Positive photosensitive resin composition

Abstract

[Problem] The purpose of the present invention is to provide a positive photosensitive resin composition capable of forming a cured film which is used for liquid-crystal display elements, organic EL display elements, and the like and has a surface with high water repellency and high oil repellency, which has little residue after patterning, and on which an organic functional ink does not overflow but wet-spreads satisfactorily within the pattern formed by patterning. [Solution] This positive photosensitive resin composition contains component (A), component (B), component (C), component (D), component (E), and solvent (F) below and contains no photoacid generator, the positive photosensitive resin composition being capable of forming a cured film. Component (A): at least one alkali-soluble polymer obtained by polymerizing a monomer mixture including (A-I) below; (A-I): N-substituted maleimide compound; component (B): surfactant; component (C): compound having a vinyl ether group; component (D): photosensitizer; component (E): crosslinking agent; and (F) 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 repellency and high 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, and as a light-shielding material or 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] 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 3). 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.

[0005] 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 4). However, in recent years, there has been an increasing demand for a bank surface that has both higher water repellency and oil repellency and inkjet wettability.

[0006] Japanese Patent Application Laid-Open No. 2000-187111 Japanese Patent Application Laid-Open No. 11-54270 Japanese Patent Application Laid-Open No. 2015-172742 Japanese Patent No. 6744577

[0007] 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 having high water repellency and high oil repellency on the surface thereof, in which organic functional ink droplets do not overflow beyond a bank and into adjacent pixels, but remain within the pattern after pattern formation, and which wets and spreads well without causing repelling or unevenness.

[0008] The present inventors have conducted extensive research to achieve the above object and have completed the present invention. A first aspect of the present invention is a cured film-forming positive photosensitive resin composition containing the following components (A), (B), (C), (D), (E), and (F) a solvent, but not containing a photoacid generator: component (A): (A-I) at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing an N-substituted maleimide compound, component (B): a surfactant, component (C): a compound having a vinyl ether group, component (D): a photosensitizer, component (E): a crosslinking agent, and (F): a solvent; a second aspect of the present invention is the positive photosensitive resin composition according to the first aspect, in which (A-I) is N-methylmaleimide, N-phenylmaleimide, or N-cyclohexylmaleimide; a third aspect of the present invention is the positive photosensitive resin composition according to the first or second aspect, in which the monomer mixture contains the following (A-II): (A-II): a monomer having a hydroxyalkyl group and a polymerizable unsaturated group; A fourth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to third aspects, wherein the monomer mixture contains the following (A-III): (A-III): a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group; A fifth aspect of the present invention is the positive photosensitive resin composition according to the fourth aspect, wherein the (A-III) is a monomer having an N-hydroxyphenyl group; A sixth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fifth aspects, wherein the component (A) is an alkali-soluble polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene; 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 (B) is a surfactant made of a polymer having a liquid-repellent group; An eighth aspect of the present invention is the positive photosensitive resin composition according to the seventh 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; and a ninth aspect of the present invention is the positive photosensitive resin composition according to the seventh or eighth aspect, wherein a monomer unit constituting the polymer having the liquid repellent group is a monomer unit derived from an unsaturated hydrocarbon having the liquid repellent group;A tenth aspect of the present invention is the positive photosensitive resin composition according to any one of the seventh to ninth 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; an eleventh aspect of the present invention is the positive photosensitive resin composition according to any one of the seventh to tenth aspects, wherein the component (B) is a surfactant consisting of a polymer having the liquid repellent group and a thermosetting group; a twelfth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to eleventh aspects, wherein the component (C) is at least one compound selected from the group consisting of cyclohexyl vinyl ether, octadecyl vinyl ether, tris[4-(vinyloxy)butyl]-1,2,4-benzenetricarboxylate, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,4-butanediol divinyl ether, and triethylene glycol divinyl ether; 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 1,2-quinonediazide compound; 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 (E) is a crosslinking agent made of a compound containing an epoxy group or a methoxymethyl group; a fifteenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fourteenth aspects, wherein, relative to 100 parts by mass of the component (A), the component (B) is contained in an amount of 0.05 to 20 parts by mass, the component (C) is contained in an amount of 0.1 to 80 parts by mass, the component (D) is contained in an amount of 5 to 100 parts by mass, and the component (E) is contained in an amount of 5 to 50 parts by mass; a sixteenth aspect of the present invention is a cured film formed from the positive photosensitive resin composition according to any one of the first to fifteenth aspects; The seventeenth aspect of the present invention is a display element comprising the cured film according to the sixteenth aspect; The eighteenth aspect of the present invention is a display element comprising the cured film according to the sixteenth aspect as an image forming bank.

[0009] 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 that allows an organic functional ink to wet and spread well within a pattern without overflowing or repelling within the pattern after pattern formation.

[0010] 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 (A), (B), (C), (D), (E), and (F) a solvent, and does not contain a photoacid generator. Component (A) is at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing the following compounds (A-I): Preferably, component (A) is an alkali-soluble polymer obtained by copolymerizing a monomer mixture containing the following compounds (A-I) and (A-II): More preferably, the component (A) is an alkali-soluble polymer obtained by copolymerizing the following (A-I), (A-II), and (A-III): (A-I): N-substituted maleimide compound, (A-II): monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A-III): monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, component (B): surfactant, component (C): compound having a vinyl ether group, component (D): photosensitizer, component (E): crosslinking agent, and (F): solvent. Each component will be described in detail below.

[0011] <Component (A)> The component (A) is at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing at least the following compound (A-I). Preferably, the component (A) is at least one alkali-soluble polymer obtained by copolymerizing a monomer mixture containing at least the following compounds (A-I) and (A-II). More preferably, the component (A) is at least one alkali-soluble polymer obtained by copolymerizing at least the following compounds (A-I), (A-II), and (A-III). (A-I): N-substituted maleimide compound, (A-II): monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A-III): monomer having a phenolic hydroxyl group and a polymerizable unsaturated group

[0012] The alkali-soluble polymer of the component (A) may be any polymer containing at least an alkali-soluble group and a structure derived from an N-substituted maleimide compound, and there are no particular limitations on the types of main chain skeleton and side chains of the polymer constituting the polymer.

[0013] As described above, the alkali-soluble polymer of component (A) can be synthesized simply by, for example, polymerizing a monomer mixture containing (AI) an N-substituted maleimide compound. In some cases, it can be copolymerized with a monomer mixture containing (AI), (A-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A-III) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

[0014] Specific examples of the constituent monomers of component (A) are listed below, but the present invention is not limited to these.

[0015] (AI) (AI) Examples of N-substituted maleimide compounds include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide, with N-cyclohexylmaleimide being preferred.

[0016] (A-II) (A-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.

[0017] (A-III) (A-III) The monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is not limited to one having one phenolic hydroxyl group, and may have a plurality of phenolic hydroxyl groups.

[0018] Specific examples of the monomer are listed below, but are not limited to these. Examples of monomers having a phenolic hydroxyl group and a polymerizable unsaturated group include p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, p-hydroxyphenylacrylate, and p-hydroxyphenylmethacrylate. Here, when the alkali-soluble polymer of component (A) contains a structural unit derived from N-hydroxyphenylmaleimide, the structural unit is derived from (A-III) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, rather than from (A-I) an N-substituted maleimide compound.

[0019] (Other Monomer A) In the present invention, when obtaining the alkali-soluble polymer of the component (A), in addition to the above-mentioned monomers (AI), (A-II), and (A-III), another monomer A copolymerizable with the monomers (AI), (A-II), and (A-III) can be used in combination. Specific examples of the other monomer A include acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, acrylonitrile, styrene compounds, and monomers having unsaturated carboxylic acids. Specific compound examples of the other monomer A are listed below, but are not limited thereto.

[0020] 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.

[0021] 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, and 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, and poly(ethylene glycol) ethyl ether methacrylate.

[0022] 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.

[0023] Examples of the styrene compound include styrenes having no hydroxy group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0024] Examples of the monomer having an unsaturated carboxylic acid include 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. Examples of the monomer having an unsaturated carboxylic acid anhydride include maleic anhydride and itaconic anhydride.

[0025] Examples of the alkali-soluble polymer of component (A) include acrylic polymers and polymaleimide polymers, etc. The acrylic polymers refer to polymerizable unsaturated groups such as acrylic acid esters, methacrylic acid esters, and styrene, while the polymaleimide polymers refer to polymers obtained using monomers having polymerizable unsaturated groups such as maleimide, i.e., polymerizable groups containing a C═C double bond in the structure.

[0026] The method for obtaining the alkali-soluble polymer 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 the N-substituted maleimide compound (AI), preferably further (A-II) or (A-III), other copolymerizable monomers, and, if desired, a polymerization initiator, etc. In this case, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble polymer and the alkali-soluble polymer. Specific examples include the solvents described below in the section on (F) solvent.

[0027] The alkali-soluble polymer thus obtained is usually in the form of a solution dissolved in a solvent.

[0028] Alternatively, the alkali-soluble polymer 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 a powder of the alkali-soluble polymer. This procedure can remove the polymerization initiator and unreacted monomers that coexist with the alkali-soluble polymer, resulting in a purified powder of the alkali-soluble polymer. If the alkali-soluble polymer cannot be sufficiently purified in a single procedure, the resulting powder can be redissolved in a solvent and the above procedure can be repeated.

[0029] In the present invention, the powder of the alkali-soluble polymer may be used as it is, or the powder may be used in the form of a solution obtained by redissolving it in the solvent (F) described below.

[0030] In the present invention, the alkali-soluble polymer of component (A) may be a mixture of a plurality of alkali-soluble polymers.

[0031] That is, the copolymer is formed using an N-substituted maleimide compound and at least one monomer selected from the group of monomers copolymerizable with these monomers as essential structural units, and if the number average molecular weight is too high, exceeding 30,000, the flattening performance for unevenness may be reduced, while if the number average molecular weight is too low, less than 2,000, the copolymer may not be sufficiently cured during thermal curing, resulting in reduced solvent resistance. Therefore, the number average molecular weight is within the range of 2,000 to 30,000.

[0032] <Component (B)> The component (B) is a surfactant made of a polymer having a liquid-repellent group.

[0033] 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.

[0034] The liquid repellent group may be, for example, at least one group selected from a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group.

[0035] 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.

[0036] 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.

[0037] The number of carbon atoms in the fluoroalkyl group is not particularly limited as long as it does not impair the liquid repellency, but is preferably 1 to 40, more preferably 1 to 30, and even more preferably 4 to 10. 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] More preferably, P represents a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit bounded by n represents the same group or different groups, and Q represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0042] 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.

[0043] 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.

[0044] Specific examples of P include -CF ２ -, -CF ２ CF ２ -, -CF ２ CF ２ CF ２ -, -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.

[0045] 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:

[0046] 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.

[0047] -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.

[0048] 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.

[0049] The Rf groups (a) in the polymer that is the component (B) may all be the same or different.

[0050] 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.

[0051] R １ , R ２ independently 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.

[0052] 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).

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.).

[0058] 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.

[0059] By copolymerizing a thermosetting functional group in the polymer of component (B), it is possible to suppress the exudation of component (B) into the openings and decomposition 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 (A), component (C), or component (E), 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.

[0060] (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 monomers constituting the acrylic polymer having liquid-repellent groups of component (B) and the acrylic polymer. Specific examples include the solvents described below in the section on solvent (F).

[0061] 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.

[0062] 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-

[0063] 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.

[0064] The acrylic polymer having a liquid-repellent group thus obtained is usually in the form of a solution dissolved in a solvent.

[0065] 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.

[0066] 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 (F) described below and used in the form of a solution.

[0067] 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.

[0068] (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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] In this case, a plurality of types of alkoxysilanes having an organic group containing a thermosetting group may be used.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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 by adding a solvent, or used after replacing with another solvent.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] Examples of phenolic resins include novolak resins obtained by polymerizing phenol having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde.

[0088] 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.

[0089] 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.

[0090] The ratio of component (B) to component (A) is 0.05 to 20 parts by mass of component (B) per 100 parts by mass of the total of component (A).

[0091] <Component (C)> The compound having a vinyl ether group, component (C), is not particularly limited in type or structure as long as it has at least one vinyl ether group in one molecule.

[0092] Examples of compounds having one vinyl ether group per molecule include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, diethylene glycol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, and octadecyl vinyl ether.

[0093] Examples of the compound having two or more vinyl ether groups in one molecule include compounds represented by formula (5) and formula (6).

[0094] (wherein n is an integer from 2 to 10, k is an integer from 1 to 10, and R 3 represents an n-valent organic group.

[0095] (In the formula, m represents an integer of 2 to 10.)

[0096] In formula (5), n represents the number of vinyl ether groups in one molecule, and n is preferably an integer of 2 to 4. In formula (6), m also represents the number of vinyl ether groups in one molecule, and m is preferably an integer of 2 to 4.

[0097] Specific examples of the compounds represented by formula (5) and formula (6) include bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, adipic acid divinyl ester, bis(4-(vinyloxy)butyl)terephthalate, bis(4-(vinyloxy)butyl isophthalate, tris[4-(vinyloxy)butyl]-1,2,4-benzenetricarboxylate, tris[4-(vinyloxy)butyl]-1,3,5-benzenetricarboxylate, and 1,4-cyclohexanedimethanol divinyl ether.

[0098] Furthermore, examples of compounds having two or more vinyl ether groups in one molecule other than the compounds represented by formula (5) and formula (6) include 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

[0099] The compound of component (C) is used in an amount of 0.1 to 80 parts by mass, preferably 0.5 to 40 parts by mass, per 100 parts by mass of the alkali-soluble polymer of component (A). If the amount of the compound of component (C) used is too small, below the lower limit of the above range, film loss in unexposed areas becomes significant, which may result in poor pattern-like relief shape and reduced water repellency. On the other hand, if the amount of the compound of component (C) used is too large, above the upper limit of the above range, the sensitivity of the film will be significantly reduced, and residues will occur between patterns after development.

[0100] <Component (D)> Examples of the photosensitizer serving as component (D) include 1,2-quinonediazide compounds. The 1,2-quinonediazide compound is a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group, in which preferably 10 to 100 mol %, and particularly preferably 20 to 95 mol %, of these hydroxy groups or amino groups (when both hydroxy groups and amino groups are present, the total amount of these groups) is esterified or amidated with 1,2-quinonediazide sulfonic acid.

[0101] Examples of the compound having a hydroxy 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 phenolic compounds such as bisphenol [phenol], 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.

[0102] 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.

[0103] Furthermore, examples of compounds containing both a hydroxy 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.

[0104] These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[0105] The content of component (D) in the positive 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, per 100 parts by mass of component (A). 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 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.

[0106] <Component (E)> Component (E) 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 phenolic hydroxyl group of component (A-III). Specific examples are listed below, but the present invention is not limited to these. Preferred examples of the thermal crosslinking agent include (E1) a crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, (E2) a crosslinkable compound represented by the following formula (7), and (E3) a crosslinking agent having two or more isocyanate groups. These crosslinking agents can be used alone or in combination of two or more.

[0107] The crosslinkable compound (E1) 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.

[0108] 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.

[0109] 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).

[0110] 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.

[0111] 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.).

[0112] 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.).

[0113] Furthermore, as the component (E1), 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.

[0114] 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.

[0115] These crosslinkable compounds may be used alone or in combination of two or more.

[0116] When component (E1) 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 component (A). 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.

[0117] The positive photosensitive resin composition of the present invention may also contain, as component (E2), a crosslinkable compound having an epoxy group represented by formula (7). (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)

[0118] 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.

[0119] 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.

[0120] When component (E2) is selected as the crosslinking agent, the content thereof 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 component (A). If the content of the crosslinkable compound is less than 5 parts by mass, the density of the crosslinks formed by the crosslinkable 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 crosslinkable 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.

[0121] <(F) Solvent> The (F) solvent used in the present invention dissolves the components (A), (B), (C), (D), and (E), and also dissolves other additives, which 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.

[0122] Examples of such solvents (F) 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.

[0123] These solvents can be used alone or in combination of two or more. Among these (F) 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.

[0124] <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.

[0125] <Photoacid Generator> The photoacid generator is an agent described in JP 2012-220860 A or WO 2007 / 132892 A, except for 1,2-quinonediazide compounds.

[0126] <Positive Photosensitive Resin Composition> The positive photosensitive resin composition of the present invention is a cured film-forming positive photosensitive resin composition that contains the following components (A), (B), (C), (D), (E), and (F) a solvent, but does not contain a photoacid generator, and can further contain one or more other additives, as desired. Component (A): an alkali-soluble polymer obtained by polymerizing at least (A-I) below; preferably an alkali-soluble polymer obtained by copolymerizing at least (A-I) below and (A-II) below; more preferably an alkali-soluble polymer obtained by copolymerizing at least (A-I), (A-II) below and (A-III) below, (A-I): an N-substituted maleimide compound, (A-II): a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A-III): a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group, component (B): a surfactant, component (C): a compound having a vinyl ether group, component (D): a photosensitizer, component (E): a crosslinking agent, and (F): a solvent.

[0127] Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows: A positive photosensitive resin composition containing, per 100 parts by mass of component (A), 0.05 to 20 parts by mass of component (B), 0.1 to 80 parts by mass of component (C), 5 to 100 parts by mass of component (D), and 5 to 50 parts by mass of component (E), and these components are dissolved in solvent (F).

[0128] 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 (F).

[0129] 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 the component (B) (polymer) is dissolved in the solvent (F), and the alkali-soluble polymer of the component (A), the compound having a vinyl ether group of the component (C), the photosensitizer of the component (D), and the crosslinker of the component (E) are mixed with this solution in predetermined proportions to prepare a homogeneous solution, or a method in which other additives are further added and mixed, if necessary, at an appropriate stage of this preparation method.

[0130] In preparing the positive photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the (F) solvent can be used as is, and in this case, when, as described above, components (A), (C), (D), and (E) are added to the solution of the (B) component to prepare a homogeneous solution, additional (F) solvent may be added for the purpose of adjusting the concentration. In this case, the (F) solvent used in the copolymer formation process and the (F) solvent used to adjust the concentration in the preparation of the positive photosensitive resin composition may be the same or different.

[0131] 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.

[0132] <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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] Thus, by such post-baking, it is possible to obtain a cured film having the desired good pattern shape.

[0143] 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, very little film loss in unexposed areas during development, excellent inkjet wettability and contact angle, and is suitable for use as a cured film. Furthermore, the resulting coating film (cured film) is characterized by almost no pattern residue. Therefore, the composition is suitable for use as various films, such as interlayer insulating films, protective films, and insulating films, in liquid crystal displays and organic EL displays, as well as light-shielding materials and partition wall materials, such as banks, compatible with inkjet printing.

[0144] 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.

[0145] (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: 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) Contact angle evaluation Device: Drop Master manufactured by Kyowa Interface Science Co., Ltd. (5) Wettability evaluation Device: Inkjet Designer manufactured by Cluster Technology Co., Ltd.

[0146] 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 QD1: A compound synthesized by the 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 QD2: A compound synthesized by the condensation reaction of 1 mol of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene 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] NHPMA: N-(4-hydroxyphenyl)methacrylamide PFHTMOS: Trimethoxy(1H,1H,2H,2H-tridecafluoro-n-octyl)silane PFBTMOS: Trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane [KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.] 35 wt% TEA Haq. : 35 wt% tetraethylammonium hydroxide solution 15JWET: Amberlyst 15JWET ion exchange resin manufactured by Organo Corporation KC Flock: KC Flock W-100GK manufactured by Nippon Paper Industries Co., Ltd. CHDVE: 1,4-cyclohexanedimethanol divinyl ether TrisVE: tris[4-(vinyloxy)butyl]-1,2,4-Benzenetricarboxylate CHVE: Cyclohexyl vinyl ether BDVE: 1,4-butanediol divinyl ether TEGDVE: Triethylene glycol divinyl ether OdVE: Octadecyl vinyl ether CHMVE: 1,4-cyclohexanedimethanol monovinyl ether PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate MeOH: Methanol TMAH: Tetramethylammonium hydroxide

[0147] 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 (solids concentration: 40% by mass) of an alkali-soluble polymer component having Mn of 3,600 and Mw of 8,600. (A1)

[0148] Synthesis Example 2: 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 PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solids concentration: 21% by mass) (A2). The resulting acrylic polymer had an Mn of 6,200 and an Mw of 9,900.

[0149] Synthesis Example 3: 4.10 g of PFBTMOS, 2.46 g of KBM-303, 0.17 g of 35 wt% TEAH, and 0.54 g of water were dissolved in 21.83 g of PGMEA and stirred at 40°C for 4 hours. Subsequently, 0.66 g of 15JWET washed with PGMEA 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 siloxane polymer solution (B1). The resulting siloxane polymer had an Mn of 2,300 and an Mw of 2,600.

[0150] Synthesis Example 4: 2.34 g of PFHTMOS, 2.29 g of KBM-303, 0.24 g of 35 wt% TEAH, 0.49 g of water, and 0.54 g of MeOH were dissolved in 15.54 g of PGMEA 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 siloxane polymer solution (B2). The resulting siloxane polymer had an Mn of 2,300 and an Mw of 2,700.

[0151] [Synthesis Example 5] 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.

[0152] [Examples 1 to 9, 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.

[0153] [Evaluation of Inkjet Wettability] The positive-type 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 irradiated with ultraviolet light at 365 nm with a light intensity of 5.5 mW / cm2 for a certain period of time through a mask patterned with numerous ellipses with long sides of 210 μm and short sides of 90 μm. The film was then developed by immersion in a 0.20% TMAH aqueous solution for 60 seconds (except for Example 9 and Comparative Example 5, which were immersed in a 2.38% TMAH aqueous solution for 50 seconds), followed by rinsing with running ultrapure water for 30 seconds. The coating film with the elliptical pattern then was postbaked 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 5 were ejected into the openings of the cured elliptical pattern and allowed to dry naturally to form an organic functional film. The state of the organic functional film was observed using an optical microscope and evaluated according to the following criteria. When considering actual specifications, at least B is required, and A is desirable. A: Good, with no cissing or overflow within 14 shots B: Good, with no cissing or overflow within 20 shots C: Cissing or overflow occurs even after 20 shots

[0154] [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 0.20% TMAH aqueous solution for 60 seconds (only Example 9 and Comparative Example 5 were immersed in a 2.38% TMAH aqueous solution for 50 seconds), followed by rinsing with running ultrapure water for 30 seconds. The film 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≧55° B: 53°≦θ<55° C: θ<53°

[0155]

[0156]

[0157] As shown in Table 2, the cured films (Examples 1 to 9) prepared using positive photosensitive compositions each containing an acrylic polymer, a surfactant, or a vinyl ether were shown to have excellent inkjet wettability and contact angle.

[0158] On the other hand, the cured films made of the positive-type photosensitive compositions of Comparative Examples 1, 3, and 5, which used an acrylic polymer and a surfactant but did not contain a vinyl ether, were shown to have excellent contact angles but poor inkjet wettability. Furthermore, the cured film made of the positive-type photosensitive composition of Comparative Example 2, in which the amount of surfactant added was reduced, was shown to have excellent inkjet wettability but poor contact angle. Next, Comparative Example 4, which used an acrylic polymer and a vinyl ether but did not contain a surfactant, was shown to have poor inkjet wettability and contact angle.

[0159] As shown in the results of the Examples above, it is only by using a positive photosensitive composition that combines an acrylic polymer, a surfactant, a vinyl ether, a crosslinking agent, and a photosensitizer that it is possible to obtain a cured film that satisfies both inkjet wettability and a contact angle.

Claims

1. A cured film-forming positive photosensitive resin composition containing the following components (A), (B), (C), (D), (E), and (F) a solvent, but not containing a photoacid generator: Component (A): at least one alkali-soluble polymer obtained by polymerizing a monomer mixture containing the following (A-I): (A-I): an N-substituted maleimide compound, Component (B): a surfactant, Component (C): a compound having a vinyl ether group, Component (D): a photosensitizer, Component (E): a crosslinking agent, and (F): a solvent.

2. The positive photosensitive resin composition according to claim 1, wherein (AI) is N-methylmaleimide, N-phenylmaleimide, or N-cyclohexylmaleimide.

3. The positive photosensitive resin composition according to claim 1, wherein the monomer mixture contains the following (A-II): (A-II): a monomer having a hydroxyalkyl group and a polymerizable unsaturated group.

4. The positive photosensitive resin composition according to claim 1, wherein the monomer mixture contains the following (A-III): (A-III): a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group.

5. The positive photosensitive resin composition according to claim 4, wherein (A-III) is a monomer having an N-hydroxyphenyl group.

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

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

8. The positive photosensitive resin composition according to claim 7, 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.

9. The positive photosensitive resin composition according to claim 7, 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.

10. The positive photosensitive resin composition according to claim 7, 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.

11. The positive photosensitive resin composition according to claim 7, wherein the component (B) is a surfactant comprising a polymer having the liquid-repellent group and the thermosetting group.

12. The positive photosensitive resin composition according to claim 1, wherein the component (C) is at least one compound selected from the group consisting of cyclohexyl vinyl ether, octadecyl vinyl ether, tris[4-(vinyloxy)butyl]-1,2,4-benzenetricarboxylate, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,4-butanediol divinyl ether, and triethylene glycol divinyl ether.

13. The positive photosensitive resin composition according to claim 1, wherein the component (D) is a 1,2-quinonediazide compound.

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

15. A positive photosensitive resin composition according to claim 1, wherein, relative to 100 parts by mass of the component (A), the component (B) is contained in an amount of 0.05 to 20 parts by mass, the component (C) is contained in an amount of 0.1 to 80 parts by mass, the component (D) is contained in an amount of 5 to 100 parts by mass, and the component (E) is contained in an amount of 5 to 50 parts by mass.

16. A cured film formed from the positive photosensitive resin composition according to any one of claims 1 to 15.

17. A display device comprising the cured film according to claim 16.

18. A display device comprising the cured film according to claim 16 as an image forming bank.