JP2021146615A - Laminate and method for making pattern using the same - Google Patents

Abstract

To provide a laminate for forming a pattern having a good shape by preventing irregular reflection of the surface of an opaque inorganic substrate caused by exposure light beam, and to provide a method for producing pattern using said laminate.SOLUTION: Provided is a laminate, which is a laminate composed of an opaque inorganic substrate and one or more organic resin layers (A), and in which at least one layer of the organic resin layers (A) is a colored layer (A1) containing an organic pigment (a1) and a binder resin (a2) and, moreover, at least one layer of the organic resin layers (A) is a photoresist layer (A2), and the colored layer (A1), when formed to have a film thickness of 2.0 μm and in the range of wavelength of 240 to 450 nm, has a maximum value of light transmittance for the light beam of 15% or less.SELECTED DRAWING: None

Description

The present invention relates to a laminate capable of obtaining a good pattern shape, and a method for producing a pattern using the laminate.

Conventionally, when a photoresist pattern is formed on a highly opaque inorganic base material such as various metals such as aluminum, copper, iron, and silicon, metal oxides, and alloys, diffuse reflection of light due to the surface shape of the base material occurs during pattern exposure. , There is a problem that it is difficult to obtain a photoresist pattern according to the exposure pattern.
Therefore, for the purpose of preventing reflection from the surface of the substrate, a technique for obtaining a good photoresist pattern by forming an antireflection film under the photoresist layer has been developed.

Inorganic films and organic films are known as antireflection films that have been conventionally used, but resin solutions containing absorbents such as dyes are mainly used because of the ease of film formation and the high antireflection effect. (Patent Documents 1 and 2).
However, the dye used as the light absorber may sublimate, which causes a problem of contaminating the exposure apparatus.
In addition, the antireflection film using the resin solution containing the dye slightly mixes with the photoresist layer, and a phenomenon called intermixing occurs, which causes deterioration of the photoresist pattern shape such as poor removal and hemming. There was a problem.

Although various antireflection films that do not cause such an intermixing phenomenon have been reported, in general, these antireflection films are inferior in solubility in an alkaline developer or show insolubility, and therefore are an upper layer of a photoresist. After the layer was developed with an alkaline aqueous solution to form a photoresist pattern, it was necessary to perform operations such as dry etching in order to remove the antireflection film (Patent Documents 3 and 4).

Special Table 2011-513772 Japanese Unexamined Patent Publication No. 2000-221698 Japanese Unexamined Patent Publication No. 10-228113 Japanese Unexamined Patent Publication No. 2001-343752

The present invention has been made in view of the above problems, and relates to a laminate capable of preventing diffuse reflection from the surface of an opaque inorganic substrate by a colored layer having low sublimation property, and a method for producing a photoresist pattern using the laminate.

As a result of diligent studies, the present inventors have found that the above problems can be solved by using a colored layer containing at least an organic pigment and a binder resin and having specific light transmission characteristics, and completed the present invention. I came to do it.

That is, the present invention is a laminate composed of an opaque inorganic base material and one or more organic resin layers (A).
At least one layer of the organic resin layer (A) is a colored layer (A1) containing an organic pigment (a1) and a binder resin (a2).
Moreover, at least one layer of the organic resin layer (A) is a photoresist layer (A2).
The colored layer (A1) relates to a laminate in which the maximum value of the light transmittance of the light beam is 15% or less in the wavelength range of 240 to 450 nm when formed to a film thickness of 2.0 μm.
However, the colored layer (A1) and the photoresist layer (A2) may be the same or different.

Further, the present invention is characterized in that the photoresist layer (A2) contains at least a binder resin (a2), a photopolymerizable monomer (a3), and a photopolymerization initiator (a4). Regarding.

The present invention also relates to the above-mentioned laminate, wherein the organic pigment (a1) contains at least one selected from the group consisting of a red pigment, a yellow pigment, and a green pigment.

Further, in the present invention, the red pigment is C.I. I. Pigment Red is at least one selected from the group consisting of 177, 254, 291, 295, and 296, and the yellow pigment is C.I. I. Pigment Yellow is at least one selected from the group consisting of 138, 139, 150, and 185, and the green pigment is C.I. I. The present invention relates to the above-mentioned laminate, which is at least one selected from the group consisting of Pigment Green 7, 36, 58, 59, 62, and 63.

Further, the present invention is a method for producing a photoresist pattern using the above-mentioned laminate.
A step of exposing the laminate with a light beam having at least a wavelength in the range of 240 to 450 nm to form a latent image of a photoresist pattern.
The present invention relates to a method for producing a photoresist pattern, which comprises a step of developing a laminate on which a latent image is formed.

The present invention also relates to a method for producing the above-mentioned photoresist in which the photoresist pattern is a perforation pattern.

According to the present invention, when a photoresist pattern is formed on an opaque inorganic substrate, diffuse reflection of light rays such as g-line (wavelength 436 nm) and i-line (wavelength 365 nm) generally used for exposure on the surface of the opaque inorganic substrate It is possible to provide a laminate capable of forming a good photoresist pattern, and to provide a photoresist pattern in which the exposure apparatus is not contaminated due to the constituent components of the colored layer having an antireflection function. can.

The terminology of the present specification is defined. Unless otherwise specified, the terms "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are used, respectively. , "Acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid".
Further, "CI" mentioned in the present specification means a color index (CI).

One of the features of the laminate of the present invention is that a colored layer (A1) containing at least an organic pigment (a1) and a binder resin (a2) is formed on the surface of an opaque inorganic base material. It suffices if the pigment (a1) can absorb a considerable amount of the wavelength of the light rays used for exposure. Specifically, the colored layer (A1) has a wavelength in the range of 240 to 450 nm when formed to a film thickness of 2.0 μm. The maximum value of the light transmittance of the light beam is 15% or less.
Hereinafter, the present invention will be described in detail.

<Colored layer (A1)>
The colored layer (A1) of the present invention contains at least an organic pigment (a1) and a binder resin (a2). In one embodiment, an organic pigment (a1), a binder resin (a2), a solvent and, if necessary, a photopolymerizable monomer (a3) described later, a photopolymerization initiator (a4) described later, a dispersant, Additives are not particularly limited, but are, for example, paint shaker (manufactured by Red Devil), ball mill, sand mill ("Dyno mill" manufactured by Simmal Enterprises, etc.), attritor, pearl mill (manufactured by Eirich). DCP mill ", etc.), Coball mill, basket mill, homomixer, homonizer (M-Technique" Clairemix ", etc.), Wet jet mill (Genus" Genus PY ", Nanomizer" Nanomizer ", etc.), Hoover A composition for forming a colored layer is prepared by performing dispersion treatment using a Marler, a 3-roll mill, an extruder (biaxial extruder), a Henschel mixer, etc., and cast, spin coat, dip coat, bar coat, spray, etc. A colored layer (A1) is applied to the substrate by a wet coating method such as blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, and inkjet, and then heated and dried to remove the solvent component. ) Can be formed.

In particular, when the colored layer (A1) is formed to have a film thickness of 2.0 μm, diffuse reflection from the surface of an opaque inorganic substrate is effective when the maximum value of light transmittance in the wavelength range of 240 to 450 nm is 15% or less. It is preferable because it can be prevented.

Further, in the case of the embodiment in which the colored layer (A1) further contains the organic pigment (a1) and the binder resin (a2), the photopolymerizable monomer (a3), and the photopolymerization initiator (a4), the above. When the colored layer (A1) is formed to a thickness of 2.0 μm and the maximum value of the light transmittance in the wavelength range of 240 to 450 nm is less than 2%, the colored layer (A1) is formed when the photoresist pattern is formed. ), Light may not reach the substrate interface, and curing failure may occur near the substrate interface, which is not preferable.
From this point of view, the maximum value of the light transmittance in the wavelength range of 240 to 450 nm is 2 to 15%, more preferably 3 to 12% or less, and most preferably 5 to 10%.

When the colored layer (A1) is formed to have a film thickness of 2.0 μm, the maximum value of light transmittance in the wavelength range of 450 to 750 nm is preferably 50% or more. The maximum value of the more preferable light transmittance is 70% or more, and more preferably 80% or more. When the maximum value of the light transmittance is 50% or more, it is preferable from the viewpoint that the surface of the opaque inorganic base material can be visually recognized from the upper surface of the colored layer (A1). If the surface of the opaque inorganic base material can be visually recognized from the upper surface of the colored layer (A1), positioning at the time of forming a photoresist pattern, which will be described later, can be performed with high accuracy.

<Organic pigment (a1)>
As the organic pigment (a1), an organic pigment containing at least one selected from the group consisting of red pigments, yellow pigments, and green pigments having an absorption region in the wavelength range of 240 to 450 nm can be used. By containing an organic pigment having an absorption region in the wavelength range of 240 to 450 nm, it is possible to form an antireflection film having a high antireflection effect on light rays in the wavelength range of 240 to 450 nm and low sublimation property.
Specifically, as each of these color organic pigments, azo pigments such as diketopyrrolopyrrole pigments, azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, antrapyrimidine, flavantron, antoanthron, indantron, and pyranthron. , Or anthraquinone pigments such as biolantron, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, phthalocyanine pigments, slene pigments or metal complex Systematic pigments and the like can be mentioned.

Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281 and 282, 283, 284, 285, 286, 287, 291, 295, 296 and the like can be mentioned.
Among these, preferably C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, 269, 291, 295, 296, more preferably C.I. I. Pigment Red 177, 254, 291, 295, or 296.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,93,94,95,97,98,100, 101, 104, 106, 108, 109, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 138, 139, 147, 150, 151, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 203, 213, 214, 215, 231 and 233 and the like can be mentioned. Among these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, 233, 233, more preferably C.I. I. Pigment Yellow 138, 139, 150, or 185.

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 etc. can be mentioned. Among these, preferably C.I. I. Pigment Green 7, 36, 58, 59, 62, or 63.

The colored layer (A1) is composed of a colored layer forming composition, and the blending amount of the organic pigment (a1) is preferably 10 to 50% by mass in 100% by mass of the non-volatile content of the colored layer forming composition. .. If the blending amount of the organic pigment (a1) is less than 10% by mass, the antireflection effect on the opaque inorganic base material becomes insufficient, and if it exceeds 50% by mass, the opaque inorganic group that is the base is formed from the surface of the colored layer (A1). It may not be preferable because it becomes difficult to visually check the surface of the material. A more preferable blending amount is 15 to 45% by mass, and even more preferably 20 to 40% by mass.

<Binder resin (a2)>
The binder resin (a2) is not particularly limited, and for example, polyurethane resin, polyester resin, polyester urethane resin, urethane urea resin, alkyd resin, butyral resin, acetal resin, polyamide resin, acrylic resin, styrene-acrylic resin, styrene resin, etc. Nitrocellulose, benzylcellulose, cellulose (tri) acetate, casein, shelac, gilsonite, styrene-maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinylidene fluoride resin, vinyl acetate resin, ethylene acetic acid Vinyl resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / maleic acid copolymer resin, fluororesin, silicon resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin , Benzoguanamine resin, ketone resin, petroleum resin, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxymethyl ethyl cellulose, Examples thereof include carboxymethyl nitrocellulose, ethylene / vinyl alcohol resin, polyolefin resin, chlorinated polyolefin resin, modified chlorinated polyolefin resin, and chlorinated polyurethane resin.

The binder resin (a2) may be a photosensitive resin described later. When the binder resin (a2) contains a photosensitive resin, it is preferable that the binder resin (a2) further contains a photopolymerizable monomer (a3) and / or a photopolymerization initiator (a4).

The blending amount of the binder resin (a2) is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, still more preferably 50 to 80% by mass, based on 100% by mass of the non-volatile content of the composition for forming the colored layer. When the blending amount is within this range, a colored layer having excellent adhesion to the substrate can be obtained.

<Solvent>
The solvent is not particularly limited, and a solvent usually used in the art can be used, and the coating conditions (speed, drying conditions, etc.) can be set in consideration of performance such as boiling point, SP value, evaporation rate, and viscosity. In addition, the type and blending amount of the solvent can be appropriately selected and used alone or in combination.

Examples of the solvent include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), and an ether ester. Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule,- O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Among these, a solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable in terms of coatability and dryness. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are further preferable.

In addition to the above solvents, for example, dispersants, wet penetrants, anti-skinning agents, ultraviolet absorbers, antioxidants, cross-linking agents, preservatives, fungicides, viscosity regulators, pH. Additives such as regulators, leveling agents and antifoaming agents can be appropriately blended as long as the object of the present invention is not impaired.

<Photoresist layer (A2)>
The photoresist layer (A2) is made of a photoresist composition, and either a positive type or a negative type can be used as the photoresist composition. For example, as a negative type photoresist composition, at least a photosensitive resin is used. It is produced by blending a photoresist monomer (a3), a photoresist initiator (a4), a solvent and, if necessary, additives, various colorants, organic pigments and the like.

The photosensitive resin preferably contains a photosensitive resin containing an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group. For example, an acrylic resin having a carboxy group and a polymerizable unsaturated group in the side chain can be mentioned.

The Mw (weight average molecular weight) of the photosensitive resin is preferably 2,000 or more and 100,000 or less, more preferably 10,000 or more and 50,000 or less, and further preferably 17,000 or more and 30,000 or less. By having an appropriate Mw, it is possible to achieve both adhesion to the base material and alkali developability at a high level. The value of Mw (weight average molecular weight) / Mn (number average molecular weight) is preferably 10 or less.

The acid value of the photosensitive resin is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. With an appropriate acid value, alkali developability, adhesion to a substrate, and developability are further improved.

The blending amount of the photosensitive resin is preferably 2 to 60% by mass, more preferably 5 to 50% by mass, based on 100% by mass of the non-volatile content of the photoresist composition.

<Photopolymerizable monomer (a3)>
The photopolymerizable monomer (a3) is a monomer or oligomer that produces a resin that is cured by light rays having a wavelength in the range of at least 240 to 450 nm.

The photopolymerizable monomer (a3) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β. -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethyl propantri ( Meta) acrylate, Phenoxytetraethylene glycol (meth) acrylate, Phenoxyhexaethylene glycol (meth) acrylate, Trimethylolpropane PO-modified tri (meth) acrylate, Trimethylolpropane EO-modified tri (meth) acrylate, Isocyanuric acid EO-modified di (meth) acrylate Meta) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di ( Meta) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) Various acrylic acid esters and methacrylate esters such as (meth) acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene Glycoldivinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned.

(Photopolymerizable monomer having an acid group)
The photopolymerizable monomer (a3) can contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

The photopolymerizable monomer having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a mono. Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

(Photopolymerizable monomer having urethane bond)
The photopolymerizable monomer (a3) can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a (meth) acrylate having a hydroxyl group by reacting an alcohol with a polyfunctional isocyanate. Examples thereof include a polyfunctional urethane acrylate obtained by the above-mentioned.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate , Glyoxide dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

The photopolymerizable monomer (a3) can be used alone or in combination of two or more.

The blending amount of the photopolymerizable monomer (a3) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile content of the photoresist composition. When an appropriate amount is blended, curability and developability are further improved.

<Photopolymerization initiator (a4)>
The photopolymerization initiator (a4) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-. On, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) ) Phenyl] -2- (phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Acetphenone compounds such as butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2 Thioxanthone compounds such as −methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) Triazine compounds such as -6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl -, 2- (O-benzoyloxime)], or etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. Oxim ester compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrene quinone, camphor Examples thereof include quinone-based compounds such as quinone and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanosen-based compounds. Among these, oxime ester compounds are preferable.

(Oxime ester compound)
When an oxime ester compound absorbs ultraviolet rays, the NO bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure.

Oxime ester compounds are described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, and the like. Ester-based photopolymerization initiators can be mentioned.

The photopolymerization initiator (a4) can be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator (a4) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the photopolymerizable monomer (a3). When an appropriate amount is blended, the photocurability and developability are further improved.

In addition, the photoresist composition may contain a sensitizer, if necessary.
The sensitizer includes, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives , Azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylglioxylates, benzyls, 9,10-phenanthrene quinones, camphorquinones, ethyl anthraquinones, 4,4'-diethylisophthalophenones, 3,3'or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like can be mentioned. Among these, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are preferable. Specific compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis. (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like are preferable.

The sensitizer can be used alone or in combination of two or more.

The blending amount of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (a4). When an appropriate amount is contained, curability and developability are further improved.

<< Pattern manufacturing method >>
<Opaque inorganic base material>
Examples of the opaque inorganic base material used in the present invention include various metals such as aluminum, copper, iron and silicon _{, metal oxides such as SiO 2} and Al ₂ O _3, and alloys such as stainless steel. Further, a base material whose partial surface or all surface of the above-mentioned various metals and alloys is coated with a metal oxide such as _{SiO 2} and Al ₂ O _{3 is also included.} Further, the surface of the non-metal material may be made into an opaque inorganic base material by subjecting a material such as the metal to a treatment such as vapor deposition or coating.

<Process for manufacturing laminate>
The composition for forming a colored layer is applied onto these opaque inorganic substrates by casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, etc. A colored layer (A1) is formed by applying by a wet coating method such as inkjet and heating and drying to remove the solvent component.
The thickness of the colored layer (A1) is preferably about 1 to 4 μm. When the film thickness is within this range, the antireflection effect on the opaque inorganic substrate becomes good.

Further, the photoresist composition is similarly cast on the colored layer (A1), spin coating, dip coating, bar coating, spray, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, By applying by a wet coating method such as inkjet and heating and drying to remove the solvent component, a laminate is created in which a photoresist layer (A2) is formed on an opaque inorganic substrate via a colored layer (A1). do.
The colored layer (A1) may be two or more layers. The photoresist layer (A2) may have two or more layers. The colored layer (A1) and the photoresist layer (A2) may be the same, and the laminate may be only two layers, an opaque inorganic base material and the colored layer (A1). The laminate may be three layers of an opaque inorganic base material, a colored layer (A1), and a photoresist layer (A2), and the colored layer (A1) may have a photoresist property. The opaque inorganic base material, the colored layer (A1), and the photoresist layer (A2) are preferably laminated in this order, but the opaque inorganic base material, the photoresist layer (A2), and the colored layer (A1) are laminated in this order. It may be.

<Exposure process, process of forming a latent image of a photoresist pattern>
A desired photomask is formed on the surface of the laminate formed on the opaque inorganic base material in the above step by a known method, and light rays having a wavelength in the range of 240 to 450 nm, specifically g-rays (wavelength 436 nm), h. A latent image of a photoresist pattern can be formed by exposure with a line (wavelength 405 nm), i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), semiconductor laser (wavelength 405 nm) or the like.
When the light beam in the wavelength range of 240 to 450 nm is a laser or LED having a wavelength width of 10 nm or less, the laser ONOFF function is used to expose the light beam by a scanning method that does not use a photomask, and the photo is taken. It is also possible to form a latent image of the resist pattern.

The laminate of the present invention is effective when the shape of the photoresist pattern is a perforation pattern. In particular, in the form of masking the perforated portion and developing and removing the unexposed portion, the light rays that have exposed the exposed portion are scattered to cure the unexposed portion, and the pores are formed. It can be prevented from being buried. Here, the perforation pattern means a pattern in which the outer edge of the developed portion on the surface of the laminated body has a closed curve. The shape of the closed curve does not necessarily have to be circular, and may be a thread-like narrow groove that does not reach the edge of the laminate. Further, the holes do not need to penetrate the organic resin layer (A). Further, the inside of the hole may not be entirely a space, but may have a serpentine shape with a partially undeveloped portion.

<Development process>
After forming a latent image of the photoresist pattern, the photoresist pattern is formed by developing with an alkaline developer.
According to this method, the colored layer (A1) suppresses diffuse reflection of light rays used for exposure on the surface of the highly opaque inorganic base material, so that a photoresist pattern faithful to the photomask used can be formed.
The photoresist pattern can be used as an etching resist for etching a material such as a metal constituting an opaque inorganic base material, and can also use an uneven design or unevenness such as reflected light control. Further, the recesses of the photoresist pattern may be filled with a surface protective agent or the like.

Here, the opaque inorganic base material, the colored layer (A1) containing the photopolymerizable monomer (a3), the photopolymerization initiator (a4), and the negative photoresist layer as the organic resin layer (A). In the case of the embodiment in which the photoresist pattern is formed on the laminate composed of (A2), the non-exposed portion of the colored layer (A1) is removed by the development treatment together with the photoresist layer (A2), so that the surface of the opaque inorganic substrate is removed. It becomes an exposed state and can be used as an etching mask or the like for forming an etching pattern on the surface of the substrate.
Further, a laminate (colored layer (A1) consisting of only an opaque inorganic base material, a photopolymerizable monomer (a3) as the organic resin layer (A), and a colored layer (A1) containing a photopolymerization initiator (a4). ) And the photoresist layer (A2) are the same), the surface of the opaque inorganic base material is exposed because the non-exposed portion is similarly removed by the development process. It can be used as an etching mask or the like.
On the other hand, in the embodiment in which a photoresist pattern is formed on a laminate composed of an opaque inorganic base material, a colored layer (A1) having no photoresist property, and a negative type photoresist layer (A2), the surface of the base material. Although the colored layer (A1) remains in the non-exposed portion of the structure, it can be used as it is, or it can be used as a structure in which the colored layer (A1) of the non-exposed portion is removed by dry etching or the like. Available.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the production examples and the examples, "parts" is "parts by mass" and "%" is "% by mass" unless otherwise specified.

First, a method for calculating the weight average molecular weight of the resin and the method for measuring the acid value of the resin will be described.

(Average molecular weight of resin)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40 ° C. , A THF solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluate and injected in 20 μl. All molecular weights are polystyrene-equivalent values.

(Acid value of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution and stirred to uniformly dissolve the solution. Using a 0.1 mol / L KOH aqueous solution as a titrator, an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo) ) Was titrated, and the acid value (mgKOH / g) of the resin solution was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

<Production example of binder resin>
(Preparation of binder resin solution)
The inside of the flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube was made into a nitrogen atmosphere, 150 parts of propylene glycol monomethyl ether acetate (PGMAc) was added, and the temperature was raised to 100 ° C. while stirring. Next, a mixed solution of 106 parts of benzyl methacrylate, 22 parts of acrylic acid, 22 parts of dicyclopentanyl methacrylate, and 3.6 parts of 2,2'-azobisisobutyronitrile was added dropwise to the flask and 5 at 100 ° C. A solution of acrylic resin was obtained by continuing stirring for a time. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 40%. Prepared a binder resin solution. The weight average molecular weight (Mw) was 20,000.

(Preparation of photosensitive resin solution)
Put 100 parts of propylene glycol monomethyl ether acetate (PGMAc) in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and heat to 120 ° C. while injecting nitrogen gas into the container at the same temperature. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 2.5 parts of 2,2'-azobisisobutyronitrile was poured from the dropping tube over 2.5 hours. The dropping was carried out and a polymerization reaction was carried out.
Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours to obtain a weight average molecular weight (Mw). Obtained about 20,000 resin solutions.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours, and PGMAc was added so that the non-volatile content became 40% to prepare a photosensitive resin solution.

<Preparation of pigment dispersion liquid>
(Preparation of Pigment Dispersion Liquid 1)
As a pigment, C.I. I. 15 parts of Pigment Green 36, 12.5 parts of BYK-LPN21116 (manufactured by Big Chemie) as a dispersant (40% by mass of non-volatile content), and 72.5 parts of propylene glycol monomethyl ether acetate (PGMAc) as a solvent are mixed and used by a bead mill. The treatment was carried out to prepare a pigment dispersion liquid 1.

(Preparation of pigment dispersion liquids 2 to 6)
As a pigment, C.I. I. Pigment dispersions 2 to 6 were prepared in the same manner as above except that the pigments shown in Table 1 were used instead of Pigment Green 36.

The pigments used in Table 1 are as follows.
PG36: Lionol Green 6YK, Toyo Color PG58: FASTGEN GREEN A110, DIC PR254: Irga Fore Red B-CF, BASF Japan PR177: Sinilex Red SR3C, Cynic PY150: Yellow Pigment E4GN, Lanxess Carbon black manufactured by MA100, manufactured by Mitsubishi Chemical Corporation

<Adjustment of composition for forming colored layer>
(A1-1)
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a colored layer forming composition (A1-1).
Pigment dispersion 1: 40.0 parts Binder resin solution (nonvolatile content 40%): 40.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts

(A1-2-7, CA1-1-2)
Colored layer forming compositions (A1-2-7, CA-1 to 2) in the same manner as the colored layer forming composition (A1-1) except that the material types and masses are changed as shown in Table 2. ) Was adjusted respectively.

The dyes used in Tables 2 and 3 are as follows.
Niglosin Dye: Niglosin Base EX, manufactured by Orient Chemical Industry Co., Ltd.

(A1-11)
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a colored layer forming composition (A1-11).
Pigment Dispersion 1: 50.0 parts Photosensitive resin solution (nonvolatile content 40%): 10.0 parts Epoxy resin (EHPE-3150, manufactured by Daicel): 1.5 parts Photopolymerizable monomer (Aronix M402, Toa Synthetic Co., Ltd.): 6.6 parts photopolymerization initiator (Irgacure OXE-02, manufactured by BASF): 0.7 parts silica dispersion (PMA-ST, PGMAc dispersion of silica fine particles manufactured by Nissan Chemical Industry Co., Ltd. (nonvolatile) 30%): 3.0 parts propylene glycol monomethyl ether acetate: 28.2 parts

(A1-12-17, CA1-3-4)
Colored layer forming compositions (A1-12-17, CA1-3-4) in the same manner as the colored layer forming composition (A1-11) except that the material types and masses are changed as shown in Table 3. ) Was adjusted respectively.

<Adjustment of photoresist composition>
(A2-1)
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photoresist composition (B-1).
Photosensitive resin solution (nonvolatile content 40%): 30.0 parts Epoxy resin (EHPE-3150, manufactured by Daicel): 1.5 parts Photopolymerizable monomer (Aronix M402, manufactured by Toa Synthetic Co., Ltd.): 5.0 Part Photopolymerization Initiator (Irgacure OXE-02, manufactured by BASF): 1.0 part Silica dispersion (PMA-ST, PGMAc dispersion of silica fine particles manufactured by Nissan Chemical Industry Co., Ltd. (nonvolatile content 30%): 9.0 parts Propropylene glycol monomethyl ether acetate: 53.5 parts

[Examples 1 to 14, Comparative Examples 1 to 4]
<Evaluation of colored layer (A1)>
Regarding the colored layer (A1) formed by using the obtained composition for forming a colored layer, the maximum light transmittance of light rays in the wavelength range of 240 to 450 nm and the colored layer (A1) formed on the opaque inorganic substrate The visual state of the substrate surface as seen from the top surface was evaluated by the following method. The results are shown in Tables 4 and 5.

(Maximum light transmittance)
The composition for forming a colored layer (A1-1-7, CA1-1-2) and (A1-11-17, CA1-3-4) are mixed with a glass substrate (Corning) having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm. A substrate coated on a glass eagle 2000) manufactured by the same company using a spin coater so as to have a dry film thickness of 2.0 μm was obtained. Next, for the colored layer forming composition (A1-1-7, CA1-1-2), the substrate was dried on a hot plate at 80 ° C. for 10 minutes, and then heated at 230 ° C. for 20 minutes to form a glass substrate. The coated colored layer (A1) was prepared. For the colored layer forming composition (A1-11-17, CA1-3-4), the substrate was dried on a hot plate at 80 ° C. for 10 minutes, and then an illuminance of 20 mW / cm ^{2 was used using an ultra-high pressure mercury lamp.} The colored layer (A1) coated on the glass substrate was prepared by exposing to ultraviolet rays at an exposure amount of 200 mJ / cm ^{2 and then heating at 230 ° C. for 20 minutes.}
The obtained colored layer (A1) was measured for an absorption spectrum in the wavelength range of 240 to 450 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), and the maximum value of the transmittance in this range was the maximum light transmission. The rate (%) was used.

(Visible state of the base material surface)
Compositions for forming a colored layer (A1-1 to 7, CA1-1 to 2) and (A1-11 to 1-11) are formed on the surface of an opaque inorganic base material in which a pattern is formed by coating a part of the silicon surface with SiO _2. A substrate was obtained by applying 17, CA1-3 to 4) using a spin coater so that the dry film thickness was 2.0 μm. Next, for the colored layer forming composition (A1-1-7, CA1-1-2), the substrate was dried on a hot plate at 80 ° C. for 10 minutes and then heated at 230 ° C. for 20 minutes to form an opaque inorganic group. A colored layer (A1) applied to the material was prepared. For the colored layer forming composition (A1-11-17, CA1-3-4), the substrate was dried on a hot plate at 80 ° C. for 10 minutes, and then an illuminance of 20 mW / cm ^{2 was used using an ultra-high pressure mercury lamp.} The colored layer (A1) coated on the opaque inorganic substrate was prepared by exposing to ultraviolet rays at an exposure amount of 200 mJ / cm ^{2 and then heating at 230 ° C. for 20 minutes.}
When the surface of the opaque inorganic base material was observed from the upper surface of the obtained colored layer (A1) with a 200x optical microscope, the visual state of the base material surface was evaluated according to the following criteria.
〇: The pattern shape on the surface of the base material can be recognized.
X: The pattern shape on the surface of the base material cannot be recognized.

[Examples 15 to 28, Comparative Examples 5, 6, 8, 9]
(Preparation of laminate)
The composition for forming a colored layer (A1-1-7, CA1-1-2, A1-11-17, CA1-3-4) is spun on the surface of an opaque inorganic base material having a coating layer _{of SiO 2 on} the silicon surface. A substrate coated with a coater so as to have a dry film thickness of 2.0 μm was obtained. Next, after drying on a hot plate heated to 80 ° C. for 10 minutes, the photoresist composition (A2-1) was applied onto the hot plate using a spin coater so that the dry film thickness was 2.0 μm. Further, it was dried on a hot plate heated to 80 ° C. for 10 minutes to obtain a laminate.

(Preparation of photoresist pattern)
The laminate obtained above was exposed to ^{2000 J / m 2} at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.). The exposure was carried out through a photomask in which a 10.0 μm square light-shielding part and a transmissive part were lined up in a checkered pattern. The coating film after exposure was paddle-developed with an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute. After paddle development, the substrate was rinsed with pure water in a spin shower for 20 seconds, the substrate was dried by spin drying, and then heated in a clean oven at 230 ° C. for 20 minutes. With respect to the obtained photoresist pattern, the photoresist pattern, which is a perforation pattern formed by the light-shielding portion, was observed using a scanning electron microscope (“S-3000N” manufactured by Hitachi High-Tech Corporation), and the resolution was determined according to the following criteria. The pattern rectangularity was evaluated. The results are shown in Tables 6 and 7.

(Resolution)
⊚: Hole size is 9.5 μm or more and less than 10.0 μm (very good level)
◯: Hole size is 9.0 μm or more and less than 9.5 μm (good level)
Δ: Hole dimensions of 8.0 μm or more and less than 9.0 μm (practical level)
X: Hole size is less than 8.0 μm (level not suitable for practical use)

(Pattern rectangularity)
◎; Upper bottom line width / lower bottom line width ≧ 0.90 (very good level)
◯; 0.80 ≤ upper bottom line width / lower bottom line width <0.90 (good level)
Δ; 0.70 ≦ upper bottom line width / lower bottom line width <0.80 (practical level)
×; Upper bottom line width / lower bottom line width <0.70 (level unsuitable for practical use)

[Comparative Example 7]
A substrate obtained by applying a photoresist composition (A2-1) to the surface of an opaque inorganic base material having a coating layer of SiO _{2 on the silicon surface using a spin coater so that the dry film thickness was 2.0 μm.} Next, it was dried on a hot plate heated to 80 ° C. for 10 minutes to form a photoresist layer (A2) on an opaque inorganic substrate.
With respect to this photoresist layer (A2), a photoresist pattern was prepared in the same manner as in Examples 15 to 28, and the resolution and pattern rectangularity were evaluated. The results are shown in Table 6.

[Example 29]
A substrate obtained by applying the composition for forming a colored layer (A1-13) to the surface of an opaque inorganic base material having a coating layer of SiO _{2 on the silicon surface using a spin coater so that the dry film thickness is 2.0 μm.} rice field. Next, it was dried on a hot plate heated to 80 ° C. for 10 minutes to form a colored layer having a photoresist property on an opaque inorganic substrate.
With respect to this colored layer having a photoresist property, a photoresist pattern was prepared in the same manner as in Examples 15 to 28 above, and the resolution and the pattern rectangularity were evaluated. The results are shown in Table 7.

Claims (6)

A laminate composed of an opaque inorganic base material and one or more organic resin layers (A).
At least one layer of the organic resin layer (A) is a colored layer (A1) containing an organic pigment (a1) and a binder resin (a2).
Moreover, at least one layer of the organic resin layer (A) is a photoresist layer (A2).
The colored layer (A1) is a laminate in which the maximum value of the light transmittance of the light beam is 15% or less in the wavelength range of 240 to 450 nm when formed to a film thickness of 2.0 μm.
However, the colored layer (A1) and the photoresist layer (A2) may be the same or different. The laminate according to claim 1, wherein the photoresist layer (A2) contains at least a binder resin (a2), a photopolymerizable monomer (a3), and a photopolymerization initiator (a4). .. The laminate according to claim 1 or 2, wherein the organic pigment (a1) contains at least one selected from the group consisting of a red pigment, a yellow pigment, and a green pigment. The red pigment is C.I. I. Pigment Red is at least one selected from the group consisting of 177, 254, 291, 295, and 296, and the yellow pigment is C.I. I. Pigment Yellow is at least one selected from the group consisting of 138, 139, 150, and 185, and the green pigment is C.I. I. The laminate according to claim 3, wherein the laminate is at least one selected from the group consisting of Pigment Green 7, 36, 58, 59, 62, and 63. A method for producing a photoresist pattern using the laminate according to any one of claims 1 to 4.
A step of exposing the laminate with a light beam having at least a wavelength in the range of 240 to 450 nm to form a latent image of a photoresist pattern.
A method for producing a photoresist pattern, which comprises a step of developing a laminate on which a latent image is formed. The method for producing a photoresist according to claim 5, wherein the photoresist pattern is a perforation pattern.