base resins”. In order to improve the adhesion of this solution to the substrate, and the abrasion resistance and scratch resistance of the formed film, an aqueous solution of a water-soluble or aqueous emulsion-forming epoxy or oxetane composite is further added. Or add an aqueous emulsion. At this time, by using a base resin, an epoxy or an oxetane compound in the form of an aqueous emulsion, a radiation-curable conductive composition can be obtained without separation of the emulsion, and the composition is excellent in transparency and heat resistance. It is preferable to use the base resin and the epoxy or epoxy resin compound in the form of an aqueous emulsion, because it is excellent in abrasion resistance, scratch resistance, and can form a conductive film.

 Hereinafter, the present invention will be described in more detail. In the present invention, an organic conductive polymer is used, and as the organic conductive polymer, for example, polyaniline or a polyaniline derivative, a polythiophen or a polythiophen derivative, a polypyrrole conventionally known as an organic conductive polymer. Any of polyacetylene, polyparaphenylene, and polyethylene can be used. Among these organic conductive polymers, preferred are poly- or poly- or poly- or poly- or poly- or poly- thio derivatives, polysulfone sulfide and the like!

 [0023] Examples of polyarrin or a derivative thereof include those obtained by acid polymerization of a phosphorus represented by the following general formula (III) or a derivative thereof.

 [Formula 9]

(Wherein R ¹ may be the same or different, and each may be a hydrogen atom, an alkyl group, an alkoxy group, an alkoxy group, an alkoxy group, an alkylthio group, an aryloxy group, Alkylthio alkyl group, aryl group, alkyl aryl group, aryl alkyl group, alkyl sulfiel group, alkoxy alkyl group, alkyl sulfo group, alkoxy carbonyl group, amino group, alkyl amino group, dialkyl amino group, Represents an arylthio group, an arylsulfyl group, an aryl sulfol group, a carboxyl group, a halogen, a cyano group, a haloalkyl group, a nitroalkyl group or a cyanoalkyl group, and n represents an integer of 0-5. )

In the formula, preferable R ¹ is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group, an aryl group, a cyano group, a halogen, an aryloxy group, etc. Specific examples of the compound include: aniline, o -Toluidine, m-toluidine, o-ethylanilin, m-ethylanilin, o-electron anthoxylin, m-butylanillin, m-hexiranilin, m-ability curtyanilin, 2, 3-dimethylanilin, 2, 5- dimethylanilin, Examples thereof include 2,5-dimethoxyvanyrin, o-cyanoanilin, 2,5-dichloroanilin, 2-bromoanilin, 5-chloro-2-methoxyvanyrin, 3-phenoxyphosphorin and the like. These phosphorus or derivatives thereof may be used alone or in combination of two or more.

 In the oxidative polymerization reaction, for example, a solution of an oxidizing agent is added to a solution or suspension of ananilin and Z or a derivative thereof represented by the above general formula (III) and a protonic acid, It is carried out by stirring at a temperature of 40 ° C. for 30 minutes with force for 48 hours under normal pressure. Examples of the oxidizing agent used in the oxidative polymerization include peroxodisulfate ammonium, hydrogen peroxide, and second base iron salts.

These polyaryls or their derivatives are usually used together with a protic acid dopant and made soluble or dispersible in an aqueous solvent or an organic solvent. As such protonic acid dopants, benzene monosulfonic acids, aromatic acids containing at least one sulfonic acid group and at least one sulfonic acid salt (for example, an alkali metal salt) in the molecule, general formula (IV) : [Chemical Formula 10]

(IV)

(Wherein, R ² , R ³ and R ² may be the same or different and each may be an alkylene group or a phenyl group, and p and r each may be the same or different) 1 to 50 Represents an integer of

 A compound represented by

 General Formula (V):

 [Formula 11]

(Wherein R ⁵ and R ° may be the same or different, and each has 1 to 10, preferably 2 to 8 carbon atoms, alkyl, alkyl, thioalkyl, aryl), A compound represented by alkylaryl group, arylalkyl group or alkoxyalkyl group), sulfonic acid group and alkali metal basic power group thereof water solubility or water dispersibility in which at least one selected group is bonded Copolymerized polyester and the like can be mentioned.

 Also, as polythiophen or polythiophen derivatives, general formula (VI):

[Formula 12]

[Wherein, R ⁷ and R ⁸ independently represent a hydrogen atom or a C 1 C alkyl group, or Taken together optionally substituted C 1 C alkylene groups, preferably optionally alkyl groups

 14

 A methylene group substituted by, optionally c

 1 C substituted with a C alkyl group or a phenyl group 12

 Represents a group forming a thylene 1, 2 group, a propylene 1, 3 group or a cyclohexylene 1, 2 group o)

 What contains the repeating unit shown by these is mentioned.

[0036] In the above formulae, R ⁷ and R ⁸ are methylene, ethylene 1, 2 and propylene 1, 3 groups, formed by joining together the forces R ⁷ and R ^{8 which} are preferably methyl or ethyl groups. And ethylene 1, 2 groups are particularly preferred.

 Examples of the dopants of the above-mentioned polythiophen or polythiophen derivatives include polymeric carboxylic acids such as polyacrylic acid, polymethacrylic acid or polymaleic acid, and polymeric sulfonic acids such as polystyrene sulfonic acid and polyaryl sulfonic acid anions. . When polyanions such as these carboxylic acids or sulfonic acids are present, polythiophen or polythiophen derivatives form a complex with these polycarboxylic acids and polysulfonic acids, and polythiophen, etc. contribute to the stabilization of the conductivity of polythiophen derivatives. Contribute to the improvement of the solubility or dispersibility in an aqueous solvent. These polymeric carboxylic acids and polymeric sulfonic acids may be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as acrylic esters and styrene. The molecular weight Mn of the polyacid supplying the polyan is preferably <1,000 to 2,000,000, particularly preferably 2,000 to 500,000. Positive acids or alkali metal salts thereof, such as polystyrene sulfonic acid and polyacrylic acid, are commercially available or can be prepared by known methods.

In the radiation-curable conductive composition of the present invention, a water-soluble or aqueous dispersion-forming compound is used. The water-soluble or aqueous emulsion-forming compound is used in an amount of 3 to 50% by weight, preferably 5 to 30% by weight, based on the composition. Among the water-soluble or water-based emulsion-forming compounds, compounds having unsaturated bonds such as unsaturated double bonds include, for example, urethane atalylate, epoxy atalylate, lauri atalylate, ethoxydiethylene glycol atalylate, methoxytrile. Ethylene glycol atalylate, vinyl nosylate atalylate, tetrahydrofurfuryl atalylate, iso Monofunctional atalylate compounds such as bornyl atalylate, 2-hydroxyatalylate, 2 -hydroxypropyl atarylate and 2 -hydroxy-3 phenoxia tarylate, neopentyl glycol diatalylate, 1 , 6 Xandiol diatalylate, 1, 6 Xandiol dimetatalylate, trimethylolpropane triarylate, pentaerythritol tritalylate, dipentaerythryl tritalylate, dipentaerythrylate hexatalialate, tripentaerythritol polyatarial Acrylic acid derivatives such as polyvalent acrylate compounds such as borate, tetrapentaerythritol polyarylate and trimethylolpropane acrylic acid benzoate, 2-ethylhexyl methacrylate, n-stearyl Monofunctional metal acrylate compounds such as ruthenium methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxy methacrylate, 2-hydroxybutyl methacrylate, 1, 6 xanthdiol dimetatalylate , Methacrylic acid derivatives such as trimethylolpropane trime methacrylate and polyfunctional methacrylate complex such as glycerin dimetatalylate, glycerin dimetatalylate hexamethylene diisocyanate and pentaerythritol tritalylate hexamethylene diiso Monomers such as urethane atalylate complexes such as cyanate and UV curable compounds such as oligomers and polymers of the above monomers are mentioned, and in the present invention, aqueous dispersions of these monomers and oligomers are particularly useful. It is suitable.

Among the above compounds, urethane atalylate monomers, oligomers of urethane atalylate, polymers and the like are described, for example, in JP-A 2003-40955, JP-A 2000-159847, JP-A 2000-118193, and JP-A 11 209448. No. 11-106468, JP-A-8-109230, JP-A-5-222145 and the like, and epoxyallylarylate monomers, oligomers of epoxyallylallylates, polymers, etc. For example, f rows are disclosed in Japanese Patent Application Laid-Open Nos. 2003-238653, 2003-183350, 2003-12660, 2002- 284842, 2002-128863, and the like. JP 2002-105168, JP 2001-183820, JP 2001-114 850, JP 2000-336144, JP 10-168033, JP 10-101770, JP-A-H10-101770. 9-48838, JP-A-8-677737 JP-A-7-316107, JP-A-7-70281, JP-A-7-48424, JP-A-5-5. No. 194708, and the like, and all of the conventional techniques are widely known. In the present invention, any of these known compounds can be used as a compound having an unsaturated bond.

 As urethane atalylates, (A) hydroxyl group-containing acrylic acid ester, (B) organic polyisocyanate, (C) polyethylene glycols containing at least one hydroxyl group in a molecule, and (D) The polyurethane acrylate which is a neutralized salt of the reaction product formed by neutralizing a reaction product consisting of a fatty acid containing at least one hydroxyl group in the molecule with (E) tertiary amine is particularly preferable It is.

 Examples of the hydroxyl group-containing acrylate ester of the component (A) used to produce the above polyurethane atalylate include, for example, 2-hydroxyl (meth) atalylate, 2-hydroxypropyl (meth) atalylate, 2-Hydroxyalkyl (meth) atalylates such as 4-hydroxybutyl (meth) atalylate, polyethylene glycol mono (meth) atalylate, hydroxy alkylene glycol mono (meth) atarilate such as polypropylene glycol mono (meth) atalylate And pentaerythritol triarylate, rosin epoxyallylate, etc., which may be used alone or in combination.

 Further, as the component (B) which is an organic polyisocyanate, an organic polyisocyanate having three or more reactive isocyanato groups in the molecule is applicable. Further, its molecular weight is preferably about 500-1000. Specific examples of the component (B) include, for example, 1,6-hexanediisosocyanate, isophoronediisosiate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, etc. And trimers obtained from various kinds of diisocyanates, prepolymers obtained by reacting the diisocyanates with polyhydric alcohols such as trimethylolpropane, polymethylenepolypolypolyisocyanate, and the like.

As polyethylene glycols of component (C), various ones having at least one hydroxyl group in the molecule can be used without particular limitation, but those represented by the following general formula (VII) are particularly used. It is suitable. [Formula 13]

H— (OCH ₂ CH ₂ ) _s — OR ⁹ (VI I)

(Wherein, R ⁹ represents an alkyl group having 1 to 14 carbon atoms, and s represents an integer of 7 to 25).

 The amount of the component (C) used is usually 3 to 12% by weight, preferably 5 to 10% by weight, based on the total amount of the polyurethane atalylate. If the content is less than 3% by weight, the water washability is not sufficient. On the other hand, if it exceeds 12% by weight, it is not preferable because the water resistance of the cured coating is insufficient or the cohesion is insufficient.

 The fatty acid of component (D) contains at least one hydroxyl group and one carboxyl group in its molecule. The acid value and the hydroxyl value are not particularly limited, but in general, the range of 150 to 500 is preferable. Specific examples of the component (D) include, for example, castor oil fatty acid, hydrogenated castor oil fatty acid, 6-hydroxycaproic acid and the like. The content of the component (D) in the polyurethane atarylate is such that the acid value of the polyurethane atarylate is 10 to 50 mg KOHZg, preferably 15 to 45 mg KOHZg. If the acid value of the polyurethane atarilate is less than 1 Omg KOHZg, insufficient hydrophilicity and stable emulsion can not be obtained. In addition, when the acid value of polyurethane atalylate exceeds 50 mg KOHZg, the hydrophilicity becomes too strong, and a solution of high viscosity can not be obtained.

 Examples of tertiary organic amine of component (E) include trimethylamine, trytylamine, N-methyldiethanolamine, triethanolamine and the like. Among these, trimethylamine and trytilamine are particularly preferred. The reason is that when the active energy ray-curable water-containing resin composition is applied and dried, trimethylamine and triethylamine relatively easily evaporate and remain in the coating.

Further, as the epoxy atalylate, those represented by the above general formula (I) can be mentioned as preferable compounds, and specifically, for example, the following compounds can be mentioned. [Formula 14]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056] [化 20]

[Formula 20]

[Formula 21]

Among these, epoxy ester (80 MFA manufactured by Kyoeisha Shigaku Co., Ltd.) having triglycerin ditalylate represented by the above-mentioned formula (II) as the main component is particularly preferable.

 In addition, examples of compounds other than the above-mentioned compounds having unsaturated double bonds include the following compounds. That is, methyl (meth) atarylate, ethyl (meth) atarylate, propyol (meth) atarylate, butyl (meth) atarylate, 2-ethylhexyl (meth) atarylate, n-nor (meth) Atalylate, lauryl (meth) atalylate, cyclohexyl (meth) atalylate, cyclohexyl methyl (meth) atalylate, methoxyethyl (meth) atalylate, etoxethyl (meth) atarylate, methoxyethoxyl (meth) Atalylate, Ethoxyethoxethyl (meth) atalylate, Methoxy polyethylene glycol (Meth) atalylate, 2-hydroxyl (meth) atalylate, 4-hydroxybutyl (meth) atalylate, polyethylene glycol (meth) atarylate ( Meta) acrylic acid, N, N-dimethylamino Chill (meth) Atari rate, alpha-hydroxymethyl acrylate methyl, alpha-hydroxymethylacrylic Sane chill, monofunctional (meth) Atari rate such as butyl alpha-hydroxymethyl acrylate;

 [0060] Monofunctional (meth) acrylamides such as Ν, Ν-dimethyl (meth) acrylamide, Ν- methylol (meth) acrylamide;

Methinolevino noreutenore, ecinolevino noreetetenore, propinore vinino ree tenore, butynorebi noenoe tenore, 2-echinore hexinorebi-noree tenore, eta-norebi-noreote nore, lauri nore ide Levinino Ree Tenore, Mocke Etche Renovino Ree Tenore, Ethoxyethyl dibi nore ether, Methoxyte qui ecyl bibi nore ether, Ethoxyeto A simple substance such as xycetyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxy ethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol mononole mono binno lee tenore, polyethylene glycono levinone lee tenole, clonole ethyle vinyl ether, etc. Functional vinyl ethers;

[0061] Monofunctional N-vinyl compounds such as N-bulone pyrrolidone, N-bulyl proratatam, N-bulyl N methylformamide, N-bulyl imidazole, N-bulyl formamide, N-bulasetoamide and the like;

 Monofunctional vinyl compounds such as styrene, α-methylstyrene, toluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate and the like;

Maleic anhydride, maleic acid, dimethyl maleate, jetyl maleate, monomethyl maleate, monoethyl maleate, fumaric acid, dimethyl fumarate, jetyl fumarate, monomethyl fumarate, monoethyl fumarate, itaconic acid anhydride, itaconic acid, Dimethyl itaconate, jetyl itaconate, monomethyl itaconate, monoethyl itaconate, methylene malonic acid, dimethyl methylene malonate, monomethyl methylene malonate, cinnamic acid, methyl cinnamic acid, ethyl cinnamic acid, crotonic acid, methyl crotonate, Monofunctional _α , β-unsaturated compounds such as ketyl crotonate;

 Ethylene glycol di (meth) atalylate, diethylene glycol di (meth) atalylate, polyethylene glycol di (meth) atalylate, propylene glycol di (meth) atalylate, butylene glycol di (meth) atalylate, hexane Diol di (meth) atalylate, Thiex Hexane dimethanol di (meth) atalylate, bisphenol Α alkylene oxide di (meth) atalylate, bis phenol F alkylene oxide di (meth) atalylate, trimethyl

Glycerin tri (meth) atalylate, pentaerythritol tetra (meth) atalylate, dipentaerythritol penta (meth) atalylate, dipentaerythritol hexa (meth) atarylate, ethylene glycol oxide methyl methacrylate propane tri ( Meta) atalylate, ethylene oxide added ditrimethylol propane tetra (meth) atalylate, ethylene oxide added pentaerythritol tetra (meth) atalylate, ethylene oxide added dipentaerythritol tritol oxa (meth) atalylate, etc. Multifunctional (meth) (meth) Atarilates; Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butyl glycol divinyl ether, hexanediol divinyl ether, bis phenol A alkylene oxide di vinyl ether, bisphenol phenol F Alkylene oxide di Vininore e nore, Trimethyl nole propane Tri Vinolee Ene Nore, ditri methylo nore propane tetra vinyl ether, glycerin trivinyl ether, pentaerythritol tetra bibi nore etenore, dipenta Erytri Toeno penta bini Nore etenore, dipenta Erys Lithonol Hexabul ether, ethylene oxide-added trimethylolpropane tri Multifunctional buffal ethers such as buff ether, ethylene oxide-added ditrimethylolpropane tetrabule ether, ethylene oxide-added pentaerythritol tetrabule ether, and ethylene oxide-added dipentaerythritol hexabole ether;

 [0064] Multifunctional vinyl compounds such as divinylbenzene;

 Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, bisphenol A alkylene oxide diglycidyl ether, bisphenol F alkylene Oxide diglycidyl ether, trimethylolpropane triglycidyl ether, ditrimethylolpropane tetraglycidyl ether, glycerin triglycidyl ether, pentaerythritole tetraglycidole ether, dipentaerythritole pentaglycidyl ether, dipentaerythryitol hexaglycidyl Ether, ethylene oxide addition Trimethylolpropane triglycidyl ether, ethylene oxide with Caro ditrimethylolpropane tetra glycidyl ether, mosquitoes with ethylene oxide 卩 Pentae Risuri tall tetraglycidyl ether, polyfunctional epoxy compounds such as hexa glycidyl ether to ethylene oxide adduct of dipentaerythritol;

Di [1 methyl (3-oxetal)] methyl ether, di [1 cetyl (3-glycetal)] methyl ether, 1, 4 bis {[(3-methyl- 3-oxeta-l) methoxy] methyl } Benzene, 1,4-bis [[(3-ethyl-3-oxetayl) methoxy] methyl} benzene, bis {4-([3-methyl-3-oxeta-l) methoxy] methyl} benzyl ether, Bis {4 1 [(3-Echi (3) R.sup.3 -C.sub.4 -C.sub.4) Methcyl) Methoxy] Methyl} Multifunctional alicyclic ether compounds such as benzyl ether and oligomers of these.

Among these, methyl (meth) atalylate, butyl (meth) atalylate, 2-ethylhexyl (meth) atalylate, methoxypolyethylene glycol (meth) atalylate, (meth) atalic acid, butylbi -Ruethers, cyclohexyl vinyl ethers, maleic anhydride, maleic acid, dimethyl maleate, jetyl maleate and their oligomers and the like are preferable.

 In addition, vinyl ether group-containing acrylic compounds are also preferable compounds. Examples of the butyl ether group-containing acrylic compound include bule ether group-containing (meth) acrylic acid esters. The following compounds are preferable as the vinyl ether group-containing (meth) acrylic acid ester.

[0067] (Meth) acrylic acid 2-bi-loxycetyl, (meth) acrylic acid 3-bi-loxypropyl, (meth) acrylic acid 1-methyl- 2-bi-loxycetyl, (meth) acrylic acid 2-bi-loxypropyl (Meth) acrylic acid 4-bi-port xylbutyl, (meth) acrylic acid 1-methyl-3-bi-hydroxypropyl, (meth) acrylic acid 1-bi-hydroxymethylpropyl, (meth) acrylic acid 2-methyl-3- Bi-hydroxypropyl, (meth) acrylic acid 3-methyl-3-bi-hydroxypropyl, (meth) atalic acid 1, 1 dimethyl-2 bi-mouth xycethyl, (meth) acrylic acid 3-bi-mouth x-butyl ( (Meta) acrylic acid 1-methyl-2-bi-hydroxypropyl, (meth) acrylic acid 2-bi-hydroxybutyl, (meth) acrylic acid 4 bi-hydroxycyclohexyl, (meth) acrylic acid 5-bi-loxy Penthyl, (meth) acrylic acid 6-bi-hydroxyhexyl, (meth) acrylic acid 4-bi-oxymethylcyclohexylmethyl, (meth) acrylic acid 3-bi-hydroxymethylcyclohexylmethyl, (meth) acrylic acid 2-Bi-hydroxymethylcyclohexyl, p-hydroxymethylphenyl (meth) acrylate, (meth) acrylic acid m-bi-hydroxymethylphenyl methyl, (meth) acrylic acid o-bioxymethylmethyl Phenylmethyl, (meth) acrylic acid 2- (bi-loxyethoxy) ethyl, (meth) acrylic acid 2- (bi-oxyisopropoxy) ethyl, (meth) acrylic acid 2- (bi-loxyethoxy) propyl, (Meth) acrylic acid 2- (bi-loxyethoxy) isopropyl ether, (meth) acrylic acid 2- (bi-loxyisopropoxy) propyl, (meth) acrylic acid 2- (bi-oxyisopropoxy) isopropyl, (meth) acrylic acid 2- (bi-oxyethoxy etho) Xyl) ethyl, (meth) acrylic acid 2- (bi-loxyethoxyisopropoxy) ethyl, (meth) acrylic acid 2-(bi-oxyisopropoxyethoxy) ethyl, (meth) acrylic acid 2-(bi-hydroxy) Isopropoxy isopropoxy) ethyl, (meth) acrylic acid 2- (bi-oxyethoxyethoxy) propyl, (meth) acrylic acid 2- (bi-oxyethoxyisopropoxy) propyl, (meth) acrylic acid 2- (bi) -Hydroxy isopropoxy ethoxy) propyl, (meth) acrylic acid 2-(bi-oxy isopropoxy isopropoxy) propyl, (meth) acrylic acid 2-(bi-ported xylethoxy) isopropyl, (meth) acrylic acid 2- (Bi-oxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (bi-oxyisopropoxyethoxy) isop ROPHIL, (Meth) acrylic acid 2- (bi-oxyisopropoxy isopropoxy) isopropyl, (meth) acrylic acid 2- (bi-oxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (bi-loxy Siethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (bi-hydroxyisopropoxyethoxy) ethyl, (meth) acrylic acid 2- (bi-oxyisopropoxyethoxy-ethoxy) ethyl, (meth) acrylic acid 2- (Bi-oxyisopropoxyethoxyethoxyethoxy) hydroxyethyl, (meth) acrylic acid 2- (bi-oxyisopropoxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid polyethylene glycol monobutyl ether, (meth) acrylic acid Polypropylene glycol monobule ether.

 [0068] These compounds may be oligomers. Among these, 2-methacrylic acid (2-meth) acrylic acid, 2-methacrylic acid (3-meth-acrylic acid), 1-methyl-2-methacrylic acid (2-methacrylic acid), 2-methacrylic acid (2-methacrylic acid) Roxypropyl, (meth) acrylic acid 4-bi-biphenyl x-butyl, (meth) acrylic acid 4-bi-port xycyclohexyl, (meth) acrylic acid 5-bi-oxypentyl, (meth) acrylic acid 6-bi- Roxyhexyl, 4-bi-hydroxymethylcyclohexyl (meth) acrylate, p-bi-hydroxymethylphenyl (meth) acrylate, 2-methacrylic acid 2- (bi-ethoxyethoxy) ethyl, (Meth) acrylic acid 2- (bi- oxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (bi-oxyethoxyethoxyethoxy) hydroxyethyl and their oligomers are preferred .

On the other hand, examples of the compound which is water-soluble or aqueous dispersion-forming and has no unsaturated bond include, for example, a vinyl acetate polymer, an ethylene / bule ester polymer, an acrylic polymer, and a vinyl chloride polymer. , Vinylidene chloride polymers, styrene polymers, Resin, polyester, epoxy resin, silicone resin, polybutene, polybutadiene, butadiene copolymer, polyisoprene, polychloroprene, polysulfide rubber, etc. may be mentioned.

. These may be used alone or in combination of two or more. Among these, polyurethane, ethylene ′ ′ boule ester copolymer, and acrylic polymer are preferable among them. These water-soluble or aqueous emulsion-forming resins may have a structure containing a radiation-polymerizable unsaturated double bond.

 In addition, as the water-soluble or aqueous dispersion-forming resin, other than the above-mentioned resins such as polyacrylamide and polyvinyl pyrrolidone, a water-soluble or water-dispersible copolymer polyester containing a hydroxyl group or a carboxylic acid group, Acrylic acid resin such as polyacrylic acid and polymethacrylic acid, acrylic acid ester resin such as polyacrylic acid ester and polymethacrylic acid ester resin, ester resin such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, poly α -Styrene-based resins such as methylstyrene, polychloromethylstyrene, polystyrene sulfone acid and polyphenylphenol, polybutyl ether, polybutyl ether, polybutyl alcohol, polyvinyl alcohol, polyvinyl formal, poly Poly Bulle alcohols such as butyral, a novolak, also like phenol 榭脂 such as Les Orres is used! /,.

In addition, the radiation-curable conductive composition of the present invention! In this regard, water-soluble or aqueous emulsion-type (forming) epoxy or oxetane blends are used. As such an epoxy or oxetane compound, for example, methyl dalysidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl dalysidyl ether, 2-ethyl hexyl glycidyl ether, _η- noyl glycidyl ether, lauryl glycidyl Monofunctional epoxy such as ether, cyclohexyl glycidyl ether, methoxy ethyl dalysyl ether, ethoxy ethyl dalysyl ether, methoxy ethoxy ethyl dalysidyl ether, ethoxy ethoxy ethyl dalysidyl ether, methoxy polyethylene glycol glycidyl ether Compounds; 3-Methyl-3-hydroxymethyloxetane, 3-Ethyl-3-hydroxymethyloxetane, 3-Methyl-3-phenoxymethyloxetane, 3-Ethyl 3 Phenyloxymethyloxetane, 3-methyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl 3- (2-acetylhexyloxymethyl) oxetane, etc. Monofunctional alicyclic ether compounds are mentioned. Epoxy or oxacene compounds are

The water-soluble or emulsion-forming compound is used in an amount of 5 to 80% by weight, preferably 10 to 50% by weight.

 Furthermore, in the present invention, as the water-soluble or aqueous emulsion type epoxy group-containing compound, a polyfunctional epoxy compound, bisphenol A type water-soluble epoxy compound, novolac type water-soluble compound. Epoxy compound may be used. Examples of multifunctional epoxy compounds include diglycerin polyglycidyl ether and the like. These are contained in an amount of 5 to 50% by weight, preferably 10 to 30% by weight, based on the water-soluble or emulsion-forming compound.

 A cationic photopolymerization initiator is used together with a radiation-curable cationic polymerization type monomer, oligomer or polymer compound, and as this cationic photopolymerization initiator, light in which an acid is generated upon irradiation with radiation is used. An acid generator is mentioned as a preferable thing. Photoacid generators that can be used as a cationic photopolymerization initiator can be roughly classified into ionic compounds and non-ionic compounds. Examples of the ionic compound include aryldiazo-m salt, diaryliodium salt, triarylsulfo-m salt and triarylphospho-m salt, and the like, and the counter ion BF-, PF-, AsF-, SbF-, etc. are used. Like this

4 6 6 6

 A photosensitizer such as anthracene or thioxanthone can be used in combination with the photoacid generator of the um salt type, if necessary. As the non-ionic photoacid generator, those capable of generating carboxylic acid, sulfonic acid, phosphoric acid, halogen hydrogen and the like by light irradiation can be used. Specifically, as the photoacid generator, sulfonic acid Nitrobenzyl ester, iminosulfonate, 1-oxo-2-diazonaphthoquinone 4 sulfonate derivative, N-hydroxyimidosulfonate, tri (methanesulfo-methoxy) benzene derivative, etc. can be used, and carboxylic acid o-tro Benzyl ester, 1-oxo 2-diazonaphthoquinone 5-aryl sulfonate, triaryl phosphate ester derivative and the like can be used. The cationic photoinitiator is used in an amount of 110% by weight, preferably 2-5% by weight, based on the water-soluble or emulsion-forming compound.

In the composition of the present invention, a radical photopolymerization initiator is optionally used to photopolymerize the compound having the unsaturated double bond. With this radical photoinitiator Any of the polymerization initiators conventionally used in photopolymerization of compounds having unsaturated double bonds can be used in the present invention. Specific examples of such radical photopolymerization initiators include benzophenone, acetophenone, benzoin and benzoin methyl, ethyl, isopropyl, butyl or isobutyl ether, α-hydroxy or α-amino aryl ketone and benzyl ketal. It is. The radical photoinitiators are used in amounts of 110% by weight, preferably 2-5% by weight, based on the water-soluble or emulsion-forming compound.

Further, when mixing the above-mentioned compounds, the viscosity can be adjusted by appropriately mixing a water-soluble organic solvent such as isopropyl alcohol (ΙΡΑ) in the case of high viscosity. In addition, when forming an emulsion, a compound insoluble in water can be emeryged with a water-soluble organic solvent using a solvating surfactant. Examples of water-soluble organic solvents include ketone-based water-soluble organic solvents, such as methyl ethyl ketone, methyl isopyl ketone, methyl butyl ketone, ethyl butyl ketone, cyclohexanone, isophorone and the like. Other water-soluble organic solvents include, for example, ethyl acetate, butyl, acetate, isopropyl acetate, isopropyl acetate, secethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, etc. Acetate ester solvents; ethanol, _η -propyl alcohol, isopropyl alcohol, η-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, η-amyl alcohol, isoamyl alcohol, secondary amyl alcohol, tasha Alcohol solvents such as lyamyl alcohol, organic acid hexanol, ethylene glycolonole, propylene glycol, butylene glycolonole; ethylene glycol Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monoethyl phenole ethylene glycol, ethylene glycol mono methyl ethyl alcohol, ethylene glycol mono methyl ethyl alcohol, ethylene glycol mono methyl ethyl ketone, ethylene glycol mono lithium methyl ether, di ethylene glycol mono methyl nore ether, di ethylene glycol mono ethyl ether Solvents: Ether-based solvents such as dioxane and dimethyl dioxane; and the like. In particular, glycol ether solvents have good compatibility with water and other organic solvents, and can dissolve organic solvent-soluble resins or other additives well, making them an optimal solvent. It can be said. In the radiation-curable conductive composition of the present invention, a dispersant S may be used to stabilize the emulsion. Examples of the dispersing agent include surfactants such as NO-ON type surfactants, cationic surfactants, and A-ON type surfactants. Polyallyn and Z or sulfonic or polyallyl ester, sulfonic acid groups and Z Alternatively, NO-ON based surfactant is particularly excellent for an aqueous solution of polythiophen in the presence of polyester resin or polyanion to which an alkali metal base is bound. The dispersant is used in an amount of 0.5-5% by weight, preferably 13% by weight, based on the radiation-curable conductive composition.

 However, since the organic conductive polymer to be used is ionic, if the photosensitizer etc. is ionic, the organic conductive polymer may be coagulated to form a precipitate. As a result of intensive studies, it was found that aggregation was not generated by lowering the mixing ratio of the photosensitizer. The mixing ratio of the ionic cationic photopolymerization initiator is preferably 3% or less with respect to the other solid content.

 The radiation-curable conductive composition of the present invention is of emulsion type and is applied to a substrate. The solid content concentration of the composition at the time of application is not particularly limited, but is 0.5 to 50% by weight, preferably 1 to 30% by weight. The substrate to be coated is not particularly limited, but usually, glass, film, fiber and the like. In particular, a film made of glass, a thermoplastic resin such as polyester, nylon, polypropylene or polyethylene, or a film made of an organic solvent-soluble resin such as aromatic polyamide, polyamideimide or polyimide is preferable.

Examples of the method for applying the conductive composition of the present invention to the surface of the substrate include gravure roll coating, reverse roll coating, knife coater, dip coater, spin coating, etc. It is not particularly limited as long as it is a method of forming a film. The formed coating is heated and dried at an appropriate temperature, and then radiation such as ultraviolet irradiation is performed to cure the coating. Thus, a conductive cured film is formed on the surface of the substrate. The heat drying is usually performed at a temperature of 50 to 200 ° C. for about 10 to 300 seconds. The radiation may be any of ultraviolet rays, far ultraviolet rays, X-rays, electron beams, etc. Usually, ultraviolet rays are preferred as the general point power of the apparatus. The radiation dose is not particularly limited as long as the coating film cures. Use UV as radiation In the case where the composition is used, although the dose varies depending on the composition of the composition to be used, the film thickness, etc., the irradiation dose is usually about 1,000 to 20, OOOmj Zcm ² , preferably about 5,000 to 15, OOOmj Zcm ² .

 Effect of the invention

 The conductive composition of the present invention can form a transparent film having excellent solvent resistance, high surface hardness, and high conductivity even under low humidity, for example, preferred as an antistatic film. Used.

 BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In the following,% indicates% by weight unless otherwise noted. Example 1

As a conductive material, an aqueous dispersion of polyethylene dioxthiophen colloid (polyvinyl-dioxthiophen solid content 2%) containing polystyrene sulfonic acid (solid content 1.2%) as a dopant is used. It was used. Separately from this, polypropylene glycol monomethyl ether was mixed with urethane atalylate aqueous emulsion (EM 90, manufactured by Arakawa Chemical Industries, Ltd., solid content 40%) to prepare a urethane atarylate 10% emulsion solution. To this solution, a 10% polypropylene glycol monomethyl ether emulsion solution of diglycerin polyglycidyl ether which is a multifunctional glycol-based epoxy compound was added and mixed to obtain a base solution having a 10% solid content. Thereafter, 2% of a cationic photopolymerization initiator (Irgacure I 250, manufactured by Ciba-Geigy) and 3% of a radical photopolymerization initiator (Irgacure I 184, manufactured by Ciba-Geigy) are added to the solid content of the base solution and mixed. Further, the above-mentioned polythiophen colloid solution is adjusted so that the solid content concentration of the organic conductive material is 10% of the solid content of the above base solution, and added under stirring of the disper, and further 1.5 h after the addition. Stir at. The emulsion solution was cloudy, and no component separation was observed. This solution is applied on a PET (polyethylene terephthalate) film using an applicator with a clearance of 10 m, dried at 100 ° C., and then irradiated with a UV irradiation device at an irradiation dose of lOO m J Was cured to form a cured coating (no coat). The surface resistance of the obtained cured film is 0.2-0.5 Ω Yes, the cured film was clear. The light transmittance, heat resistance, adhesion, and surface hardness of the obtained film were measured based on the following measurement methods. The results are shown in Table 1.

(Light transmittance)

 The hard coat produced on PET was measured as light transmittance of PET incorporated by Nippon Denshoku COH 300A.

 (Heat test)

 After holding in an oven at 80 ° C. for 1000 hours, the resistance value of the film was measured to examine the change from the resistance value before the heat resistance test.

(Attachment test)

 Using a cutter, scratch the surface of the hard coat at a distance of 1 mm x 1 mm and stick Sellotape (registered trademark; made by Nichiban Co., Ltd.) No. 405 to 100 squares, and remove the tape after 30 seconds. The number of squares peeled off or missing edges was observed. A sample in which 100 squares were left was marked with 〇, a sample in which a part of squares was covered was marked △, and a sample in which squares were peeled off was marked X.

(Surface Hardness)

 The surface hardness was determined by a pencil hardness test (pencil pull test). That is, the surface hardness was determined by using a prepared pencil coated film and a pencil for testing specified by JIS-S-6006, according to the pencil hardness evaluation method specified by JIS-K 5400, with a load of 9. 7N. Is the value of the hardness of the pencil.

 Example 2

Instead of a 10% polypropylene glycol monomethyl ether solution of diglycerin polyglycidyl ether which is a polyfunctional glycol epoxy compound, 10% polypropylene glycol monomethyl ether of a polyfunctional glycol epoxy compound (80 MF manufactured by Kyoeisha Gakugaku Co., Ltd.) A radiation curable conductive composition is prepared in the same manner as in Example 1 except that a monotelluric solution is used, and the radiation curable conductive composition is coated on a PET film in the same manner as in Example 1. The coating was dried at 100 ° C. and then irradiated with an irradiation dose of lOOoiuJ in a UV irradiation apparatus to cure the coating, thereby forming a cured coating. The surface resistance of the obtained film was 0.8-10.3 Ω, and the cured film was transparent. The light of the coating obtained in the same manner as in Example 1 The transmittance, heat resistance, adhesion, and surface hardness were measured. The results are shown in Table 1.

 Example 3

 A radiation-curable conductive composition was produced in the same manner as in Example 1 except that MP-triazine (manufactured by Sanwa Chemical Co., Ltd.) was used in place of IRGACURE-I 250 as a cationic photopolymerization initiator, This radiation-curable conductive composition is applied onto a PET film in the same manner as in Example 1, dried at 100 ° C., and then the coating is cured by irradiation with an irradiation dose of lOOOmJ in an ultraviolet irradiation device. , Hardened film was formed. The surface resistance of the obtained film was 1.0 to 1.5 Ω and the cured film was transparent. The light transmittance, heat resistance, adhesion and surface hardness of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 1.

 Example 4

 [0088] In the same manner as Example 1, except that WP AG-145 (manufactured by Wako Pure Chemical Industries; bis (cyclohexyl sulfol) diazomethane) was used in place of Irgacure I 250 as the cationic photopolymerization initiator, A radiation-curable conductive composition is produced, and the radiation-curable conductive composition is applied onto a PET film in the same manner as in Example 1, dried at 100 ° C., and then irradiated with an ultraviolet radiation device to obtain lOOOmJ The coating film was cured by irradiation with an irradiation dose to form a cured film. The surface resistance of the obtained film was 0.5-0.7Μ Ω, and the cured film was transparent. The light transmittance, heat resistance, adhesion, and surface hardness of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 1.

 Example 5

[0089] In place of a 10% solution of a urethane atarilate produced by mixing a polypropylene glycol monomethyl ether with a urethane atarilate aqueous emulsion (EM 90, manufactured by Arakawa Chemical Industries, solid content 40%), an epoxy ester (Kyoeisha Ltd. Using a 10% solution of epoxy ester prepared by mixing polypropylene glycol monomethyl ether with Gakusan 80 MFA, and replacing it with IRGACURE-I 250 as a cationic photopolymerization initiator, WP AG-170 (Wako Pure Chemical Industries, Ltd.) A radiation curable conductive composition is prepared in the same manner as in Example 1 except that bis (t-butylsulfo) diazomethane) is used, and the radiation curable conductive composition is produced in the same manner as in Example 1. The composition is coated on a PET film, dried at 100 ° C., and then irradiated with an irradiation dose of lOOOmJ in an ultraviolet irradiation device to cure the coating and cure. A film was formed. The surface resistance of the obtained film was 0.3 to 0.8 Ω and the cured film was transparent. The light transmittance, heat resistance, adhesion, and surface hardness of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 1.

 Example 6

 [0090] In place of a 10% solution of a urethane atarilate produced by mixing a polypropylene glycol monomethyl ether with an urethane atarilate aqueous emulsion (EM 90, manufactured by Arakawa Chemical Industries, solid content 40%), an epoxy ester (Kyoeisha Ltd. A radiation curable conductive composition was prepared in the same manner as in Example 1 except that a 10% solution of epoxy ester prepared by mixing polypropylene glycol monomethyl ether with Gakusan 80 MFA was used. This radiation-curable conductive composition is applied onto a PET film in the same manner, dried at 100 ° C., and then irradiated with an irradiation dose of 100OmJ with an ultraviolet irradiation device to cure the coating and cure. A film was formed. The surface resistance of the obtained film was 0.3 to 0.8 Ω and the cured film was transparent. The light transmittance, heat resistance, adhesion, and surface hardness of the resulting film were measured in the same manner as in Example 1. The results are shown in Table 1.

 Example 7

As a conductive material, an aqueous dispersion of polyethylene dioxthiophen colloid (polyvinyl-dioxthiophen solid content 2%) containing polystyrene sulfonic acid (solid content 1.2%) as a dopant is used. It was used. Separately, urethane atalylate aqueous emulsion (EM 90, Arakawa Chemical Industries, EM 90, 40%) was mixed with IPA (isopropyl alcohol) to prepare a urethane atarylate 10% emulsion solution. A 10% IPA (isopropyl alcohol) solution of diglycerin polyglycidyl ether, which is a multifunctional glycol-based epoxy compound, was mixed with this solution to obtain a base solution having a 10% solid content. After that, 2% of photopower thione polymerization agent WPAG-199 (manufactured by Wako Pure Chemical Industries; bis (p-toluenesulfonyl) diazomethane) and radical photopolymerization initiator (IRGACURE I) with respect to the emulsion solid content of this base solution 184, Ciba-Geigy Co., Ltd. 3% are mixed, and the above-mentioned polythiophen colloid solution is adjusted so that the solid content concentration of the organic conductive material is 10% of the solid content of the above base solution, and under agitation of disper. After addition, the mixture was further stirred for 1.5 hours in a desiccant. This emerald solution is cloudy, and no component separation is observed. won. This solution is applied on a PET film using an applicator with a clearance of 10 m, dried at 100 ° C., and then irradiated with an irradiation dose of lOO m J in an ultraviolet irradiation device to cure the coating film, and a cured film is formed. Formed. The surface resistance of the obtained cured film was 0.5-0.7Μ Ω, and the cured film was transparent. The light transmittance, heat resistance, adhesion, and surface hardness of the resulting film were measured in the same manner as in Example 1. The results are shown in Table 1.

 Example 8

 As the conductive material, an aqueous dispersion of polyethylene dioxthiophen colloid (polyvinyl-dioxthiophen solid content 2%) containing polystyrene sulfonic acid (solid content 1.2%) as a dopant is used. It was used. Separately from this, methyl ethyl ketone was mixed with urethane atalylate aqueous emulsion (EM 90, manufactured by Arakawa Chemical Industries, Ltd., 40%) to prepare a 10% emulsion solution of urethane atarylate. To this solution was added a 10% methyl ketone solution of diglycerin polyglycidyl ether, which is a polyfunctional glycol epoxy compound, and mixed to obtain a base solution having a 10% solid content. After that, 2% of photopower thione polymerization agent (WPAG-145, manufactured by Wako Pure Chemical Industries, Ltd.) and 3% of a radical photopolymerization initiator (IRGACURE I-184, manufactured by Ciba-Geigy) are added to the solid content of the base solution, After mixing, the above-mentioned polythiophen colloid solution is adjusted so that the solid content concentration of the organic conductive material is 10% of the solid content of the base solution, and added under stirring of the disperser, and after addition 1. The mixture was further stirred for 5 hours with a disperser. This solution is coated on a PET film using an applicator with a clearance of 10 m, dried at 100 ° C., and then irradiated with an irradiation dose of lOO m J in an ultraviolet irradiation device to cure the coating, A cured film was formed. The surface resistance of the resulting cured film was 0.5-0.7 Ω and the cured film was transparent. The light transmittance, heat resistance, adhesion, and surface hardness of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 1.

[Table 1] table 1

実施例 9

Example 9

 A sulfonic acid group and / or an alkali metal base thereof relative to 100 parts by weight of poly (arene) instead of an aqueous dispersion of polyethylene dihydroxy thiophen colloid containing polystyrene sulfonic acid as a dopant as a conductive material A radiation curing method was carried out in the same manner as in Example 1 except that a polyadiphosphorus and a sulfone or polyapoline emulsion solution containing 300 parts by weight of a water-soluble or water-dispersible copolymerized polyester was used. Mold conductive compositions were produced. This solution is applied on a glass plate using an applicator with a clearance of 10 m, dried at 100 ° C., and then irradiated with an irradiation dose of 100 OmJ in an ultraviolet irradiation device to cure the coating film, thereby curing the film. Formed. The surface resistance of the obtained cured film was 1.0-1. 5 Ω, and all the cured films were transparent.

 Example 10

As a conductive material, an aqueous dispersion of polyethylene dioxthiophen colloid (polyvinyl-dioxthiophen solid content 2%) containing polystyrene sulfonic acid (solid content 1.2%) as a dopant is used. It was used. Separately, polyethylene glycol dibutyl ether was mixed with methacrylic acid polyethylene glycol monobutyl ether aqueous emulsion to make a 10% solution. In this solution, 1 _O o / ₀ propylene of diglycerin polyglycidyl ether which is an emulsion type multifunctional glycol-based epoxy compound is used. The glycol monomethyl ether emulsion solution was mixed to obtain a base solution having 10% solids. Thereafter, 3% of light-power thione polymerization agent (manufactured by Sumi Chemical Co., Ltd., MP-triazine) is added to the solid content of the base solution and mixed, and the above-mentioned polythiophen colloid solution is further added to solid matter of organic conductive material. The concentration was adjusted so as to be 10% of the solid content of the base solution, added with stirring of the disperser, and after the addition, it was further stirred by the disperser for 1.5 hours. The emulsion solution was cloudy, and separation of the solution was not possible. This solution is applied on a glass plate using an applicator with a clearance of 10 / zm, dried at 100 ° C., and then irradiated with an irradiation dose of lOOOmJ using a UV irradiation device to cure the coating, and cure. A film was formed. The surface resistance of the resulting cured film was 0.5.0-1.0 Ω, and the cured film was transparent.

 Example 11

 As a conductive material, polystyrene sulfonic acid (solid content: 1.2%) is contained as a dopant! /, An aqueous dispersion of polyethylene dioxithiophen colloid (solid state of polyethylene dioxythiophen) An amount of 2% was used. Separately, the polyvinyl butyral aqueous emulsion was diluted with water to make a 10% solids solution. This solution was mixed with a 10% emulsion type polypropylene glycol monomethyl ether solution of diglycerin polyglycidyl ether which is a multifunctional glycol based epoxy compound to obtain a base solution having a 10% solid content. Thereafter, 3% of a light power thione polymerization agent (manufactured by Sanwa Chemical Co., Ltd., MP-triazine) is mixed with the solid content of this base solution, and the above-mentioned polythiolene colloid solution is further mixed with The solution was adjusted to 10% of the solid content of the base solution, added while stirring with a disperser, and after the addition, the mixture was further stirred for 1.5 hours with a disperser. This solution is applied on a glass plate using an applicator with a clearance of 10 m, dried at 100 ° C., and then irradiated with an irradiation dose of lOOOmJ by an ultraviolet irradiation device to cure the coating film, thereby curing the cured film. It formed. The surface resistance of the obtained cured film was 0.5-1.0 Ω.

 Comparative Example 1

As a conductive material, polystyrene sulfonic acid (solid content 1.2%) is contained as a dopant! /, Aqueous dispersion of polyethylene dioxythiophen colloid (polyethylene The solid content of dioxithofen (2%) was used. Separately, urethane atalylate is dissolved in IPA, and non-emergence type urethane atalylate (manufactured by Kyoeisha Chemical Co., Ltd .; 3061 (main component: pentaerythritol triarylate isophorone diisocyanate urethane prepolymer) A 10% solution was made. This solution was mixed with a 10% polypropylene glycol monomethyl ether solution of diglycerin polyglycidyl ether which is a polyfunctional glycol-based epoxy compound, to obtain a base solution having a solid content of 10%. Thereafter, 3% of light-power thione polymerization agent (manufactured by Sanwa Chemical Co., Ltd., MP-triazine) is mixed with the solid content of the base solution, and the above-mentioned polythiophene colloid solution is further mixed with the solid concentration of the organic conductive material. The solution was adjusted to 10% of the solid content of the base solution, added while stirring with a disperser, and further stirred with a disperser for 1.5 hours after addition. This solution was applied on a glass plate using an accreditor with a clearance of 10 m and dried at 100 ° C., and the formed film became cloudy and cracked.

Industrial application field

 The radiation curable conductive composition of the present invention can be used to impart antistatic properties to magnetic tapes, various packaging materials, for example, packaging materials for packaging semiconductor devices, etc. It is preferably used as

Claims

The scope of the claims  [1] Organic conductive polymer, water-soluble or aqueous emulsion-forming compound, water-soluble or aqueous emulsion-forming epoxy or oxetane compound, photosensitizer, and water and / or water-soluble organic solvent A radiation curable conductive composition characterized by containing.  [2] The radiation-curable conductive composition according to claim 1, wherein the water-soluble! /, Water-based emulsion-forming compound is a urethane atarilate-ion compound.  [3] The radiation-curable conductive material according to claim 2, characterized in that the above-mentioned urethane atalylate is a water-soluble or aqueous emulsion-forming polyfunctional acrylic compound having an acrylic group. Sex composition.  [4] The above-mentioned urethane atalylate complexed compound (Α) hydroxyl group-containing acrylic acid ester, (Β) organic polyisocyanate, (C) polyethylene glycol containing at least one hydroxyl group in a molecule, D) A fatty acid containing at least one hydroxyl group in the molecule, and a polyurethane atallate which is a neutralized salt of the reaction product obtained by neutralizing a strong reaction product with (Ε) tertiary amine. The radiation curable conductive composition according to claim 2, characterized in that  [5] The radiation-curable conductive composition according to claim 1, wherein the water-soluble! /, Water-based emulsion-forming compound is an epoxy atalylate complex.  [6] The above epoxy atalylate mixture is a compound of the general formula (I): [Formula 1]

 — (I) (Wherein, R represents a hydrogen atom or a methyl group, X represents CH 2 CH 2 O—, — [CH 2 CH 2 (CH 2) 2]  2 2 2 3 0] One, one [CH CH (OH) CH O] one,  k 2 2 m [Formula 2]

Or [Chemical 3]

And k and m represent integers of 1 to 4. )  6. The radiation curable conductive composition according to claim 5, which is a compound represented by the formula:  [7] The epoxy atallylate compound represented by the above general formula (I) has the general formula (Π):  [Formula 4] CH ₂ = CH-C-0-CH ₂ -CH-CH ₂ -0-CH ₂ -CH ₂ -CH ₂ -0-CH ₂ -CH-CH ₂ -0-C-CH = CH ₂  0 OH OH OH O  The radiation-curable conductive composition according to claim 6, which is a compound represented by (6).  8. The radiation-curable conductive composition according to claim 1, wherein the water-soluble to water-based emulsion-forming compound is a bule ether group-containing atalyl compound.  [9] The organic conductive polymer according to any one of claims 1 to 18, characterized in that it is at least one selected from the group consisting of polyarylin, polyaniline derivatives, polythiophen and polythiophen derivatives. Radiation curable conductive composition. [10] The radiation-curable conductive composition according to any one of claims 1 to 18, characterized in that the organic conductive polymer, the polythiophen or the polythiophen derivative, and the polystyrene sulfonic acid are used. [11] A polyaryne or polyaryne derivative, a sulfone polyary linker, a polyester resin combined with a sulfonic acid group and Z or an alkali metal base thereof, or a polythiophen or polythiophen derivative in the presence of a polyanion The radiation-curable conductive composition according to any one of claims 1 to 18, which is a water-soluble or water-dispersible dispersed organic conductive polymer. [12] The radiation-curable conductive composition according to any one of claims 1 to 18, wherein the photosensitizer is a radical polymerization photosensitizer and Z or a photopower thione polymerization photosensitizer.  [13] The radiation-curable conductive material according to any one of claims 1 to 18, wherein the water-soluble or aqueous dispersion-forming epoxy compound comprises a multifunctional glycidyl compound. Composition.