JP2001133983A - Pattern forming laminated film, method for producing same and pattern forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a pattern forming laminated film and to provide a pattern forming method using the film. SOLUTION: A thermic ray sensitive resin film layer (A), a sheet layer (B) transparent to thermic rays, a thermic ray shielding layer (C) capable of forming a pattern with a developing solution and an energy beam sensitive film layer (D) are successively laminated on the surface of a substrate to obtain the objective pattern forming laminated film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

2. Description of the Related Art Hitherto, lithography using an exposure technique has been used for a wiring board, a display panel, an etching and the like as a method of forming a pattern on, for example, a plastic or an inorganic substance.

As a method of forming the above-mentioned pattern,
For example, after forming a photosensitive insulating or conductive coating layer by applying a photosensitive insulating or conductive composition on the substrate surface,
There is known a method of irradiating an electron beam or a heat beam from the surface through a photomask, and then developing the photosensitive insulating or conductive film layer to obtain a desired pattern.

However, the above method has a problem that a sharp pattern cannot be formed due to insufficient photosensitivity of the insulating or conductive coating layer.

[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, by using a film in which a specific photosensitive film is laminated, the above-mentioned problems have been solved. The inventors have found that the present invention can be solved, and have completed the present invention.

That is, the present invention provides: 1. a heat-sensitive resin coating layer (A) on the surface of a substrate, a sheet layer (B) that transmits heat rays, a heat ray shielding layer (C) capable of forming a pattern with a developer, and A layered film for pattern formation characterized by sequentially laminating an energy-sensitive ray coating layer (D); 2. the heat-sensitive resin layer (A) is a negative or positive type heat-sensitive resin layer ( 2. The pattern-forming laminated film according to the above item 1, which is A), 3. The pattern according to the above item 1, wherein the energy-sensitive ray-coating layer (D) is a negative or positive type energy-sensitive ray-coating layer (D). Any one of the above-mentioned items 1 to 3, wherein the heat-sensitive resin coating layer (A) is dissolved or dispersed in a treatment solution containing at least one compound selected from water, an organic solvent, an acid and an alkali; 5. The laminated film for forming a pattern according to the item 5, 5. The pattern-forming laminated film according to any one of the above items 1 to 4, wherein the heat ray shielding layer (C) is dissolved or dispersed in a treatment liquid containing at least one compound selected from water, an organic solvent, an acid and an alkali. 6. The above-mentioned 1 to 5, wherein the negative energy-sensitive radiation-sensitive coating layer (D) is dissolved or dispersed in a treatment liquid containing at least one compound selected from water, an organic solvent, an acid and an alkali.
7. The laminated film for pattern formation according to any one of the above items 7, wherein the heat-sensitive resin film layer (A) is a conductive film as a pattern finally formed. 7. The laminated film for pattern formation according to any one of the above items, 8, wherein the pattern finally formed of the heat-sensitive resin film layer (A) is an insulating film. Or 9. a heat-sensitive resin coating layer (A) is formed on the surface of the substrate, then a sheet layer (B) that transmits heat rays is formed, and the pattern is formed by a developer. A method for producing a laminated film for pattern formation, comprising sequentially laminating a heat ray shielding layer (C) and an energy-sensitive ray coating layer (D), which can be formed; Heat-sensitive resin coating layer (A), heat-transmitting sheet layer ( ), The heat ray shielding layer (C) capable of forming a pattern with a developer and the energy sensitive ray coating layer (D) are laminated so as to be in contact with the coating layer (A) surface of the laminate. A method for producing a layered film for pattern formation; 11, forming a heat-sensitive resin film layer (A) on the substrate surface,
Next, a laminate in which a heat ray shielding layer (C) capable of forming a pattern with a developer and an energy-sensitive ray coating layer (D) are formed on one surface of the surface of the coating layer (A) and one side of the sheet layer (B) transmitting heat rays. A method for producing a layered film for pattern formation, which comprises laminating an object so as to be in contact with the sheet layer (B) surface, 12. forming a heat-sensitive resin film layer (A) on the substrate surface,
Next, the surface of the coating layer (A) and the sheet layer (B) surface of a laminate in which a heat ray shielding layer (C) that can be patterned by a developer is formed on one side of the sheet layer (B) that transmits heat rays. Are laminated so as to be in contact with each other, and then an energy-sensitive radiation coating layer (D) is formed on the surface of the heat ray shielding layer (C). The laminate is formed such that the surface of the base material and the surface of the coating layer (A) of the laminate formed with the heat-sensitive resin coating layer (A) and the heat-transmitting sheet layer (B) are in contact with each other, and then the sheet layer (B A) forming a heat ray shielding layer (C) capable of forming a pattern with a developer on the surface of (d), and then forming an energy-sensitive ray coating layer (D); On the material surface, the substrate surface and the heat-sensitive resin coating layer (A) The laminate is formed so that the sheet layer (B) which transmits heat rays and the coating layer (A) surface of the laminate formed with the heat ray shielding layer (C) which can be formed into a pattern by a developer are in contact with each other, and then the heat ray shielding layer (C) A method for producing a layered film for pattern formation, comprising forming an energy-sensitive ray coating layer (D) on the surface of (C), 15, the following steps (1) The method according to any one of (1) to (8) above. A heat-sensitive resin coating layer (A), a heat-transmitting sheet layer (B), a heat-ray shielding layer (C) that can be patterned by a developer, and an energy-sensitive ray coating layer (D) are sequentially laminated on the substrate surface. Using a laminated film for forming a pattern formed as described above, irradiating or directly irradiating an active energy ray through a mask so as to obtain a desired pattern from the surface of the energy-sensitive radiation coating layer (D) of the laminated film; (2) Energy sensitive radiation An unnecessary portion of the coating layer (D) is removed by developing the layer (D) to form a resist pattern coating, and then (3) the exposed portion of the heat ray shielding layer (C) is developed. (4) Then, after irradiating the entire surface with heat rays,
(5) The laminate of the sheet layer (B) that transmits heat rays, the heat ray shielding layer (C), and the energy-sensitive ray coating layer (D) is peeled from the heat-sensitive resin coating layer (A) of the laminated coating, A laminate comprising a heat-sensitive resin coating layer (A) formed on the surface of the base material is produced. (6) Then, the coating layer (A) exposed by the heat ray transmitted through the sheet layer (B) is developed by a developer. A pattern forming method comprising a step of developing; 16, forming a heat-sensitive resin coating layer (A) on the substrate surface,
Next, a sheet layer (B) that transmits heat rays is formed, and then an energy-sensitive ray coating layer (D) is formed on one surface of the heat ray shielding layer (C) that can be formed with a developer on the surface of the sheet layer (B). A method for producing a layered coating for pattern formation, comprising laminating a laminated body so that the sheet layer (C) surface of the laminated body is in contact with the sheet layer, 17, the substrate surface, the heat-sensitive resin, The laminate having the coating layer (A) and the sheet layer (B) that transmits heat rays is laminated so that the surface of the coating layer (A) is in contact with the laminate, and then a pattern is formed on the surface of the sheet layer (B) with a developer. A laminate for forming a pattern, comprising: laminating on one side of a possible heat ray shielding layer (C) a laminate having an energy-sensitive radiation coating layer (D) in contact with the sheet layer (C). The present invention relates to a method for producing a coating.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate used in the laminated coating of the present invention is a conventionally known electrically insulating glass-epoxy plate,
Plastic sheets and plastic sheets such as polyethylene terephthalate sheets and polyimide sheets; by bonding metal foils such as copper and aluminum to the surfaces of these plastic sheets and plastic sheets, or metals such as copper, nickel and silver or indium-tin oxide (I
Compounds such as conductive oxides represented by TO) having a conductive coating formed by a method such as vacuum deposition, chemical vapor deposition, plating, etc .: The surface of a plastic plate or a plastic sheet provided with through holes and through holes. Formed with a conductive film: a metal plate such as a copper plate, a patterned copper through-hole printed wiring board, and the like.

In the heat-sensitive resin coating layer (A) used in the laminated coating of the present invention, the portion of the film which has not been irradiated with heat rays is removed by dissolving or dispersing with a developer and the portion of the portion which has been irradiated with heat rays is developed. A negative-type coating layer that remains as a resist coating without being dissolved or dispersed by a liquid, and a coating of a portion that has not been irradiated with heat rays remains as a resist coating without being dissolved or dispersed and removed by a developer,
The film exposed to the heat ray is used without any particular limitation as long as it is a conventionally known positive type coating layer in which the film is dissolved or dispersed by a developer to remove the film by decomposition of the film. can do.

[0008] The resin composition for forming the negative heat-sensitive coating will be described below. As the negative-type heat-sensitive coating resin composition, for example, a conventionally known resin containing a heat-ray-curable resin and a reaction initiator can be used. For example, hydroxyl-containing resin / amino resin, hydroxyl-containing resin / blocked isocyanate, melamine resin, hydrolyzable group (alkoxysilyl group, hydroxysilyl group, etc.)
Containing silicon resin, 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 above-mentioned heat ray-curable resin is a commonly used curable resin having a photosensitive group which can be cross-linked by irradiation with heat rays, and a film of an unexposed portion is contained in the resin in an alkaline developer or 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 an acidic developer.

Examples of the unsaturated group contained in the heat ray-curable resin include 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, and the content of the carboxyl group is about 10 to 700 mg KO in the acid value of the resin.
H / g, especially in the range of about 20-600 mg KOH / g, is 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,
On the other hand, if the acid value exceeds about 700, there is a disadvantage that the resist coating (hardened coating) tends to be removed, which is not preferable. Further, as the cationic group, an amino group may be mentioned as a typical example, and as the content of the amino group,
The amine value of the resin is about 20-650, especially about 30-600.
Are preferred. When the amine value is less than about 20, there is a disadvantage that the solubility of the uncured film due to the treatment with the developer is inferior, as described above. On the other hand, when the amine value is more than about 650, the resist film is easily removed. Is not preferred.

Examples of the anionic resin include those obtained by reacting a monomer such as glycidyl (meth) acrylate with a polycarboxylic acid resin 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 Japanese Patent Application Laid-Open No. 3-223759, which is a photo-curable resin, and therefore, the detailed description will be replaced by reference.

Examples of the reaction initiator include benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone,
Aromatic carbonyl compounds such as anthraquinone; acetophenones such as acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, diacetylacetophenone and acetophenone; benzoyl peroxide; t-butyl peroxy-2-ethylhexanoate, t-butyl hydroperoxide, di-tert-butyl diperoxyisophthalate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, etc. Organic peroxides; diphenylhalonium salts such as diphenyliodobromide and diphenyliodonium chloride; organic halides such as carbon tetrabromide, chloroform and iodoform; -Phenyl-5 over iso oxazolone, 2,4,6 Torisu heterocyclic such as (trichloromethyl) over triazine benzanthrone and polycyclic compounds; 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 reaction initiators, di-tert-butyl diperoxyisophthalate, 3,3 ′, 4,4 ′
-Tetra (t-butylperoxycarbonyl) benzophenone, an iron-allene complex and a titanocene compound are preferably used because they have high activity for crosslinking or polymerization.

The trade names include, for example, Irgacure 651 (trade name, manufactured by Ciba Geigy, acetophenone-based light (heat) radical polymerization initiator), Irgacure 18
4 (manufactured by Ciba-Geigy, trade name, acetophenone-based light (heat) radical polymerization initiator), Irgacure 1850
(Ciba-Geigy, trade name, acetophenone-based light (heat) radical polymerization initiator), Irgacure 907 (Ciba-Geigy, trade name, aminoalkylphenone-based light (heat) radical polymerization initiator), Irgacure 369 (Ciba-Geigy) , Trade name, aminoalkylphenone-based photo (thermal) radical polymerization initiator), lucilin TPO (BAS
Company F, trade name, 2,4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure DETX
S (manufactured by Nippon Kayaku Co., Ltd., trade name), CGI-784
(Trade name, titanium complex compound, manufactured by Ciba Geigy). These can be used alone or in combination of two or more.

The mixing ratio of the reaction initiator is as follows.
The amount is 0.1 to 25 parts by weight, preferably 0.2 to 10 parts by weight based on 00 parts by weight.

In addition to the above, saturated resins can be used. As the saturated resin, the solubility of the thermosetting resin composition (the solubility of the resist film in an alkali developing solution and the use of a thermosetting resin in removing the thermosetting film, for example, an inhibitor of the solubility in a strong alkali solution) is suppressed. 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.

The resin composition is obtained by dissolving or dispersing in an organic solvent and water. Examples of the organic solvent include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, and the like. Further, it can be applied by means of, for example, a roller, a roll coater, a spin coater, a curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating and the like. Next, after setting as necessary, a resist film can be obtained by drying.

The aqueous negative-type heat-sensitive resin composition can be obtained by dissolving or dispersing the above-mentioned negative-type heat-sensitive resin composition in water.

Water-solubilization or water-dispersion of the negative-type heat-sensitive resin composition is carried out by anionic groups (for example,
Carboxyl group) is neutralized with an alkali (neutralizing agent) or a cationic group (for example, amino group) in the heat ray-curable resin composition is neutralized with an acid (neutralizing agent). The water-developable composition can be produced by dispersing or dissolving in water as it is.

In addition to the above, conventionally known water-developable heat-curable resin compositions can be used. For example, an aqueous resin having a heat-curable unsaturated group and an ion-forming group in a novolak phenol type epoxy resin can be used. The resin has some epoxy groups of the novolak phenol type epoxy resin and (meth)
It is obtained by adding photopolymerizability to the resin by adding acrylic acid and forming a water-soluble onium base by reacting the epoxy group with, for example, a tertiary amine compound. The exposed part is hardened by heat rays 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. , Amino groups, etc.) and salts thereof (salts in a developing solution) can be formed with excellent resist properties. Further, in addition to the novolak phenol epoxy resin, for example, glycidyl (meth) acrylate, 3,
4-epoxycyclohexylalkyl (meth) acrylate, the same polymer of an epoxy group-containing radically polymerizable unsaturated monomer such as vinyl glycidyl ether, or one or more of these monomers and another radically polymerizable unsaturated monomer (for example, carbon number Heat-ray curing by adding a copolymer of 1 to 24 alkyl or cycloalkyl (meth) acrylates, radically polymerizable unsaturated aromatic compounds, etc. and (meth) acrylic acid in the same manner as described above. A radical polymer obtained by forming a water-soluble onium base by causing the epoxy group to react with, for example, a tertiary amine compound, to be contained in a hydrophilic resin can also be used.

The negative type heat-sensitive resin composition is subjected to an alkaline development process when the negative-type heat-sensitive resin composition is anionic, and an acidic development process when the negative type heat-sensitive resin composition is cationic. Is performed. In addition, those in which the resin itself dissolves in water (for example, an onium base-containing resin or the like) can be subjected to water development treatment.

The negative-type heat-sensitive resin film may be conductive or insulating in itself. Further, a conductive material (e.g., a conventionally known conductive pigment such as silver, copper,
Metals such as iron, manganese, nickel, aluminum, cobalt, chromium, lead, zinc, bismuth, and ITO, one or more of these alloys, their oxides, and these conductive materials are coated and deposited on the surface of insulating materials. Or an insulating material (plastic fine powder, insulating inorganic powder, etc.). Insulating coating is typically that volume resistivity of the coating film to be finally formed is more than 10 ⁹ Ω · cm, be in particular in the range of ^{10 10 Ω · cm~10 18 Ω ·} cm, and The conductive film usually has a volume resistivity of less than 10 ⁹ Ω · cm, particularly 1
Those having a range of Ω · cm to 10 ⁸ Ω · cm are preferable.

The resin composition for forming the positive heat-sensitive resin coating layer will be described below. As the positive-type heat-sensitive resin composition, for example, a composition containing an acid generator and a resin can be used. The resin is decomposed by an acid generated by heat rays to change the properties of the resin such as polarity, molecular weight, etc., so that the resin exhibits solubility in an alkaline, acidic aqueous developer, water developer, and organic solvent developer. It becomes.
These resins may further contain other resins for adjusting the solubility of the developer, if necessary.

As the positive-type heat-sensitive resin composition, for example, a composition mainly composed of a resin obtained by bonding a quinonediazidesulfonic acid to a base resin such as an acrylic resin having an ion-forming group via a sulfonic acid ester bond. (JP
No. 61-206293, JP-A-7-133449), that is, a naphthoquinonediazide-sensitive energy ray system utilizing a reaction in which a quinonediazide group is thermally decomposed by irradiation light to form indenecarboxylic acid via ketene. Composition: A crosslinked film which is insoluble in an alkaline developer or an acidic developer is formed by heating, and the crosslinked structure is cut by an acid generator which generates an acid group by irradiation with heat rays. Positive active energy ray-sensitive compositions utilizing a mechanism that becomes soluble in a developer (JP-A-6-295064, JP-A-6-308733, JP-A-6-31
3134, JP-A-6-313135, JP-A-6-313136, JP-A-77-146552, etc.) and the like.

With respect to the above-mentioned positive type thermosensitive resin,
Since it is described in the above-mentioned publication, the detailed description is replaced with a reference.

The acid generator is a compound that generates an acid upon irradiation with heat rays. The generated acid is used as a catalyst to decompose the resin. Conventionally known ones can be used. Examples thereof include sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, onium salts such as selenium salts, iron-allene complexes, ruthenium-allene complexes, silanol-metal chelate complexes, triazine compounds, Diazidonaphthoquinone compounds, sulfonic acid esters, sulfonic acid imide esters, halogen compounds and the like can be used. In addition to the above, acid generators described in JP-A-77-146552 and Japanese Patent Application No. 9-289218 can also be used. This acid generator component may be a mixture with the above-mentioned resin or a compound bonded to the resin. The compounding ratio of the acid generator is about 0.1 to 100 parts by weight of the resin.
It is preferred that the content be 40 parts by weight, particularly about 0.2 to 20 parts by weight.

The resin composition is obtained by dissolving or dispersing in an organic solvent and water. Examples of the organic solvent include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, and the like. Further, it can be applied by means of, for example, a roller, a roll coater, a spin coater, a curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating and the like. Next, after setting as necessary, a resist film can be obtained by drying. Further, the aqueous positive-type heat-sensitive resin composition,
It is obtained by dissolving or dispersing the above-mentioned positive-type heat-sensitive resin composition in water.

The water-soluble or water-dispersible positive-type heat-sensitive resin composition is prepared by neutralizing an anionic group (for example, a carboxyl group) in the resin with an alkali (neutralizing agent) or a cationic group in the resin. This is performed by neutralizing (for example, an amino group) with an acid (neutralizing agent). The water-developable composition can be produced by dispersing or dissolving in water as it is.

The positive-type heat-sensitive resin composition can be subjected to setting and the like, if necessary, and dried at a temperature in the range of about 50 to 130 ° C. to form a positive-type heat-sensitive linear coating. . As the above-mentioned development processing, when the positive-type heat-sensitive resin composition is anionic, alkali development processing is performed, and when it is cationic, acid development processing is performed. In addition, those in which the resin itself is dissolved in water (for example, an onium base-containing resin or the like) can be subjected to a water development treatment.

The positive-type heat-sensitive resin film may be conductive or insulating in itself. Further, a conductive material (e.g., a conventionally known conductive pigment such as silver, copper,
Metals such as iron, manganese, nickel, aluminum, cobalt, chromium, lead, zinc, bismuth, and ITO, one or more of these alloys, their oxides, and these conductive materials are coated and deposited on the surface of insulating materials. Or an insulating material (plastic fine powder, insulating inorganic powder, etc.). Insulating coating is typically that volume resistivity of the coating film to be finally formed is more than 10 ⁹ Ω · cm, be in particular in the range of ^{10 10 Ω · cm~10 18 Ω ·} cm, and The conductive film usually has a volume resistivity of less than 10 ⁹ Ω · cm, particularly 1
Those having a range of Ω · cm to 10 ⁸ Ω · cm are preferable.

The thickness of the heat-sensitive resin film may be appropriately determined according to the intended use, but is usually preferably in the range of about 1 μm to about 5 mm, particularly preferably in the range of about 2 μm to about 500 μm.

Sheet layer (B) used in the laminated coating of the present invention
Any known heat-transmitting sheet layer can be used without particular limitation. As this, for example, polyethylene terephthalate sheet,
Polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, cellulosic, polyurethane, polyacrylate,
Any of sheets such as aramid, Kapton, polymethylpentene, polyethylene and polypropylene can be used,
In particular, it is preferable to use a polyethylene terephthalate sheet. The thickness of the sheet layer is usually about 10 μm to about 5 μm.
mm, especially in the range of about 15 μm to about 500 μm.

The heat ray shielding layer (C) used in the present invention is a layer formed between the sheet layer (B) and the energy-sensitive ray coating layer (D), and the upper surface of the coating layer (D) The active energy ray irradiated from the above is absorbed and / or reflected by the heat ray shielding layer (C) patterned by developing the heat ray shielding layer (C) so that the lower energy sensitive ray coating layer (D) can be patterned. It is a layer provided.

As described above, the heat ray shielding layer (C) absorbs and / or reflects the energy rays irradiated from the upper surface of the coating layer (D) to thereby form the lower coating layer (A) by irradiation with active energy rays. The heat ray shielding layer (C) itself is provided so as not to be substantially cured or decomposed, and is dissolved or dispersed in a treatment liquid such as water, an organic solvent, an alkali, or an acid, and is similar to the coating layer (A). A pattern can be formed.

The heat ray shielding layer (C) absorbs energy rays to be irradiated, for example, an absorbent (a visible ray absorbent, a heat ray absorbent, a heat ray absorbent, etc.), a colorant (color pigment, coloring dye). And the like, and a filler that is contained in the heat ray shielding layer (C) 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 heat ray absorber include benzotriazole, benzophenone, oxalic anilide, cyanoacrylate, benzophenone, and benzotriazole.

Examples of the coloring agent include titanium oxide, zinc white, lead white, basic lead sulfate, lead sulfate, lithopone,
White pigments such as zinc sulfide and antimony white; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, 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 pigments 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 navy blue, cobalt blue, cerulean blue, phthalocyanine blue, and fast sky blue; and green pigments such as chrome green and phthalocyanine green.

As the filler, for example, barita powder,
Precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, mica powder and the like can be mentioned.

The mixing ratio of the absorbing agent, coloring agent and filler used may be appropriately determined according to the intensity of the irradiated energy rays and the thickness of the heat ray shielding layer (C). In the layer from 0.01% to 50% by weight, preferably from 0.02% to 30% by weight, and in the case of colorants and fillers from 0.5% to 90% by weight; Preferably it is in the range of 1% to 50% by weight.

Heat ray shielding layer for reflecting energy rays (C)
As the material, for example, a material containing a reflective agent (a scaly metal pigment or the like) that reflects the energy rays applied to the coating layer (A) can be used.

As the above-mentioned reflecting agent, for example, (flaky)
Metal powder pigments such as 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 ray to be irradiated and the thickness of the heat ray shielding layer (C).
It is desirable to fall within the range of 90% by weight, preferably 1% to 50% by weight. The above-mentioned energy ray absorber and reflector can be used in combination with each other.

Examples of the above-mentioned heat ray shielding layer (C) which can be dissolved or dispersed in water include starches such as potato starch, potato starch, wheat starch, corn starch, konjac and other mannan, seaweed, agar, sodium alginate and the like. Natural polymers such as seaweeds, glue, gelatin, casein, proteins such as collagen; semi-synthetic resins such as cellulose such as viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, and starch such as soluble starch and carboxymethylstarch. ; Polyvinyl alcohol, polyvinyl butyral, polyethylene oxide, water-soluble phenol, water-soluble melamine, sodium polyacrylate, water-soluble polyester resin, acrylic emulsion, polyester emulsion, Synthetic resins such as epoxy resin emulsion and the like include those that a resin component.

Examples of the heat ray shielding layer (C) which can be dissolved or dispersed in the above organic solvent include phenols for oils, acrylic resins, polyester resins, vinyl chloride resins, vinyl acetate resins, phthalic acid resins, amino resins, epoxy resins. Examples include resins containing resins that can be dissolved or dispersed in organic solvents such as resins, xylene resins, petroleum resins, ketone resins, coumarone resins, and urethane resins.

Examples of the heat ray shielding layer (C) which 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 heat ray shielding layer (C) is, for example, a neutralized anionic resin obtained by neutralizing an anionic resin with a basic compound (amine compound, ammonia, alkali metal compound, etc.). can do.

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,
Examples include an acid group-containing urethane resin, an acid group-containing vinyl resin, an acid group-containing organic silicon-based resin, an acid group-containing phenolic resin, an acid group-containing fluorine-based resin, and two or more kinds of modified resins thereof.

A typical example of the acidic group is a carboxyl group. The content of the carboxyl group is in the range of about 10 to 700 mgKOH / g, particularly about 20 to 600 mgKOH / g, based on the acid value of the resin. preferable.
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.
On the other hand, if the ratio exceeds the above, the filter layer is delaminated to an unnecessary portion, and there is a disadvantage that a pattern having excellent resolution cannot be formed.

The heat ray shielding layer (C) which can be dissolved or dispersed in the above-mentioned acid treatment liquid includes, for example, 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 heat ray shielding layer (C) is removed. As the resin composition for forming the heat ray shielding layer (C), for example, a resin composition formed by neutralizing a cationic resin with an acidic compound (organic acid compound, inorganic acid compound, etc.) is used. Can be.

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 urethane resin. Examples include a group-containing vinyl resin, a basic group-containing organic silicon-based resin, a basic group-containing phenolic resin, a basic group-containing fluororesin, an alkali silicate resin, and two or more kinds of modified resins thereof.

Representative examples of the alkaline group include amino groups. The content of the amino group is in the range of about 20 to 650, particularly about 30 to 600, in terms of the amine value of the resin for forming the filter layer. Is preferred. 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 monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, and the like.
Monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, ammonia, caustic soda, caustic potash, sodium metasilicate, potash metasilicate, carbonic acid Aqueous liquids such as soda and tetraethylammonium hydroxide.

Examples of the acidic treatment liquid include aqueous liquids such as formic acid, crotonic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. The concentration of the acidic or alkaline substance in these treatment solutions is usually preferably in the range of 0.05 to 10% by weight.

Examples of the organic solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride and trichloroethylene; alcohols such as methanol, ethanol, propanol and butanol; diethyl ether; Ethers such as dipropyl ether, dibutyl ether, ethyl vinyl ether, dioxane, propylene oxide, tetrahydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone Ketones, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc., pyridine, formamide , N, other solvents such as N- dimethylformamide.

The processing conditions of the developing solution are not particularly limited, but the development of the energy-sensitive radiation-sensitive coating layer is usually performed at a developing solution temperature of about 10 to 50 ° C., preferably 15 to 40 ° C.
The development time can be about 10 seconds to 20 minutes, preferably about 15 seconds to 15 minutes.

The energy-sensitive ray coating layer (D) used in the present invention has a different solubility in a developing solution due to curing or decomposition of a portion irradiated with active energy rays, thereby forming a resist pattern coating. Can be used without particular limitation.

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 the like, a negative-type heat-sensitive resin composition, a positive-type heat-sensitive resin composition, and the like.

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 heat ray curing type. In the negative type and the positive type, as the heat-sensitive wire type, those similar to the resin composition forming the heat-sensitive resin coating layer (A) can be used. Further, as the negative type and the positive type visible light sensitive type, those obtained by blending a photosensitizer in a resin composition for forming the coating layer (A) can be used. As the photosensitizer, a conventionally known photosensitizing dye can be used. This includes, for example, thioxanthene, xanthene, ketone, thiopyrylium salt, basestyryl, merocyanine,
3-substituted coumarins, 3.4-substituted coumarins, cyanines, acridines, thiazines, phenothiazines,
Anthracene, coronene, benzanthracene,
Examples include perylene, merocyanine, ketocoumarin, fumaline, and borate dyes. These can be used alone or in combination of two or more. As borate-based photosensitizing dyes, for example,
JP-A-5-241338, JP-A-7-5685 and JP-A-7-2254
No. 74 and the like. The mixing ratio of the photosensitizer is in the range of about 0.1 to 20% by weight, preferably about 0.2 to 10% by weight, based on (D) (solid content) in the coating layer.

The heat-sensitive resin composition, which is a heat-sensitive resin composition, is obtained by dissolving or dispersing a resin composition which is crosslinked or decomposed by heat rays such as infrared rays in an organic solvent or water. 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. In addition, a thermal acid generator (for example, the same as the above-mentioned photoacid generator) may be blended with these to be used as a positive type.

For forming the energy-sensitive radiation coating layer (D), a composition obtained by dissolving or dispersing the resin composition in an organic solvent or water can be used. As the above organic solvent,
Examples include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, and the like.

The composition can be applied by means of, for example, a roller, roll coater, spin coater, curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating, or the like. Then
After setting if necessary, a resist film can be obtained by drying.

The resist film 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 thickness of the energy-sensitive radiation coating layer (D) is usually preferably in the range of about 1 μm to about 500 μm, particularly preferably in the range of about 2 μm to about 100 μm.

The method for producing a laminated film for pattern formation of the present invention can be produced by any of the following methods 1 to 8. 1. A heat-sensitive resin coating layer (A) is formed on the surface of a substrate, a sheet layer (B) that transmits heat rays is formed, and a heat-ray shielding layer (C) that can be formed into a pattern with a developer, and It can be manufactured by sequentially laminating the energy ray coating layer (D). The coating layer (A) is formed by coating or laminating the resin composition for forming the coating layer (A) on the surface of the substrate as described above, or, if necessary, by coating the resin layer (A).
And a sheet layer (B) formed by heat laminating the sheet on the surface of the coating layer (A) or, if necessary, a sheet. A pressure-sensitive or heat-sensitive pressure-sensitive adhesive (adhesive) layer is provided on the surface of the layer (B), and the layer can be attached using this layer. The heat ray shielding layer (C) is coated with a composition for forming the heat ray shielding layer (C), laminated, or, if necessary, a coating layer (C).
By providing a photosensitive or heat-sensitive pressure-sensitive adhesive (adhesive) layer on the surface, the energy-sensitive ray coating layer (C) forms the energy-sensitive ray coating layer (D) on the surface of the heat ray shielding layer (C). The resin composition can be laminated by painting or laminating or, if necessary, providing a photosensitive or heat-sensitive pressure-sensitive adhesive (adhesive) layer on the coating layer (D).

2. A heat-sensitive resin coating layer (A), a heat-permeable sheet layer (B), a heat ray shielding layer (C) capable of forming a pattern with a developer, In addition, it can be manufactured by laminating so that the surface of the coating layer (A) of the laminate on which the energy-sensitive radiation coating layer (D) is formed is in contact with the surface. The laminate is obtained, for example, by coating the resin composition for the coating layer (A) on one surface of the sheet layer (B) and drying it as necessary, and then coating the resin composition for the shielding layer (C) on the other surface. Can be produced by coating and drying, and then coating the resin composition for the energy-sensitive radiation coating layer (D). Furthermore, in order to apply the coating layer (A) of the laminate to the surface of the substrate, for example, it can be applied by heat lamination or via an adhesive or an adhesive.

3. Heat-sensitive resin coating layer (A) on substrate surface
Then, a heat ray shielding layer (C) capable of forming a pattern with a developing solution on the surface of the coating layer (A) and one surface of the sheet layer (B) transmitting heat rays, and an energy-sensitive ray coating layer (D) Can be produced by contacting the sheet layer (B) surface of the laminate formed with the above. Heat-sensitive resin coating layer (A)
Is a method in which a resin composition for a heat-sensitive resin coating layer (A) is coated on the substrate surface, dried or laminated, or a photosensitive or heat-sensitive adhesive is applied to the coating layer (A) as required. It can be obtained by providing an (adhesive) layer. The laminate is coated with a resin composition for a heat ray shielding layer (C) on one side of a sheet layer (B) that transmits heat rays, dried, and then coated and dried with a resin composition for an energy sensitive ray coating layer (D). It can be obtained by: Further, the sheet layer (B) and the coating layer (A) of the laminate can be attached by, for example, heat lamination or via an adhesive or an adhesive.

4. Heat-sensitive resin coating layer (A) on substrate surface
And then forming a heat ray shielding layer (C) capable of patterning with a developer on one surface of the coating layer (A) and one side of the sheet layer (B) that transmits heat rays. It can be manufactured by laminating so that the surface B) is in contact with the surface, and then forming the energy-sensitive radiation coating layer (D) on the surface of the heat ray shielding layer (C). The heat-sensitive resin coating layer (A) is coated with a resin composition for a heat-sensitive resin coating layer (A) on the surface of a substrate,
Obtained by drying. A laminate in which a heat ray shielding layer (C) capable of forming a pattern with a developer is formed on one surface of a sheet layer (B) that transmits heat rays, is coated with a resin composition for the shielding layer (C) on the surface of the sheet layer (B). Obtained by drying. Further, the coating layer (A) and the sheet layer (B) of the laminate can be attached, for example, by heat lamination or via an adhesive or an adhesive. Then, the obtained heat ray shielding layer (C) is coated with a resin composition for an energy-sensitive ray coating layer (D) on the surface thereof, dried or laminated, or, if necessary, coated with a photosensitive layer. Alternatively, it can be obtained by providing a heat-sensitive adhesive (adhesive) layer.

5. On the surface of the base material, the surface of the base material and the surface of the coating layer (A) of the laminate formed with the heat-sensitive resin coating layer (A) and the sheet layer (B) that transmits heat rays are interviewed. Then, a heat ray shielding layer (C) capable of forming a pattern with a developer is formed on the surface of the sheet layer (B), and then an energy-sensitive ray coating layer (D) is formed. The laminate formed with the heat-sensitive resin coating layer (A) and the sheet layer (B) that transmits heat rays is obtained by coating and drying the resin composition for the coating layer (A) on the surface of the sheet layer (B). . Interview between the substrate surface and the coating layer (A) surface of the laminate,
For example, it can be stuck by heat lamination or via an adhesive or an adhesive. Heat ray shielding layer (C)
And the energy-sensitive radiation coating layer (D) is formed by coating, drying, or laminating the resin composition forming these layers, or, if necessary, the coating layers (C) and (D).
It can be manufactured by providing a photosensitive or heat-sensitive pressure-sensitive adhesive (adhesive) layer on the substrate.

6. On the surface of the substrate, the surface of the substrate, a heat-sensitive resin coating layer (A), a sheet layer that transmits heat rays (B), and a heat ray shielding layer (C) that can be formed into a pattern by a developer. Can be manufactured by laminating so that the surface of the coating layer (A) of the layered product on which is formed is in contact with each other, and then forming the energy-sensitive radiation coating layer (D) on the surface of the heat ray shielding layer (C). Heat-sensitive resin coating layer (A), sheet layer transmitting heat rays (B)
And the laminate on which the heat ray shielding layer (C) is formed is coated with the resin composition for the coating layer (A) on the surface of the sheet layer (B), dried, and coated on the other side of the sheet layer (B) with the heat ray shielding layer ( It is obtained by coating and drying the resin composition for C). The surface of the base material and the surface of the coating layer (A) of the laminate can be interviewed by, for example, heat lamination or via an adhesive or an adhesive. The energy-sensitive radiation coating layer (D) is formed by coating, drying, or laminating the resin composition forming this layer, or, if necessary, by adding a photosensitive or heat-sensitive adhesive ( (Adhesive) layer.

7. A heat-sensitive resin coating layer (A) is formed on the substrate surface, and then a sheet layer (B) that transmits heat rays
And then forming the sheet layer (C) of the laminate having the surface of the coating layer (B) and the energy-sensitive radiation coating layer (D) formed on one side of the heat ray shielding layer (C) capable of patterning with a developer. ) It can be manufactured by laminating so as to be in contact with the surface. The coating layer (A) is formed by coating or laminating the resin composition for forming the coating layer (A) on the surface of the base material as described above, or by photosensitizing or heat-sensitive the coating layer (A) as necessary. The sheet layer (B) is formed by heat laminating the sheet on the surface of the coating layer (A) or, if necessary, the surface of the sheet layer (B). A pressure-sensitive or heat-sensitive pressure-sensitive adhesive (adhesive) layer is provided, and this layer can be used for application. The laminate in which the heat ray shielding layer (C) capable of forming a pattern with a developer and the energy-sensitive ray coating layer (D) are formed on one surface of the heat ray shielding layer (C) is a resin composition for the energy-sensitive ray coating layer (D). It is obtained by painting. Interview between the surface of the sheet layer (B) and the surface of the coating layer (C) of the laminate can be performed, for example, by heat lamination or by applying an adhesive or an adhesive.

8. On the surface of the substrate, the surface of the substrate is in contact with the surface of the coating layer (A) of the laminate formed with the heat-sensitive resin coating layer (A) and the sheet layer (B) that transmits heat rays. The sheet layer of the laminate in which the energy-sensitive radiation coating layer (D) is formed on the surface of the coating layer (B) and on one surface of the heat ray shielding layer (C) that can be patterned by a developer, and (C) It can be manufactured by laminating so that the surface is in contact with the surface. The laminate formed with the heat-sensitive resin coating layer (A) and the sheet layer (B) that transmits heat rays is obtained by coating and drying the resin composition for the coating layer (A) on the surface of the sheet layer (B). . The surface of the base material and the surface of the coating layer (A) of the laminate can be interviewed by, for example, heat lamination or via an adhesive or an adhesive. The laminate in which the heat ray shielding layer (C) capable of forming a pattern with a developer and the energy-sensitive ray coating layer (D) are formed on one surface of the heat ray shielding layer (C) is a resin composition for the energy-sensitive ray coating layer (D). It is obtained by painting. Interview between the surface of the sheet layer (B) and the surface of the coating layer (C) of the laminate can be performed, for example, by heat lamination or by applying an adhesive or an adhesive.

The pattern forming method of the present invention comprises the following steps: (1) a heat-sensitive resin coating layer (A) on a substrate surface, a sheet layer (B) transmitting heat rays, and a heat ray shielding layer capable of forming a pattern with a developer. (C) and an energy-sensitive ray coating layer (D)
Are sequentially irradiated with an active energy ray through a mask so as to obtain a desired pattern from the surface of the energy-sensitive ray coating layer (D) of the layered coating. After irradiating, (2) developing the energy-sensitive radiation coating layer (D) to remove an unnecessary portion of the coating layer (D) to form a resist pattern film, and (3) heating the exposed portion of the heat ray The shielding layer (C) is removed by developing treatment. (4) Then, after irradiating the entire surface with heat rays, (5) a sheet layer (B) which transmits heat rays from the heat-sensitive resin coating layer (A) of the laminated film. A laminate comprising a heat-sensitive resin coating layer (A) formed on the substrate surface by peeling off the laminate of the heat ray shielding layer (C) and the energy-sensitive ray coating layer (D), 6) Then, by the heat rays transmitted through the sheet layer (B) It shines the coating layer (A) is a pattern forming method comprising the step of developing with a developer.

Examples of the light source used for the active energy ray include, but are not particularly limited to, ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, tungsten lamps, and the like. Argon laser (488 nm), YAG-SHG laser (532 nm), UV laser (351-364 nm)
A laser having an oscillation line can also be used.

Examples of the heat rays include a semiconductor laser (830 nm), a YAG laser (1.06 μm), and infrared rays.

The developer used for the coating (A), the shielding layer (C) and the coating layer (D) is treated with an alkaline developer when the coating is anionic, and is treated when the coating is cationic. Is processed with an acidic developer. Further, development can be performed with an organic solvent or water depending on the properties of the film.

The developing process is performed, for example, by using a developing solution of about 10 to 8
0 ° C., preferably at a liquid temperature of about 15 to 50 ° C. for about 10 seconds to
It can be performed by spraying or dipping for 60 minutes, preferably for about 30 seconds to 30 minutes.

Examples of the alkaline developer include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, and the like.
Monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, ammonia, caustic soda, caustic potash, sodium metasilicate, potash metasilicate, carbonic acid Aqueous liquids such as soda and tetraethylammonium hydroxide.

Examples of the acidic developer include aqueous solutions of formic acid, crotonic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like.

Examples of the organic solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as methanol, ethanol, propanol and butanol; diethyl ether; Ethers such as dipropyl ether, dibutyl ether, ethyl vinyl ether, dioxane, propylene oxide, tetrahydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone Ketones, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc., pyridine, formamide , N, other solvents such as N- dimethylformamide.

The method of the present invention can be applied to a substrate surface such as a black matrix pattern, a color filter pattern, an electronic component coating pattern (solder coating), a ceramic or phosphor pattern, a display panel partition pattern and the like. The present invention can be applied to an insulating substrate such as a pattern to be formed, a plastic substrate for wiring, a plastic substrate for build-up, and a conductive pattern provided on these.

[0079]

EXAMPLES The present invention will be described more specifically with reference to examples. Parts and% are based on weight. Example of Production of Heat-Sensitive Composition (i) As a heat-curable resin (polymer binder), an acrylic resin (resin acid value 155 mg KOH / g, methyl methacrylate / butyl acrylate / acrylic acid = 40/40)
/ 20 weight ratio) and 24 parts by weight of glycidyl methacrylate (a resin solid content of 55% by weight, an organic solvent of propylene glycol monomethyl ether, a resin acid value of 50 mg KOH / g, and a number average molecular weight of about 2).
100,000 parts (solid content) in a photopolymerizable initiator (CGI-7
84, trade name, Ciba-Geigy, titanocene compound)
10 parts of (V-59) and 10 parts of (V-59) were blended to prepare a photosensitive solution to obtain a composition (i) (solid content: 15%).

Production Example of Resin Composition (ii) for Heat Ray Shielding Layer A water-soluble composition having a solid content of 40%, in which 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.

Production Example of Visible Light-Sensitive Composition (iii) NKX-1595 (photosensitizing dye,
A photosensitive solution was prepared by blending 1.5 parts of a coumarin-based dye (trade name, manufactured by Japan Photographic Dye Laboratories Inc.) to prepare a composition (ii)
i) (15% solids) was obtained.

Example 1 (1) Heat Sensitive Wire on Copper Foil (200 × 200 × 1.1 mm)
Coating composition (i) with a bar coater,
Preliminary drying for 0 minutes and coating of heat-sensitive resin
Film (i) was formed. Next, a polyether
Paste a Tylene terephthalate sheet (38 μm),
Next, the heat ray shielding resin composition (ii) was dried to a thickness of 6 μm.
m and dried at 65 ° C for 10 minutes
To form a heat ray shielding layer (ii).
Apply the photosensitive composition (iii) with a bar coater
And pre-dried at 80 ° C. for 10 minutes to form a film having a thickness of about 30 μm.
A visible light-sensitive coating (iii) was formed. (2) Next, argon ion from the surface of the coating (iii)
Laser (5mj / cm ^Two) Is irradiated directly in a pattern
Exposure. Next, an alkaline developer a (sodium carbonate aqueous solution)
(0.25 wt% solution) at 60 ° C for 60 seconds
Under layer (iii) and exposed layer (iii)
Part of the heat ray shielding layer (ii) is simultaneously developed and removed.
Was. (3) Xenon lamp (1 J /
cm^Two). (4) Next, the sheet layer, the heat ray shielding layer (ii) and the coating
The laminate of the layer (iii) is removed from the heat-sensitive resin coating layer (i).
After peeling, the laminate of copper foil and heat-sensitive resin coating (i)
Obtained. (5) Then, into a 0.75% by weight aqueous sodium carbonate solution
Uncured (unexposed part) heat ray by immersion at 25 ° C for 60 seconds
The conductive resin coating layer (i) was developed and removed. Got
The pattern is line (pattern width) / space = 100μ
m / 20 μm stripe pattern
there were.

Example 2 In the same manner as in (1) of Example 1, the composition (i) was roller-coated on one side of a polyethylene terephthalate sheet (38 μm), dried at 80 ° C. for 10 minutes, and then coated on one side of the other sheet. Roll the object (ii) and apply 80 ° C
After drying for 10 minutes, the composition (iii) was roller-coated and dried at 80 ° C. for 10 minutes to obtain a laminate. The test was carried out in the same manner as in Example 1 except that a coating of the composition (i) of the laminate was heat-laminated by applying pressure to the surface of the copper foil at 80 ° C. and then applied. As a result, the obtained pattern is line (pattern width) / space = 10
It was patterned into a stripe of 0 μm / 20 μm, which was good.

Example 3 The heat-sensitive composition (i) was applied onto the above-mentioned copper foil with a bar coater, and was preliminarily dried at 80 ° C. for 10 minutes to obtain a film thickness of about 30 μm.
m of the coating (i) was formed. The composition (ii) is roller-coated on one side of a polyethylene terephthalate sheet (38 μm), dried at 80 ° C. for 10 minutes, and then the composition (ii)
i) was coated with a roller and dried at 80 ° C. for 10 minutes to obtain a laminate. Next, the sheet layer of the laminate and the coating (i) were
Heat lamination was performed by pressing at 0 ° C., and the film was attached.
Tests (2) to (5) were carried out in the same manner as in Example 1 using the obtained material. As a result, the obtained pattern has a line (pattern width) / space = 100 μm /
It was patterned into a 20 μm stripe and was good.

Example 4 The heat-sensitive composition (i) was applied on the above-mentioned copper foil with a bar coater, and was preliminarily dried at 80 ° C. for 10 minutes to form a film having a thickness of about 30 μm.
m of the coating (i) was formed. The composition (ii) was roller-coated on one side of a polyethylene terephthalate sheet (38 μm) and dried at 80 ° C. for 10 minutes to obtain a laminate. Next, the sheet layer of the laminate and the coating (i) were heat-laminated by pressing at 80 ° C., and attached. Next, the composition (iii) was roller-coated on the surface of the coating of the composition (ii), and dried at 80 ° C for 10 minutes. Tests (2) to (5) were carried out in the same manner as in Example 1 using the obtained material. As a result, the obtained pattern was patterned in a stripe shape of line (pattern width) / space = 100 μm / 20 μm, and was favorable.

Example 5 A composition (i) was roller-coated on one side of a polyethylene terephthalate sheet (38 μm) and dried at 80 ° C. for 10 minutes to obtain a laminate. Then, the sheet layer of the laminate and the copper foil were
Heat lamination was performed by pressing at 0 ° C., and the film was attached.
Next, the composition (ii) was roller-coated on the sheet surface and dried at 80 ° C. for 10 minutes. Further, the composition (iii) was roller-coated on the coating surface of the composition (ii) and dried at 80 ° C. for 10 minutes. Tests (2) to (5) were carried out in the same manner as in Example 1 using the obtained material. As a result, the obtained pattern is line (pattern width) / space = 1.
It was patterned into a stripe pattern of 00 μm / 20 μm, which was good.

Example 6 The composition (i) was roller-coated on one side of a polyethylene terephthalate sheet (38 μm) and dried at 80 ° C. for 10 minutes. Then, the composition (i) was applied on one side of the other sheet.
i) was coated with a roller and dried at 80 ° C. for 10 minutes to obtain a laminate. Then, the coating of the composition (i) of the laminate was heat-laminated by applying pressure to the surface of the copper foil at 80 ° C., and the composition was further applied to the surface of the coating of the composition (ii) of the laminate. Was coated with a roller and dried at 80 ° C. for 10 minutes.
Tests (2) to (5) were carried out in the same manner as in Example 1 using the obtained material. As a result, the obtained pattern has a line (pattern width) / space = 100 μm /
It was patterned into a 20 μm stripe and was good.

Example 7 A release-treated polyethylene terephthalate sheet (
The composition (iii) was roller-coated on one side of the film (38 μm) and dried at 80 ° C. for 10 minutes. Then, the composition (ii) was roller-coated and dried at 80 ° C. for 10 minutes to obtain a laminate. Then, the composition (ii) was roller-coated on the surface of the copper foil, and 8
It was dried at 0 ° C. for 10 minutes. Subsequently, a polyethylene terephthalate sheet (38 μm) was thermally laminated by applying a pressure at 80 ° C., and the composition was further laminated. (Ii)
The surface of the film was surface-contacted with the surface of the polyethylene terephthalate sheet, pressed at 80 [deg.] C., thermally laminated and attached, and the release polyethylene terephthalate sheet was peeled off. Tests (2) to (5) were carried out in the same manner as in Example 1 using the obtained material. As a result, the obtained pattern is line (pattern width) / space = 100
It was patterned into a stripe of μm / 20 μm, which was good.

Example 8 A release-treated polyethylene terephthalate sheet (
The composition (iii) was roller-coated on one side of the film (38 μm) and dried at 80 ° C. for 10 minutes. Then, the composition (ii) was roller-coated and dried at 80 ° C. for 10 minutes to obtain a laminate. Then, a polyethylene terephthalate sheet (38μ)
m) on one side by roller coating the composition (i)
After drying for a minute, a laminate was obtained. The copper foil surface and the surface of the composition (i) were in contact with each other, and the laminate was heat-laminated by applying a pressure at 80 ° C. and bonded. The sheets were contacted, heat-laminated by applying a pressure at 80 ° C., and bonded, and the release polyethylene terephthalate sheet was peeled off. Example 1 using what was obtained above
Tests (2) to (5) were performed in the same manner as described above. As a result, the obtained pattern was patterned in a stripe shape of line (pattern width) / space = 100 μm / 20 μm, and was favorable.

Comparative Examples 1 to 8 In each of Examples 1 to 8, a laminated film was formed in the same manner as in Examples 1 to 8, except that the film of the composition (ii) was not formed. The test was performed. As a result, all of the obtained films were poor in line persistence and poor in space developability in all of Nos. 1 to 8.

[0091]

According to the present invention having the above-described structure, there were aspects in which a single photosensitive resin film could not be applied depending on the application, but by separating this into multiple layers, the functions were separated. A wide range of applications has been made possible.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/40 G03F 7/40 (72) Inventor Genji Imai 4-7-17-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. F term (reference) 2H025 AA01 AA19 AA20 AB03 AB11 AB15 AB17 AC08 AD01 AD03 DA13 DA14 DA40 EA08 FA06 FA17 FA39 2H096 AA06 AA26 AA27 BA01 BA09 CA16 EA04 GA03 GA09 HA03 HA30

Claims (17)

[Claims] 1. A heat-sensitive resin coating layer (A) on a substrate surface,
A laminated film for pattern formation, which is formed by sequentially laminating a sheet layer (B) that transmits heat rays, a heat ray shielding layer (C) capable of forming a pattern with a developer, and an energy-sensitive ray coating layer (D). 2. The laminated film for pattern formation according to claim 1, wherein the heat-sensitive resin coating layer (A) is a negative or positive heat-sensitive resin coating layer (A). 3. The laminated film for pattern formation according to claim 1, wherein the energy-sensitive ray coating layer (D) is a negative or positive type energy-sensitive ray coating layer (D). 4. The heat-sensitive resin coating layer (A) is dissolved or dispersed in a processing solution containing at least one compound selected from water, organic solvents, acids and alkalis. 5. The laminated film for forming a pattern according to item 1. 5. The method according to claim 1, wherein the heat ray shielding layer (C) is dissolved or dispersed in a treatment liquid containing at least one compound selected from water, an organic solvent, an acid and an alkali. Multilayer coating for pattern formation. 6. The method according to claim 1, wherein the negative or positive energy-sensitive radiation-sensitive coating layer (D) is dissolved or dispersed in a processing solution containing at least one compound selected from water, an organic solvent, an acid and an alkali. The multilayer coating for pattern formation according to any one of claims 1 to 7. 7. The pattern forming method according to claim 1, wherein a pattern finally formed of the heat-sensitive resin coating layer (A) is a conductive coating. Laminated coating. 8. The pattern forming method according to claim 1, wherein a pattern finally formed of the heat-sensitive resin layer (A) is an insulating film. Laminated coating. 9. A heat-sensitive resin coating layer (A) is formed on the surface of a substrate, a sheet layer (B) which transmits heat rays is formed, and a heat-ray shielding layer (C) which can be formed into a pattern by a developer. And a layer for energy-sensitive radiation (D), which is sequentially laminated. 10. A heat-sensitive resin coating layer (A), a heat-transmitting sheet layer (B), a heat ray shielding layer (C) capable of forming a pattern with a developer, And laminating the laminate on which the energy-sensitive radiation coating layer (D) is formed so as to be in contact with the coating layer (A) surface. 11. A heat-sensitive resin coating layer (A) on a substrate surface
Then, a heat ray shielding layer (C) capable of forming a pattern with a developing solution on the surface of the coating layer (A) and one surface of the sheet layer (B) transmitting heat rays, and an energy-sensitive ray coating layer (D) A method for producing a layered film for pattern formation, comprising laminating a laminate having the above-mentioned layer so that the sheet layer (B) surface is in contact with the sheet layer (B). 12. A heat-sensitive resin coating layer (A) on a substrate surface.
And then forming a heat ray shielding layer (C) capable of patterning with a developer on one surface of the coating layer (A) and one side of the sheet layer (B) that transmits heat rays. B) A method for producing a laminated film for forming a pattern, comprising laminating the surfaces so as to be in contact with each other, and then forming an energy-sensitive radiation coating layer (D) on the surface of the heat ray shielding layer (C). 13. The surface of the base material is in contact with the surface of the base material and the surface of the coating layer (A) of the laminate formed with the heat-sensitive resin coating layer (A) and the sheet layer (B) that transmits heat rays. A pattern, wherein a heat ray shielding layer (C) capable of forming a pattern with a developer is formed on the surface of the sheet layer (B), and then an energy-sensitive ray coating layer (D) is formed. A method for producing a laminated film for formation. 14. A heat-sensitive resin coating layer (A), a heat-permeable sheet layer (B), and a heat-ray shielding layer (C) capable of forming a pattern with a developer on the surface of the substrate. Forming a pattern so that the surface of the heat ray shielding layer (C) is formed with an energy-sensitive ray coating layer (D) on the surface of the heat ray shielding layer (C). Method of manufacturing laminated film for use. 15. The following step (1): A heat-sensitive resin coating layer (A), a sheet layer (B) that transmits heat rays, and a developer on the substrate surface according to any one of claims 1 to 8. Using a laminated film for forming a pattern in which a heat-ray shielding layer (C) and an energy-sensitive ray coating layer (D) capable of forming a pattern are sequentially laminated, from the surface of the energy-sensitive ray coating layer (D) of the laminated coating Irradiation or direct irradiation with an active energy ray through a mask so that a desired pattern is obtained, and (2) an unnecessary portion of the coating layer (D) by developing the energy-sensitive ray coating layer (D). Is removed to form a resist pattern film, and (3) the exposed portion of the heat ray shielding layer (C) is removed by developing treatment. (4) Then, the entire surface is irradiated with heat rays.
(5) The laminate of the sheet layer (B) that transmits heat rays, the heat ray shielding layer (C), and the energy-sensitive ray coating layer (D) is peeled off from the heat-sensitive resin coating layer (A) of the laminated coating, A laminate is formed by forming a heat-sensitive resin coating layer (A) on the surface of the base material. (6) Then, the coating layer (A) exposed to heat rays transmitted through the sheet layer (B) is developed with a developer. A pattern forming method, comprising a step of developing. 16. A heat-sensitive resin coating layer (A) on a substrate surface.
Is formed, and then a sheet layer (B) that transmits heat rays is formed. Then, on one surface of the heat ray shielding layer (C) that can be formed with a developer on the surface of the sheet layer (B), an energy-sensitive ray coating layer ( A method for producing a laminated film for pattern formation, comprising laminating the laminate having D) formed thereon so as to be in contact with the sheet layer (C) surface. 17. The surface of the base material is in contact with the surface of the base material and the surface of the coating layer (A) of the laminate formed with the heat-sensitive resin coating layer (A) and the sheet layer (B) that transmits heat rays. The heat-shielding layer (C) capable of forming a pattern with a developing solution on the surface of the sheet layer (B), and the energy-sensitive radiation coating layer (D) formed on one side of the sheet layer (B). C) A method for producing a layered film for pattern formation, wherein the layers are laminated so as to be in surface contact with each other.