JP2000321775A - Three layers laminated film for forming pattern and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to design by separating functions and separating the photosensitive resin composition so far used as a conductive layer into a energy sensitive layer and a filter layer and a conductive layer and to enlarge its use. SOLUTION: These 3 layer laminated film comprises (A) an energy ray sensitive layer and (B) a filter layer and (C) an energy ray sensitive conductive film-forming resin layer successively laminated from an upper layer, and the pattern is formed by irradiating the upper surface of the layer (A) with the energy rays and absorbing the rays and/or reflecting the rays with the filter layer (B) so as not to adversely affect the pattern formation of the energy ray sensitive conductive film-forming resin layer (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD [0001] The present invention relates to
An energy-sensitive radiation coating layer, a filter layer, and a resin layer for forming an energy-sensitive conductive film are laminated, and energy rays irradiated from the upper surface of the coating layer are absorbed and / or reflected by the filter layer to form a lower layer. A novel three-layer laminated film for forming a pattern, comprising a three-layer laminated film in which energy rays are prepared so as not to adversely affect the pattern formation of the resin layer for forming an energy-sensitive conductive film, and a method for forming the pattern About.

[0002]

2. Description of the Related Art Conventionally, in lithography using an exposure technique, a method of forming a pattern on, for example, plastic or inorganic material is used for a wiring board, a display panel, and the like. As a method of forming the above-mentioned pattern, for example, after forming a photosensitive conductive layer by applying a conductive pigment paste obtained by dispersing a conductive pigment such as silver powder to a photosensitive resin on the surface of the base material, Electron beam from the surface,
There is known a method of irradiating ultraviolet rays through a photomask and then developing the photosensitive conductive layer to obtain a desired conductive pattern.

[0003] However, the above-mentioned method is problematic in that, for example, a sharp pattern cannot be formed due to insufficient photosensitivity of the conductive layer, and a large amount of photosensitive resin increases the amount of gas generated during firing, resulting in environmental pollution. In addition, there is a problem that it is difficult to increase the thickness of the conductive layer, so that the use is restricted.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, in particular, a resin layer (C) for forming an energy-sensitive conductive film and an energy-sensitive beam coating By absorbing and / or reflecting the energy rays irradiated from the upper surface of the coating layer (A) between the layer (A) and the layer (A), the lower resin layer (C) for forming the energy-sensitive conductive film can be formed. The inventors have found that a three-layer laminated film having a filter layer (B) capable of preparing an energy ray so as not to exert a bad influence and a pattern forming method using the same are a laminate and a forming method which solve the above-mentioned problems. Thus, the present invention has been completed. That is, the present invention comprises, in order from the upper layer, an energy-sensitive radiation coating layer (A), a filter layer (B) and a resin layer (C) for forming an energy-sensitive radiation conductive coating, and the coating layer (A) The energy rays irradiated from the upper layer surface are absorbed and / or reflected by the filter layer (B) so as not to adversely affect the pattern formation of the lower energy-sensitive conductive film forming resin layer (C). And a method for forming a pattern of the film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The energy-sensitive ray coating layer (A) used in the present invention has a different solubility in a developing solution due to curing or decomposition of a portion irradiated with an active energy ray. Any known materials can be used without any particular limitation as long as they can form.

Examples of the above include, for example, an organic solvent-based positive photosensitive resin composition, an organic solvent-based negative photosensitive resin composition, an aqueous positive photosensitive resin composition, and an aqueous negative photosensitive resin composition. And other liquid resist photosensitive resin compositions; photosensitive dry films such as positive photosensitive dry films and negative photosensitive dry films; organic solvent-based negative thermosensitive resin compositions, aqueous negative thermosensitive resin compositions, etc. And a heat-sensitive dry film of a negative type heat-sensitive dry film. In the above-mentioned composition for energy-sensitive rays, the photosensitive resin composition is preferably a negative or positive type of visible ray type and ultraviolet ray curing type. As the negative photosensitive resin composition, for example, a conventionally known one containing a photocurable resin, a photoreaction initiator and, if necessary, a photosensitizing dye can be used. The above-described photocurable resin is a commonly used photocurable resin having a photosensitive group that can be crosslinked by light irradiation, and a film of an unexposed portion in the resin is an alkaline developer or an acidic developer. There is no particular limitation as long as it has an ionic group (anionic group or cationic group) that can be dissolved and removed by the liquid.

The unsaturated group contained in the photocurable resin includes, for example, an acryloyl group, a methacryloyl group, a vinyl group, a styryl group and an allyl group.

As the ionic group, for example, a carboxyl group is a typical example of the anionic group. The content of the carboxyl group is about 10 to 700 mg KOH / g, particularly about 20 ~ 600mg
Those in the range of KOH / g are preferred. When the acid value is less than about 10, there is a disadvantage that the solubility of the uncured film due to the processing of the developer is poor, and when the acid value is more than about 700, the resist film portion (cured film portion) tends to be removed. It is not preferred because it has disadvantages. The cationic group is typically an amino group, and the content of the amino group is about 20 to 65 in terms of the amine value of the resin.
0, especially in the range of about 30 to 600 is preferred. When the amine value is less than about 20, there is a disadvantage that the solubility is inferior as described above. On the other hand, when the amine value is more than about 650, there is a disadvantage that the resist film is apt to be removed. Examples of the anionic resin include a resin obtained by reacting a polycarboxylic acid resin with a monomer such as glycidyl (meth) acrylate to introduce an unsaturated group and a carboxyl group into the resin. Examples of the cationic resin include a resin obtained by adding a reaction product of a hydroxyl group-containing unsaturated compound and a diisocyanate compound to a hydroxyl group- and tertiary amino group-containing resin. The above-mentioned anionic resin and cationic resin are described in the photocurable resin of JP-A-3-223759.

Examples of the photoreaction initiator include aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone and anthraquinone; acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α Acetophenones such as dichlororu 4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, diacetylacetophenone, and acetophenone; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butyl hydroperoxide, and t-butyl Organic peroxides such as diperoxyisophthalate and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; Diphenylhalonium salts such as phenyliodobromide and diphenyliodonium chloride; organic halides such as carbon tetrabromide, chloroform and iodoform; 3-phenyl-5-isoxazolone, and 2,4,6-tris (trichloromethyl) -1,3 Heterocyclic and polycyclic compounds such as 5-triazinebenzanthrone; 2,2′-azo (2,4-
Dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1
Azo compounds such as -carbonitrile) and 2,2'-azobis (2-methylbutyronitrile); iron-allene complexes (see EP 152377); titanocene compounds (see JP-A-63-221110) and bisimidazole compounds N-arylglycidyl compounds; acridine compounds; aromatic ketone / aromatic amine combinations;
And peroxyketal (see JP-A-6-321895). Among the above-mentioned photo-radical polymerization initiators,
G-tert-butyl diperoxyisophthalate, 3,
Since 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, iron-allene complex and titanocene compound have high activity for crosslinking or polymerization, it is preferable to use these compounds.

The trade names include, for example, Irgacure 651 (manufactured by Ciba-Geigy, trade name, acetophenone-based photo-radical polymerization initiator), Irgacure 184 (manufactured by Ciba-Geigy, trade name, acetophenone-based photo-radical polymerization initiator), Irgacure 1850 (Ciba-Geigy, trade name, acetophenone-based photoradical polymerization initiator), Irgacure 907 (Ciba-Geigy, trade name, aminoalkylphenone-based photoradical polymerization initiator), Irgacure 369 (Ciba-Geigy, trade name, Aminoalkylphenone-based photo-radical polymerization initiator), lucilin TPO (trade name, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure DETX-S (Nippon Kayaku Co., Ltd.)
CGI-784 (manufactured by Ciba-Geigy Corporation)
Trade names, titanium complex compounds). These can be used alone or in combination of two or more. The mixing ratio of the photoreaction initiator is 0.1 to 25 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the photocurable resin. As the photosensitizer, a conventionally known photosensitizing dye can be used. This includes, for example, thioxanthene-based, xanthene-based,
Ketones, thiopyrylium salts, base styryls, merocyanines, 3-substituted coumarins, 3.4-substituted coumarins, cyanines, acridines, thiazines, phenothiazines, anthracenes, coronenes, benzanthracenes, Examples include perylene, merocyanine, ketocoumarin, fumaline, and borate dyes. These can be used alone or in combination of two or more. Examples of borate-based photosensitizing dyes include those described in JP-A-5-241338, JP-A-7-5685, and JP-A-7-225474. In addition to the above, saturated resins can be used. The saturated resin is used to suppress the solubility of the photopolymerizable composition (the solubility of the resist film in an alkali developing solution and the use of a photocured film in removing a photocured film, for example, a solubility inhibitor in a strong alkaline solution). Can be used for This includes, for example, polyester resin, alkyd resin, (meth) acrylic resin, vinyl resin, epoxy resin, phenol resin, natural resin, synthetic rubber, silicone resin, fluororesin, polyurethane resin and the like. These resins can be used alone or in combination of two or more. As the organic solvent type of the negative photosensitive resin composition described above, the photosensitive resin composition described above is treated with an organic solvent (ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, (Eg, halogenated hydrocarbons). In addition to the above, conventionally known water-developable photosensitive resin compositions can be used. For example, an aqueous resin having a photopolymerizable unsaturated group and an ion-forming group in a novolak phenol type epoxy resin can be used. The resin is made to contain a photopolymerizable resin by adding a part of epoxy group of the novolak phenol type epoxy resin and (meth) acrylic acid, and the epoxy group and a tertiary amine compound are added to the resin. It is obtained by reacting to form a water-soluble onium base. The exposed part is photocured and does not dissolve in water, but the unexposed part can be developed with water by an ion-forming group. Further, it is post-heated (for example, at about 140 to 200 ° C. for 10 ° C.). For 30 minutes), the coating film becomes hydrophobic by volatilization of the ion-forming group. Therefore, a hydrophilic group (carboxyl group) is contained in the resist coating film as in the above-mentioned alkali or acid developable photosensitive composition. ,
It is possible to form a film having excellent resist properties without amino groups or the like (salts by a developer). In addition to the novolak phenol epoxy resin, for example, the same polymer of an epoxy group-containing radical polymerizable unsaturated monomer such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylalkyl (meth) acrylate, and vinyl glycidyl ether; Copolymers of one or more monomers with other radically polymerizable unsaturated monomers (eg, alkyl or cycloalkyl (meth) acrylates having 1 to 24 carbon atoms, radically polymerizable unsaturated aromatic compounds, etc.) And adding (meth) acrylic acid in the same manner as described above to make the resin have photopolymerizability, and reacting the epoxy group with, for example, a tertiary amine compound to form a water-soluble onium base. It is also possible to use a radical polymer obtained by forming Kill. Further, as a method of coating these resin compositions on a substrate, for example, a roller, a roll coater, a spin coater, a curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating, etc. can do.

Then, after setting if necessary,
By drying, a resist film can be obtained.
Further, the resist coating may be provided with a cover coat layer on the surface of the material before being exposed to light and cured. The cover coat layer is formed in order to block oxygen in the air, prevent radicals generated by exposure from being deactivated by oxygen, and smoothly cure the photosensitive material by exposure. The negative photosensitive resin aqueous resist composition can be obtained by dissolving or dispersing the negative photosensitive resin composition in water.

The water-soluble or water-dispersible aqueous photosensitive resin composition is prepared by neutralizing an anionic group (for example, a carboxyl group) in the photopolymerizable composition with an alkali (neutralizing agent) or by photopolymerizing. This is performed by neutralizing a cationic group (for example, an amino group) in the composition with an acid (neutralizing agent). Also,
The water-developable composition can be produced by dispersing or dissolving in water as it is. The negative photosensitive resin film obtained by coating an organic solvent-based or aqueous negative photosensitive resin composition on a substrate is directly exposed to active energy rays so as to obtain a desired resist film (image). The unexposed portion of the film is removed by developing with a developer. As the above-mentioned development processing, an alkaline development processing is performed when the negative photosensitive resin composition is anionic, and an acidic development processing is performed when the negative photosensitive resin composition is cationic. These development processes can be performed by a conventionally known method.
The negative photosensitive dry film is obtained, for example, by coating the above negative photosensitive resin composition on a release paper such as polyethylene terephthalate and drying to volatilize water and an organic solvent. Next, the positive photosensitive resin composition will be described below.

As the positive photosensitive resin composition, for example, those containing a photoacid generator, a resin and, if necessary, a photosensitizer can be used. The resin changes its properties such as polarity and molecular weight by decomposing the resin and the photosensitizer by light, or by decomposing the resin and the photosensitizer by the acid generated by the light, so that an alkaline or acidic aqueous developer can be obtained. In this case, it shows solubility. These resins may further contain other resins for adjusting the solubility of the developer, if necessary. As the positive photosensitive resin composition, for example, a composition mainly composed of a resin in which quinonediazidesulfonic acid is bonded to a base resin such as an acrylic resin having an ion-forming group through a sulfonic acid ester bond (Japanese Patent Application Laid-Open No. No. 61-206293, JP-A-7-133449, etc., that is, a naphthoquinonediazide photosensitive composition utilizing a reaction in which a quinonediazide group is photolyzed by irradiation light to form indenecarboxylic acid via ketene: A crosslinked film insoluble in an alkaline developer or an acidic developer is formed by heating, and the crosslinked structure is cut by a photoacid generator that generates an acid group by irradiation with light, and the irradiated part is an alkaline developer or an acidic developer. Positive photosensitive composition utilizing a mechanism that becomes soluble in water (JP-A-6-295064, JP-A-6-308733, JP-A-6-308733)
313134, JP-A-6-313135, JP-A-6-313136
And Japanese Patent Application Laid-Open No. Hei 7-65565). The above-mentioned positive photosensitive resin composition is described in the above-mentioned gazette, so that the detailed description is replaced by reference. The photoacid generator is a compound that generates an acid upon exposure to light and decomposes the resin by using the generated acid as a catalyst. Conventionally known photoacid generators can be used. This includes, for example, sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, onium salts such as selenium salts,
Iron-allene complexes, ruthenium-allene complexes, silano-
Le-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfonic acid esters, sulfonic acid imide esters, halogen compounds, and the like can be used. In addition, in addition to the above,
No. 52, Japanese Patent Application No. 9-289218, and a photoacid generator described in Japanese Patent Application No. 9-289218 can also be used. This photoacid generator component may be a mixture with the above-mentioned resin or a resin-bonded resin. The content of the photoacid generator is preferably about 0.1 to 40 parts by weight, particularly about 0.2 to 20 parts by weight, based on 100 parts by weight of the resin. As the organic solvent type of the positive photosensitive resin composition described above, an organic solvent (ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols) , Halogenated hydrocarbons, etc.). In addition, as a method of coating this on a substrate, for example, a roller, a roll coater, a spin coater, a curtain roll coater, spraying, electrostatic coating, dip coating, silk printing, spin coating, and the like can be applied by means such as it can.

Then, after setting as required,
By drying, a resist film can be obtained.
The aqueous positive photosensitive resin composition is obtained by dissolving or dispersing the above positive photosensitive resin composition in water. The aqueous positive photosensitive resin composition is made water-soluble or water-dispersed by neutralizing a carboxyl group or an amino group in the positive photosensitive resin composition with an alkali or an acid (neutralizing agent). The positive photosensitive film obtained by coating an organic solvent-based or aqueous positive photosensitive resin composition on a substrate is subjected to setting or the like as necessary, and is subjected to about 50 to 50
By drying at a temperature in the range of 130 ° C., a positive photosensitive film can be formed. Next, the resist film is exposed directly to active energy rays so that a desired resist film (image) is obtained, and the exposed portion of the film is developed and removed with a developing solution.

As the light source used for exposure, the same light sources as described above can be used. As the above-mentioned development processing, when the positive photosensitive resin composition is anionic, alkali development processing is performed, and when it is cationic, acid development processing is performed. Also,
The above-mentioned resin itself dissolves in water (for example,
Onium base-containing resin) can be subjected to a water development treatment. For the positive photosensitive dry film, for example, the above-described positive photosensitive resin composition is applied to a release paper such as polyethylene terephthalate, dried, and water or an organic solvent is volatilized or cured by heating. can do. The organic solvent-based negative type thermosensitive resin composition which is a thermosensitive resin composition is obtained by dissolving or dispersing a resin composition which is crosslinked by heat rays such as infrared rays in an organic solvent. As the resin composition, conventionally known ones can be used. For example, a hydroxyl group-containing resin / amino resin, a hydroxyl group-containing resin / block isocyanate, a melamine resin, a hydrolyzable group (alkoxysilyl group, hydroxysilyl group) Etc.) containing silicon resin and acrylic resin, epoxy resin / phenolic resin, epoxy resin / (anhydride) carboxylic acid, epoxy resin / polyamine, unsaturated resin / radical polymerization catalyst (peroxide etc.), carboxyl group (and / or) Olefinically unsaturated compounds containing a hydroxyphenyl group / ether bond are exemplified. The aqueous negative-type thermosensitive resin composition contains an acid group or a basic group in the resin that is crosslinked by heat rays such as infrared rays as described above,
A product obtained by neutralizing the product with a neutralizing agent for a base compound or an acidic compound and dissolving or dispersing in water can be used. The negative-type heat-sensitive dry film may be obtained, for example, by coating the above-mentioned negative-type heat-sensitive resin composition on release paper such as polyethylene terephthalate and drying it to evaporate water or an organic solvent.

The coating formed from the above-described heat-sensitive resin composition is directly heated with heat rays so that a desired resist coating (image) is obtained, and the unexposed portion of the coating is coated with an organic solvent, acid,
It is removed by developing with a suitable developing solution such as an alkali. After the formation of the resist pattern film of the energy-sensitive ray coating layer, the exposed non-energy-sensitive ray coating layer is removed by a developing treatment.

The developing solution for the coating layer (A) will be described below. Examples of the alkaline processing liquid include, for example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine,
Monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, ammonia, caustic soda, caustic potash, sodium metasilicate, potash metasilicate, sodium carbonate,
An aqueous liquid such as tetraethylammonium hydroxide is exemplified. Examples of the acidic treatment liquid include formic acid, crotonic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid,
Aqueous liquids such as phosphoric acid are mentioned.

The concentration of the acidic or alkaline substance in these treatment liquids is usually preferably in the range of 0.05 to 10% by weight. As the organic solvent, for example, hexane, heptane,
Hydrocarbons such as octane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as methanol, ethanol, propanol, and butanol; diethyl ether, dipropyl ether, dibutyl ether, ethyl vinyl ether, dioxane, and propylene oxide , Tetrahydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, ether such as diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, ketone such as cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, Ester solvents such as butyl acetate, and other solvents such as pyridine, formamide, N, N-dimethylformamide, and the like. That. The processing conditions of the developing solution are not particularly limited, but usually, the development of the energy-sensitive radiation coating layer is performed at a developing solution temperature of about 10 to 50 ° C., preferably 1 to 50 ° C.
The development can be performed at about 5 to 40 ° C. for about 10 seconds to 20 minutes, and preferably for about 15 seconds to 15 minutes. The active energy rays irradiated to the energy-sensitive ray coating layer (A) include conventionally known visible rays, ultraviolet rays, electron rays (α rays, β rays, γ rays, etc.) and heat rays (infrared rays, far infrared rays, etc.). Included. As a light source used for the irradiation, for example, an ultra-high pressure, a high pressure, a medium pressure, a low pressure mercury lamp, a chemical lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a tungsten lamp and the like can be used without any particular limitation. Argon laser (488 nm), YAG-SHG
Laser (532nm), UV laser (351-36)
4 nm) can also be used. Examples of the heat rays include a semiconductor laser (830 nm) and a YAG laser (1.06 μm).
m), an infrared lamp, a far infrared lamp and the like.

The filter layer (B) used in the present invention
Is a layer formed between the energy-sensitive radiation coating layer (A) and the energy-sensitive conductive film-forming resin layer (C). The energy ray irradiated from the upper surface of the coating layer (A) is The energy beam is adjusted so that absorption and / or reflection do not adversely affect the pattern formation of the underlying resin layer (C) for forming an energy-sensitive conductive film. Further, the filter layer (B) may be a film layer (A) or a film-forming resin layer (C) so as to obtain a desired pattern.
Is a layer provided for facilitating separation and removal by the development process. As described above, the filter layer (B) substantially absorbs and / or reflects the energy beam irradiated from the upper surface of the film layer (A), thereby substantially forming the lower film-forming resin layer (C) by irradiation with the active energy beam. The filter layer (B) itself is provided so as not to be hardened or decomposed, and can be dissolved or dispersed in a treatment liquid such as water, an organic solvent, an alkali or an acid to form a pattern similar to that of the coating layer (A). And a film layer (A) and a filter layer (B), or a film layer (A), a filter layer (B), and a film layer when the resin layer (C) for film formation is developed. The resin layer (C) is peeled off and removed, and any conventionally known material can be used without any particular limitation as long as it satisfies these requirements. As the filter layer (B) for absorbing energy rays, those that absorb the irradiated energy rays, for example, absorbers (visible light absorbers, ultraviolet absorbers, heat ray absorbers, etc.), colorants (color pigments, coloring Dyes), fillers and the like in the filter layer (B) can be used.
The type of the absorbent, the colorant, and the filler to be used can be appropriately selected according to the type of the irradiated energy ray. Examples of the ultraviolet absorber include benzotriazole, benzophenone, anilide oxalate, cyanoacrylate, benzophenone, and benzotriazole. Examples of the coloring agent include white pigments such as titanium oxide, zinc white, lead white, basic lead sulfate, lead sulfate, lithopone, zinc sulfide, and antimony white; carbon black, acetylene black, lamp black, bone black, and graphite. Black pigments such as iron black and aniline black; orange pigments such as naphthol yellow S, Hansa yellow 10G, permanent yellow and permanent orange; brown pigments such as iron oxide and amber; red pigment such as red iron oxide, lead red, permanent red and quinacridone. Red pigments; purple pigments such as cobalt purple, manganese purple, fast violet B, and methyl violet lake; blue pigments such as ultramarine blue, navy blue, cobalt blue, cerulean blue, phthalocyanine blue, and fast sky blue; chrome green, phthalocyanine green And the like green pigments such as. Examples of the filler include barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, and mica powder. The mixing ratio of the absorbing agent, the coloring agent and the filler may be appropriately determined according to the intensity of the irradiated energy beam and the thickness of the filter layer (B). 0.01% to 50% by weight, preferably 0.02% to 30% by weight, and in the case of colorants and fillers 0.5% to 90% by weight, preferably 1% by weight. % To 50
% By weight. As the filter layer (B) that reflects energy rays, for example, a filter layer (B) that contains a reflector (such as a scaly metal pigment) that reflects the irradiated energy rays is used. Can be.
Examples of the reflecting agent include metal powder pigments such as (flaky) aluminum powder, bronze powder, copper powder, tin powder, lead powder, zinc powder, iron phosphide, pearl-like metal-coated mica powder, and mica-like iron oxide. And metallic luster pigments. The proportion of the reflective agent to be used may be appropriately determined according to the intensity of the energy beam to be irradiated and the thickness of the filter layer (B), but usually 0.5 to 90% by weight in the layer.
Preferably, it falls within the range of 1% by weight to 50% by weight. The above-mentioned energy ray absorber and reflector can be used in combination with each other. Examples of the filter layer (B) that can be dissolved or dispersed in water include starches such as potato starch, potato starch, wheat starch, corn starch, mannan such as konjac, seaweeds such as seaweed, agar, and sodium alginate;
Natural polymers such as glue, gelatin, casein, proteins such as collagen; viscose, methylcellulose,
Semi-synthetic resins such as cellulose such as ethyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose, soluble starch and starch such as carboxymethyl starch; polyvinyl alcohol, polyvinyl butyral, polyethylene oxide, water-soluble phenol, water-soluble melamine, sodium polyacrylate, water-soluble And a synthetic resin such as a conductive polyester resin, an acrylic emulsion, a polyester emulsion, and an epoxy resin emulsion as a resin component. As the filter layer (B) that can be dissolved or dispersed in the organic solvent described above,
For example, oil-based phenol, acrylic resin, polyester resin, vinyl chloride resin, vinyl acetate resin, phthalic acid resin, amino resin, epoxy resin, xylene resin, petroleum resin, ketone resin, coumarone resin, urethane resin and other organic solvents Those containing a resin that can be dissolved or dispersed as a component are exemplified. Examples of the filter layer (B) that can be dissolved or dispersed in the above-mentioned alkali treatment liquid include those formed of an anionic resin component having an acidic hydrophilic group such as a carboxyl group or a phosphoric acid group. The layer formed of such a resin is dispersed and dissolved in the anionic resin by neutralizing the anionic resin with the alkaline processing liquid to remove the filter layer. The resin composition for forming the filter layer (B) is formed, for example, from a neutralized anionic resin obtained by neutralizing an anionic resin with a basic compound (amine compound, ammonia, alkali metal compound, etc.). be able to. Examples of the anionic resin include an acid group-containing acrylic resin, an acid group-containing polyester resin, an acid group-containing alkyd resin, an acid group-containing epoxy polyester resin, an acid group-containing urethane resin, an acid group-containing vinyl resin, and an acid group-containing organic. Examples include a silicon-based resin, an acid-containing phenolic resin, an acid-containing fluorine-based resin, and two or more kinds of modified resins thereof. A typical example of the acidic group is a carboxyl group, and the content of the carboxyl group is about 10 to 700 mg KOH /
g, especially in the range of about 20-600 mg KOH / g. When the acid value is less than about 10, there is a disadvantage that the filter layer is inferior in delamination property due to treatment with an alkali developer and a pattern having excellent resolution cannot be formed. It is not preferable because there is a drawback that a pattern having excellent resolution cannot be formed since the layer is delaminated to an undesired portion. Examples of the filter layer (B) that can be dissolved or dispersed in the above-mentioned acid treatment liquid include those formed of a cationic resin component having a hydrophilic group such as a basic group. The layer formed of such a resin is dispersed and dissolved in the treatment liquid by neutralizing the cationic resin with the acid treatment liquid, and the filter layer is removed. As the resin composition for forming the filter layer (B), for example, it is possible to form the resin composition using a neutralized cationic resin obtained by neutralizing a cationic resin with an acidic compound (organic acid compound, inorganic acid compound, etc.). it can. Examples of the cationic resin include a basic group-containing acrylic resin, a basic group-containing polyester resin, a basic group-containing alkyd resin, a basic group-containing epoxy polyester resin, a basic group-containing urethane resin, and a basic group-containing vinyl. Examples include resins, basic group-containing organic silicon-based resins, basic group-containing phenolic resins, basic group-containing fluororesins, alkali silicate resins, and modified resins of two or more of these. As the alkaline group, an amino group may be mentioned as a typical example, and the content of the amino group may be about 20 to 650, particularly about 30 in terms of an amine value of the resin for forming a filter layer.
Those having a range of from 600 to 600 are preferable. When the amine value is less than about 20, there is a disadvantage that the filter layer is inferior in the same manner as described above and a pattern having excellent resolution cannot be formed. It is not preferable because there is a disadvantage that a pattern having excellent resolution cannot be formed because the layer is removed to the extent. Examples of the alkaline processing liquid include, for example, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, Aqueous liquids such as dimethylaminoethanol, diethylaminoethanol, ammonia, caustic soda, caustic potash, sodium metasilicate, potash metasilicate, sodium carbonate, tetraethylammonium hydroxide and the like. Examples of the acidic treatment liquid include formic acid, crotonic acid,
Aqueous liquids such as acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are included.

The concentration of the acidic or alkaline substance in these treatment liquids is usually preferably in the range of 0.05 to 10% by weight. As the organic solvent, for example, hexane, heptane,
Hydrocarbons such as octane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as methanol, ethanol, propanol, and butanol; diethyl ether, dipropyl ether, dibutyl ether, ethyl vinyl ether, dioxane, and propylene oxide , Tetrahydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, ether such as diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, ketone such as cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, Ester solvents such as butyl acetate, and other solvents such as pyridine, formamide, N, N-dimethylformamide, and the like. That. The processing conditions of the developing solution are not particularly limited, but usually, the development of the energy-sensitive radiation coating layer is performed at a developing solution temperature of about 10 to 50 ° C., preferably 1 to 50 ° C.
The development can be performed at about 5 to 40 ° C. for about 10 seconds to 20 minutes, and preferably for about 15 seconds to 15 minutes.

The resin layer (C) for forming an energy-sensitive conductive film used in the present invention comprises a resist pattern coating layer formed of an energy-sensitive ray layer (A) and a filter layer (B), and a resin layer for forming a film. This is a resin layer on which a conductive pattern is finally formed by irradiating energy rays from the surface of (C) and then developing. The film-forming resin layer (C) is cured or decomposed by the irradiated active energy rays to enable development processing. The resin layer (C) has different solubility in a developing solution due to curing or decomposition of the portion irradiated with the active energy ray, whereby a resist pattern film can be formed and finally formed. As long as the formed pattern has conductivity, a conventionally known pattern can be used without any particular limitation.

The resin used for the conductive film forming resin layer (C) may or may not have conductivity. That is, in the resin component constituting the conductive coating layer, the resin having conductivity itself forms the conductive resin layer by itself, so that not only transparent conductive pigments and conductive color pigments but also non-conductive Transparent or colored pigments such as conductive or semiconductor can be used in combination. On the other hand, when the resin itself does not have conductivity, for example, the resin can be made conductive by using a transparent conductive pigment, a conductive coloring pigment, or the like in combination.
In addition, the non-conductive resin can be volatilized by, for example, post-heating, and the remaining component (conductive pigment or the like) can be made conductive.

The conductive film forming resin layer (C) may or may not have the developing resin remaining in the finally formed film. As the material of the resin for development processing, particularly, the glass transition temperature of the resin layer for forming a conductive film is a temperature at the time of development processing (in the case of a liquid development processing liquid, processing liquid temperature or powder such as sand blast was used. In the case of development processing, it is preferable that the temperature is higher than the processing atmosphere temperature), particularly higher by about 5 ° C. or more, and further higher by about 10 ° C. to 200 ° C. When the glass transition temperature is lower than the development processing temperature, there is a disadvantage that a pattern having excellent resolution cannot be obtained by the development processing. The glass transition temperature can be measured by DSC (differential thermal analysis). The conductive film-forming resin layer (C) is a film finally formed and has a volume resistivity of 10 ⁹ Ω · cm or less, particularly 1 Ω · cm.
It is preferably from 10 to 10 ⁸ Ω · cm. As the resin component used in the resin layer (C) for forming a conductive film, the same resin component as the above-mentioned film layer (A) can be used. The layer is
For example, a liquid resist photosensitive resin composition such as an organic solvent-based positive photosensitive resin composition, an organic solvent-based negative photosensitive resin composition, an aqueous positive photosensitive resin composition, and an aqueous negative photosensitive resin composition. A photosensitive dry film such as a positive photosensitive dry film or a negative photosensitive dry film; a liquid heat sensitive resin composition such as an organic solvent-based negative heat sensitive resin composition or an aqueous negative heat sensitive resin composition; It can be formed of a heat-sensitive dry film of a type heat-sensitive dry film.

In the above-mentioned curable conductive film forming resin layer, when the energy ray irradiated from the surface of the energy sensitive ray coating layer is a heat ray, for example, the conductive film forming resin layer may be sensitive to (thermal) energy. A non- (low) heat-sensitive resin film for forming a conductive film that does not cure (may be cured to substantially no problem) with heat rays irradiated compared to the wire layer can be used. Examples of the heat-sensitive type include a combination of a self-curing resin or a resin having a curable functional group and a curing agent. Examples of the self-curing resin include a melamine resin, a silicon resin containing a hydrolyzable group (alkoxysilyl group, hydroxysilyl group, etc.) and a resin curable by a curing agent include an acrylic resin, an epoxy resin / phenol resin, and a hydroxyl group-containing resin. / Polyisocyanate, hydroxyl group-containing resin / amino resin, epoxy resin / (anhydride) carboxylic acid, epoxy resin / polyamine and the like.

After the development process (pattern formation) is completed, the resin layer (C) for forming a conductive film can be subjected to crosslinking or firing (such as a conductive pigment paste) by heating, standing at room temperature, or light. Examples of the type of the resin layer (C) for forming a conductive film include a conductive pattern for a black matrix, a conductive pattern for a color filter, a conductive pattern for various display panels, a plastic substrate and a plastic substrate for build-up. And a conductive pattern. The development processing solution for the resin layer (C) can be performed using the same processing solutions and conditions as those described for the coating layer (A), such as water, organic solvents, alkalis, and acids. In the conductive film-forming resin, for example, when an acidic group is contained in the conductive film-forming resin, an alkaline developer can be used, and a basic group is contained in the conductive film-forming resin. In such a case, an acidic developer can be used. If the conductive film-forming resin is soluble in water, a water developer can be used. In addition, if the conductive film-forming resin is dissolved (or dispersed) in an organic solvent, the organic developer can be used. Solvent developers can be used. As the conductive pigment (material) that can be used, a conventionally known conductive pigment can be used, for example, silver,
Metals such as copper, iron, manganese, nickel, aluminum, cobalt, chromium, lead, zinc, bismuth, and ITO;
One or more of these alloys, their oxides, and those in which these conductive materials are coated or vapor-deposited on the surface of an insulating material, etc., are mentioned. In addition, as long as these pigments have conductivity, those other than metals, for example, a conductive polymer can also be used.

Furthermore, tin dioxide powder doped with antimony (this may be abbreviated as "tin oxide / antimony (dope)") can also be used. This forms an electron donor level by doping a semiconductive substance tin dioxide component with an antimony component,
It has improved conductivity. This includes tin oxide / antimony (dope) alone or a coated product in which another substrate is coated with tin oxide / antimony (dope). Other substrates used for coating the tin oxide / antimony (dope) include, for example, titanium oxide, potassium titanate, borane aluminum, barium sulfate, mica, silica and the like. The resin layer for forming a conductive film may contain other colorants (eg, pigments and dyes), fillers, additives, and the like as necessary. As a method of forming the conductive film forming resin layer,
It can be formed according to the purpose without any particular limitation. Typical examples thereof include, for example, dissolving or dispersing the above-mentioned resin for forming a conductive film in a suitable organic solvent, a solvent such as water to produce a resin liquid for forming a conductive film, and then coating and printing on a substrate. Is performed, then the method of volatilizing the solvent, the method of thermoforming the above-mentioned conductive film forming resin pellets into a required shape, applying the conductive film forming resin powder to the required places, heating and Examples of the method include melting. The resin layer for forming a conductive film may be laminated on the surface of another substrate (such as glass or a circuit substrate), or may be the substrate itself (such as a circuit substrate). I do not care. The thickness of the conductive film-forming resin layer varies depending on the application to be used.
μm, or about 100 μm to 10 mm, especially about 200 μm to 5
The range of mm is preferred. The liquid development can be performed using the same developer as described in the coating layer (A), such as water, an organic solvent, an acid, or an alkali. Is preferably sprayed or immersed at about 15 to 50 ° C. for a development time of about 15 seconds to 60 minutes, preferably for about 1 minute to 20 minutes.
In the method of the present invention, after forming a pattern by developing the conductive film forming resin layer, the remaining energy-sensitive ray layer and filter layer are decomposed by active energy ray irradiation if necessary, and dissolved in a developer. Then, the energy-sensitive coating layer and the filter layer can be removed as required. The resin layer for forming a conductive film can be cross-linked by heating or irradiation with active energy rays as needed. The pattern forming method of the present invention comprises the steps of: (1) absorbing and / or reflecting the energy rays irradiated in the following step (2) on the surface of the resin layer (C) for forming an energy-sensitive conductive film; After the filter layer (B) and the energy-sensitive coating layer (A) prepared so as not to adversely affect the pattern formation of the resin layer (C) are laminated to form a three-layer laminated coating, (2) a desired pattern (3) Unnecessary by irradiating or directly irradiating an active energy ray from the surface of the energy-sensitive ray coating layer (A) through a mask so as to obtain (3) the energy-sensitive ray coating layer (A). Part of the energy-sensitive radiation coating layer (A)
Is removed to form a resist pattern film. (4) Next, the filter layer (B) newly appearing in the step (3) is treated with the filter layer treating solution to form a resist pattern film, which is the same as that formed in the step (3). After the formation of the resist pattern coating layer of (5), energy rays are irradiated from the surfaces of the coating layer (A) and the newly formed resin layer (C) for coating formation,
(6) A pattern forming method, further comprising a step of removing the coating layer (A), the filter layer (B), and the resin layer (C) for forming a coating by a development treatment so that a desired pattern is obtained. Can be formed by The pattern forming method of the present invention will be described below with reference to the drawings. FIG. 1 shows, in order from the upper layer, a negative-type energy-sensitive radiation coating layer (A1), a filter layer (B), and a resin layer (C) for forming a negative-type energy-sensitive conductive film.
FIG. 3 is a schematic cross-sectional view showing a process of a method for forming a pattern using a three-layer laminated film obtained by laminating 1). a
Indicates a laminated film of A1 / B / C1. “b” indicates an irradiated portion and an unirradiated portion of the A1 film obtained by irradiating the active energy ray by direct drawing or irradiating through a pattern mask so as to obtain a target pattern. c shows a layered coating in which the filter layer is partially exposed by removing the unirradiated portion by developing the A1 coating. "d" indicates a laminated film from which the exposed filter layer B was treated with the treatment liquid to remove the filter layer B. e is irradiation of an unirradiated portion where the active energy ray is not substantially irradiated and a portion where the active energy ray is not irradiated and a portion where there is no filter layer b, by irradiating the entire surface with the active energy ray. 3 shows a laminated film of a film portion. f indicates a pattern formed by the resin layer (C1) by removing the three-layered laminated film in the unirradiated portion by performing the developing treatment. In the pattern forming method, a difference in solubility occurs between an exposed portion and an unexposed portion of the resin layer (C1) for forming an energy-sensitive conductive film in the developing step of f, and a sharp pattern can be formed. FIG. 2 shows a three-layer structure in which a negative-type energy-sensitive radiation-sensitive coating layer (A1), a filter layer (B), and a resin layer for forming a positive-type energy-sensitive radiation-sensitive conductive film (C2) are sequentially laminated from the upper surface on the substrate surface. FIG. 4 is a schematic cross-sectional view of a film showing a process chart of a method of forming a pattern using a laminated film. a is A1
3 shows a laminated film of / B / C2. “b” indicates an irradiated portion and an unirradiated portion of the A1 film obtained by irradiating the active energy ray by direct drawing or irradiating through a pattern mask so as to obtain a target pattern. c shows a layered coating in which the filter layer is partially exposed by removing the unirradiated portion by developing the A1 coating. "d" indicates a laminated film from which the exposed filter layer B was treated with the treatment liquid to remove the filter layer B. e, by irradiating the entire surface with an active energy ray, the active energy ray
2 shows a laminated film of a non-irradiated portion where the active energy ray is not substantially irradiated and absorbed by or reflected by the laser beam and an irradiated portion where no filter layer b is provided. f is developed to remove the C2 film in the irradiated area, and at the same time, removes the laminated film of the filter layer B and the A1 film layer in the development, and forms a pattern by the resin layer (C2) remaining behind. In the pattern forming method, the resin layer for forming the energy-sensitive conductive film (C
A solubility difference occurs between the exposed part and the unexposed part in 1), and a sharp pattern can be formed. FIG. 3 shows a three-layer structure in which a positive-type energy-sensitive radiation-sensitive coating layer (A2), a filter layer (B), and a resin layer for forming a negative-type energy-sensitive radiation-sensitive conductive film (C1) are sequentially laminated on the substrate surface from the upper layer. FIG. 4 is a schematic cross-sectional view of a film showing a process chart of a method of forming a pattern using a laminated film. a shows a laminated film of A2 / B / C1.
“b” indicates an irradiated portion and an unirradiated portion of the A2 film obtained by irradiating the active energy ray by direct drawing or irradiating through a pattern mask so as to obtain a target pattern. “c” indicates a laminated film in which the filter layer is partially exposed by developing the A2 film to remove the film in the irradiated area. "d" indicates a laminated film from which the exposed filter layer B was treated with the treatment liquid to remove the filter layer B. e is irradiation of an unirradiated portion where the active energy ray is not substantially irradiated and a portion where the active energy ray is not irradiated and a portion where there is no filter layer b, by irradiating the entire surface with the active energy ray. 3 shows a laminated film of a film portion. f indicates a pattern formed by the resin layer (C1) by removing the three-layered laminated film in the unirradiated portion by performing the developing treatment.
In the pattern forming method, a difference in solubility occurs between an exposed portion and an unexposed portion of the resin layer (C1) for forming an energy-sensitive conductive film in the developing step of f, and a sharp pattern can be formed. FIG. 4 shows a three-layer structure in which a positive energy ray-sensitive coating layer (A2), a filter layer (B), and a positive energy ray-sensitive conductive film forming resin layer (C2) are sequentially laminated on the surface of the base material from the upper layer. FIG. 4 is a schematic cross-sectional view of a film showing a process chart of a method of forming a pattern using a laminated film. a shows a laminated film of A2 / B / C2. “b” indicates an irradiated portion and an unirradiated portion of the A2 film obtained by irradiating the active energy ray by direct drawing or irradiating through a pattern mask so as to obtain a target pattern. “c” indicates a laminated film in which the filter layer is partially exposed by developing the A2 film to remove the film in the irradiated area.
"d" indicates a laminated film from which the exposed filter layer B was treated with the treatment liquid to remove the filter layer B. e is irradiation of an unirradiated portion where the active energy ray is not substantially irradiated and a portion where the active energy ray is not irradiated and a portion where there is no filter layer b, by irradiating the entire surface with the active energy ray. 3 shows a laminated film of a film portion. f
Indicates a pattern formed by the resin layer (C2) by removing the three-layer laminated film in the unirradiated portion by performing a developing treatment. In the pattern forming method, a difference in solubility occurs between an exposed portion and an unexposed portion of the resin layer (C1) for forming an energy-sensitive conductive film in the developing step of f, and a sharp pattern can be formed. Further, in the present invention, after the steps (1) to (6) are completed, a method for peeling off the energy-sensitive ray coating layer can be performed by a conventionally known method. As the method, for example, when the energy-sensitive radiation coating layer has an acid group, it is dissolved in alkaline water, when it has a basic group, it is dissolved in acid water, and the layer is dissolved in an organic solvent. In the case of a resist film in which a cross-linked film is formed by heating with an organic solvent, the acid group generated by decomposing the cross-linked film by exposure is exposed to alkaline water (a weak alkali such as sodium carbonate is also possible). It can be removed by summing. In the method of the present invention, at least one of the energy-sensitive radiation coating layer (A), the filter layer (B), and the conductive coating-forming resin layer (C) can be formed by a dry film. Examples of the dry film include a composition in which a composition for forming the energy-sensitive radiation coating layer (A) is coated on a support film layer (release paper), dried, and the coating layer (A) is laminated on the support film layer. A composition for forming a filter layer (B) on a support film layer (release paper) is coated and dried to laminate the filter layer (B) on the support film layer. The conductive film is applied to the support film layer (release paper). The composition for forming the resin layer (C) for forming a functional film is coated and dried to laminate the resin layer (C) on the support film layer. A composition in which the composition for forming A) and the composition for forming the filter layer (B) are coated and dried to form a laminate of the coating layer (A) and the filter layer (B) on the support film layer; (Release paper) with energy The composition for forming the wire layer (A), the composition for forming the filter layer (B) and the resin layer (C) for forming the conductive film are coated and dried to form a coating layer (A) on the support film layer. , A filter layer (B) and a resin layer (C) for forming a conductive film, a composition for forming an energy-sensitive film layer (A) on a support film layer (release paper), a filter layer (B) ) And a composition for forming the insulating film-forming resin layer (C) are coated and dried to form a film layer (A), a filter layer (B) and a conductive film-forming resin layer (C) on the support film layer. A composition for forming a filter layer (B) and a resin layer (C) for forming a conductive film on a support film layer (release paper), followed by drying to form a filter layer on the support film layer. B)
And a resin film (C) for forming a conductive film. These dry films can be appropriately used depending on the layer to be formed. This dry film can be laminated, for example, by heating a substrate. After lamination, the support film layer is peeled off and removed. The support film layer is made of a conventionally known material, for example, a paper or sheet (polyethylene terephthalate, polyvinyl chloride, Polyethylene, nylon, polyester, fluororesin, silicone resin, etc.) or a sheet which exhibits releasability itself. The thickness of the sheet is about 10 to 2
00 microns, preferably in the range of about 20-100 microns. The method of the present invention can be applied without any particular limitation such as the use as long as it includes the above-mentioned steps.

As the use, for example, according to the industrial field,
Electrical components, lighting, electrical elements, semiconductors,
Electricity such as printing, printed circuit, electronic communication, and power; Measurements, optics, display, sound, control, vending, signal, information recording, and other physical properties; inorganic chemistry Chemistry, metallurgy and textiles such as chemistry, organic chemistry, polymer chemistry, metallurgy, and fiber; separation and mixing, metalworking, plastic working, printing, containers, packaging, etc. And household goods such as agricultural and marine products-related, food-related, fermentation-related, household goods-related, and health / entertainment-related; and mechanical engineering. The method of the present invention comprises:
As long as it includes the steps described above, it can be applied without any particular limitation such as the application. Further, the method of the present invention can be used in combination with an insulating film or an insulating pattern film as required. Representative examples to which the method of the present invention is applied will be briefly described below. The present invention is not limited to the following examples. Method for forming transparent electrode for display panel: forming a transparent conductive film layer (resin layer for forming a conductive film used in the present invention) on the entire surface of a glass substrate, and then applying a filter to the surface of the obtained transparent conductive film layer The active energy ray is irradiated from the surface of the energy-sensitive radiation coating layer directly or through a pattern mask so that the transparent conductive film has a desired pattern. Next, the energy-sensitive ray coating layer is developed, then the exposed filter layer is treated, and after irradiating active energy rays from the surface of these layers, the conductive layer forming resin layer is developed, and A transparent electrode pattern can be formed by peeling off the wire coating layer and the filter layer. The glass transition temperature of the resin forming the transparent conductive film layer is preferably higher than the processing temperature when developing the conductive film layer. The transparent conductive coating layer after the development treatment is, for example, at about 300 ° C. to 800 ° C. for about 20 to
By baking for 60 minutes, a conductive film can be formed. By the baking, the resin component for forming a conductive film is volatilized, and a transparent conductive film can be formed by fusing or melting the remaining transparent conductive pigment component. Further, the peeling of the energy-sensitive radiation coating layer and the filter layer can be removed by the above-mentioned firing. Examples of the transparent conductive pigment include ITO and tin dioxide.

Method for forming colored electrode for display panel: A colored conductive film layer (resin layer for forming a conductive film used in the present invention) is formed on the entire surface of a glass substrate. A filter layer and an energy-sensitive ray coating layer are laminated on the surface, and then an active energy ray is irradiated directly or through a pattern mask from the surface of the energy-sensitive ray coating layer so that a desired pattern of the colored conductive film is obtained. Next, the energy-sensitive ray coating layer is developed,
Next, the exposed filter layers are treated, and the surface of these layers is irradiated with active energy rays. Then, the colored conductive film forming resin layer is developed, and the energy-sensitive ray coating layers and the filter layers are further removed. Thus, a colored electrode pattern can be formed. Further, in the developing treatment, the energy-sensitive radiation film layer and the conductive film forming resin layer can be simultaneously developed. The glass transition temperature of the resin forming the colored conductive coating layer is preferably higher than the processing temperature when developing the conductive coating layer. The colored conductive coating layer after the above-mentioned development processing is, for example, about 300 ° C.
By firing at about 800 ° C. for about 20 to 60 minutes, a colored conductive film can be formed. By the baking, the resin component for forming the conductive film is volatilized, and the colored conductive film component can be formed by fusing or melting the remaining colored conductive pigment component. Further, the peeling of the energy-sensitive radiation coating layer and the filter layer can also be removed by the above-described firing. Silver, copper, nickel and the like are generally used as the colored conductive pigment. If necessary, a coloring pigment such as carbon black may be used in combination. By combining the method of the present invention described above, for example, a black conductive coating layer on the whole or a part of the surface of the transparent electrode pattern layer, a pattern of a bus electrode or an address electrode of a plasma display in which a silver conductive coating layer is laminated. Can be formed.

[0029]

EXAMPLES The present invention will be described more specifically with reference to examples. Parts and% are based on weight. Production Example of Aqueous Negative-Type Photosensitive Anion Composition 1 (a1) As a photocurable resin (polymer binder), an acrylic resin (resin acid value: 155 mg KOH / g, methyl methacrylate / butyl acrylate / acrylic acid = 40/40 /
Photocurable resin (resin solid content 55%, propylene glycol monomethyl ether organic solvent, resin acid value 5) obtained by reacting 24 parts of glycidyl methacrylate with 20 weight ratio.
100 parts (solid content) of 0 mg KOH / g, number average molecular weight of about 20,000, 1 part of a photopolymerizable initiator (CGI-784, trade name, manufactured by Ciba Geigy, titanocene compound), and a photosensitizer (LS-148, 1 part of coumarin dye compound (trade name, manufactured by Mitsui Toatsu Co., Ltd.) was blended to prepare a photosensitive solution. 7 parts of triethylamine was mixed and stirred with 100 parts (solid content) of the obtained photosensitive solution, and then dispersed in deionized water to obtain a water-dispersed resin solution (solid content: 15%).

Aqueous negative photosensitive cationic composition 2 (a
Production example of 2) Methyl acrylate / styrene / butyl acrylate /
Photocurable resin obtained by adding 15 parts of acrylic acid to an acrylic copolymer of glycidyl methacrylate / dimethylaminoethyl methacrylate = 20/10/22/30/18 (amine value: about 56, degree of unsaturation: 1.83) Mol / Kg) 100 parts, photosensitizer 0.5 used in composition 1
Parts, 55 parts of trimethylolpropane triacrylate,
A photosensitive solution 100 (solid content) obtained by mixing 20 parts of the same titanocene compound as used in the composition 1 was mixed with 3 parts of acetic acid, and then dispersed in deionized water to obtain a water-dispersed resin solution (solid content 15%). %). Production Example of Aqueous Positive Photosensitive Anion Composition 3 (a3) 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 28 parts of n-butyl acrylate, acrylic acid 1
1 part and 3 parts of azobisisobutyronitrile are mixed with 1 part
The reaction product obtained by reacting at 00 ° C. for 2 hours is 1500 c
The resulting mixture was poured into a toluene solvent (c) to precipitate and separate the reaction product. The precipitate was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5200 and a hydroxyphenyl group content of 4.6 mol / Kg. Then, 100 parts of this product were mixed with 60 parts of a divinyl ether compound (condensate of 1 mol of a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether) and NAI-105 (photoacid generator, manufactured by Midori Kagaku Co., Ltd., trade name).
10 parts and NKX-1595 as photosensitizing dye (photosensitizing dye, Coumarin dye, trade name, manufactured by Nippon Kogaku Dyestuffs Co., Ltd.)
After mixing and stirring 7 parts of triethylamine in 100 parts (solid content) of 1.5 parts of the mixture, the mixture was dispersed in deionized water to obtain a water-dispersed resin solution (solid content: 15%). Production Example of Organic Solvent-Based Negative-Type Photosensitive Composition 4 (a4) The photosensitive solution of the aqueous negative-type photosensitive composition 1 (composition before mixing amine and water) was dissolved in diethylene glycol dimethyl ether solvent to form an organic solvent. Resin solution (solid content 3
0%).

Organic solvent-based negative photosensitive composition 5 (a5)
A photosensitive solution of the aqueous negative photosensitive composition 2 (composition before mixing acid and water) is dissolved in diethylene glycol dimethyl ether solvent to prepare an organic solvent resin solution (solid content 30).
%).

Organic solvent-based positive photosensitive composition 6 (a6)
Production Example of Photosensitive solution of aqueous positive-type photosensitive anion composition 3 (composition before mixing amine and water) was dissolved in diethylene glycol dimethyl ether solvent to obtain an organic solvent resin solution (solid content: 30%). Production Example of Negative-Type Dry Film 1 (a7) An organic solvent-based negative-type photosensitive composition 4 was roller-coated on a polyethylene terephthalate film so that the dry film thickness became 20 μm, and the organic solvent was volatilized. Production Example of Positive Dry Film 2 (a8) An organic solvent-based positive photosensitive composition 6 was roller-coated on a polyethylene terephthalate film so as to have a dry film thickness of 20 μm, and after setting, heated at 90 ° C. for 30 minutes. Manufactured. Production Example of Aqueous Negative-Type Photosensitive Anion-Conductive Film-Forming Resin Composition 1 (c1) Solid Content of Aqueous Negative-Type Photosensitive Anion Composition 1
After mixing 660 parts of silver powder per part, the pigment was dispersed with a pebble mill to obtain a silver paste. This silver paste 32
0 parts were mixed with 780 parts of 3-methoxybutyl acetate. Production Example of Aqueous Negative-Type Photosensitive Cationic Conductive Film-Forming Resin Composition 2 (c2) Solid Content of Aqueous Negative-Type Photosensitive Anion Composition 2
After mixing 660 parts of silver powder per part, the pigment was dispersed with a pebble mill to obtain a silver paste. This silver paste 32
0 parts were mixed with 780 parts of 3-methoxybutyl acetate. Production Example of Aqueous Positive Photosensitive Anion-Conductive Film-Forming Resin Composition 3 (c3) Solid Content of Aqueous Positive Photosensitive Anion Composition 3
After mixing 660 parts of silver powder per part, the pigment was dispersed with a pebble mill to obtain a silver paste. This silver paste 32
0 parts were mixed with 780 parts of 3-methoxybutyl acetate. Production Example of Negative Conductive Film-Forming Resin Composition 4 (c4) Cresol novolak epoxy resin (epoxy equivalent 2
17, an average of 7 phenolic nucleus residues and epoxy group-containing in one molecule) and a reaction product obtained by reacting 1.0 equivalent of acrylic acid with 0.67 equivalent of tetrahydrophthalic anhydride. The reaction was carried out by a conventional method using phenoxyethyl acrylate as a solvent. This was a viscous liquid containing 35 parts of phenoxyethyl acrylate, and the mixture had an acid value of 63.4 mgKOH / g. Phenoxyethyl acrylate 40 obtained above
Part, 2-hydroxyethyl acrylate 15 parts, benzyl diethyl ketal 2.5 parts, 1-benzyl-2-
After mixing 660 parts of silver powder with 100 parts of the solid content of 1.0 part of methylimidazole, the pigment was dispersed with a pebble mill to obtain a silver paste. This silver paste 320
To this part, 780 parts of 3-methoxybutyl acetate were blended. Production Example of Negative Conductive Film-Forming Resin Composition 5 (c5) For 100 parts of the aqueous negative photosensitive anion composition 1, 660 parts of silver powder, glass frit (PbO 60%, B ₂
After mixing 500 parts of 20% O ₃ , 15% SiO ₂ , and 5% Al ₂ O _{3 having} an average particle diameter of 1.6 μm, the pigment was dispersed with a pebble mill to obtain a silver paste. Composition 5 was obtained by mixing 780 parts of 3-methoxybutyl acetate with 320 parts of this silver paste.

Production Example of Water-Soluble Composition 1 (b1) (for Filter Layer Formation) A black paste composition of 100 parts by weight of polyvinyl alcohol and 20 parts by weight of carbon black pigment was dissolved and dispersed in water to obtain a water-soluble composition having a solid content of 40%. Composition.

Example 1 The composition (c1) was applied to the entire surface of a transparent glass plate by a spin coater, and preliminarily dried at 80 ° C. for 10 minutes to obtain a composition (c1) having a film thickness of about 5 μm for a conductive material. A coating was formed.

Next, the water-soluble composition 1 (b1) and the aqueous negative photosensitive anionic composition 1
(A1) is coated with a roller so that the dry film thickness becomes 6 μm, and dried at 80 ° C. for 10 minutes to form a water-soluble resin composition coating layer (filter layer) on the conductive material coating, a negative photosensitive anion. A coating layer was formed.

Next, an argon laser (oscillation line 4) is used so that the conductive material film has a desired electrode pattern after development.
88 nm) 5 mJ / cm ² at line / space = 50 /
Irradiation was performed by irradiating directly from the surface of the negative photosensitive anion film so as to have a thickness of 100 μm. Then, 25% of an alkali developer a (aqueous sodium carbonate solution 0.25% by weight, the same applies hereinafter).
By immersing at 60 ° C. for 60 seconds, an anionic film of the composition (a1) and a film of the water-soluble composition 1 (b1) other than the exposed portions were simultaneously subjected to the first development treatment.

Next, using an ultra-high pressure mercury lamp, 5
Irradiation with ultraviolet light of 00 mJ / cm ² , followed by an alkali developing solution b (3% by weight of aqueous sodium hydroxide solution, the same applies hereinafter)
To perform a second development treatment to form a pattern. As a result, the line survivability was good and the space developability was good. The volume resistivity of the formed conductive material film is 1
It was good at less than 0 ³ Ω · cm. Example 2 In Example 1, the composition (a) was used instead of the composition (a1).
2) and the first development treatment is performed with an acid developer a (acetic acid aqueous solution 1).
% By weight, the same applies hereinafter).
% By weight, the same applies hereinafter), and a pattern was formed in the same manner as in Example 1. As a result, the line survivability was good and the space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 3 The composition (c1) was applied to the entire surface of a transparent glass plate by a spin coater and dried at 80 ° C. for 10 minutes to form a coating of the composition (c1) for a conductive material having a film thickness of about 5 μm. .

Next, the water-soluble composition 1 (b1) and the aqueous positive photosensitive anionic composition 1
(A3) is coated with a roller so that the dry film thickness becomes 6 μm, and heated at 120 ° C. for 8 minutes to form a water-soluble resin composition coating layer (filter layer) on the conductive material coating, a positive photosensitive anion. A coating layer was formed.

Next, an argon laser (oscillation line 4) is used so that the conductive material film has a desired electrode pattern after development.
88 nm) 5 mJ / cm ² at line / space = 50 /
Irradiation was performed by direct irradiation from the surface of the positive-type photosensitive anion film so that the thickness became 100 μm. Then, add 2
By dipping at 5 ° C. for 60 seconds, the first development treatment was simultaneously performed on the anionic film of the composition (a3) and the water-soluble composition 1 (b1) film on the exposed portion.

Then, using an ultra-high pressure mercury lamp, 5
The pattern was formed by irradiating with ultraviolet rays of 00 mJ / cm ² , heating at 120 ° C. for 8 minutes, and subsequently performing a second development process with an alkaline developer a. As a result, the line survivability was good and the space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 4 In Example 1, the composition (a) was used in place of the composition (a1).
A pattern was formed in the same manner as in Example 1 except that 4) was used. As a result, the line survivability was good and the space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 5 In Example 2, the composition (a) was used instead of the composition (a2).
A pattern was formed in the same manner as in Example 2 except that 5) was used. As a result, the line survivability was good and the space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 6 In Example 3, the composition (a) was used instead of the composition (a3).
A pattern was formed in the same manner as in Example 3, except that 6) was used. As a result, the line survivability was good and the space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 7 The composition (c1) was applied to the entire surface of a transparent glass plate using a spin coater and dried at 80 ° C. for 10 minutes to form a coating of a conductive film of the composition (c1) having a thickness of about 5 μm. .

Next, the water-soluble composition 1 (b1) was applied to the obtained coating for conductive material with a roller so as to have a dry film thickness of 6 μm, and heated at 80 ° C. for 10 minutes. A water-soluble resin composition coating layer (filter layer) was formed.

Next, the negative type dry film 1 (a7) is laminated on the obtained filter layer surface so that the photosensitive surface thereof overlaps, and then the polyethylene terephthalate release paper is peeled off to form a negative type photosensitive dry film on the filter layer. did.

Next, an argon laser (oscillation line 4) is used so that the conductive material film has a desired electrode pattern after development.
88 nm) 5 mJ / cm ² at line / space = 50 /
Irradiation was performed by irradiating directly from the surface of the negative photosensitive dry film so as to have a thickness of 100 μm.

Next, the alkaline developer a was added at 25 ° C. for 6 hours.
By immersing for 0 second, the unexposed portion of the anionic film (a7) and the water-soluble resin composition 1 (b1) film were simultaneously developed.

Then, using an ultra-high pressure mercury lamp, 5
An ultraviolet ray of 00 mJ / cm ² was irradiated. Next, the film was immersed in the above-mentioned alkaline developer b at 25 ° C. for 60 seconds and developed to form a pattern. As a result, the line survivability is good,
The space developability was good. Further, the volume resistivity of the formed conductive film was less than 10 ³ Ω · cm, which was good. Example 8 The composition (c1) was applied to the entire surface of a transparent glass plate using a spin coater, and dried at 80 ° C. for 10 minutes to form a coating of the composition (c1) for a conductive material having a film thickness of about 5 μm. .

Next, the obtained water-soluble composition 1 (b1) was roller-coated on the obtained conductive material coating so as to have a dry film thickness of 6 μm, and heated at 80 ° C. for 10 minutes to form a coating on the conductive material coating. A water-soluble resin composition coating layer (filter layer) was formed.

Next, the obtained filter layer surface was laminated so that the photosensitive surface of the positive type dry film 1 (a8) overlapped with the filter layer, and heat-treated at 120 ° C. for 8 minutes. A positive photosensitive dry film was formed.

Next, an argon laser (oscillation line 4) is used so that the conductive material film has a desired electrode pattern after development.
88 nm) 5 mJ / cm ² at line / space = 50 /
Irradiation was performed by direct irradiation from the surface of the positive photosensitive dry film so as to have a thickness of 100 μm.

Next, the alkaline developer a was added at 25 ° C. for 6 hours.
By immersing for 0 second, the anionic film (a8) and the water-soluble resin composition 1 (b1) film in the exposed area were simultaneously subjected to development processing.

Then, using an ultra-high pressure mercury lamp, 5
An ultraviolet ray of 00 mJ / cm ² was irradiated. Then, it was immersed in the above-mentioned alkaline developer a at 25 ° C. for 60 seconds to carry out a developing treatment to form a pattern. As a result, the line survivability is good,
The space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 9 In Example 1, the composition (c) was used instead of the composition (c1).
In 2), a pattern was formed in the same manner as in Example 1 except that the acid developing solution b was used as the second developing treatment. As a result, the line survivability was good and the space developability was good. The volume resistivity of the formed conductive material film is 1
It was good at less than 0 ³ Ω · cm.

Example 10 The composition (c3) was applied to the entire surface of a transparent glass plate by a spin coater and heated at 120 ° C. for 8 minutes to form a coating of the composition (c3) having a film thickness of about 5 μm for a conductive material. Was formed.

Next, the water-soluble composition 1 (b1) and the aqueous negative photosensitive anionic composition 1
(A1) is coated with a roller so that the dry film thickness becomes 6 μm, and dried at 80 ° C. for 10 minutes to form a water-soluble resin composition coating layer (filter layer) on the conductive material coating, a negative photosensitive anion. A coating layer was formed.

Next, an argon laser (oscillation line 4
88 nm) 5 mj / cm ² at line / space = 50 /
Irradiation was performed by irradiating directly from the surface of the negative photosensitive anion film so as to have a thickness of 100 μm. Then, add 2
By dipping at 5 ° C. for 60 seconds, the first development treatment was simultaneously performed on the anionic film of the composition (a1) and the water-soluble composition 1 (b1) film other than the exposed portions.

Then, using an ultra-high pressure mercury lamp, 5
The pattern was formed by irradiating with an ultraviolet ray of 00 mJ / cm ² and subsequently performing a second developing treatment with an alkali developing solution b. As a result, the line survivability was good and the space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 11 In Example 9, the composition (c) was used instead of the composition (c2).
A pattern was formed in the same manner as in Example 11 except that 4) was used. As a result, the line survivability was good and the space developability was good. Further, the volume resistivity of the formed conductive material film was less than 10 ³ Ω · cm, which was good. Example 12 In Example 9, the composition (c) was used instead of the composition (c2).
A pattern was formed in the same manner as in Example 11 except that 5) was used. Next, the substrate was left at 450 ° C. for 30 minutes, heated and baked at 575 ° C. for 30 minutes to form a substrate. As a result, the line survivability was good and the space developability was good. The volume resistivity of the formed conductive material film is 1
It was good at less than 0 ³ Ω · cm. Comparative Example 1 A pattern was formed in the same manner as in Example 1 except that the composition (b1) was not used. Composition (a
The coating of 1) and the coating of composition (b1) could not be separated.

[0055]

According to the present invention, the photosensitive resin composition is conventionally used as the conductive layer because of having the above-mentioned structure. By dividing into products, functions can be designed separately, and a wide range of applications has been made possible.

[Brief description of the drawings]

FIG. 1 is a diagram showing a pattern using a three-layer laminated film formed by laminating a negative-type energy-sensitive radiation-sensitive coating layer (A1), a filter layer (B), and a resin layer for forming a negative-type energy-sensitive radiation-conductive film (C1). FIG. 4 is a schematic cross-sectional view showing a process chart of a method for forming a film.

FIG. 2 shows a pattern formed by using a three-layer laminated film formed by laminating a negative-type energy-sensitive radiation-sensitive coating layer (A1), a filter layer (B), and a resin layer (C2) for forming a positive-type energy-sensitive radiation-conductive film. FIG. 3 is a schematic cross-sectional view showing a process chart of a method of forming a film.

FIG. 3 is a diagram showing a pattern using a three-layer laminated film formed by laminating a positive-type energy-sensitive radiation-sensitive coating film layer (A2), a filter layer (B), and a resin layer for forming a negative-type energy-sensitive radiation-sensitive conductive film (C1). FIG. 3 is a schematic cross-sectional view showing a process chart of a method of forming a film.

FIG. 4 is a diagram showing a pattern using a three-layer laminated film formed by laminating a positive-type energy-sensitive radiation-sensitive coating layer (A2), a filter layer (B), and a resin layer (C2) for forming a positive-type energy-sensitive radiation-conductive film. FIG. 3 is a schematic cross-sectional view showing a process chart of a method of forming a film.

[Explanation of symbols]

 A1 Negative-type energy-sensitive radiation-sensitive coating layer A2 Positive-type energy-sensitive radiation-sensitive coating layer B Filter layer C1 Negative-type energy-sensitive radiation-sensitive conductive coating-forming resin layer C2 Positive-type energy-sensitive radiation-sensitive conductive coating-forming resin layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/40 501 G03F 7/40 501 7/42 7/42 H05K 3/02 H05K 3/02 BF term (Reference) 2H025 AA00 AB15 AB16 AC01 AC08 AD01 AD03 CC08 CC09 CC20 DA14 DA34 DA40 EA08 FA06 FA17 FA29 FA48 2H096 AA26 AA27 BA01 BA09 BA20 CA16 EA02 EA04 EA14 GA08 HA01 HA30 JA04 KA07 KA08 KA14 KA15 BC05 BC05 BE05 CC01 CC02 CD01 CE12 CE14 CE19 CF06 CF16 CF17 DD02 DD04 GG02

Claims (19)

[Claims] An energy-sensitive coating layer (A), a filter layer (B) and a resin layer (C) for forming an energy-sensitive conductive film are laminated in this order from the upper layer. The energy rays irradiated from the upper layer surface are absorbed and / or reflected by the filter layer (B) so that the energy rays are not adversely affected on the pattern formation of the lower energy-sensitive conductive film forming resin layer (C). A three-layer laminated film for pattern formation, comprising the prepared three-layer laminated film. 2. The method according to claim 1, wherein a negative-type energy-sensitive radiation coating layer (A1), a filter layer (B) and a resin layer (C1) for forming a negative-type energy-sensitive conductive film are sequentially laminated from the upper layer. The three-layer laminated film according to the above. 3. The method according to claim 1, wherein a negative type energy ray sensitive coating layer (A1), a filter layer (B) and a positive type energy ray sensitive conductive film forming resin layer (C2) are sequentially laminated from the upper layer. The three-layer laminated film according to the above. 4. The method according to claim 1, wherein a positive energy ray-sensitive coating layer (A2), a filter layer (B), and a negative energy ray-sensitive conductive film forming resin layer (C1) are sequentially laminated from the upper layer. The three-layer laminated film according to the above. 5. The method according to claim 1, wherein a positive type energy ray sensitive coating layer (A2), a filter layer (B) and a positive type energy ray sensitive conductive film forming resin layer (C2) are sequentially laminated from the upper layer. The three-layer laminated film according to the above. 6. The three-layer laminated film according to claim 1, wherein the filter layer (B) is a non-energy-sensitive layer. 7. The filter according to claim 1, wherein the filter layer (B) is dissolved or dispersed in a treatment liquid containing at least one compound selected from water, an organic solvent, an acid and an alkali. Three-layer laminated coating. 8. The resin for forming a film by absorbing and / or reflecting the energy rays irradiated in the following step (1) on the surface of the resin layer (C) for forming an energy-sensitive conductive film. Layer (C)
After the filter layer (B) and the energy-sensitive radiation coating layer (A) prepared so as not to adversely affect the pattern formation are laminated to form a three-layer laminated coating, (2) a desired pattern is obtained. Irradiation or direct irradiation of active energy rays from the surface of the energy-sensitive ray coating layer (A) through a mask, and (3) development of the energy-sensitive ray coating layer (A) causes unnecessary portions of the energy-sensitive ray to be developed. Removing the coating layer (A) to form a resist pattern coating;
(4) Next, the filter layer (B) newly appearing in the step (3) is treated with a filter layer treating solution to form a resist pattern coating layer similar to that formed in the step (3). 5) Irradiation of energy rays from the surfaces of the coating layer (A) and the newly formed coating forming resin layer (C); and (6) a coating layer (A) and a filter layer so as to obtain a desired pattern. (B) and a step of removing the resin layer (C) for film formation by a development treatment. 9. A three-layered laminated film is formed from the upper layer in the order of a negative-type energy-sensitive radiation-sensitive coating layer (A1), a filter layer (B), and a negative-type energy-sensitive radiation-sensitive conductive coating forming resin layer (C).
The pattern forming method according to claim 8, wherein 1) is laminated. 10. A three-layer laminated film is formed from a top layer in the order of a negative-type energy-sensitive ray coating layer (A1) and a filter layer (B).
And a resin layer for forming a negative-type energy-sensitive conductive film (C
9. The pattern forming method according to claim 8, wherein 2) are laminated. 11. A three-layered laminated film is formed from a top layer in the order of a positive-type energy-sensitive radiation layer (A2) and a filter layer (B).
And a resin layer for forming a negative-type energy-sensitive conductive film (C
The pattern forming method according to claim 9, wherein 1) is laminated. 12. A three-layer laminated film is composed of a positive type energy-sensitive radiation layer (A2) and a filter layer (B) in this order from the upper layer.
And a resin layer for forming a positive type energy-sensitive conductive film (C
The pattern forming method according to claim 8, wherein 2) is laminated. 13. The conductive film-forming resin layer (C) contains a resin having a glass transition temperature higher than the temperature at which the conductive film-forming resin layer (C) is subjected to a developing process as a developing resin. 8. The method according to claim 8, wherein
3. The pattern forming method according to any one of 2. 14. The resin layer (C) for forming a conductive film is a thermoplastic resin layer.
The pattern forming method according to any one of the above. 15. The conductive film forming resin layer (C) is a curable resin layer, and the curable resin layer is not substantially cured in the step (2), and the conductive film is formed. The resin layer for forming a conductive film (C) is cured after developing the resin layer for forming a conductive layer (C).
The pattern forming method according to any one of the above. 16. The resin layer (C) for forming a conductive film,
The pattern forming method according to any one of claims 8 to 15, wherein the pattern forming method is a curable resin layer that is post-cured by light and heat after the step (6). 17. The conductive film-forming resin layer (C) is a layer containing a conductive powder, a resin and, if necessary, an inorganic powder that is fused by heat, and the conductive film-forming resin layer (C). The pattern forming method according to any one of claims 8 to 16, wherein the resin layer (C) for forming a conductive film is heated after the developing process (C). 18. The method according to claim 1, wherein at least one of the energy-sensitive radiation coating layer (A), the filter layer (B) and the conductive coating-forming resin layer (C) is formed of a liquid or dry film. Item 18. The pattern forming method according to any one of Items 8 to 17. 19. The energy-sensitive radiation-sensitive coating layer (A) after forming a pattern by performing the steps (1) to (6) according to claim 8, or after post-curing after the step (6).
The pattern forming method according to any one of claims 8 to 18, wherein the filter layer (B) is separated from the resin layer (C) for forming a film.