Positive-type photosensitive resin composition

Abstract

[Problem] The purpose of the present invention is to provide a positive-type photosensitive resin composition that is for use in liquid-crystal display elements, organic EL display elements, and the like, that provides high water repellency and oil repellency to surfaces of cured films, that generates less residue after pattern formation, and from which it is possible to form a cured film on which an organic functional ink finely spreads within a pattern while wetting the same without spilling outside. [Solution] A positive-type photosensitive resin composition from which it is possible to form a cured film containing the following component (A1), component (A2), component (B), component (C), component (D), and a solvent (E). Component (A1): An alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride. Component (A2): An alkali-soluble resin having an N-hydroxy phenyl group but not having a carboxy group. Component (B): A surfactant. Component (C): A 1,2-quinone diazide compound. Component (D): A crosslinking agent. (E) A solvent.

Description

Positive photosensitive resin composition

[0001] The present invention relates to a positive-type photosensitive resin composition and a cured film formed therefrom. More specifically, the present invention relates to a positive-type photosensitive resin composition capable of forming a cured film that is less likely to leave residue during pattern formation, has high water and oil repellency on the cured film surface, and allows organic functional ink to wet and spread well within a surrounded pattern without overflowing, a cured film formed therefrom, and various materials using the cured film. This positive-type photosensitive resin composition is particularly suitable for use as an interlayer insulating film in display elements such as liquid crystal displays, electroluminescent displays, and micro LED displays, as well as a light-shielding material and partition wall material compatible with inkjet printing.

[0002] In general, display elements such as thin film transistor (TFT) liquid crystal display elements and organic electroluminescent (EL) elements are provided with patterned electrode protection films, planarizing films, insulating films, etc. As materials for forming these films, photosensitive resin compositions have been widely used because they require fewer steps to obtain the required pattern shape and have sufficient planarity.

[0003] In recent years, full-color display substrate fabrication techniques using inkjet printing have also been actively investigated in the fabrication of display elements. For example, in the fabrication of color filters for liquid crystal display elements, in contrast to conventional printing, electrodeposition, dyeing, or pigment dispersion methods, a color filter and manufacturing method thereof (Patent Document 1) have been proposed in which pre-patterned pixel-defining sections (hereinafter referred to as banks) are formed using a light-blocking photosensitive resin layer, and ink droplets are dispensed into openings surrounded by these banks. For organic EL display elements, a method has also been proposed in which banks are prepared in advance and ink that will form the light-emitting layer is dispensed in a similar manner (Patent Document 2). However, when dispensing ink droplets surrounded by banks using the inkjet method, the substrate must be ink-philic (hydrophilic), and the bank surface must be water-repellent, to prevent the ink droplets from spilling over the bank and into adjacent pixels.

[0004] Meanwhile, in recent years, techniques using grayscale masks or halftone masks in the bank fabrication process have also been actively investigated. For example, with regard to the fabrication of color filters, a method using a halftone mask has been proposed (Patent Document 3) for forming a grid-like bank pattern in which the film thickness of the bank pattern in one direction is thinner than that of the bank pattern perpendicular to it. Also, in the case of organic EL display elements, a method of exposure via a halftone mask has been proposed (Patent Document 4) for forming a line-shaped bank pattern A and a bank pattern B for defining pixel regions arranged within the line shape, such that B is a thin film. In such techniques, a photosensitive resin composition is required in which the half-exposed portion has sufficient flatness.

[0005] To achieve the above object, a negative-type photosensitive resin composition has been proposed in which a fluorine-based surfactant or a fluorine-based polymer is blended into a photosensitive organic thin film (Patent Document 5). However, it is difficult to improve the resolution, and the application of a positive-type photosensitive resin is required to achieve high-definition display elements.

[0006] On the other hand, there is a positive-tone photosensitive resin composition that can form a pattern with high sensitivity while maintaining adhesion during development and can form a cured film with little residue in the pattern (Patent Document 6). However, there are problems in that the residue is not completely removed, and the inkjet wettability and flatness of the half-exposed area are low.

[0007] Japanese Patent Publication No. 2000-187111 Japanese Patent Publication No. 11-54270 Japanese Patent Publication No. 2009-258669 Japanese Patent No. 4495781 Japanese Patent Publication No. 2015-172742 Japanese Patent No. 6744577

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a positive photosensitive resin composition that can be used in liquid crystal display elements, organic EL display elements, etc., and that can form a cured film, which has high water repellency and high oil repellency on the surface of the cured film, leaves almost no residue after pattern formation even when a low-concentration developer is used, and is capable of simultaneously achieving high inkjet wettability, a high contact angle, and high flatness in half-exposed areas.

[0009] As a result of intensive research to achieve the above object, the present inventors have found that by mixing different alkali-soluble polymers, that is, by using an alkali-soluble resin having an N-hydroxyphenyl group in addition to a conventional alkali-soluble polymer, it is possible to weaken the alkali-insoluble group-mediated inhibitory effect of the high-acidity carboxylic acid together with a large amount of low-acidity phenol, on the penetration of a low-concentration developer, and since the development is carried out while the polymer is dissolved in the low-concentration developer, almost no residue is left after pattern formation. They have also found that by using a surfactant having a liquid-repellent group, it is possible to form a cured film that has high water repellency and high oil repellency, and that is capable of simultaneously achieving high inkjet wettability, a high contact angle, and high flatness in half-exposed areas, and have completed the present invention. A first aspect of the present invention is a cured film-forming positive photosensitive resin composition comprising the following components (A1), (A2), (B), (C), (D), and (E) a solvent: component (A1): an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride; component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and no carboxy group; component (B): a surfactant; component (C): a 1,2-quinonediazide compound; component (D): a crosslinking agent; and (E) a solvent; a second aspect of the present invention is the positive photosensitive resin composition according to the first aspect, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the above-mentioned compounds (A1-I) and the following compounds (A1-II) and (A1-III); (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A1-III) an N-substituted maleimide compound; A third aspect of the present invention is the positive photosensitive resin composition according to the second aspect, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the compounds (A1-I), (A1-II), and (A1-III) and the following compound (A1-IV); (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group;A fourth aspect of the present invention is the positive photosensitive resin composition according to the third aspect, in which the monomer (A1-IV) having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl(meth)acrylate; a fifth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fourth aspects, in which the component (A1) is an alkali-soluble acrylic polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene; a sixth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fifth aspects, in which the component (A2) is a polymer containing a structural unit derived from at least one monomer selected from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide; A seventh aspect of the present invention is the positive photosensitive resin composition according to any one of the first to sixth aspects, wherein the component (A2) is an alkali-soluble resin having a number average molecular weight of 2,000 to 60,000 in terms of polystyrene; an eighth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to seventh aspects, wherein the component (B) is a surfactant composed of a polymer having a liquid-repellent group; a ninth aspect of the present invention is the positive photosensitive resin composition according to the eighth aspect, wherein the liquid-repellent group is at least one group selected from the group consisting of a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group; a tenth aspect of the present invention is the positive photosensitive resin composition according to the eighth or ninth aspect, wherein a monomer unit constituting the polymer having a liquid-repellent group is a monomer unit derived from an unsaturated hydrocarbon having the liquid-repellent group; An eleventh aspect of the present invention is the positive photosensitive resin composition according to any one of the eighth to tenth aspects, wherein the monomer unit constituting the polymer having the liquid repellent group is a monomer unit derived from an alkoxysilane compound having the liquid repellent group; and a twelfth aspect of the present invention is the positive photosensitive resin composition according to any one of the eighth to eleventh aspects, wherein the component (B) is a surfactant composed of a polymer having the liquid repellent group and a thermosetting group.A thirteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to twelfth aspects, wherein the component (D) is a crosslinking agent made of a compound containing an epoxy group or a methoxymethyl group; a fourteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to thirteenth aspects, wherein the component (B) is contained in an amount of 0.05 to 20 parts by mass relative to 100 parts by mass of the total of the components (A1) and (A2); a fifteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fourteenth aspects, wherein the component (C) is contained in an amount of 5 to 100 parts by mass relative to 100 parts by mass of the total of the components (A1) and (A2); a sixteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fifteenth aspects, wherein the component (D) is contained in an amount of 5 to 50 parts by mass relative to 100 parts by mass of the total of the components (A1) and (A2); The seventeenth aspect of the present invention is a cured film formed from the positive photosensitive resin composition according to any one of the first to sixteenth aspects; the eighteenth aspect of the present invention is a display element having the cured film according to the seventeenth aspect; and the nineteenth aspect of the present invention is a display element having the cured film according to the seventeenth aspect as an image formation bank.

[0010] The positive photosensitive resin composition of the present invention has high water repellency and high oil repellency on the surface of a cured film, and can form a cured film with high inkjet wettability and a high contact angle, leaving little residue after pattern formation even when using a low-concentration developer.Furthermore, it can also form a cured film with high flatness in the half-exposed area.

[0011] The photosensitive resin composition of the present invention is a positive-type photosensitive resin composition capable of forming a cured film, which contains the following components (A1), (A2), (B), (C), (D), and (E) a solvent: Component (A1): an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least the following compound (A1-I); preferably an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing the following compounds (A1-I), (A1-II), and (A1-III); more preferably an alkali-soluble acrylic polymer obtained by copolymerizing the following compounds (A1-I), (A1-II), (A1-III), and (A1-IV); (A1-I) an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A1-III) an N-substituted maleimide compound (N-(hydroxyphenyl)maleimide is defined as (A1-IV)), (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group; component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and no carboxy group; component (B): a surfactant; Component (C): 1,2-quinonediazide compound, Component (D): crosslinking agent, and (E): solvent. Each component will now be described in detail.

[0012] <Component (A1)> The component (A1) is an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride. Preferably, the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least (A1-I), (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A1-III) an N-substituted maleimide compound. More preferably, the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least (A1-I), (A1-II), (A1-III), and (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0013] The acrylic polymer refers to a polymer obtained using a monomer having a polymerizable unsaturated group, i.e., a polymerizable group containing a C═C double bond in its structure, such as an acrylic acid ester, a methacrylic acid ester, styrene, or maleimide. The alkali-soluble acrylic polymer of component (A1) may be any alkali-soluble acrylic polymer, and there are no particular limitations on the types of main chain skeleton and side chains of the polymer constituting the acrylic polymer.

[0014] If the number-average molecular weight of the alkali-soluble acrylic polymer of component (A1) is too high, exceeding 30,000, the ability to flatten uneven surfaces will be reduced, while if the number-average molecular weight is too low, less than 2,000, the polymer may not be sufficiently cured during heat curing, resulting in reduced solvent resistance. Therefore, the number-average molecular weight is preferably in the range of 2,000 to 30,000.

[0015] As described above, a convenient method for synthesizing the alkali-soluble acrylic polymer of component (A1) is, for example, a method of polymerizing a monomer mixture containing (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride. In some cases, a method of copolymerizing a monomer mixture containing (A1-I), (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A1-III) an N-substituted maleimide compound. In other cases, a method of copolymerizing a monomer mixture containing (A1-I), (A1-II), (A1-III), and (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is also available.

[0016] Specific examples of constituent monomers of component (A1) include, but are not limited to, the following: Monomers containing unsaturated carboxylic acid for component (A1-I) include, for example, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide; and monomers containing unsaturated carboxylic acid anhydrides include maleic anhydride and itaconic anhydride.

[0017] (A1-II) Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0018] (A1-III) Examples of N-substituted maleimide compounds include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0019] Examples of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group for component (A1-IV) include p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, p-hydroxyphenylacrylate, and p-hydroxyphenyl methacrylate, which can be used alone or in combination of two or more. Of these, monomers selected from p-hydroxyphenyl acrylate and p-hydroxyphenyl methacrylate are preferred.

[0020] Furthermore, in the present invention, when obtaining the acrylic polymer of component (A1), other monomers A that are copolymerizable with the above-mentioned monomers (A1-I), (A1-II), (A1-III), and (A1-IV) can be used in combination. Specific examples of other monomers A include acrylic acid ester compounds, methacrylic acid ester compounds, maleimides, acrylamide compounds, acrylonitrile, and styrene compounds. Specific compound examples of other monomers A are listed below, but are not limited to these.

[0021] Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether acrylate.

[0022] Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether methacrylate.

[0023] Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

[0024] Examples of the styrene compound include styrenes having no hydroxy group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0025] The method for obtaining the alkali-soluble acrylic polymer used in the present invention is not particularly limited, but can be obtained, for example, by polymerization reaction at a temperature of 50 to 110°C in a solvent containing alkali-soluble monomers (A1-I), preferably (A1-II), (A1-III), and (A1-IV), other copolymerizable monomers, and optionally a polymerization initiator. The solvent used in this process is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer having a specific functional group. Examples of the specific functional group include a carboxy group and an acid anhydride. Specific examples of the solvent used include the solvents described below in the section on (E) solvent.

[0026] The alkali-soluble acrylic polymer having a specific functional group obtained in this manner is called a specific copolymer, and is usually in the form of a solution dissolved in a solvent.

[0027] In addition, the solution of the specific copolymer obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer.By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained.If the specific copolymer cannot be sufficiently purified by a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

[0028] In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in the solvent (E) described below and used in the form of a solution.

[0029] In the present invention, the acrylic polymer of component (A1) may be a mixture of multiple specific copolymers.

[0030] <Component (A2)> The component (A2) of the present invention is an alkali-soluble resin having an N-hydroxyphenyl group but no carboxy group. The alkali-soluble resin of the component (A2) may be any alkali-soluble resin having such a structure, and there are no particular limitations on the types of main chain skeleton and side chains of the polymer constituting the resin.

[0031] The component (A2) is preferably an alkali-soluble resin having a number-average molecular weight in the range of 2,000 to 60,000. If the number-average molecular weight is too high, exceeding 60,000, development residues are likely to be generated and sensitivity will be significantly reduced, while if the number-average molecular weight is too low, less than 2,000, a considerable amount of film loss will occur in exposed areas during development, which may result in insufficient curing.

[0032] Examples of the alkali-soluble resin (A2) that has an N-hydroxyphenyl group but no carboxy group include acrylic resins and polymaleimide resins.

[0033] In the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing multiple types of monomers can also be used as component (A2). In this case, the alkali-soluble resin of component (A2) may be a blend of multiple types of copolymers.

[0034] That is, the copolymer is formed from, as essential structural units, a monomer having an N-hydroxyphenyl group but not having a carboxy group and at least one monomer selected from the group of monomers copolymerizable with the N-hydroxyphenyl group but not having a carboxy group, and has a number average molecular weight of 2,000 to 60,000. If the number average molecular weight is greater than 60,000, residues may be generated.

[0035] The above-mentioned monomer having an N-hydroxyphenyl group but no carboxy group is not limited to one having one N-hydroxyphenyl group, but may also have a plurality of N-hydroxyphenyl groups.

[0036] Specific examples of the monomer are listed below, but are not limited to these. Examples of the monomer having an N-hydroxyphenyl group but no carboxy group include N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide.

[0037] Examples of the monomer having an N-hydroxyphenyl group and having no carboxy group that is copolymerizable with a monomer having no carboxy group include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isomethyl methacrylate, ... isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, N-phenylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, hydroxystyrene, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trimethyl- Fluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl) Examples of the methacrylic acid ester include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0038] The proportion of monomers having an N-hydroxyphenyl group but no carboxy group in the production of the alkali-soluble resin of component (A2) is preferably 10 to 90 mol %, more preferably 20 to 85 mol %, and most preferably 30 to 80 mol % of all monomers used in the production of the alkali-soluble resin of component (A2). If the proportion of monomers having an N-hydroxyphenyl group but no carboxy group is less than 10 mol %, the alkali solubility of the polymer will be insufficient.

[0039] In the production of the alkali-soluble resin (A2), the proportion of the monomer having an N-hydroxyphenyl group and not having a carboxy group that is copolymerizable with the monomer having an N-hydroxyphenyl group and not having a carboxy group is preferably 80% by weight or less, more preferably 50% by weight or less, and even more preferably 20% by weight or less. If the proportion exceeds 80% by weight, the amount of the essential components will be relatively reduced, making it difficult to fully obtain the effects of the present invention.

[0040] The method for obtaining the alkali-soluble resin, component (A2) used in the present invention, is not particularly limited, but can be obtained, for example, by carrying out a polymerization reaction at a temperature of 50 to 110°C in a solvent containing a monomer having an N-hydroxyphenyl group but not having a carboxy group, optionally other copolymerizable monomers not having a carboxy group, and optionally a polymerization initiator, etc. The solvent used in this process is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble resin, component (A2), and the alkali-soluble resin. Specific examples include the solvents described below in the section on solvent (E).

[0041] The alkali-soluble resin thus obtained is usually in the form of a solution dissolved in a solvent.

[0042] Alternatively, the alkali-soluble resin solution obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain an alkali-soluble resin powder. This procedure can remove polymerization initiators and unreacted monomers that coexist with the alkali-soluble resin, resulting in a purified alkali-soluble resin powder. If the alkali-soluble resin cannot be sufficiently purified in a single procedure, the resulting powder can be redissolved in a solvent and the above procedure can be repeated.

[0043] In the present invention, the powder of the alkali-soluble resin may be used as it is, or the powder may be redissolved in, for example, the solvent (E) described below and used in the form of a solution.

[0044] In the present invention, the alkali-soluble resin of the component (A2) may be a mixture of multiple types of alkali-soluble resins.

[0045] <Component (B)> The component (B) is a surfactant made of a polymer having a liquid-repellent group.

[0046] The polymer refers to an acrylic polymer having a liquid-repellent group obtained using a monomer having a polymerizable unsaturated group such as an acrylic acid ester, a methacrylic acid ester, styrene, or maleimide, i.e., a polymerizable group containing an unsaturated hydrocarbon (C=C double bond) in the structure, or a polysiloxane obtained by hydrolysis polycondensation of a polyfunctional alkoxysilane monomer.

[0047] The liquid repellent group may be, for example, at least one group selected from a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group.

[0048] The fluoroalkyl group includes an Ra group having a fluoroalkyl structure represented by the following formula 1: -X-Y Formula 1 In formula 1, X represents a single bond or an optionally substituted divalent saturated hydrocarbon group, and Y represents a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, provided that the total number of fluorine atoms in formula 1 is 3 or more.

[0049] When X is a divalent saturated hydrocarbon group, the number of carbon atoms is not particularly limited as long as it does not impair the liquid repellency.

[0050] The number of carbon atoms in the fluoroalkyl group is not particularly limited as long as it does not impair the liquid repellency. Examples of such fluoroalkyl groups include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2-(perfluorobutyl)ethyl group, a 3-perfluorobutyl-2-hydroxypropyl group, a 2-(perfluorohexyl)ethyl group, a 3-perfluorohexyl-2-hydroxypropyl group, a 2-(perfluorooctyl)ethyl group, a 3-perfluorooctyl-2-hydroxypropyl group, a 2-(perfluorodecyl)ethyl group, a 2-(perfluoro-3-methylbutyl)ethyl group, a 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl group, a 2-(perfluoro-5-methylhexyl)ethyl group, a 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl group, a 2-(perfluoro-7-methyloctyl)ethyl group, and a 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl group.

[0051] To introduce a fluoroalkyl group into the polymer (B) of the present invention, a monomer having a fluoroalkyl group can be copolymerized. Alternatively, a polymer having a reactive site can be reacted with a compound having a functional group that reacts with the fluoroalkyl group and the reactive site of the polymer.

[0052] The polyfluoroether group includes an Rf group (a) having a polyfluoroether structure represented by the following formula 2: —(P—O) ｎ-Q Formula 2 In Formula 2, P represents a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and each unit grouped by n may be the same or different, Q represents a hydrogen atom (only when a fluorine atom is not bonded to the carbon atom adjacent to the oxygen atom adjacent to Q), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer from 2 to 50, provided that the total number of fluorine atoms in Formula 2 is 2 or more.

[0053] As a preferred embodiment of P and Q in formula 2, P is a C1 to C10 alkylene group fluorinated by removing one hydrogen atom or a C1 to C10 perfluorinated alkylene group, and each unit grouped by n represents the same group or different groups, and Q is a C1 to C20 alkyl group fluorinated by removing one hydrogen atom or a C1 to C20 perfluorinated alkyl group.

[0054] More preferably, P represents a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit bounded by n may be the same or different, and Q represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0055] In formula 2, n represents an integer of 2 to 50. n is preferably 2 to 30, and more preferably 2 to 15. When n is 2 or more, good liquid repellency is achieved. When n is 50 or less, when the polymer of component (B) is synthesized by copolymerization of a monomer having an Rf group (a) with other monomers, good compatibility of the monomers is achieved.

[0056] The total number of carbon atoms in the Rf group (a) consisting of the polyfluoroether structure represented by formula 2 is preferably 2 to 50, and more preferably 2 to 30. Within this range, the polymer that is component (B) exhibits good liquid repellency.

[0057] Specific examples of P include -CF ２ -, -CF ２ CF ２ -, -CF ２ CF ２ CF２ -, -CF ２ CF (CF ３ ) -, -CF ２ CF ２ CF ２ CF ２ -, -CF ２ CF ２ CF (CF ３ ) - and CF ２ CF (CF ３ )CF ２ - are listed.

[0058] Specific examples of Q include -CF ３ , -CF ２ CF ３ , -CF ２ CHF ２ , -(CF ２ ) ２ CF ３ , -(CF ２ ) ３ CF ３ , -(CF ２ ) ４ CF ３ , -(CF ２ ) ５ CF ３ , -(CF ２ ) ６ CF ３ , -(CF ２ ) ７ CF ３ , -(CF ２ ) ８ CF ３ , -(CF ２ ) ９ CF ３ , and (CF ２ ) １１ CF ３ , -(CF ２ ) １５ CF ３ Examples include:

[0059] A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by formula 2 is the Rf group (a) represented by formula 3.

[0060] -C ｐ－１ F ２（ｐ－１） -O-(C ｐ F ２ｐ-O) ｎ－１ -C ｑ F ２ｑ＋１ In formula 3, p represents an integer of 2 or 3, and each unit grouped by n represents the same group; q represents an integer of 1 to 20; and n represents an integer of 2 to 50.

[0061] Specific examples of the Rf group (a) represented by formula 3 include: ２ O (CF ２ CF ２ O) ｎ－１ CF ３ (n is 2 to 9), -CF(CF ３ ) O(CF ２ CF (CF ３ ) O) ｎ－１ C ６ F １３ (n is 2 to 6), -CF(CF ３ ) O(CF ２ CF (CF ３ ) O) ｎ－１ C ３ F ７ (n is 2 to 6) is preferred from the viewpoint of ease of synthesis.

[0062] The Rf groups (a) in the polymer that is the component (B) may all be the same or different.

[0063] The polysiloxane group includes a group (b) having a polysiloxane structure represented by formula 4. Hereinafter, the group (b) having a polysiloxane structure represented by formula 4 will be referred to as a pSi group (b). -(SiR １ R ２ -O) ｎ -SiR １ R ２ R ３ ...Equation 4 (where R １ , R ２ independently represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group; R ３ represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200.

[0064] R １ , R ２independently represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group, and may be the same or different for each siloxy unit. １ , R ２ is preferably a hydrogen atom, a methyl group, or a phenyl group, and further, R of all the siloxy units １ , R ２ is preferably a methyl group. ３ may contain a nitrogen atom, an oxygen atom, etc.

[0065] Examples of methods for introducing the pSi group (b) into the polymer, which is the component (B), include a method of copolymerizing a monomer having the pSi group (b), various modification methods in which a polymer having a reactive site is reacted with a compound having the pSi group (b), and a method using a polymerization initiator having the pSi group (b).

[0066] Examples of the monomer having the pSi group (b) include CH ２ =CHCOO(pSi), CH ２ =C(CH ３ )COO(pSi), etc., where pSi represents a pSi group (b). The monomer having a pSi group (b) may be used alone or in combination of two or more kinds.

[0067] Examples of various modification methods for reacting a polymer having a reactive site with a compound having a pSi group (b) include the following methods.

[0068] There are three methods: a method in which a monomer having an epoxy group is copolymerized in advance, followed by a reaction with a compound having a carboxyl group at one end and a pSi group at the other end; a method in which a monomer having an epoxy group is copolymerized in advance, followed by a reaction with a compound having an amino group at one end and a pSi group at the other end; a method in which a monomer having an epoxy group is copolymerized in advance, followed by a reaction with a compound having a mercapto group at one end and a pSi group at the other end; and a method in which a monomer having an amino group is copolymerized in advance, followed by a reaction with a compound having a carboxyl group at one end and a pSi group at the other end.

[0069] Other examples include a method in which a monomer having an amino group is copolymerized in advance and then reacted with a compound having an epoxy group at one end and a pSi group at the other end; a method in which a monomer having a carboxyl group is copolymerized in advance and then reacted with a compound having an epoxy group at one end and a pSi group at the other end; a method in which a monomer having a carboxyl group is copolymerized in advance and then reacted with a compound having an amino group at one end and a pSi group at the other end; a method in which a monomer having a carboxyl group is copolymerized in advance and then reacted with a compound having a silyl chloride group at one end and a pSi group at the other end; and a method in which a monomer having a hydroxyl group is copolymerized in advance and then reacted with a compound having a silyl chloride group at one end and a pSi group at the other end.

[0070] The polymerization initiator having a pSi group (b) may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or may contain a group having a monovalent polysiloxane structure in the terminal portion or side chain of the initiator molecule. Examples of initiators containing a group having a divalent polysiloxane structure in the main chain of the initiator molecule include compounds having alternating groups having a divalent polysiloxane structure and azo groups. Commercially available products include VPS-1001 and VPS-0501 (both manufactured by Wako Pure Chemical Industries, Ltd.).

[0071] In the polymer of component (B), the amount of the liquid repellent group introduced is preferably 5 to 60 mol % based on all repeating units. If it is less than 5 mol %, the liquid repellency effect may not be achieved. If it is more than 60 mol %, problems such as aggregation may occur.

[0072] The polymer of component (B) can be copolymerized with a thermosetting functional group to suppress the exudation and decomposition of component (B) into the openings during heat curing. The thermosetting functional group is not particularly limited as long as it is a group that forms a covalent bond upon heating, and may be a functional group that reacts with component (A1), component (A2), or component (D), or a functional group that self-crosslinks between components (B). Examples of such thermosetting functional groups (thermosetting groups) include hydroxy groups, carboxyl groups, amide groups, amino groups, N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, mercapto groups, and blocked isocyanate groups.

[0073] (Method for producing acrylic polymer having liquid-repellent groups) The method for producing the acrylic polymer having liquid-repellent groups of component (B) is not particularly limited, but can be obtained by polymerizing a radically polymerizable monomer having a liquid-repellent group, such as at least one of a monomer having a fluoroalkyl group, a monomer having a polyfluoroether group, and a monomer having a polysiloxane group, a radically polymerizable monomer having a thermosetting group, and optionally a monomer other than the above (hereinafter also referred to as other monomer B), in a solvent in the presence of a polymerization initiator at a temperature of 50 to 110°C. The solvent used in this process is not particularly limited as long as it dissolves the monomer constituting the acrylic polymer having liquid-repellent groups of component (B) and the acrylic polymer having liquid-repellent groups. Specific examples include the solvents described below in the section on solvent (E).

[0074] Specific examples of radically polymerizable monomers having a liquid repellent group include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, and 3-perfluorobutyl-2-hydroxypropyl Methacrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-( (perfluorodecyl)ethyl acrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-methylbutyl)ethyl acrylate, 2-(perfluoro-3-methylbutyl)ethyl methacrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl)ethyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl methacrylate acrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-7-methyloctyl)ethyl acrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate.

[0075] Specific examples of radically polymerizable monomers having a thermosetting group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylate, 2-hydroxypropyl acrylate ... carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trimethyl- Fluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyl Examples of suitable acrylates include 2-(2-(2-hydroxypropyl)-4-methylpropanol), ...hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-hydroxypropyl)-4-methylpropanol, 2-(2-

[0076] Specific examples of other monomers B include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl methacrylate, methyl ... isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, styrene, vinylnaphthalene, vinylanthracene, and vinylbiphenyl.

[0077] The acrylic polymer having a liquid-repellent group thus obtained is usually in the form of a solution dissolved in a solvent.

[0078] Furthermore, the solution of the acrylic polymer having liquid-repellent groups obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the acrylic polymer having liquid-repellent groups. This procedure can remove the polymerization initiator and unreacted monomers that coexist with the acrylic polymer having liquid-repellent groups, resulting in a purified powder of the acrylic polymer having liquid-repellent groups. If sufficient purification cannot be achieved in a single procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated.

[0079] In the present invention, the powder of the acrylic polymer having the liquid-repellent group may be used as it is, or the powder may be redissolved in, for example, the solvent (E) described below and used in the form of a solution.

[0080] In the present invention, the acrylic polymer having a liquid repellent group as component (B) may be a mixture of acrylic polymers having a plurality of types of liquid repellent groups.

[0081] (Method for Obtaining Polysiloxane) The method for obtaining the polysiloxane of component (B) above is not particularly limited, but a polysiloxane obtained by polycondensation of an alkoxysilane having a liquid-repellent group, an alkoxysilane having a thermosetting group, and, if desired, an alkoxysilane having other organic groups is preferred.

[0082] Specific examples of alkoxysilane monomers having a liquid repellent group include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, 2-(perfluorohexyl)ethyltrimethoxysilane, 2-(perfluorohexyl)ethyltriethoxysilane, 2-(perfluorobutyl)ethyltrimethoxysilane, and 2-(perfluorobutyl)ethyltriethoxysilane.

[0083] In the present invention, at least one type of alkoxysilane having a liquid repellent group may be used, but multiple types may be used as needed.

[0084] Specific examples of alkoxysilane monomers having a thermosetting group include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, vinyltris(2-ethoxy)silane, vinyltris(2-methoxy)silane, m-styryltriethoxysilane, m-styryltrimethoxysilane, p-styryltriethoxysilane, and p-styryltrimethoxysilane. silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2-aminoethyl)propyldimethoxysilane, 3-(2-aminoethyl)propyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, 3-mercaptopropyl(dimethoxy)methylsilane, (3-mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, 3-(triethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl acrylate , 3-(trimethoxysilyl)propyl acrylate, 2-(triethoxysilyl)ethyl methacrylate, 2-(trimethoxysilyl)ethyl methacrylate, 2-(triethoxysilyl)ethyl acrylate, 2-(trimethoxysilyl)ethyl acrylate, (triethoxysilyl)methyl methacrylate, (trimethoxysilyl)methyl methacrylate, (triethoxysilyl)methyl acrylate, (trimethoxysilyl)methyl acrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, 1-[3-(trimethoxysilyl)propyl]urea, and the like.

[0085] Furthermore, it is also preferable to use 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which undergo a crosslinking reaction due to heat.

[0086] In this case, a plurality of types of alkoxysilanes having an organic group containing a thermosetting group may be used.

[0087] Other examples of alkoxysilanes having an organic group include tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane. Examples of such silanes include alkyltrialkoxysilanes such as ethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, and octadecyltriethoxysilane; trialkoxysilanes having an aromatic group such as phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, and benzyltriethoxysilane; dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; cyclohexyltriethoxysilane; and cyclohexyltrimethoxysilane.

[0088] The polysiloxane of component (B) contains alkoxysilanes containing a liquid repellent group in an amount of preferably 5 to 70 mol % of all alkoxysilanes, and alkoxysilanes containing a thermosetting group in an amount of preferably 10 to 95 mol % of all alkoxysilanes, with the remainder being obtained by polycondensation of other alkoxysilanes.

[0089] Considering the liquid repellency and solvent resistance of the coating, the content of the alkoxysilane containing a liquid repellent group is more preferably 10 to 60 mol %, and the content of the alkoxysilane containing a thermosetting group is more preferably 30 to 80 mol % of the total alkoxysilane.

[0090] Examples of methods for obtaining the polysiloxane of component (B) include a method in which an alkoxysilane containing a liquid-repellent group, an alkoxysilane containing a thermosetting group, and optionally other alkoxysilanes are heated in an organic solvent in the presence of an aqueous tetraethylammonium hydroxide solution to polycondense the mixture. Specifically, an aqueous tetraethylammonium hydroxide solution is first added to an organic solvent to form a tetraethylammonium hydroxide solution, and then the resulting solution is heated and mixed with the various alkoxysilanes. The amount of the aqueous tetraethylammonium hydroxide solution is preferably 0.01 to 0.2 moles per mole of the total alkoxy groups in the alkoxysilanes used. The heating can be carried out at a liquid temperature of preferably 0 to 100°C, and is preferably carried out under reflux in a container equipped with a reflux condenser for several tens of minutes to several tens of hours to prevent evaporation or volatilization of the liquid.

[0091] When a plurality of types of alkoxysilanes are used, the alkoxysilanes may be mixed in advance as a mixture, or a plurality of types of alkoxysilanes may be mixed sequentially. When polycondensing the alkoxysilanes, the concentration of all silicon atoms of the charged alkoxysilanes converted into oxides (hereinafter referred to as SiO ２ It is preferable to heat the solution so that the concentration (referred to as the converted concentration) is 40% by mass or less, and particularly preferably in the range of 10 to 30% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous polysiloxane-containing solution can be obtained.

[0092] The organic solvent used in polycondensing alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane having a liquid-repellent group, the alkoxysilane having a thermosetting group, and other alkoxysilanes as necessary, but the use of solvent (E) is preferred. Among them, since alcohol is produced by the polycondensation reaction of alkoxysilane, alcohols or organic solvents that are highly compatible with alcohols are used.

[0093] Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, and n-butanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether, and ethers such as tetrahydrofuran. In the present invention, a mixture of two or more of the above organic solvents may be used.

[0094] In the present invention, the solution of the specific polysiloxane obtained by the above method may be used as is in the photosensitive resin composition of the present invention, or, if necessary, the solution of the specific polysiloxane obtained by the above method may be concentrated, diluted with a solvent, or substituted with another solvent before use.

[0095] The solvent used for dilution by adding the solvent (also referred to as an additive solvent) may be the solvent used in the polycondensation reaction or another solvent. This additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved therein, and one or more additive solvents may be selected and used. Examples of such additive solvents include the solvent used in the polycondensation reaction, as well as ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate.

[0096] Furthermore, in the present invention, when a polymer other than polysiloxane is used in the photosensitive resin composition, it is preferable to distill off the alcohol generated during the polycondensation reaction of the polysiloxane under normal pressure or reduced pressure before mixing the polymer other than polysiloxane.

[0097] Furthermore, examples of the polymer that is component (B) include, in addition to the above-mentioned acrylic polymers and polysiloxanes having a liquid-repellent group, polyamic acids, polyimides, polyamides, polyureas, polyurethanes, phenolic resins, epoxy resins, polyesters, and polymers in which a quinonediazide group has been introduced into an acrylic polymer having a liquid-repellent group.

[0098] Examples of polyamic acids, polyimides, polyamides, and polyureas include polyamic acids obtained by reacting a diamine having a fluoroalkyl group or a fluoroalkoxy group and a diamine having a hydroxy group with an acid dianhydride, polyimides obtained by imidizing polyamic acids, polyamides obtained by reacting the diamines with dicarboxylic acid anhydrides, and polyureas obtained by reacting the diamines with diisocyanates.

[0099] Examples of polyurethanes include polyurethanes obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.

[0100] Examples of phenolic resins include novolak resins obtained by polymerizing phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.

[0101] Examples of the epoxy resin include those obtained by reacting bisphenol A and / or bisphenol F having a fluoroalkyl group or a fluoroalkoxy group with a diglycidyl ether of the bisphenol A and / or bisphenol F.

[0102] Examples of the polyester include polyesters obtained by reacting a dicarboxylic acid having a fluoroalkyl group or a fluoroalkoxy group with a diol having a fluoroalkyl group or a fluoroalkoxy group.

[0103] The ratio of component (B) to components (A1) and (A2) is 0.05 to 20 parts by mass of component (B) per 100 parts by mass of the total of components (A1) and (A2).

[0104] <Component (C)> The 1,2-quinonediazide compound serving as component (C) is a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, in which preferably 10 to 100 mol %, and particularly preferably 20 to 95 mol %, of these hydroxyl groups or amino groups (when both hydroxyl groups and amino groups are present, the total amount of these groups) is esterified or amidated with 1,2-quinonediazide sulfonic acid.

[0105] Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl)butane, 4,4-isopropylidenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4',4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene] Examples of the alcohol include phenol compounds such as bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, and 2,5-bis(2-hydroxy-5-methylbenzyl)methyl; and aliphatic alcohols such as ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

[0106] Examples of the compound containing an amino group include anilines such as aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, and 4,4'-diaminodiphenyl ether, and aminocyclohexane.

[0107] Furthermore, examples of compounds containing both a hydroxyl group and an amino group include aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4',4''-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane; and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

[0108] These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[0109] The content of component (C) in the positive-type photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 80 parts by mass, and even more preferably 10 to 60 parts by mass, relative to 100 parts by mass of the total of components (A1) and (A2). If the content is less than 5 parts by mass, the difference in dissolution rate in a developer between exposed and unexposed portions of the positive-type photosensitive resin composition may become small, making patterning by development difficult. If the content exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be sufficiently decomposed by short-term exposure, resulting in reduced sensitivity or the generation of residues between patterns.

[0110] <Component (D)> Component (D) is a crosslinking agent, and more specifically, it is a compound having a structure capable of forming a crosslinked structure upon thermal reaction with the N-hydroxyphenyl group of component (A2). Specific examples are listed below, but the present invention is not limited to these. Preferred examples of the thermal crosslinking agent include (D1) a crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, (D2) a crosslinkable compound represented by the following formula (5), and (D3) a crosslinking agent having two or more isocyanate groups. These crosslinking agents can be used alone or in combination of two or more.

[0111] The crosslinkable compound (D1) having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups undergoes a dehydration condensation reaction when exposed to high temperatures during thermal curing. Examples of such compounds include alkoxymethylated glycolurils, alkoxymethylated benzoguanamines, alkoxymethylated melamines, and phenoplast compounds.

[0112] Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation.

[0113] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

[0114] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, 508) manufactured by Mitsui Cytec Co., Ltd., and methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0115] The compound may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, or a benzoguanamine compound in which the hydrogen atom of the amino group has been substituted with a methylol group or an alkoxymethyl group. For example, the compound may be a high molecular weight compound produced from a melamine compound or a benzoguanamine compound as described in U.S. Patent No. 6,323,310. Commercially available melamine compounds include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available benzoguanamine compounds include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0116] Specific examples of the phenoplast-based compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxmethyl)phenol], 2,6-bis(methoxymethyl)phenol], 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy-5-methylbenzenemethanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol], and the like. These are also commercially available, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

[0117] Furthermore, as the component (D1), polymers produced using an acrylamide compound or methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, or N-butoxymethylmethacrylamide, can also be used.

[0118] Examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight-average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

[0119] These crosslinkable compounds may be used alone or in combination of two or more.

[0120] When component (D1) is selected as the crosslinking agent in the positive-type photosensitive resin composition of the present invention, the content thereof is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the total of components (A1) and (A2). If the content is less than 5 parts by mass, outgassing may increase during the display element production process, components of the positive-type photosensitive resin composition may leach into other layers, and the element characteristics and reliability may deteriorate. Furthermore, if the content exceeds 50 parts by mass, storage stability may decrease, adhesion during development may decrease, and sensitivity may decrease.

[0121] The positive photosensitive resin composition of the present invention may also contain, as component (D2), a crosslinkable compound having an epoxy group represented by formula (5). (wherein k is an integer of 2 to 10, m is an integer of 0 to 4, R １１ represents a k-valent organic group)

[0122] Commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021P, and Celloxide 3000 (trade names manufactured by Daicel Corporation), and alicyclic epoxy resins such as Denacol EX-252 (trade name manufactured by Nagase Chemtex Corporation), Epiclon 200, and Epiclon 400 (trade names manufactured by DIC Corporation), Epicoat 871 and 872 (trade names manufactured by Yuka Shell Epoxy Co., Ltd.), and ED-5661 and ED-5662 (trade names manufactured by Celanese Coatings Co., Ltd.). These crosslinkable compounds may be used alone or in combination of two or more.

[0123] Of these, compounds having a cyclohexene oxide structure, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021P, and Celloxide 3000 are preferred from the viewpoint of process resistance such as heat resistance, solvent resistance, and long-term baking resistance.

[0124] When component (D2) is selected as the crosslinking agent, the content is 5 to 50 parts by mass, preferably 7 to 40 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the total of components (A1) and (A2). If the content of the crosslinking compound is less than 5 parts by mass, the density of the crosslinks formed by the crosslinking compound is insufficient, which may result in increased outgassing during the display element production process, elution of components of the positive-type photosensitive resin composition into other layers, and deterioration of element characteristics and reliability. On the other hand, if the content exceeds 50 parts by mass, uncrosslinked crosslinking compound may remain, reducing the heat resistance, solvent resistance, and resistance to long-term baking after pattern formation, and may also deteriorate the storage stability of the photosensitive resin composition.

[0125] <Solvent (E)> The solvent (E) used in the present invention dissolves the components (A1), (A2), (B), (C), and (D), and also dissolves other additives that are added as desired, as described below. There are no particular limitations on the type or structure of the solvent, as long as it is a solvent that has such dissolving ability.

[0126] Examples of such (E) solvents 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, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl 2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 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.

[0127] These solvents can be used alone or in combination of two or more. Among these (E) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. are preferred from the viewpoints of good film-forming properties and high safety. These solvents are generally used as solvents for photoresist materials.

[0128] <Other Additives> Furthermore, the positive photosensitive resin composition of the present invention may contain, as necessary, a rheology adjuster, a pigment, a dye, a coloring matter, a storage stabilizer, an antifoaming agent, an adhesion promoter, or a dissolution promoter such as a polyhydric phenol or a polycarboxylic acid, as long as the effects of the present invention are not impaired.

[0129] <Positive Photosensitive Resin Composition> The positive photosensitive resin composition of the present invention is a cured film-forming positive photosensitive resin composition containing the following components (A1), (A2), (B), (C), (D), and (E) a solvent, and each of these compositions may further contain one or more other additives, as desired. Component (A1): an alkali-soluble acrylic polymer obtained by copolymerizing at least (A1-I) below; preferably an alkali-soluble acrylic polymer obtained by copolymerizing at least (A1-I), (A1-II), and (A1-III) below; more preferably an alkali-soluble acrylic polymer obtained by copolymerizing at least (A1-I), (A1-II), (A1-III), and (A1-IV) below; (A1-I) an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride; (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group; (A1-III) an N-substituted maleimide compound; (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group; component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and no carboxy group; component (B): a surfactant; component (C): a 1,2-quinonediazide compound; component (D): a crosslinking agent (E) Solvent

[0130] Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows: A positive photosensitive resin composition containing 0.05 to 20 parts by mass of component (B), 5 to 100 parts by mass of component (C), and 5 to 50 parts by mass of component (D) relative to 100 parts by mass of the total of component (A1) and component (A2), and these components dissolved in solvent (E).

[0131] The proportion of solids in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80 mass %, or 5 to 60 mass %, or 10 to 50 mass %. Here, the solids refer to all components of the positive photosensitive resin composition excluding the solvent (E).

[0132] The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited, but examples of the preparation method include a method in which component (B) (polymer) is dissolved in solvent (E), and the resulting solution is mixed with the alkali-soluble acrylic polymer of component (A1), the alkali-soluble resin of component (A2), the 1,2-quinonediazide compound of component (C), and the crosslinking agent of component (D) in predetermined proportions to prepare a homogeneous solution, or a method in which other additives are further added and mixed, as necessary, at an appropriate stage of this preparation method.

[0133] In preparing the positive-type photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the solvent (E) can be used as is. In this case, when the solution of the component (B) is added with the components (A1), (A2), (C), and (D) as described above to prepare a homogeneous solution, the solvent (E) may be further added for the purpose of adjusting the concentration. In this case, the solvent (E) used in the copolymer formation process and the solvent (E) used to adjust the concentration in the preparation of the positive-type photosensitive resin composition may be the same or different.

[0134] The prepared solution of the positive photosensitive resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

[0135] <Coated Film and Cured Film> The positive photosensitive resin composition of the present invention can be applied onto a semiconductor substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, or the like, and then pre-dried on a hot plate or in an oven, etc., to form a coated film. The coated film is then heat-treated to form a positive photosensitive resin film.

[0136] The conditions for this heat treatment are, for example, a heating temperature of 70° C. to 160° C. and a heating time of 0.3 to 60 minutes, and the heating temperature and heating time are preferably 80° C. to 140° C. and 0.5 to 10 minutes.

[0137] The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 μm, or, for example, 0.2 to 10 μm, or, further, for example, 0.3 to 5 μm.

[0138] By attaching a mask having a predetermined pattern to the coating film obtained above, irradiating the film with light such as ultraviolet light, and developing the film with an alkaline developer, the exposed areas are washed out, resulting in a sharp relief pattern at the edge. Furthermore, the positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention can also be used as a grayscale mask or a halftone mask. Simply by attaching a grayscale mask or a halftone mask having a predetermined pattern to the coating film obtained above, irradiating the film with light such as ultraviolet light, and developing the film with an alkaline developer, it is possible to form lyophilic and lyophobic portions with sufficient flatness using a single material.

[0139] Examples of alkaline developers that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers.

[0140] Among the above, an aqueous solution containing 0.1 to 3% by mass of tetramethylammonium hydroxide is generally used as a developer for photoresists, and the photosensitive resin composition of the present invention can also be developed satisfactorily using this alkaline developer without causing problems such as swelling. Preferably, a relief pattern can be obtained more effectively by using an aqueous solution containing 0.2 to 2.38% by mass of tetramethylammonium hydroxide.

[0141] The developing method may be any of the puddle method, dipping method, and swing immersion method, etc. The developing time is usually 15 to 180 seconds.

[0142] After development, the positive photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen or by spinning, thereby removing water from the substrate and obtaining a patterned film.

[0143] Subsequently, the pattern-forming film is post-baked for thermal curing, specifically by heating using a hot plate, oven, or the like, to obtain a film having excellent heat resistance, transparency, flattening properties, low water absorption, chemical resistance, and the like, and having a good relief pattern.

[0144] Post-baking is generally performed at a heating temperature selected from the range of 140°C to 270°C for 5 to 30 minutes on a hot plate or for 15 to 90 minutes in an oven.

[0145] Thus, by such post-baking, it is possible to obtain a cured film having the desired good pattern shape.

[0146] As described above, the positive photosensitive resin composition of the present invention can form a coating film having a fine pattern, which has high storage stability, sufficiently high sensitivity, and very little film loss in unexposed areas during development. Furthermore, the coating film (cured film) thus obtained is characterized by leaving almost no pattern residue. Therefore, the composition is suitable for use as a light-shielding material or partition wall material compatible with inkjet printing, as well as various films, such as interlayer insulating films, protective films, and insulating films, in liquid crystal displays and organic EL displays.

[0147] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows:

[0148] (1) Ultraviolet irradiation device Device: PLA-600FA manufactured by Canon Inc. (2) Developing device Device: AD-1200 manufactured by Takizawa Sangyo Co., Ltd. (3) Gel permeation chromatography (GPC) Device: manufactured by Shimadzu Corporation Column: Shodex (registered trademark) GPC K-803L, GPC K-804L manufactured by Showa Denko K.K. Column temperature: 40°C Eluent: tetrahydrofuran The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) are expressed in polystyrene equivalent values. (4) Residue evaluation Equipment: S-4800 scanning electron microscope manufactured by Hitachi High-Technologies Corporation (5) Contact angle evaluation Equipment: Drop Master manufactured by Kyowa Interface Science Co., Ltd. (6) Wettability evaluation Equipment: Inkjet Designer manufactured by Cluster Technology Co., Ltd. (7) Evaluation of flatness of half-exposed area Equipment: MX61A semiconductor motorized inspection microscope manufactured by Olympus Corporation

[0149] The abbreviations have the following meanings: MMA: methyl methacrylate, HEMA: 2-hydroxyethyl methacrylate, HPMA: 4-hydroxyphenyl methacrylate, CHMI: N-cyclohexylmaleimide, MAA: methacrylic acid, AIBN: α,α'-azobisisobutyronitrile, QD: a compound synthesized by condensation reaction of 1 mol of 4,4'-[4-(4-hydroxyphenyl)butane-2,2-diyl]diphenol with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, GT-401: butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone [Epolead GT-401, manufactured by Daicel Corporation], 2021P: 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate [Celloxide 2021P, manufactured by Daicel Corporation]. PFHMA: (1H,1H,2H,2H-tridecafluoro-n-octyl) methacrylate KBM-503: 3-methacryloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503] NHPMA: N-(4-hydroxyphenyl) methacrylamide PFHTMOS: trimethoxy(1H,1H,2H,2H-tridecafluoro-n-octyl)silane KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., KBM-303] 35 wt% TEA Haq. : 35 wt% tetraethylammonium hydroxide aqueous solution 15JWET: Amberlyst 15JWET ion exchange resin manufactured by Organo Corporation KC Flock: KC Flock W-100GK manufactured by Nippon Paper Industries Co., Ltd. PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate MeOH: Methanol DMI: 1,3-dimethyl-2-imidazolidinone 2,3-BD: 2,3-butanediol DPM: Dipropylene glycol monomethyl ether TMAH: Tetramethylammonium hydroxide

[0150] Synthesis Example 1 Using 6.0 g of MAA, 16.0 g of CHMI, 10.0 g of HEMA, 2.0 g of HPMA, and 6.0 g of MMA, and using 2.5 g of AIBN as a radical polymerization initiator, these were subjected to a polymerization reaction in 63.6 g of PGME solvent at a temperature of 60° C. to 100° C., to obtain a solution (specific copolymer concentration: 40% by mass) of an alkali-soluble acrylic polymer component (specific copolymer) having Mn of 3,600 and Mw of 8,600. (A1-1)

[0151] Synthesis Example 2 7.8 g of MAA, 20.4 g of CHMI, 14.7 g of HEMA, and 14.8 g of MMA were used, and 3.8 g of AIBN was used as a radical polymerization initiator. These were subjected to a polymerization reaction in 92.3 g of PGMEA solvent at a temperature of 60° C. to 100° C., to obtain a solution (specific copolymer concentration: 40% by mass) of an alkali-soluble acrylic polymer component (specific copolymer) having Mn of 4,400 and Mw of 7,700. (A1-2)

[0152] Synthesis Example 3: 3.00 g of NHPMA, 0.98 g of HEMA, 2.34 g of CHMI, and 0.12 g of AIBN were dissolved in 24.20 g of a solvent, PGME, and the mixture was allowed to react at 90° C. for 20 hours to obtain an alkali-soluble resin solution (solids concentration: 21% by mass) (A2-1). The resulting alkali-soluble resin had an Mn of 6,200 and an Mw of 9,900.

[0153] Synthesis Example 4 3.00 g of NHPMA, 1.11 g of HEMA, 3.04 g of CHMI, and 0.14 g of AIBN were dissolved in 27.30 g of PGME solvent and reacted at 90° C. for 20 hours to obtain an alkali-soluble resin solution (solids concentration 21% by mass) (A2-2). The resulting alkali-soluble resin had an Mn of 5,600 and an Mw of 9,300.

[0154] [Synthesis Example 5] 2.34 g of PFHTMOS, 2.29 g of KBM-303, 0.24 g of 35 wt% TEA Haq, 0.49 g of water, and 0.54 g of MeOH were dissolved in 15.54 g of PGMEA solvent and stirred at 40°C for 4 hours. Subsequently, 0.93 g of 15JWET washed with a mixed solvent of PGMEA and MeOH was added, and the mixture was stirred at 25°C for 1 hour. The waste 15JWET was then filtered through a membrane filter equipped with KC floc to obtain a polysiloxane solution (B1). The Mn of the obtained polysiloxane was 2,300 and the Mw was 2,700.

[0155] Synthesis Example 6: 5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN were dissolved in 25.32 g of a solvent, PGME, and the mixture was allowed to react at 80° C. for 20 hours to obtain an acrylic polymer solution (solids concentration: 30% by mass) having liquid-repellent groups (B2). The Mn and Mw of the obtained acrylic polymer having liquid-repellent groups were 4,800 and 6,700, respectively.

[0156] [Synthesis Example 7] An organic functional ink was obtained in the same manner as in Comparative Example 1-2 of WO 2019 / 124413, except that the solid content concentration was 1.7% by mass.

[0157] [Examples 1 to 6, Comparative Examples 1 to 5] Positive photosensitive resin compositions were prepared by mixing the following components according to the description in Table 1. In the table, [parts] represents [parts by mass], and the solid content ratio was adjusted to the numerical value in the table.

[0158] [Evaluation of Opening Residues] The positive photosensitive resin composition was applied to ITO glass using a spin coater, and then prebaked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.15 μm. This coating film was irradiated with ultraviolet light at 365 nm with a light intensity of 5.5 mW / cm2 for a certain period of time through a 10 μm line and space pattern mask. The coating film was then developed by immersion in a 0.40% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. The coating film with the line and space pattern formed thereon was then post-baked and cured by heating at 230°C for 30 minutes. The opening residues of the cured line and space pattern were observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation and evaluated according to the following criteria. Considering actual specifications, a grade of at least B is required, and a grade of A is desirable. A: No residue in the pattern, particularly good B: No residue in the pattern, good C: Residue present in the pattern

[0159] [Evaluation of Inkjet Wettability] The positive photosensitive resin composition was applied to ITO-glass using a spin coater, and then prebaked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.15 µm. This coating film was then exposed to a light intensity of 5.5 mW / cm at 365 nm through a mask with a pattern of many rectangles with long sides of 160 µm and short sides of 80 µm. ２ The film was irradiated with ultraviolet light of 1000 kJ / cm² for a certain period of time. The film was then developed by immersion in a 0.40% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. The coating film with the rectangular pattern formed thereon was then post-baked and cured by heating at 230°C for 30 minutes. A certain number of shots (approximately 3 pL per shot) of the organic functional ink prepared in Synthesis Example 7 were ejected into the openings of the cured rectangular pattern, followed by natural drying to form an organic functional film. The appearance of the organic functional film was observed using an optical microscope and evaluated according to the following criteria. Considering actual specifications, at least B is required, and A is desirable. A: Good after 2 shots, with no repellency or overflow. B: Good after 6 shots, with no repellency or overflow. C: Repelling or overflow occurred even after 6 shots.

[0160] [Contact Angle Evaluation] The positive photosensitive resin composition was applied to a silicon wafer using a spin coater and then prebaked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.15 μm. The coating film was developed by immersing it in a 0.40% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. It was then postbaked and cured by heating at 230°C for 30 minutes. 1 μL of anisole was applied to the cured coating film, and the contact angle θ was measured at five points after 7 seconds. The average value was used as the contact angle value and evaluated according to the following criteria. Considering actual specifications, at least B is required, and A is desirable. A: θ≧53° B: 50°≦θ<53° C: θ<50°

[0161] [Evaluation of Flatness of Half-Exposed Area] The positive photosensitive resin composition was applied to ITO-glass using a spin coater, and then prebaked on a hot plate at 100°C for 120 seconds to form a coating film with a thickness of 1.15 µm. This coating film was exposed to a light intensity of 5.5 mW / cm at 365 nm through a half-tone mask with a pattern of many rectangles with a long side of 50 µm and a short side of 30 µm and a transmittance of 50%. ２ The film was irradiated with ultraviolet light of 1000 W for a certain period of time so that the film thickness of the rectangular pattern would be thinner than 1.15 μm. The film was then developed by immersing in a 0.40% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. The coating film on which the rectangular pattern was formed was then post-baked by heating at a temperature of 230° C. for 30 minutes to harden it. The surface of the hardened rectangular pattern was observed using an optical microscope and evaluated according to the following criteria: A: Good, with no peeling or unevenness; C: Peeling or unevenness occurred.

[0162]

[0163]

[0164] As shown in Table 2, the cured films (Examples 1 to 6) prepared using positive photosensitive compositions each containing A1-1 or A1-2 as the alkali-soluble acrylic polymer A1, A2-1 or A2-2 as the alkali-soluble resin A2, and B1 or B2 as the surfactant were shown to be excellent in terms of residue, inkjet wettability, and contact angle, and also to be excellent in terms of flatness in the half-exposed area.

[0165] On the other hand, the cured films made from the positive photosensitive compositions of Comparative Examples 1 and 3, which used A1-1 and A1-2 as the alkali-soluble acrylic polymer A1 but did not use the alkali-soluble resin A2, were shown to be poor in inkjet wettability and contact angle. Furthermore, the cured film made from the positive photosensitive composition of Comparative Example 5, which used A1-2 as the alkali-soluble acrylic polymer A1 but did not use the alkali-soluble resin A2, was shown to be excellent in inkjet wettability and contact angle, but was poor in residue and flatness of the half-exposed area. Next, Comparative Examples 2 and 4, which used A1-1 as the alkali-soluble acrylic polymer A1, A2-1 as the alkali-soluble resin A2, and did not add a surfactant, were shown to be excellent in residue, but were poor in inkjet wettability and contact angle.

[0166] As shown in the results of the Examples above, it is only by using a positive photosensitive composition that combines an alkali-soluble acrylic polymer A1, an alkali-soluble resin A2, a surfactant, a crosslinking agent, and a photosensitizer that it is possible to obtain a cured film that satisfies the requirements for residue, inkjet wettability, contact angle, and flatness of half-exposed areas.

Claims

1. A cured film-forming positive photosensitive resin composition containing the following components (A1), (A2), (B), (C), (D), and (E) a solvent: component (A1): an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride; component (A2): an alkali-soluble resin having an N-hydroxyphenyl group and no carboxy group; component (B): a surfactant; component (C): a 1,2-quinonediazide compound; component (D): a crosslinking agent; and (E) a solvent.

2. The positive photosensitive resin composition according to claim 1, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the compounds (A1-I) and the following compounds (A1-II) and (A1-III): (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A1-III) an N-substituted maleimide compound.

3. The positive photosensitive resin composition according to claim 2, wherein the component (A1) is an alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing at least the compounds (A1-I), (A1-II), and (A1-III) and the following compound (A1-IV): (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group:

4. The positive photosensitive resin composition according to claim 3, wherein (A1-IV) the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl (meth)acrylate.

5. The positive photosensitive resin composition according to claim 1, wherein the component (A1) is an alkali-soluble acrylic polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene.

6. The positive photosensitive resin composition according to claim 1, wherein the component (A2) is a polymer containing a structural unit derived from at least one monomer selected from the group consisting of N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide.

7. The positive photosensitive resin composition according to claim 1, wherein the component (A2) is an alkali-soluble resin having a number average molecular weight of 2,000 to 60,000 in terms of polystyrene.

8. The positive photosensitive resin composition according to claim 1, wherein the component (B) is a surfactant comprising a polymer having a liquid-repellent group.

9. The positive photosensitive resin composition according to claim 8, wherein the liquid repellent group is at least one group selected from the group consisting of a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group.

10. The positive photosensitive resin composition according to claim 8, wherein the monomer unit constituting the polymer having the liquid repellent group is a monomer unit derived from an unsaturated hydrocarbon having the liquid repellent group.

11. The positive photosensitive resin composition according to claim 8, wherein the monomer unit constituting the polymer having the liquid repellent group is a monomer unit derived from an alkoxysilane compound having the liquid repellent group.

12. The positive photosensitive resin composition according to claim 8, wherein the component (B) is a surfactant comprising a polymer having the liquid-repellent group and the thermosetting group.

13. The positive photosensitive resin composition according to claim 1, wherein component (D) is a crosslinking agent comprising a compound containing an epoxy group or a methoxymethyl group.

14. The positive photosensitive resin composition according to claim 1, wherein the component (B) is contained in an amount of 0.05 to 20 parts by mass per 100 parts by mass of the total of the components (A1) and (A2).

15. The positive photosensitive resin composition according to claim 1, wherein the component (C) is contained in an amount of 5 to 100 parts by mass per 100 parts by mass of the total of the components (A1) and (A2).

16. The positive photosensitive resin composition according to claim 1, wherein the component (D) is contained in an amount of 5 to 50 parts by mass per 100 parts by mass of the total of the components (A1) and (A2).

17. A cured film formed from the positive photosensitive resin composition according to any one of claims 1 to 16.

18. A display device having the cured film according to claim 17.

19. A display device having the cured film according to claim 17 as an image forming bank.