JP6420191B2 - Nickel film forming composition and method for producing nickel film using the same - Google Patents

Description

  The present invention relates to a composition for forming a nickel film for forming a nickel film on various substrates, and a method for producing a nickel film using the composition.

  Thin films containing nickel are mainly used for members of electronic parts such as resistance films and barrier films, members for recording media such as magnetic films, and members for thin film solar cells such as electrodes.

  For example, Patent Document 1 discloses a nickel film forming coating solution containing nickel formate and an amine solvent having a boiling point in a range of 180 ° C. or higher and lower than 300 ° C. as main solvents. Further, Patent Document 2 contains nickel acetate, nickel formate, an alkanolamine solvent, and a glycol solvent as main components, and the nickel film forming coating is 10 parts by weight or more of nickel formate with respect to 100 parts by weight of nickel acetate. A liquid is disclosed. Patent Document 3 discloses a nickel compound-containing solution containing a nickel compound obtained by reacting an N-substituted 2-aminoethanol with a nickel salt of an organic acid and using terpineol as a solvent.

International Publication No. 2006/135113 JP 2008-153136 A JP 2005-33658 A

  In order to produce a fine wiring or film at a low cost in a liquid process using a composition for forming a nickel film, it is desired to provide a composition that satisfies the following requirements. That is, it is a solution type that does not contain a solid phase such as fine particles, gives a nickel film with excellent conductivity, can be converted to a nickel film at low temperature and low energy, has good coating properties, and has storage stability. It is desired that the film thickness is good, that the film thickness obtained by one application can be easily controlled, and that the obtained film and the substrate have high adhesion. However, when a conventionally known composition for forming a nickel film is used, it is necessary to bake at a temperature of 200 ° C. or higher in order to convert the composition for forming a nickel film into a nickel film. For this reason, for example, when a nickel film is formed on an organic resin substrate typified by polyethylene terephthalate (hereinafter also referred to as “PET”) resin, there is a problem that the organic resin substrate is deteriorated by heat. It was.

  Accordingly, an object of the present invention is to apply a nickel film having sufficient conductivity and high adhesion to the substrate at a low temperature and low energy by coating on the substrate and processing by a flash lamp method using a xenon lamp. An object of the present invention is to provide a solution-like composition for forming a nickel film that does not contain a solid phase such as fine particles.

  As a result of repeated investigations in view of the above circumstances, the present inventors, as a result, nickel film containing nickel formate or a hydrate thereof, N-methylethanolamine, and a dye compound having a specific structure in a specific ratio. The present inventors have found that the forming composition satisfies the above required performance and have reached the present invention.

  That is, the present invention is represented by at least one nickel compound selected from nickel formate and hydrates thereof, N-methylethanolamine, the following general formula (AI) and the following general formula (A-II). At least one dye compound selected from the group consisting of the above compounds and an organic solvent for dissolving them, and the concentration of the nickel compound is 0.01 to 3.0 mol / kg, -The composition for forming a nickel film is provided wherein the concentration of methylethanolamine is 0.1 to 6.0 times the concentration of the nickel compound, and the concentration of the dye compound is 0.001 to 20% by mass. To do.

（前記一般式（Ａ−Ｉ）中、Ａｒ¹及びＡｒ²は、それぞれ独立に、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、カルボキシ基、ハロゲン原子、シアノ基、若しくはビニル基で置換されていてもよいベンゼン環又はナフタレン環を表し、Ｒ^aは、ヒドロキシ基、アミノ基、アルキルアミノ基、又はジアルキルアミノ基を表し、ｐは、Ａｒ²が置換又は無置換のベンゼン環である場合には１〜５の整数を表し、Ａｒ²が置換又は無置換のナフタレン環である場合には１〜７の整数を表す。Ｒ^a及びＡｒ²は、相互に結合して環構造を形成してもよく、ｐが２〜７の整数である場合には、複数のＲ^aは相互に異なっていてもよい）

(In the general formula (AI), Ar ¹ and Ar ² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a halogen atom, or a cyano group. Or a benzene ring or a naphthalene ring optionally substituted with a vinyl group, R ^a represents ^a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents a substituted or unsubstituted Ar ² group. And when Ar ² is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7. R ^a and Ar ² are bonded to each other. A ring structure may be formed, and when p is an integer of 2 to 7, a plurality of R ^a may be different from each other)

（前記一般式（Ａ−ＩＩ）中、Ａｒ³〜Ａｒ⁵は、それぞれ独立に、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、カルボキシ基、ハロゲン原子、シアノ基、若しくはビニル基で置換されていてもよいベンゼン環又はナフタレン環を表し、Ｒ^bは、ヒドロキシ基、アミノ基、アルキルアミノ基、又はジアルキルアミノ基を表し、ｑは、Ａｒ⁵が置換又は無置換のベンゼン環である場合には１〜５の整数を表し、Ａｒ⁵が置換又は無置換のナフタレン環である場合には１〜７の整数を表す。Ｒ^b及びＡｒ⁵は、相互に結合して環構造を形成してもよく、ｑが２〜７の整数である場合、複数のＲ^bは相互に異なっていてもよく、複数の異なっていてもよいＲ^bはＡｒ⁵と相互に結合して環構造を形成してもよい）

(In the general formula (A-II), Ar ^{3 to} Ar ⁵ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a halogen atom, or a cyano group. Or a benzene ring or a naphthalene ring optionally substituted with a vinyl group, R ^b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and q is substituted or unsubstituted by Ar ⁵ And when Ar ⁵ is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7. R ^b and Ar ⁵ are bonded to each other. may form a ring structure Te, when q is 2-7 integer, the plurality of R ^b may be different from each other, good R ^b be the number of different bonded to each other and Ar ⁵ To form a ring structure)

  The present invention also provides a coating step of coating the above-described nickel film forming composition on a substrate, and irradiation film formation in which at least a part of the applied nickel film forming composition is irradiated with light using a xenon lamp. And a process for producing a nickel film comprising the steps.

  According to the present invention, a nickel film having sufficient electrical conductivity and high adhesion to the substrate can be obtained at low temperature and low energy by coating on the substrate and processing by a flash lamp method using a xenon lamp. A solution-like composition for forming a nickel film that does not contain a solid phase such as fine particles is provided.

  One of the features of the composition for forming a nickel film of the present invention is that at least one nickel compound selected from nickel formate and a hydrate thereof is used as a precursor (precursor) of the nickel film. The nickel compound used in the composition for forming a nickel film of the present invention may be an hydrate, a hydrate, or a combination of two or more. Specifically, anhydrous nickel (II) formate, nickel formate (II) dihydrate, and the like can be used. These nickel compounds may be mixed as they are, or may be mixed as an aqueous solution, an organic solvent solution, or an organic solvent suspension.

  The density | concentration of the nickel compound in the composition for nickel film formation of this invention is 0.01-3.0 mol / kg, and it is preferable that it is 1.0-2.5 mol / kg. If the concentration of the nickel compound is less than 0.01 mol / kg, a thin film may not be obtained. On the other hand, when the concentration of the nickel compound exceeds 3.0 mol / kg, the stability of the solution decreases. Here, “mol (mol) / kg” in the present invention represents “amount (mol) of solute dissolved in 1 kg of solution”. For example, since the molecular weight of nickel (II) formate is 148.73, when 148.73 g of nickel (II) formate is contained in 1 kg of the composition for forming a nickel film of the present invention, 1.0 mol / kg.

  N-methylethanolamine, which is a component constituting the composition for forming a nickel film of the present invention, exhibits an effect as a solubilizer for nickel formate or nickel formate hydrate. Moreover, while improving the storage stability of the composition for nickel film formation, the effect which improves electroconductivity, when converted into a film | membrane is shown.

  The concentration of N-methylethanolamine in the composition for forming a nickel film of the present invention is 0.1 to 6.0 times the concentration of the nickel compound. For example, when the concentration of the nickel compound is 1 mol / kg, the concentration of N-methylethanolamine is in the range of 0.1 to 6.0 mol / kg. When the concentration of N-methylethanolamine is less than 0.1 times the concentration of the nickel compound, the resulting nickel film has insufficient conductivity. On the other hand, if it exceeds 6.0 times, the coatability deteriorates and a uniform nickel film cannot be obtained. A preferable range is 0.2 to 5.0 times, and 1.0 to 3.0 times is particularly preferable because the stability of the composition is particularly high.

  The dye compound which is a component constituting the composition for forming a nickel film of the present invention is at least one selected from the group consisting of compounds represented by the following general formula (AI) and the following general formula (A-II). A kind of compound. According to studies by the present inventors, a flash lamp method using a xenon lamp when this dye compound is contained in a nickel film forming composition in combination with nickel formate or a hydrate thereof and N-methylethanolamine. It was found that the energy required for conversion into a nickel film can be reduced.

（前記一般式（Ａ−Ｉ）中、Ａｒ¹及びＡｒ²は、それぞれ独立に、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、カルボキシ基、ハロゲン原子、シアノ基、若しくはビニル基で置換されていてもよいベンゼン環又はナフタレン環を表し、Ｒ^aは、ヒドロキシ基、アミノ基、アルキルアミノ基、又はジアルキルアミノ基を表し、ｐは、Ａｒ²が置換又は無置換のベンゼン環である場合には１〜５の整数を表し、Ａｒ²が置換又は無置換のナフタレン環である場合には１〜７の整数を表す。Ｒ^a及びＡｒ²は、相互に結合して環構造を形成してもよく、ｐが２〜７の整数である場合には、複数のＲ^aは相互に異なっていてもよい）

(In the general formula (AI), Ar ¹ and Ar ² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a halogen atom, or a cyano group. Or a benzene ring or a naphthalene ring optionally substituted with a vinyl group, R ^a represents ^a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents a substituted or unsubstituted Ar ² group. And when Ar ² is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7. R ^a and Ar ² are bonded to each other. A ring structure may be formed, and when p is an integer of 2 to 7, a plurality of R ^a may be different from each other)

（前記一般式（Ａ−ＩＩ）中、Ａｒ³〜Ａｒ⁵は、それぞれ独立に、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、カルボキシ基、ハロゲン原子、シアノ基、若しくはビニル基で置換されていてもよいベンゼン環又はナフタレン環を表し、Ｒ^bは、ヒドロキシ基、アミノ基、アルキルアミノ基、又はジアルキルアミノ基を表し、ｑは、Ａｒ⁵が置換又は無置換のベンゼン環である場合には１〜５の整数を表し、Ａｒ⁵が置換又は無置換のナフタレン環である場合には１〜７の整数を表す。Ｒ^b及びＡｒ⁵は、相互に結合して環構造を形成してもよく、ｑが２〜７の整数である場合、複数のＲ^bは相互に異なっていてもよく、複数の異なっていてもよいＲ^bはＡｒ⁵と相互に結合して環構造を形成してもよい）

(In the general formula (A-II), Ar ^{3 to} Ar ⁵ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a halogen atom, or a cyano group. Or a benzene ring or a naphthalene ring optionally substituted with a vinyl group, R ^b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and q is substituted or unsubstituted by Ar ⁵ And when Ar ⁵ is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7. R ^b and Ar ⁵ are bonded to each other. may form a ring structure Te, when q is 2-7 integer, the plurality of R ^b may be different from each other, good R ^b be the number of different bonded to each other and Ar ⁵ To form a ring structure)

  Examples of the dye compound represented by formula (AI) include the following compound No. 1-No. 4 can be mentioned.

  Examples of the dye compound represented by formula (A-II) include the following compound No. 5-No. 7 can be mentioned.

  The content of the dye compound in the composition for forming a nickel film of the present invention is 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and 0.01 to 15% by mass. More preferably it is. When the amount is less than 0.001% by mass, the effect of blending the coloring compound is not recognized. On the other hand, when it exceeds 20 mass%, the effect by having mix | blended will be saturated. Moreover, the said pigment compound may be used independently and may mix and use 2 or more types.

  Among the dye compounds listed above, 4-phenylazophenol (Compound No. 1), Solvent Black 3 (Compound No. 5), Sudan 3 (Compound No. 6), Sudan R (Compound No. 2), And methyl red (Compound No. 3) were added to nickel formate or a hydrate thereof and N-methylethanolamine in a nickel film-forming composition by a flash lamp method using a xenon lamp. This is preferable because the effect of reducing the energy required for conversion into a film is great. Among the dye compounds listed above, 4-phenylazophenol (Compound No. 1), Solvent Black 3 (Compound No. 5), Sudan 3 (Compound No. 6), and Sudan R (Compound No. 2) Is preferable because a nickel film having good conductivity can be formed, and 4-phenylazophenol (compound No. 1) and Sudan R (compound No. 2) form a nickel film having better conductivity. This is particularly preferable because it becomes possible.

  The organic solvent constituting the composition for forming a nickel film of the present invention may be any one that can stably dissolve a nickel compound, N-methylethanolamine, a dye compound, and other components. The organic solvent may be a single composition or a mixture. Specific examples of the organic solvent used in the composition for forming a nickel film of the present invention include alcohol solvents, diol solvents, ketone solvents, ester solvents, ether solvents, aliphatic or alicyclic hydrocarbon solvents. , Aromatic hydrocarbon solvents, hydrocarbon solvents having a cyano group, other solvents, and the like.

  Examples of alcohol solvents include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, and third pen. Tanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, Benzyl alcohol, ethylene glycol monoacetate, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, 2- ( 2-methoxyethoxy) ethanol, 2- (N, N-dimethylamino) ethanol, 3- (N, N-dimethylamino) propanol and the like.

  Examples of the diol solvent include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and isoprene glycol (3 -Methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl- 1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, Examples include 1,4-cyclohexanedimethanol.

  Examples of the ketone solvent include acetone, ethyl methyl ketone, methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and methylcyclohexanone.

  Examples of the ester solvent include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, triamyl acetate, Phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, butyl propionate, tert-butyl propionate, amyl propionate, isoamyl propionate, 3 amyl propionate, propionate Acid phenyl, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhexanoate, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl Methyl xylpropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono Butyl ether acetate, ethylene glycol mono secondary butyl ether acetate, ethylene glycol mono isobutyl ether acetate, ethylene glycol mono tertiary butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropylene Ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether Acetate, Butylene glycol monopropyl ether acetate, Butylene glycol monoisopropyl ether acetate, Butylene glycol monobutyl ether acetate, Butylene glycol mono sec-butyl ether acetate, Butylene glycol monoisobutyl ether acetate, Butylene glycol mono tertiary Examples include butyl ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutanoate, ethyl oxobutanoate, γ-lactone, and δ-lactone.

  Examples of ether solvents include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, and dioxane.

  Examples of the aliphatic or alicyclic hydrocarbon solvent include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decalin, and solvent naphtha.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, cymene, and tetralin.

  Examples of the hydrocarbon solvent having a cyano group include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6- Examples include dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene, and the like.

  Examples of other organic solvents include N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide and the like.

  In the present invention, among the above organic solvents, alcohol-based solvents, diol-based solvents and ester-based solvents are inexpensive and exhibit sufficient solubility in solutes. Further, silicon substrates, metal substrates, ceramic substrates, glass It is preferable because it exhibits good coating properties as a coating solvent for various substrates such as a substrate and a resin substrate. Among these, a solvent having a hydroxyl group in the structure such as an alcohol solvent and a diol solvent is particularly preferable because of its high solubility in a solute.

  The content of the organic solvent in the composition for forming a nickel film of the present invention is not particularly limited, and may be appropriately adjusted according to the thickness of the nickel film to be formed and the method for manufacturing the nickel film. Good. For example, when a nickel film is produced by a coating method, the organic solvent is added in an amount of 0.01 to 100 parts by mass of nickel formate (even in the case of nickel formate hydrate, converted to nickel formate, the same shall apply hereinafter). It is preferable to use 5,000 parts by mass. If the amount of the organic solvent is less than 0.01 parts by mass, there may be a problem that cracks occur in the obtained nickel film or the coating property deteriorates. Moreover, since the nickel film obtained becomes thin, so that the ratio of an organic solvent increases, it is preferable not to exceed 5,000 mass parts from the surface of productivity. More specifically, when a nickel film is produced by a spin coating method, it is preferable to use 20 to 1,000 parts by mass of an organic solvent with respect to 100 parts by mass of nickel formate. Moreover, when manufacturing a nickel film by the screen printing method, it is preferable to use 0.01-20 mass parts of organic solvents with respect to 100 mass parts of nickel formate.

  The composition for forming a nickel film of the present invention may contain any component other than the essential components as long as the effects of the present invention are not impaired. As optional components, additives such as dyes, pigments, developers, sensitizers, anti-gelling agents, stabilizers and the like for imparting stability to the coating liquid composition; antifoaming agents, thickeners, Examples include additives for improving the coating properties of coating liquid compositions such as thixotropic agents and leveling agents; and film forming aids such as combustion aids and crosslinking aids. The content in the case of using these optional components is a proportion of the total composition for forming a nickel film, preferably 50% by mass or less, and more preferably 20% by mass or less.

  Examples of the dye include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (2-phenyl-3-indolyl) phthalide, 3 -(P-dimethylaminophenyl) -3- (1,2-dimethyl-3-indolyl) phthalide, 3,3-bis (9-ethyl-3-carbazolyl) -5-dimethylaminophthalide, 3,3- Bis (2-phenyl-3-indolyl) -5-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis [Triarylmethane compounds such as [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) vinyl] -4,5,6,7-tetrachlorophthalide; -Diphenylmethane compounds such as bis (dimethylamino) benzhydrin benzyl ether and N-2,4,5-trichlorophenylleucooramine; (3) Rhodamine-β-anilinolactam, 3- (N-methyl-N -Cyclohexylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-7- (2-fluoro) Anilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (2,4-dimethylanilino) fluorane, 3-diethylamino-7-dibenzylamino Fluorane, 3-diethylamino-6-chloro-7- (β-ethoxyethyl Mino) fluorane, 3-diethylamino-6-chloro-7- (γ-chloropropylamino) fluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3- ( N-ethyl-N-ethoxyethylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3- Dibutylamino-7- (2-chloroanilino) fluorane, 3- (N-ethyl-N-tolylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl- 7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3- (4-a Nilino) xanthene compounds such as anilino-6-methyl-7-chlorofluorane; thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue; 3-methylspirodinaphthopyrans, 3-ethylspirodinaphthopyrans Spiro compounds such as 3-benzylspirodinaphthopyran and 3-methylnaphtho- (3-methoxybenzo) spiropyran; and other 3,5 ′, 6-tris (dimethylamino) -spiro [9H-fluorene-9,1 ′ -(3'H) -isobenzofuran] -3'-one, 1,1-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7 -Tetrachloro (3H) isobenzofuran-3-one, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-Ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindol-3-yl) ) -4-azaphthalide and the like. These dyes can be used alone or in combination of two or more.

  Examples of the pigment include iron oxide pigments, titanium pigments, blue and green inorganic pigments, carbon pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Examples of iron oxide pigments include iron black, red pepper, and zinc ferrite pigments. Examples of the titanium pigment include titanium oxide, nickel antimony titanium yellow, and chromium antimony titanium yellow. Examples of blue and green inorganic pigments include ultramarine blue, cobalt blue, chromium oxide, and spinel green. Examples of the azo pigment include azo lake pigments such as Lake Red C, Watching Red, Brilliant Carmine 6B; Hosta Palm Yellow H4G, Nova Palm Yellow H2G, Nova Palm Red HFT, PV Fast Yellow HG, PV Fast Yellow H3R, PV Bordeaux Benzimidazolone pigments such as HF3R, PV Carmine HF4C, PV Red HF2B, PV Fast Maroon HMF01, and PV Fast Brown HFR; Yellow 8GN, chromophthal yellow 6G, chromophthal yellow 3G, chromophthal yellow GR, chromophthal orange 4R, chromophthal orange GP, chromophthalska Let RN, may be mentioned Chromophthal Red G, chromophthal red BRN, chromophthal red BG, chromophthal red 2B, a condensed azo pigments such as Chromophthal Brown 5R. Examples of the phthalocyanine pigment include phthalocyanine blue and phthalocyanine green. Examples of the condensed polycyclic pigment include quinacridone pigments such as PV Fast Pink E, Shinkasha Red B and Shinkasha Red Y; isoindolinone pigments such as Irgazine Yellow 2GLT, Irgazine Yellow 3RLTN and Chromophthal Orange 2G Perylene pigments such as perylene red, perylene maroon, and perylene scarlet; perinone pigments such as perinone orange; dioxazine pigments such as dioxazine violet; Quinophthalone pigments such as Paliotol Yellow L0960HG. Moreover, these pigments can be used individually by 1 type or in combination of 2 or more types. The addition amount of the dye and the pigment is preferably 0.02 to 20% by mass and more preferably 0.1 to 15% by mass with respect to the amount of nickel in the nickel film forming composition.

  Next, the manufacturing method of the nickel film of this invention is demonstrated. The method for producing a nickel film of the present invention includes a coating step of applying the composition for forming a nickel film of the present invention described above onto a substrate, and a xenon lamp on at least a part of the applied composition for forming a nickel film. And an irradiation film forming step of irradiating with light. If necessary, it may further include a drying step for holding the substrate at 50 to 200 ° C. and volatilizing a low boiling point component such as an organic solvent before the irradiation film forming step. Moreover, you may further have the annealing process which maintains the base | substrate at 200-500 degreeC after the irradiation film-forming process, and improves the electroconductivity of a nickel film.

  As the coating method in the above coating process, spin coating method, dip method, spray coating method, mist coating method, flow coating method, curtain coating method, roll coating method, knife coating method, bar coating method, slit coating method, screen Examples thereof include a printing method, a gravure printing method, an offset printing method, an ink jet method, and a brush coating.

Although the irradiation conditions in said irradiation film-forming process are not specifically limited, For example, irradiation conditions, such as irradiation time 0.1-100 milliseconds, voltage 400-4,000V, irradiation energy 0.1-25J / cm < ² >, are used. Can be mentioned.

  Moreover, in order to obtain a required film thickness, a plurality of steps from the above coating step to an arbitrary step can be repeated. For example, all the processes from the coating process to the irradiation film forming process may be repeated a plurality of times, and the coating process and the drying process may be repeated a plurality of times.

  The atmosphere of the drying step and the irradiation film forming step is usually any one of air, a reducing gas, and an inert gas, and it is economical in the air. The atmosphere of the annealing process is usually either a reducing gas or an inert gas. Annealing in a reducing gas atmosphere is preferable because a nickel film with better conductivity can be obtained. An example of the reducing gas is hydrogen. Moreover, helium, nitrogen, and argon can be mentioned as an inert gas. The inert gas may be used as a diluent gas for the reducing gas. In each step, plasma; discharge lamp such as laser; energy other than heat such as various radiations may be applied or irradiated.

  Applications of the film produced by the nickel film production method of the present invention include electrode films, barrier films, resistance films, magnetic films, liquid crystal barrier metal films, thin film solar cell members, semiconductor device members, and nanostructures. , Hydrogen storage alloys, and microelectromechanical actuators.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

<Preparation 1 of nickel film forming composition>
[Examples 1 to 16]
The compounds shown in Table 1 were blended so as to have numerical values in parentheses (mol / kg, mass%) to obtain compositions for forming a nickel film 1-16. Specifically, as shown in Table 1, 16 types of nickel film forming compositions 1 to 16 were produced by changing the types and amounts of nickel formate compound, N-methylethanolamine, and dye compound. . The remainder is all butanol. Moreover, the density | concentration (mol / kg) of each compound described in Table 1 is the quantity in 1 kg of manufactured compositions.

[Comparative Examples 1 to 20]
Comparative compounds 1 to 20 were obtained by blending the compounds shown in Table 2 so as to obtain numerical values in parentheses (mol / kg). The remainder was all butanol. Moreover, the density | concentration (mol / kg) of each compound described in Table 2 is the quantity in 1 kg of manufactured compositions. The structures of dye compounds 1 to 3 used for the preparation of comparative compositions 1 to 12 are shown below.

<Manufacture of nickel film 1>
[Nickel films for evaluation 1-16]
Each of the nickel film forming compositions 1 to 16 was cast on a PET substrate (50 mm × 50 mm, thickness 0.1 mm). Each nickel film forming composition was applied by spin coating under conditions of 500 rpm for 5 seconds and 2,000 rpm for 20 seconds. Subsequently, it dried in air | atmosphere for 30 second at 100 degreeC using the hotplate. The dried PET substrate was irradiated with light using the xenon flash lamp apparatus (trade name “SUS686”, manufactured by USHIO INC.) In the atmosphere under the conditions shown in Table 3, and a nickel thin film (evaluation nickel films 1 to 16) Formed. In addition, discoloration and deformation did not occur in the PET substrate irradiated with light with a xenon flash lamp.

[Comparison Nickel Films 1-16]
Comparative compositions 1 to 16 were each cast on a PET substrate (50 mm × 50 mm, thickness 0.1 mm). Each comparative composition was applied by spin coating under conditions of 500 rpm for 5 seconds and 2,000 rpm for 20 seconds. Subsequently, it dried in air | atmosphere for 30 second at 100 degreeC using the hotplate. The dried PET substrate was irradiated with light under the conditions shown in Table 3 in the atmosphere using a xenon flash lamp apparatus (trade name “SUS686”, manufactured by USHIO INC.), And a nickel thin film (comparative nickel films 1 to 16) Formed. In addition, discoloration and deformation did not occur in the PET substrate irradiated with light with a xenon flash lamp.

<Evaluation 1>
[Measurement of surface resistance]
Using a resistivity meter (Loresta GP: manufactured by Mitsubishi Chemical Analytech), the surface resistance values of the evaluation nickel films 1 to 16 and the comparative nickel films 1 to 16 were measured. Table 3 shows the measured surface resistance values.

  As shown in Table 3, the evaluation nickel films 1 to 16 were all films having good conductivity, but the comparative nickel films 1 to 16 were all films having no conductivity. Among them, the evaluation nickel films 1 to 7, 9 to 12 and 14 showed excellent conductivity, and among these, the evaluation nickel films 1 and 3 were found to show particularly excellent conductivity.

<Evaluation 2>
[Evaluation of adhesion]
Evaluation samples were prepared by cross-cutting the evaluation nickel films 1 to 16 in a 10 × 10 grid pattern at intervals of 1 mm. About the produced sample for evaluation, the peeling test based on JISK-5600 was implemented, and adhesiveness was evaluated according to the evaluation criteria shown below. The results are shown in Table 4.
○: The area of the peeled portion is 0% or more and less than 10% of the entire area.
X: The area of the peeled part is 10% or more of the entire area.

  As shown in Table 4, it can be seen that the evaluation nickel films 1 to 16 are all films having high adhesion.

Claims (3)

A group consisting of at least one nickel compound selected from nickel formate and hydrates thereof, N-methylethanolamine, and compounds represented by the following general formula (AI) and the following general formula (A-II) Containing at least one dye compound selected from the above, and an organic solvent for dissolving them,
The concentration of the nickel compound is 0.01 to 3.0 mol / kg,
The concentration of the N-methylethanolamine is 0.1 to 6.0 times the concentration of the nickel compound,
The composition for forming a nickel film, wherein the concentration of the dye compound is 0.001 to 20% by mass.

(In the general formula (AI), Ar ¹ and Ar ² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a halogen atom, or a cyano group. Or a benzene ring or a naphthalene ring optionally substituted with a vinyl group, R ^a represents ^a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents a substituted or unsubstituted Ar ² group. And when Ar ² is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7. R ^a and Ar ² are bonded to each other. A ring structure may be formed, and when p is an integer of 2 to 7, a plurality of R ^a may be different from each other)

(In the general formula (A-II), Ar ^{3 to} Ar ⁵ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a halogen atom, or a cyano group. Or a benzene ring or a naphthalene ring optionally substituted with a vinyl group, R ^b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and q is substituted or unsubstituted by Ar ⁵ And when Ar ⁵ is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7. R ^b and Ar ⁵ are bonded to each other. may form a ring structure Te, when q is 2-7 integer, the plurality of R ^b may be different from each other, good R ^b be the number of different bonded to each other and Ar ⁵ To form a ring structure)   2. The composition for forming a nickel film according to claim 1, wherein the coloring compound is at least one selected from the group consisting of 4-phenylazophenol, solvent black 3, Sudan 3, Sudan R, and methyl red. An application step of applying the nickel film-forming composition according to claim 1 or 2 on a substrate;
An irradiation film-forming step of irradiating at least part of the applied composition for forming a nickel film with light using a xenon lamp.