Method for forming pattern on laminate and composition used therefor

Abstract

An exposure light absorbing film-forming composition for forming an exposure light absorbing film pattern that prevents exposure light from transmitting therethrough, the exposure light absorbing film-forming composition comprising: an alkali-soluble resin; a light absorber that absorbs the exposure light; and a solvent, wherein the exposure light absorbing film is formed by firing the exposure light absorbing film-forming composition, exhibits dissolving agent resistance to a dissolving agent contained in a resist material for forming a resist film disposed on the exposure light absorbing film in order to form the exposure light absorbing film pattern by processing the exposure light absorbing film in a pattern-like manner, and exhibits solubility to an alkaline developing solution for the resist film.

Description

Method for forming a pattern on a laminate and composition used therein

[0001] The present invention relates to a composition for forming an exposure light-absorbing film, an exposure light-absorbing film, a laminate, a method for forming a pattern on a laminate, an exposure light-absorbing layer, and a display device.

[0002] In electronic devices using display elements such as organic light-emitting diodes (OLEDs) that utilize organic electroluminescence (EL), color filters, circular polarizers, touch panels, etc. may be formed on the display elements. Methods for forming color filters or touch panels on display elements generally include a method in which a color filter, a film-like circular polarizer, or a touch panel that has been previously fabricated on a glass substrate is attached to the display element, and a method in which the color filter, circular polarizer, touch panel, etc. is formed on the display element. In the case of a method in which a color filter, circular polarizer, touch panel, etc. is formed on a display element, exposure may be performed when forming the color filter, circular polarizer, or touch panel. In this case, ultraviolet light used for exposure may damage the display element.

[0003] Therefore, as a technology for preventing damage to organic EL elements due to exposure to light, an organic EL display device has been proposed that includes an organic EL element, a color filter or touch panel formed above the organic EL element, and a layer between the organic EL element and the color filter or touch panel, the layer having a light transmittance of 30% or less at a wavelength of 313 nm (see Patent Document 1).

[0004] Japanese Patent Application Laid-Open No. 2018-147812

[0005] In the technology of Patent Document 1, a layer having a light transmittance of 30% or less at a wavelength of 313 nm is provided between the organic EL element and the color filter or touch panel as a layer for preventing transmission of exposure light.

[0006] When manufacturing a display device having a display element, a layer provided on the display element is required to be easily processable into a desired pattern.

[0007] The present invention has been made in view of the above circumstances, and has an object to provide an exposure-light-absorbing film-forming composition capable of forming an exposure-light-absorbing film that can be easily processed into a desired pattern and that can prevent transmission of exposure light, an exposure-light-absorbing film formed from the exposure-light-absorbing film-forming composition, a laminate using the exposure-light-absorbing film, a method for forming a pattern of the laminate, an exposure-light-absorbing layer obtained by the method for forming a pattern of the laminate, and a display device that uses the exposure-light-absorbing layer.

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0009] That is, the present invention encompasses the following aspects. [1] A composition for forming an exposure-light-absorbing film for forming an exposure-light-absorbing film pattern that prevents transmission of exposure light, the composition for forming an exposure-light-absorbing film containing an alkali-soluble resin, a light absorber that absorbs the exposure light, and a solvent, and the exposure-light-absorbing film formed by baking the composition for forming an exposure-light-absorbing film exhibits solvent resistance to a solvent contained in a resist material for forming a resist film that is disposed on the exposure-light-absorbing film to process the exposure-light-absorbing film into a pattern to form the exposure-light-absorbing film pattern, and exhibits solubility in an alkaline developer for the resist film. [2] The composition for forming an exposure-light-absorbing film according to [1], wherein the alkali-soluble resin is a polyamic acid. [3] The composition for forming an exposure-light-absorbing film according to [1] or [2], which contains a crosslinking agent. [4] The composition for forming an exposure-light-absorbing film according to [3], wherein the crosslinking agent is an epoxy compound. [5] The composition for forming an exposure-light-absorbing film according to any one of [1] to [4], which contains a development speed adjuster. [6] The composition for forming an exposure-light-absorbing film according to [5], wherein the development speed adjuster is a compound containing a phenolic hydroxyl group or a carboxy group. [7] The composition for forming an exposure-light-absorbing film according to any one of [1] to [6], wherein the light absorber is an ultraviolet absorber. [8] The composition for forming an exposure-light-absorbing film according to any one of [1] to [7], which is a cured film of the composition for forming an exposure-light-absorbing film according to any one of [1] to [7]. [9] The exposure-light-absorbing film according to [8], which is non-photosensitive.

[10] A laminate comprising a substrate on which a plurality of display elements are arranged, and the exposure-light-absorbing film according to [8] or [9] arranged on the substrate.

[11] The laminate according to

[10] , wherein the exposure light absorbing film has a solvent resistance exhibiting temperature to a solvent contained in a resist material for forming a resist film to be disposed on the exposure light absorbing film in order to process the exposure light absorbing film into a pattern to form an exposure light absorbing film pattern, the temperature being set to be lower than a developer insolubilization temperature of the exposure light absorbing film in an alkaline developer.

[12] A method for forming a pattern on a laminate, the method comprising: forming an exposure-light-absorbing film on a substrate having a plurality of display elements arranged thereon using the composition for forming an exposure-light-absorbing film according to any one of [1] to [7]; forming a resist film on the exposure-light-absorbing film; exposing the resist film to light and developing a desired portion of the resist film and the exposure-light-absorbing film formed under the desired portion of the resist film; and removing the patterned resist film obtained by the development.

[13] The method for forming a pattern on a laminate according to

[12] , the method further comprising: thermally curing the patterned exposure-light-absorbing film obtained by the development by baking.

[14] The method for forming a pattern on a laminate according to

[12] or

[13] , the baking performed when forming the exposure-light-absorbing film is performed under a temperature condition between a temperature at which the exposure-light-absorbing film develops solvent resistance to a solvent contained in a resist material for forming the resist film and a temperature at which the exposure-light-absorbing film becomes insolubilized in an alkaline developer.

[15] An exposed light absorbing layer, which is one of a plurality of exposed light absorbing layers obtained by dividing the exposed light absorbing film by the method for forming a laminate pattern according to any one of

[12] to

[14] .

[16] A display device having the exposed light absorbing layer according to

[15] and an organic light emitting element or a quantum dot light emitting element.

[0010] According to the present invention, it is possible to provide an exposure-light-absorbing film-forming composition capable of forming an exposure-light-absorbing film that can be easily processed into a desired pattern and that can prevent transmission of exposure light, an exposure-light-absorbing film formed from the exposure-light-absorbing film-forming composition, a laminate using the exposure-light-absorbing film, a method for forming a pattern of the laminate, an exposure-light-absorbing layer obtained by the method for forming a pattern of the laminate, and a display device using the exposure-light-absorbing layer.

[0011] FIG. 1 is a graph showing the relationship between the baking temperature of an exposure light-absorbing film and the degree of solvent resistance exhibited by the exposure light-absorbing film as a result of the baking, and the relationship between the baking temperature of an exposure light-absorbing film and the degree of insolubilization in a developer exhibited by the exposure light-absorbing film as a result of the baking. FIG. 2A is a schematic diagram illustrating an example of a method for forming a pattern of a laminate (Part 1). FIG. 2B is a schematic diagram illustrating an example of a method for forming a pattern of a laminate (Part 2). FIG. 2C is a schematic diagram illustrating an example of a method for forming a pattern of a laminate (Part 3). FIG. 2D is a schematic diagram illustrating an example of a method for forming a pattern of a laminate (Part 4). FIG. 2E is a schematic diagram illustrating an example of a method for forming a pattern of a laminate (Part 5). FIG. 2F is a schematic diagram illustrating an example of a method for forming a pattern of a laminate (Part 6). FIG. 3 is a graph showing the results of measuring the transmittance of the exposure light-absorbing film obtained in the example at 300 nm to 800 nm. FIG. 4 is an SEM image of the pattern of the obtained exposure light-absorbing film.

[0012] (Composition for forming an exposure-light-absorbing film) The composition for forming an exposure-light-absorbing film of the present invention contains an alkali-soluble resin, a light absorber, and a solvent. The composition for forming an exposure-light-absorbing film is a composition for forming an exposure-light-absorbing film pattern that prevents transmission of exposure light. The light absorber absorbs exposure light. The exposure-light-absorbing film formed by baking the composition for forming an exposure-light-absorbing film exhibits solvent resistance to solvents contained in resist materials for forming a resist film that is placed on the exposure-light-absorbing film in order to process the exposure-light-absorbing film into a pattern to form an exposure-light-absorbing film pattern, and exhibits solubility in an alkaline developer for the resist film.

[0013] The composition for forming an exposure light-absorbing film may contain a crosslinking agent, a development speed adjuster, and the like.

[0014] By using an exposure-light-absorbing film formed from the composition for forming an exposure-light-absorbing film of the present invention, the resist film formed on the exposure-light-absorbing film can be exposed and developed to pattern the resist, and the exposure-light-absorbing film can also be patterned. Therefore, for example, an independent exposure-light-absorbing layer obtained by patterning can be disposed on each display element of a substrate on which a plurality of display elements are arranged. The composition for forming an exposure-light-absorbing film of the present invention contains a light absorber that absorbs exposure light. Therefore, each exposure-light-absorbing layer of a patterned exposure-light-absorbing film (exposure-light-absorbing film pattern) formed from the composition for forming an exposure-light-absorbing film can prevent the transmission of exposure light. Therefore, by providing an exposure-light-absorbing layer between a display element (e.g., an organic EL element) and a color filter, a circular polarizer, or a touch panel, it is possible to prevent exposure light from reaching the display element and deteriorating the display element when producing the color filter, circular polarizer, or touch panel.

[0015] The exposure light used when producing a color filter, circularly polarizing plate, or touch panel is not particularly limited, and examples thereof include exposure light containing any light in the wavelength range of 313 nm to 436 nm, KrF excimer laser, ArF excimer laser, etc. Examples of exposure light containing at least any light in the wavelength range of 313 nm to 436 nm include exposure light containing at least any of g-line (436 nm), h-line (405 nm), and i-line (365 nm). The light used for exposure may be laser or non-laser. Non-laser exposure is performed using, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, etc. The irradiation energy used for exposure is not particularly limited.

[0016] <Alkali-Soluble Resin> The alkali-soluble resin is not particularly limited and can be appropriately selected depending on the purpose, as long as the composition for forming an exposure light-absorbing film of the present invention, which is formed by baking the composition for forming an exposure light-absorbing film containing an alkali-soluble resin, exhibits solvent resistance to the solvent contained in the resist material for forming the resist film and exhibits solubility in the alkaline developer of the exposure light-absorbing film. It is more preferable that the alkali-soluble resin is a polyamic acid.

[0017] <<Polyamic Acid>> The polyamic acid that is the alkali-soluble resin according to the present invention is preferably a polyamic acid having a repeating unit represented by the following formula (1).

[0018] (R １ is a tetravalent organic group constituting a tetracarboxylic acid or a derivative thereof, and R ２ is a divalent organic group constituting a diamine, and k is a natural number.

[0019] The method for obtaining this polyamic acid is not particularly limited, but it can generally be obtained by reacting and polymerizing a diamine with a tetracarboxylic acid or its derivatives such as a tetracarboxylic acid dianhydride or a dicarboxylic acid dihalide, etc. Also, a method that usually can be used is to react and polymerize a diamine with a tetracarboxylic acid dianhydride (hereinafter abbreviated as acid dianhydride) in a polar solvent such as N-methylpyrrolidone.

[0020] The diamines that can be used to obtain polyamic acid are not particularly limited, and may be used alone or in combination of two or more. Specific examples include p-phenylenediamine, m-phenylenediamine, 4,4-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3',5,5'- Tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aniline) Hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluyl)hexafluoropropane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,10-bis(4-aminophenoxy)deca Examples of suitable diamines include bis[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3,5-diaminobenzoic acid, 4-aminobenzoic acid-4-aminophenyl, and 4,4'-diaminobenzanilide. It is also preferable to use a siloxane-containing diamine to enhance adhesion to the substrate. Examples of suitable siloxane-containing diamines include the following diamines:

[0021] (wherein p represents an integer of 1 to 10)

[0022] The acid dianhydride that can be used to obtain the polyamic acid is not particularly limited, and one or more of these may be used simultaneously. Specific examples of the acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride. In addition, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, Examples of the tetracarboxylic acid dianhydride include hydrates, alicyclic tetracarboxylic acid dianhydrides such as 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride and 3,5,6-tricarboxy-2-norbornane acetic acid dianhydride, and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butane tetracarboxylic acid dianhydride.

[0023] In terms of the solubility of the polyamic acid resin coating film in an alkaline developer, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenetetracarboxylic acid dianhydride, Acid dianhydrides consisting of tetracarboxylic acids in which four carbonyl groups are not directly bonded to aromatic rings, such as lenthrin succinic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, and 3,5,6-tricarboxy-2-norbornane acetic dianhydride, are preferred, and 1,2,3,4-cyclobutane tetracarboxylic dianhydride is more preferred.

[0024] In the polymerization of polyamic acid, the ratio of the total number of moles of diamine to the total number of moles of acid dianhydride is preferably 0.8 to 1.2. As with ordinary polycondensation reactions, the closer this molar ratio is to 1, the higher the degree of polymerization of the resulting polymer. If the degree of polymerization is too low, the film strength will be insufficient. On the other hand, if the degree of polymerization is too high, workability during film production may be impaired. Therefore, the degree of polymerization of the product in the present invention is preferably such that the reduced viscosity is 0.05 to 5.0 dl / g (in N-methylpyrrolidone at a temperature of 30°C, at a concentration of 0.5 g / dl). In particular, the reduced viscosity is preferably 0.2 to 2.0 dl / g. Examples of polar solvents that can be used when reacting a diamine and an acid dianhydride in a polar solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-propyl ether. These may be used alone or in combination. Furthermore, even if a solvent does not dissolve polyamic acid, it may be mixed with the above solvent as long as the polyamic acid produced by the polymerization reaction does not precipitate. The reaction temperature between the diamine and the acid dianhydride can be selected from the range of −20 to 150°C, preferably −5 to 100°C. The polyamic acid thus obtained can be used as it is, or can be recovered and used after isolation by precipitation in a poor solvent such as methanol, ethanol, or water.

[0025] The content of the alkali-soluble resin in the composition for forming an exposure light-absorbing film is not particularly limited, but is preferably 10% by mass to 95% by mass, and more preferably 20% by mass to 90% by mass, based on the film-constituting components. The film-constituting components refer to components other than the solvent in the composition for forming an exposure light-absorbing film.

[0026] <Light absorber> The light absorber is not particularly limited as long as it can prevent the transmission of exposure light. Examples of the light absorber include ultraviolet absorbers. Examples of the ultraviolet absorber include ultraviolet absorbers such as benzotriazoles, benzophenones, salicylic acid esters, oxalic acid amides, nickel complex salts, triazines, benzoates, zinc oxide, and titanium oxide.

[0027] The benzotriazole-based ultraviolet absorber is an ultraviolet absorber having a benzotriazole skeleton, and examples thereof include compounds in which an aryl group (e.g., a substituted or unsubstituted phenyl group) is directly bonded to the nitrogen atom at the 2-position of benzotriazole. Examples of the benzotriazole-based ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-t-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, and the like. 2-(3-t-butyl-4-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-sec-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, TINUVIN 1130 (reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300), and the like.

[0028] The benzophenone-based ultraviolet absorber is an ultraviolet absorber having a benzophenone skeleton. Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone (oxybenzone), 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 1,4-bis(4-benzoyl-3-hydroxyphenyl)-butane.

[0029] The salicylate ester-based ultraviolet absorber is an ultraviolet absorber having a salicylate ester structure, and examples thereof include esters of salicylic acid and a compound having an OH group (e.g., phenol, etc.). Examples of the salicylate ester-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate.

[0030] The oxalic acid amide-based ultraviolet absorber is an ultraviolet absorber having an oxalic acid skeleton and an amide bond, and examples thereof include oxalic acid anilide derivatives, etc. Examples of the oxalic acid amide-based ultraviolet absorber include 2-ethoxy-2'-ethyl oxalic acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid bisanilide, etc.

[0031] The nickel complex salt-based ultraviolet absorber is an ultraviolet absorber that is a nickel complex salt. Examples of the nickel complex salt-based ultraviolet absorber include [2,2'-thiobis(4-t-octylphenolate)]-2-ethylhexylamine nickel salt (II) and [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine nickel salt (II).

[0032] Further examples of the ultraviolet absorber include octyl methoxycinnamate, t-butylmethoxydibenzoylmethane, hydroxyphenyltriazine-based ultraviolet absorbers [that is, ultraviolet absorbers having a hydroxyphenyltriazine skeleton; for example, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl, and derivatives thereof], diethylaminohydroxybenzoyl hexyl benzoate, zinc oxide, titanium oxide, and ethylhexyl triazone.

[0033] These may be used alone or in combination of two or more.

[0034] The content of the light absorber in the composition for forming an exposure light-absorbing film is not particularly limited, but is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on the alkali-soluble resin.

[0035] <Solvent> The composition for forming an exposure light-absorbing film of the present invention can be easily prepared by uniformly mixing the components, and is used in the form of a solution dissolved in a suitable solvent. Examples of such solvents that can be used include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents can be used alone or in combination of two or more kinds. Furthermore, high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be mixed and used.

[0036] The solution of the composition for forming an exposure light-absorbing film is preferably filtered using a filter appropriately selected according to the solution to be used, and then used. The pore size of the filter may be, for example, about 5 μm.

[0037] The content of the solvent in the composition for forming an exposure light-absorbing film is not particularly limited, but is preferably 50% by mass to 99.5% by mass, more preferably 70% by mass to 99% by mass, and particularly preferably 80% by mass to 98% by mass.

[0038] <Material Properties of Exposure-Light-Absorbing Film-Forming Composition> The exposure-light-absorbing film-forming composition of the present invention can change the developer dissolution rate of the exposure-light-absorbing film in an alkaline developer of a resist film, depending on the temperature conditions of the baking performed when forming the exposure-light-absorbing film. The exposure-light-absorbing film-forming composition of the present invention exhibits properties, for example, as shown in FIG. 1, depending on the baking temperature. FIG. 1 is a graph showing the degree of solvent resistance and the degree of insolubilization in a developer of the exposure-light-absorbing film, as a result of baking at different baking temperatures. In FIG. 1, the degree of resistance of the exposure-light-absorbing film to a solvent contained in the resist material for forming the resist film is indicated by symbol A. Furthermore, in FIG. 1, the degree of insolubilization of the exposure-light-absorbing film in a developer is indicated by symbol B. For example, when the composition for forming an exposure-light-absorbing film contains a polyamic acid, as shown by a1 in the broken line of symbol A, the exposure-light-absorbing film obtained by baking the composition for forming an exposure-light-absorbing film of the present invention at a temperature of a1 or higher exhibits increased resistance to the solvent contained in the resist material due to the onset of imidization and crosslinking reactions. Up to a2, the higher the baking temperature, the higher the solvent resistance, and at a2 or higher, the solvent resistance reaches an acceptable level. The exposure-light-absorbing film obtained by baking at a baking temperature of a2 or higher does not undergo mixing even when a resist material is applied onto the exposure-light-absorbing film. Here, the baking temperature a2 is also referred to as the "solvent resistance development temperature" of the exposure-light-absorbing film against the solvent contained in the resist material. On the other hand, as shown by b1 in the broken line of symbol B, in the exposure-light-absorbing film obtained by baking the composition for forming an exposure-light-absorbing film of the present invention at a temperature of b1 or higher, an imidization reaction or a crosslinking reaction begins, and as the imidization or crosslinking progresses, the proportion of carboxylic acid in the composition decreases, and the degree of insolubilization of the exposure-light-absorbing film in an alkaline developer increases. Note that if the baking temperature is b2 or higher, the exposure-light-absorbing film becomes insoluble in the developer. Here, the baking temperature of b2 is also referred to as the "developer insolubilization temperature" of the exposure-light-absorbing film in an alkaline developer.

[0039] In the present invention, it is preferable to use a composition for forming an exposure-light-absorbing film in which the "solvent resistance developing temperature" is set lower than the "developer insolubilization temperature." Furthermore, in the present invention, it is preferable that the baking performed when forming the exposure-light-absorbing film is performed under temperature conditions between the "solvent resistance developing temperature" and the "developer insolubilization temperature" (corresponding to the temperature range indicated by symbol T in FIG. 1). A preferable baking temperature is, for example, around 130°C to 220°C when the composition for forming an exposure-light-absorbing film contains a polyamic acid. Note that baking will also be explained in the section on the method for forming a pattern of a laminate below.

[0040] As described above, the composition for forming an exposure-light-absorbing film of the present invention may contain, in addition to the alkali-soluble resin and solvent, a crosslinking agent, a development speed adjuster, and the like. The crosslinking agent and development speed adjuster will be described in detail below. For example, when the composition for forming an exposure-light-absorbing film contains a polyamic acid as the alkali-soluble resin and an epoxy compound as the crosslinking agent, baking the composition for forming an exposure-light-absorbing film will cause a portion of the polyamic acid to be imidized, and another portion to react with the epoxy compound. By adjusting the content of the polyamic acid, the content of the epoxy compound, the content of the development speed adjuster, and the like, which are subjected to the imidization reaction in the composition for forming an exposure-light-absorbing film, it is possible to adjust the interval between the "solvent resistance exhibiting temperature" and the "developer insolubilization temperature" (corresponding to the temperature range indicated by symbol T in FIG. 1 ) and the slope of the developer dissolution rate of the exposure-light-absorbing film (corresponding to the slope from b1 to b2 in the broken line indicated by symbol B in FIG. 1 ). The wider the interval between the "solvent resistance exhibiting temperature" and the "developer insolubilizing temperature" (corresponding to the temperature range indicated by symbol T in FIG. 1 ), the easier the handling when preparing the exposure-light-absorbing film. Furthermore, the smaller the gradient of the dissolution rate of the exposure-light-absorbing film in the developer (corresponding to the gradient from b1 to b2 in the broken line indicated by symbol B in FIG. 1 ), the wider the temperature margin. Furthermore, in the present invention, the gradient of the dissolution rate of the exposure-light-absorbing film in the developer (corresponding to the gradient from b1 to b2 in the broken line indicated by symbol B in FIG. 1 ) can be adjusted by adding a development speed adjuster to the composition for forming an exposure-light-absorbing film.

[0041] <Crosslinking Agent> The composition for forming an exposure light-absorbing film of the present invention may contain a crosslinking agent in addition to the alkali-soluble resin, the light absorber, and the solvent. Examples of the crosslinking agent include epoxy compounds. Such compounds are not particularly limited as long as they have an epoxy group. For example, examples of compounds having at least two epoxy groups include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A diglycidyl ether, and pentaerythritol polyglycidyl ether. Furthermore, polymers having epoxy groups can also be used as compounds having at least two epoxy groups. Such polymers can be used without particular limitation as long as they have epoxy groups. Such polymers can be produced by addition polymerization using an addition-polymerizable monomer having an epoxy group, or by reacting a polymer compound having a hydroxyl group with a compound having an epoxy group, such as epichlorohydrin or glycidyl tosylate. Examples of such polymers include addition-polymerized polymers such as polyglycidyl methacrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate, styrene, and 2-hydroxyethyl methacrylate, and poly(3,4-epoxycyclohexylmethyl methacrylate), as well as condensation-polymerized polymers such as epoxy novolac. The weight-average molecular weight of such polymers is, for example, 300 to 200,000.

[0042] Examples of compounds having at least two epoxy groups include Sumiepoxy ELM434 and Sumiepoxy ELM434L (manufactured by Sumitomo Chemical Co., Ltd.), which are epoxy resins having an amino group; Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (manufactured by Daicel Corporation), which are epoxy resins having a cyclohexene oxide structure; JER1001, JER1002, JER1003, JER1004, JER1007, JER1009, JER1010, and JER828 (all manufactured by Mitsubishi Chemical Corporation), which are bisphenol A epoxy resins; and bisphenol F epoxy resins. phenol novolac epoxy resins such as JER152 and JER154 (all manufactured by Mitsubishi Chemical Corporation), EPPN201 and EPPN202 (all manufactured by Nippon Kayaku Co., Ltd.), cresol novolac epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.) and JER180S75 (manufactured by Mitsubishi Chemical Corporation), alicyclic epoxy resins such as Denacol EX-252 (manufactured by Nagase Chemtex Corporation), CY175, CY177 and CY179 (all manufactured by CIBA-GEIGY) AG), Araldite CY-182, CY-192, CY-184 (all manufactured by CIBA-GEIGY AG), Epiclon 200, 400 (all manufactured by Dainippon Ink Mfg. Co., Ltd.), JER871, JER872 (all manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5662 (all manufactured by Celanese Coatings Co., Ltd.), and the like, together with aliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-62 2, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, and EX-321 (manufactured by Nagase Chemtex Corporation), and triazine epoxy compounds such as TEPIC-S, TEPIC-SS, TEPIC-HS, TEPIC-VL, and TEPIC-FL (manufactured by Nissan Chemical Industries, Ltd.).The content of the epoxy group-containing compound is, for example, 70 parts by mass or less, preferably 50 parts by mass or less, and more preferably 45 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin. If the content of the epoxy group-containing compound is more than 70 parts by mass, sufficient solubility in the photoresist developer may not be obtained.

[0043] The content of the crosslinking agent in the composition for forming an exposure light-absorbing film is not particularly limited, but is, for example, 70% by mass or less, and preferably 50% by mass or less, based on the alkali-soluble resin.

[0044] <Development Speed ​​Adjuster> The composition for forming an exposure light-absorbing film of the present invention may contain a development speed adjuster in addition to the alkali-soluble resin, light absorber, and solvent. The development speed adjuster can be used for the purpose of adjusting the dissolution rate in a photoresist developer. Examples of the development speed adjuster include compounds containing a phenolic hydroxyl group or a carboxyl group.

[0045] For example, compounds having an aromatic ring substituted with a phenolic hydroxyl group or a carboxyl group are preferred. Examples include 1-naphthoic acid, 2-naphthoic acid, 1-naphthol, 2-naphthol, 1-aminonaphthalene, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 6-bromo-2-hydroxynaphthalene, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic ...2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid, 2-naphthalenedicarboxylic acid ,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy- 2-Naphthoic acid, 6-hydroxy-2-naphthoic acid, 1-bromo-2-hydroxy-3-naphthoic acid, 1-bromo-4-hydroxy-3-naphthoic acid, 1,6-dibromo-2-hydroxy-3-naphthoic acid, 3-hydroxy-7-methoxy-2-naphthoic acid, 1-amino-2-naphthol, 1,5-dimercaptonaphthalene, 1,4,5,8-naphthalenetetracarboxylic acid, 3,5-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2,6-dichloro-1 -naphthol, 2-hydroxy-3-naphthalenecarboxylic acid methyl ester, 6-hydroxy-2-naphthalenecarboxylic acid methyl ester, 3-hydroxy-7-methoxy-2-naphthalenecarboxylic acid methyl ester, 3,7-dihydroxy-2-naphthalenecarboxylic acid methyl ester, 2,4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-naphthalenethiol, 4-methoxy-1-naphthol, 6-acetoxy-2-naphthoic acid, 1,6-dibromo-1-naphthol, 2,6-dibromo-1,5-dihydroxynaphthalene, 1-acetyl-2-naphthol, 9-anthracenecarboxylic acid, 1,4,9,10-tetrahydroxyanthracene, and 1,8,9-trihydroxyanthracene, benzoic acid, 4-methylbenzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, 2-methoxybenzoic acid, isophthalic acid, terephthalic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid Acid, 2-acetoxybenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, trimesic acid, 1,4-benzenedicarboxylic acid, 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-acetylbenzoic acid, pyrrole Examples of the hydroxybenzoic acid include butyl hydroxybenzoic acid, ...

[0046] These compounds can also be used by reacting them with a polymer or a compound having one or more reactive groups. For example, in the case of a compound having a carboxy group or a phenolic hydroxyl group, compounds obtained by reacting with an epoxy compound such as tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris(p-(2,3-epoxypropoxy)phenyl)propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether, or a polymer containing a structure having an epoxy group such as glycidyl methacrylate, can be used. Examples of such development speed adjusters include compounds represented by the following formula (45): In formula (45), Ar is a benzene ring, a naphthalene ring, or an anthracene ring substituted with one or more hydroxyl groups and / or carboxy groups, and may be substituted with a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a thiol group, a thioalkyl group having 1 to 5 carbon atoms, a phenoxy group, an acetyl group, an alkoxycarbonyl group having 1 to 5 carbon atoms, and a vinyl group.

[0047]

[0048] Examples of the development speed adjuster include a combination of the above-mentioned epoxy compounds such as tris(2,3-epoxypropyl)isocyanurate and 1,4-butanediol diglycidyl ether, and 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-hydroxy- Preferred are compounds obtainable by reacting 1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-bromo-2-hydroxy-3-naphthoic acid, 1-bromo-4-hydroxy-3-naphthoic acid, 1,6-dibromo-2-hydroxy-3-naphthoic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,5-dihydroxy-2-naphthoic acid, and 1,4-dihydroxy-2-naphthoic acid with an aromatic compound having two or more carboxy groups or phenolic hydroxyl groups, such as terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, and gallic acid.

[0049] The content of the development speed adjuster is, for example, 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of the alkali-soluble resin.

[0050] The exposure light-absorbing film formed from the exposure light-absorbing film-forming composition of the present invention is preferably a non-photosensitive film. For example, when a photosensitive component is added to the exposure light-absorbing film-forming composition in order to use a photosensitive film as the exposure light-absorbing film, the light absorber contained in the exposure light-absorbing film-forming composition tends to inhibit the function of the photosensitive component (e.g., radical generation). Therefore, the photosensitivity of the exposure light-absorbing film itself may make it difficult to pattern the exposure light-absorbing film. Therefore, it is preferable to use an exposure light-absorbing film that is non-photosensitive rather than photosensitive.

[0051] (Exposure-light-absorbing film) The exposure-light-absorbing film of the present invention is a cured product of the above-mentioned composition for forming an exposure-light-absorbing film. The exposure-light-absorbing film can be produced, for example, by applying the above-mentioned composition for forming an exposure-light-absorbing film onto a substrate and baking it.

[0052] (Laminate) The laminate of the present invention comprises a substrate on which a plurality of light-emitting elements are arranged and the exposure light-absorbing film of the present invention. The laminate may further comprise a resist film. The substrate and the resist film will be described in detail below.

[0053] In preparing the laminate, it is preferable that the solvent resistance developing temperature of the exposure light absorbing film is set lower than the developer insolubilization temperature. That is, for example, as shown in FIG. 1, it is preferable that the solvent resistance developing temperature of the exposure light absorbing film (see symbol a2 in FIG. 1) is lower than the developer insolubilization temperature (see symbol b2 in FIG. 1). The baking conditions for forming the exposure light absorbing film will be explained in detail below. Note that the laminate of the present invention may be subjected to the (laminar pattern forming method) described below to prepare a laminate in which an exposure light absorbing film and a resist film are patterned.

[0054] (Method for forming a pattern of a laminate) The method for forming a pattern of a laminate of the present invention comprises at least the following steps: - a step of forming an exposure light-absorbing film on a substrate on which a plurality of display elements are arranged using the composition for forming an exposure light-absorbing film of the present invention; - a step of forming a resist film on the exposure light-absorbing film, and - a step of exposing the resist film and developing the resist film in a desired portion and the exposure light-absorbing film formed under the resist film in a desired portion, thereby obtaining a pattern of the laminate; and - a step of removing the resist film in the pattern obtained by development.

[0055] The method for forming a pattern on a laminate may further include a step of thermally curing the patterned exposure light absorbing film by baking.

[0056] <Step of forming an exposure light-absorbing film> In the step of forming an exposure light-absorbing film, for example, a composition for forming an exposure light-absorbing film is applied onto a substrate on which a plurality of display elements are arranged, and then baked to form an exposure light-absorbing film.

[0057] Examples of the substrate include glass substrates, quartz substrates, glass substrates coated with metals such as aluminum, molybdenum, and chromium, polysilicon, ITO, IZO, SiN, and SiO ２ Examples of the organic film include glass substrates on which an inorganic film such as a polyimide film, a polyethylene terephthalate film, a polycarbonate film, and a cycloolefin polymer film are formed, and semiconductor substrates such as silicon wafers, gallium arsenide, and gallium nitride. Examples of the organic film include, but are not limited to, films obtained from UV-curable resins such as color filters, overcoats, and planarizing films.

[0058] A plurality of display elements are arranged on the substrate. Examples of the display elements include organic light-emitting elements and quantum dot light-emitting elements. Examples of the organic light-emitting elements include organic EL elements. There is no particular limitation on the number of the plurality of display elements on the substrate. There is no particular limitation on the arrangement of the plurality of display elements on the substrate. There is no particular limitation on the size, structure, or shape of the display elements. There is no particular limitation on the method for forming the plurality of display elements on the substrate, and for example, a known method can be used. Each of the plurality of display elements is used, for example, as a display panel of a display device. There is no particular limitation on the display panel of a smartphone.

[0059] Examples of coating methods for the exposure-light-absorbing film-forming composition include suitable coating methods such as spinners and slit coaters. Baking is performed using heating means such as hot plates, hot-air circulating ovens, and far-infrared heating furnaces. Baking, performed when forming the exposure-light-absorbing film, is preferably performed under temperature conditions between the "solvent resistance temperature" (see symbol a2 in Figure 1 ) of the exposure-light-absorbing film in the solvent contained in the resist material used to form the resist film and the "developer insolubilization temperature" (see symbol b2 in Figure 1 ) of the exposure-light-absorbing film in the alkaline developer of the resist film. That is, the exposure-light-absorbing film is preferably formed by baking a coating film made of the exposure-light-absorbing film-forming composition at a desired temperature within the temperature range indicated by symbol T in Figure 1 . For example, if the baking temperature is higher than b2, the exposure-light-absorbing film will not dissolve in the developer; therefore, the baking temperature must be lower than b2. On the other hand, if the baking temperature is lower than a2, the exposure-light-absorbing film will dissolve in the solvent of the resist material, resulting in mixing with the resist material. Therefore, it is preferable to bake at a temperature in the range of a2 or higher and lower than b2, at which a desirable development dissolution rate is exhibited.

[0060] The film thickness of the exposed light absorbing film is, for example, 0.05 μm (50 nm) to 10 μm, 0.1 μm (100 nm) to 8 μm, or 0.5 μm (500 nm) to 5 μm.

[0061] <Step of forming resist film> A resist film is formed on the exposure light absorbing film. The method for forming the resist film is not particularly limited, and can be performed, for example, by applying a resist material on the exposure light absorbing film and baking it.

[0062] The resist material may be either a negative photoresist or a positive photoresist, and is not particularly limited as long as it responds to light or electron beams (EB) used for irradiation.

[0063] Preferred embodiments of resist materials will be described below. In this specification, resists that respond to electron beams (EB) are also referred to as photoresists. Examples of photoresists include positive photoresists composed of an alkali-soluble resin such as a phenol novolac resin, a cresol novolac resin, an acrylic acid copolymer, a methacrylic acid copolymer, a hydroxystyrene copolymer, a hydroxyphenylacrylamide copolymer, a hydroxyphenylmethacrylamide copolymer, or a hydroxyphenylmaleimide copolymer and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified positive photoresists composed of a binder having a group that is decomposed by acid to increase the alkali dissolution rate and a photoacid generator; and chemically amplified positive photoresists composed of a binder having a group that is decomposed by acid to increase the alkali dissolution rate of the photoresist. Examples of such photoresists include chemically amplified positive photoresists that consist of a low molecular weight compound that increases the dissolution rate, an alkali-soluble binder, and a photoacid generator; chemically amplified positive photoresists that consist of a binder having a group that decomposes in acid to increase the alkali dissolution rate, a low molecular weight compound that decomposes in acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator; resists containing metal elements; negative photoresists that consist of an alkali-soluble resin, a polyunsaturated group-containing monomer, and a photoradical initiator; and negative photoresists that consist of an alkali-soluble resin, a polyfunctional cationically polymerizable monomer, and a photocationic initiator.

[0064] The thickness of the resist film is, for example, 10 μm or less, 5 μm or less, or 2 μm or less.

[0065] The ratio of the thickness of the resist film to the thickness of the exposure light absorbing film (resist film / exposure light absorbing film) is not particularly limited, but is, for example, 0.01 to 10, preferably 0.03 to 5, and more preferably 0.05 to 2.

[0066] <Step of Obtaining a Pattern of Laminate> The step of obtaining a pattern of the laminate is carried out by exposing the resist film to light and developing the resist film in the desired portion and the exposed light absorbing film formed under the resist film in the desired portion.

[0067] The light used for exposure is not particularly limited, and examples thereof include exposure light containing any light in the wavelength range of 313 nm to 436 nm, KrF excimer laser, ArF excimer laser, etc. Examples of exposure light containing at least any light in the wavelength range of 313 nm to 436 nm include exposure light containing at least any of g-line (436 nm), h-line (405 nm), and i-line (365 nm). The light used for exposure may be laser or non-laser. Non-laser exposure is carried out using, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, etc. The irradiation energy used for exposure is not particularly limited.

[0068] For example, an alkaline developer is used for development. The development temperature can be, for example, 5°C to 50°C. The development time can be, for example, 10 seconds to 300 seconds. Examples of alkaline developers that can be used include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-butylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole and piperidine). Furthermore, the aqueous solutions of the alkalis can be used by adding an appropriate amount of alcohols (e.g., isopropyl alcohol) or a nonionic surfactant. Among these, preferred developers are aqueous solutions of potassium hydroxide and quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like can also be added to these developers.

[0069] For example, if the resist film is a positive resist film, the exposed portion of the resist film is dissolved by the developer, while the unexposed portion remains. In this case, during development, not only the exposed portion of the resist film but also the exposure light absorbing film formed under the exposed portion of the resist film is dissolved by the developer. That is, the exposure light absorbing film corresponding to the exposed portion where the resist film has disappeared by development is also removed by development. By removing the exposure light absorbing film, the residue of the resist film after development is also removed. In this way, the desired portion of the exposure light absorbing film and the exposure light absorbing film formed under the desired portion of the resist film are removed by development, so that no resist film residue is generated, and the patterned exposure light absorbing film is not peeled off, resulting in the formation of a good resist pattern and a pattern of the exposure light absorbing film underneath. Alternatively, if the resist film is a negative resist film, the unexposed portion of the resist film is dissolved by the developer, while the exposed portion of the resist film remains. In this case, during development, not only the resist film in the unexposed portions but also the exposure light absorbing film formed under the resist film in the unexposed portions is dissolved by the developer. That is, the exposure light absorbing film corresponding to the unexposed portions from which the resist film has been removed by development is also removed by development. By removing the exposure light absorbing film, the residue of the exposure light absorbing film after development is also removed. In this way, the resist film in the desired portions and the exposure light absorbing film formed under the resist film in the desired portions are removed by development, so that no residue of the resist film is generated, and no peeling of the patterned resist film occurs, and a good resist pattern and a pattern of the exposure light absorbing film thereunder are formed.

[0070] The shape of the pattern is not particularly limited, and examples of the pattern include a pattern in which one large exposure light absorbing film is divided into a plurality of small exposure light absorbing films (exposure light absorbing layers).

[0071] <Step of Removing the Obtained Patterned Resist Film> The removal method in the step of removing the patterned resist film obtained by development is not particularly limited. The patterned resist film is removed using, for example, a stripping solution. Removal using a stripping solution may be performed, for example, by immersing the patterned resist film in the stripping solution, or by applying the stripping solution to the patterned resist film. Examples of application methods include spray coating. Examples of stripping solutions include stripping solutions obtained by dissolving an inorganic alkali component or an organic alkali component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of inorganic alkali components include sodium hydroxide and potassium hydroxide. Examples of organic alkali components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Examples of alkaline organic compounds include tetramethylammonium hydroxide or alkanolamine compounds.

[0072] <Thermal Curing Step> The patterned exposure light-absorbing film obtained by development is thermally cured, thereby improving the film properties of the exposure light-absorbing film. The heating temperature during thermal curing is not particularly limited, and may be, for example, 150°C to 300°C. The heating time during thermal curing is not particularly limited, and may be, for example, 1 minute to 5 hours.

[0073] The thermal curing step is usually carried out after the step of removing the resist film.

[0074] An example of a method for forming a pattern on a laminate is described below using Figures 2A to 2F. First, a substrate 1 on which a plurality of display elements 1A are arranged is prepared (Figure 2A). The plurality of display elements 1A are spaced apart from one another on the substrate 1. Next, an exposure-light-absorbing film 2 is formed on the substrate 1 on which the plurality of display elements 1A are arranged (Figure 2B). The exposure-light-absorbing film 2 can be formed, for example, by applying an exposure-light-absorbing film-forming composition of the present invention and baking it. The baking conditions are appropriately adjusted so that the exposure-light-absorbing film 2 is insoluble in the solvent contained in the resist material used to form the resist film, and is soluble in the alkaline developer used to pattern the resist film. The exposure-light-absorbing film 2 is non-photosensitive. Next, a resist film 3 is formed on the exposure-light-absorbing film 2 using a negative resist material, and is exposed to light L through a mask 10 (Figure 2C). The light L can be appropriately selected depending on the photosensitivity of the resist film 3. Next, the resist film 3 and the exposure-light-absorbing film 2 are developed using an alkaline developer to obtain a patterned resist film 3A and a patterned exposure-light-absorbing film (exposure-light-absorbing film pattern 2A) (FIG. 2D). Because the exposure-light-absorbing film 2 is non-photosensitive, the entire surface of the exposure-light-absorbing film 2 is soluble in alkaline development, but the exposed portions of the resist film 3 are insoluble in alkaline development, so the exposed portions act as a mask during development, resulting in a patterned exposure-light-absorbing film (exposure-light-absorbing film pattern 2A). Next, the patterned resist film 3A is removed (FIG. 2E). The patterned resist film 3A can be removed, for example, by immersion in an alkaline stripper. Next, the exposure-light-absorbing film pattern 2A is baked (FIG. 2F). By baking, an exposure-light-absorbing film pattern 2B with improved chemical resistance is obtained.

[0075] (Exposure light absorbing layer) The exposure light absorbing layer is, for example, a layer disposed on a display element to prevent the display element from being exposed to exposure light. The exposure light absorbing layer is, for example, one of a plurality of exposure light absorbing layers obtained by dividing the exposure light absorbing layer by the laminate pattern forming method of the present invention. Therefore, the exposure light absorbing layer can be said to be a small exposure light absorbing film obtained by dividing the exposure light absorbing film.

[0076] (Display Device) The display device of the present invention includes, for example, the exposure light-absorbing layer of the present invention and a display element. The display element is, for example, an organic light-emitting element or a quantum dot light-emitting element. The display device may further include, for example, a color filter, a circular polarizer, a touch panel, etc.

[0077] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In the examples, the apparatus and conditions used for sample preparation and analysis of physical properties are as follows:

[0078] <Abbreviations of compounds> CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride APAB: 4-aminophenyl 4-aminobenzoate NMP: N-methyl-2-pyrrolidone TMAH: tetramethylammonium hydroxide PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate

[0079] (1) Ultraviolet irradiation device: PLA-600FA manufactured by Canon Inc. (2) Developing device: AD-1200 manufactured by Takizawa Sangyo Co., Ltd. (3) Gel permeation chromatography (GPC) Device: manufactured by JASCO Corporation Column: Shodex (registered trademark) GPC KD-803 and GPC KD-805 manufactured by Resonaq Co., Ltd. Column temperature: 50°C Eluent: dimethylformamide / LiBr.H ２ O (30 mM) / H ３ P.O. ４ (30 mM) / tetrahydrofuran (1%) Flow rate: 1.0 mL / min Weight average molecular weight (hereinafter referred to as Mw): Standard polyethylene oxide equivalent value (4) Residue evaluation Apparatus: Optical microscope MX61A manufactured by Olympus Corporation Apparatus: Scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation

[0080] Synthesis Example 1 Synthesis of Polyamic Acid A1 (Polyamic Acid) 8.07 g (35.3 mmol) of APAB was dissolved in 114.75 g of NMP, and then cooled to 5 to 15°C in an ice bath under a nitrogen atmosphere. 6.93 g (35.3 mmol) of CBDA and 20.25 g of NMP were added to the resulting solution, and the temperature was returned to room temperature and reacted for 24 hours. The resulting polyamic acid A1 had an Mw of 31,200 and an Mw / Mn ratio of 1.8.

[0081] Example 1 Preparation of Exposure-Light-Absorbing Film-Forming Composition 0.19 g of Uvinul (registered trademark, manufactured by BASF) 3050, an ultraviolet absorber, and 1.72 g of NMP were added to 4.78 g of a solution containing polyamic acid A1 (polyamic acid), and the mixture was stirred at room temperature for 2 hours to prepare an exposure-light-absorbing film-forming composition [1].

[0082] (Evaluation 1) <Measurement of transmittance> The composition for forming an exposure light-absorbing film [1] was applied to a quartz substrate using a spinner, and then dried on a hot plate at 90°C for 3 minutes. This was then baked on a hot plate at 190°C for 3 minutes to form an exposure light-absorbing film with a film thickness of 3 μm. The transmittance of the resulting exposure light-absorbing film in the 300 nm to 800 nm range was measured using a UV-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation). The results are shown in FIG. 3.

[0083] (Evaluation 2) <Patterning Evaluation of Laminate and Patterning Evaluation of Exposed Light Absorbing Layer Film After Peeling Off Resist Film> The composition for forming an exposed light absorbing film [1] was applied to a glass substrate with an ITO film using a spinner, and then dried on a hot plate at 90°C for 3 minutes. This was then baked on a hot plate at 190°C for 3 minutes to form an exposed light absorbing film with a film thickness of 3 μm. THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), a positive photosensitive resist, was applied to the obtained exposed light absorbing film using a spinner, and then dried on a hot plate at 90°C for 90 seconds to form a resist film with a film thickness of 1 μm. I-rays were applied at 120 mJ / cm through a mask set so as to form a 50 μm line / space pattern on the obtained laminated film. ２The resist was irradiated with light. Thereafter, paddle development was performed with a 2.38% TMAH aqueous solution at 23°C for 50 seconds, followed by rinsing with running ultrapure water for 30 seconds. The pattern of the obtained laminate was observed using an optical microscope and a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. Next, the resist was immersed in a mixed solution of PGME:PGMEA = 70:30 (mass%) for 60 seconds, and the resist was peeled off. This resulted in the formation of a line / space pattern of the exposure light absorbing layer. The pattern of the obtained exposure light absorbing film was observed using an optical microscope and a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. An SEM photograph is shown in Figure 4.

[0084] As shown in Figure 3, the transmittance of the exposed light absorbing film was 0% near 365 nm, indicating strong absorption in the i-line region. Furthermore, as shown in Figure 4, a line pattern was formed in the laminate in which a resist film was laminated on the exposed light absorbing film, according to the mask pattern, and no residue or remaining film was observed in the openings (spaces). Furthermore, as shown in the SEM image of the pattern after resist peeling in Figure 4, the pattern of the exposed light absorbing layer was maintained even after the resist film was peeled off.

[0085] REFERENCE SIGNS LIST 1 Substrate 1A Display element 2 Exposure light absorbing film 2A Exposure light absorbing film pattern 2B Exposure light absorbing film pattern 3 Resist film 3A Patterned resist film 10 Mask L Light

Claims

1. A composition for forming an exposure-light-absorbing film for forming an exposure-light-absorbing film pattern that prevents transmission of exposure light, the composition for forming an exposure-light-absorbing film containing an alkali-soluble resin, a light absorber that absorbs the exposure light, and a solvent, and the exposure-light-absorbing film formed by baking the composition for forming an exposure-light-absorbing film exhibits solvent resistance to a solvent contained in a resist material for forming a resist film that is placed on the exposure-light-absorbing film in order to process the exposure-light-absorbing film into a pattern to form the exposure-light-absorbing film pattern, and exhibits solubility in an alkaline developer for the resist film.

2. The composition for forming an exposure light absorbing film according to claim 1, wherein the alkali-soluble resin is a polyamic acid.

3. The composition for forming an exposure light-absorbing film according to claim 1, which contains a crosslinking agent.

4. The composition for forming an exposure light-absorbing film according to claim 3, wherein the crosslinking agent is an epoxy compound.

5. The composition for forming an exposure light-absorbing film according to claim 1, which contains a development speed adjuster.

6. The composition for forming an exposure light-absorbing film according to claim 5, wherein the development speed adjuster is a compound containing a phenolic hydroxyl group or a carboxyl group.

7. The composition for forming an exposure light-absorbing film according to claim 1, wherein the light absorber is an ultraviolet absorber.

8. An exposure light absorbing film, which is a cured film of the exposure light absorbing film forming composition according to any one of claims 1 to 7.

9. The exposed light absorbing film according to claim 8, which is non-photosensitive.

10. A laminate comprising a substrate on which a plurality of display elements are arranged, and the exposure light absorbing film according to claim 8 arranged on said substrate.

11. The laminate according to claim 10, wherein the temperature at which the exposure light absorbing film develops solvent resistance to a solvent contained in a resist material for forming a resist film that is disposed on the exposure light absorbing film in order to process the exposure light absorbing film into a pattern to form an exposure light absorbing film pattern is set lower than the temperature at which the exposure light absorbing film becomes insolubilized in an alkaline developer of the resist film.

12. A method for forming a pattern of a laminate, comprising the steps of: forming an exposure light absorbing film on a substrate on which a plurality of display elements are arranged using the composition for forming an exposure light absorbing film according to any one of claims 1 to 7; forming a resist film on the exposure light absorbing film; exposing the resist film to light, and developing the resist film in a desired portion and the exposure light absorbing film formed under the resist film in the desired portion; and removing the patterned resist film obtained by the development.

13. The method for forming a pattern on a laminate according to claim 12, further comprising a step of thermally curing the patterned exposed light absorbing film obtained by the development by baking.

14. The method for forming a laminate pattern according to claim 12, wherein the baking performed when forming the exposure light absorbing film is performed under temperature conditions between a temperature at which the exposure light absorbing film exhibits solvent resistance to a solvent contained in a resist material for forming the resist film and a temperature at which the exposure light absorbing film becomes insolubilized in an alkaline developer of the resist film.

15. An exposed light absorbing layer, which is one of a plurality of exposed light absorbing layers obtained by dividing the exposed light absorbing film by the method for forming a laminate pattern according to claim 12.

16. A display device comprising the exposed light absorption layer according to claim 15 and an organic light-emitting element or a quantum dot light-emitting element.

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