Positive-acting photosensitive resin composition

Abstract

[Problem] To obtain a positive-acting photosensitive resin composition which is used for liquid-crystal display elements, organic EL display elements, etc., gives cured films having surfaces with high water repellency and high oil repellency, leaves little residue after patterning even with a high-concentration developing solution, and can form a cured-film image that is reduced in outgassing during high-temperature burning. [Solution] This positive-acting photosensitive resin composition comprises (A) component, which is a polymer having a liquid-repellent group, (B) component, which is an alkali-soluble resin having an N-hydroxyphenyl group, (C) component, which is a 1,2-quinonediazide compound, (D) component, which is a crosslinking agent, and (E) a solvent.

Description

Positive photosensitive resin composition

[0001] The present invention relates to a positive-type photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a positive-type photosensitive resin composition capable of forming images that are less likely to leave residues during pattern formation, emit less outgassing during high-temperature baking, and have high water and oil repellency on the cured film surface, a cured film thereof, 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] 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, as a positive-tone material, International Publication No. 2007-132890 (Patent Document 4) discloses a polymer having a carboxyl group as an alkali-soluble polymer, but when the tetraethylammonium hydroxide in the alkaline developer used is highly concentrated, residues tend to form between patterns, making it difficult to use on all production lines. Furthermore, as a positive-tone material that can form patterns even using a high-concentration developer, Japanese Patent Application Laid-Open No. 2009-251327 and Japanese Patent Application Laid-Open No. 2015-215449 (Patent Documents 5 and 6) disclose alkali-soluble polymers having phenolic hydroxyl groups, but these materials have problems such as low heat resistance and reduced lifespan of display elements due to outgassing generated during baking. If a high-concentration developer could be used, it could be shared with developers for TFT-forming resists, TFT planarization layers, etc., which would lead to cost reduction and process optimization, but this is currently difficult.

[0006] JP 2000-187111 A JP 11-54270 A JP 2015-172742 A JP 2007-132890 A JP 2009-251327 A JP 2015-215449 A

[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 has high water repellency and high oil repellency on the surface of a cured film, that leaves little residue after pattern formation even when a high-concentration developer is used, and that is capable of forming an image on a cured film with little outgassing during high-temperature baking.

[0008] As a result of extensive research to achieve the above object, the present inventors have found that the use of an alkali-soluble resin having an N-hydroxyphenyl group improves developability when a high-concentration aqueous solution of tetramethylammonium hydroxide is used as a developer, suppresses the generation of residues between patterns, and further significantly reduces outgassing, which is observed with resins containing phenolic hydroxyl groups, and have completed the present invention. A first aspect of the present invention is a heat-curable positive photosensitive resin composition containing the following components (A), (B), (C), (D), and (E) a solvent: component (A): a polymer having a liquid-repellent group, component (B): an alkali-soluble resin having an N-hydroxyphenyl group, 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 component (B) 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 third aspect of the present invention is the positive photosensitive resin composition according to the first or second aspect, wherein the liquid-repellent group of component (A) is at least one group selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, and a polysiloxane 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 unit constituting the polymer of component (A) is a unit derived from an unsaturated hydrocarbon having the liquid repellent group.A fifth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to third aspects, in which the monomer units constituting the polymer of component (A) are units derived from an alkoxysilane compound having the liquid repellent group; 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 (A) is a polymer having the liquid repellent group and a thermosetting group; a seventh aspect of the present invention is the positive photosensitive resin composition according to any one of the first to sixth aspects, in which the crosslinking agent of component (D) contains an epoxy group or a methoxymethyl group; an eighth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to seventh aspects, in which the alkali-soluble resin of component (B) has a number average molecular weight of 2,000 to 60,000 in terms of polystyrene; A ninth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to eighth aspects, characterized in that the component (A) is contained in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of the component (B); A tenth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to ninth aspects, characterized in that the component (C) is contained in an amount of 5 to 100 parts by mass relative to 100 parts by mass of the component (B); An eleventh aspect of the present invention is the positive photosensitive resin composition according to any one of the first to tenth aspects, characterized in that the component (D) is contained in an amount of 5 to 50 parts by mass relative to 100 parts by mass of the component (B); A twelfth aspect of the present invention is a cured film obtained using the positive photosensitive resin composition according to any one of the first to eleventh aspects; A thirteenth aspect of the present invention is a display element having the cured film according to the twelfth aspect; A fourteenth aspect of the present invention is a display element having the cured film according to the twelfth aspect as an image formation bank.

[0009] The positive photosensitive resin composition of the present invention can form a cured film having high water repellency and high oil repellency on the surface thereof, leaving little residue after pattern formation, and generating little outgassing when baked at high temperatures.

[0010] The photosensitive resin composition of the present invention is a positive-type photosensitive resin composition containing the following components (A), (B), (C), (D), and (E) a solvent: Component (A): a polymer having a liquid-repellent group, Component (B): an alkali-soluble resin having an N-hydroxyphenyl group, Component (C): a 1,2-quinonediazide compound, Component (D): a crosslinking agent, and (E) a solvent. Each component will be described in detail below.

[0011] <Component (A)> The component (A) is a polymer having a liquid repellent group.

[0012] In the present invention, the term "polymer" refers to an acrylic polymer 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 polysilsesquioxane obtained by hydrolytic polycondensation of a polyfunctional alkoxysilane monomer.

[0013] The liquid repellent group may be, for example, at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, and a polysiloxane group.

[0014] The fluoroalkyl group has 3 to 10 carbon atoms, and preferably has 4 to 10 carbon atoms. Examples of such fluoroalkyl groups include 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.

[0015] To introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer that is component (A) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms 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 having 3 to 10 carbon atoms and the reactive site of the polymer.

[0016] The polyfluoroether group includes an Rf group (a) having a polyfluoroether structure represented by the following formula 1: —(X—O) ｎ -Y Formula 1 In Formula 1, X 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, Y represents a hydrogen atom (only when a fluorine atom is not bonded to the carbon atom adjacent to the oxygen atom adjacent to Y), 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 1 is 2 or more.

[0017] As a preferred embodiment of X and Y in Formula 1, X is a C1-10 alkylene group fluorinated by removing one hydrogen atom or a C1-10 perfluorinated alkylene group, and each unit grouped by n represents the same group or different groups, and Y is a C1-20 alkyl group fluorinated by removing one hydrogen atom or a C1-20 perfluorinated alkyl group.

[0018] As a more preferred embodiment of X and Y in Formula 1, X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit grouped by n may be the same or different, and Y is a perfluorinated alkyl group having 1 to 20 carbon atoms.

[0019] In formula 1, 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 (A) is synthesized by copolymerization of a monomer having an Rf group (a) with other monomers, good compatibility of the monomers is achieved.

[0020] Furthermore, the total number of carbon atoms in the Rf group (a) consisting of the polyfluoroether structure represented by formula 1 is preferably 2 to 50, and more preferably 2 to 30. Within this range, the polymer that is component (A) exhibits good liquid repellency.

[0021] Specific examples of X 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 some examples.

[0022] Specific examples of Y 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:

[0023] A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by formula 1 is the Rf group (a) represented by formula 2.

[0024] -C ｐ－１ F ２（ｐ－１） -O-(C ｐ F ２ｐ -O) ｎ－１ -C ｑ F ２ｑ＋１ In formula 2, 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.

[0025] Specific examples of the Rf group (a) represented by formula 2 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.

[0026] The Rf groups (a) in the polymer that is the component (A) may all be the same or different.

[0027] The polysiloxane group may be a group (b) having a polysiloxane structure represented by formula 3. Hereinafter, the group (b) having a polysiloxane structure represented by formula 3 will be referred to as a pSi group (b). -(SiR １ R ２ -O) ｎ -SiR １ R ２ R ３ ...Equation 3 (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.

[0028] 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.

[0029] Examples of methods for introducing the pSi group (b) into the polymer that is component (A) 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).

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.).

[0035] In the polymer of component (A), 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.

[0036] By copolymerizing a thermosetting functional group in the polymer of component (A), it is possible to suppress the exudation of component (A) 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 (B) or component (D), or a functional group that self-crosslinks with component (A). Examples of such thermosetting functional groups (thermosetting groups) include hydroxyl 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.

[0037] The method for producing the acrylic polymer of component (A) is not particularly limited, but it can be obtained by polymerizing a monomer having a liquid-repellent group, for example, at least one of a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, a monomer having a polyfluoroether group, and a monomer having a polysiloxane group, the monomer having a thermosetting group, and, if desired, a monomer other than the above (hereinafter also referred to as other monomer A), 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 that constitute the alkali-soluble acrylic polymer and the acrylic polymer having the specific functional group. Specific examples include the solvents described below in the section on solvent (E).

[0038] 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.

[0039] 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 methacrylates include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0040] Specific examples of other monomers A 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, 2-propyl-2-adamantyl 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, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, styrene, vinylnaphthalene, vinylanthracene, and vinylbiphenyl.

[0041] The acrylic polymer having a specific functional group thus obtained is usually in the form of a solution dissolved in a solvent.

[0042] Furthermore, the acrylic 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 specific copolymer. This procedure can remove polymerization initiators and unreacted monomers coexisting with the specific copolymer, resulting in a purified powder of the specific copolymer. If sufficient purification cannot be achieved by a single procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated. In the present invention, the powder of the specific copolymer can be used as is, or the powder can be redissolved in, for example, the solvent (E) described below and used in the form of a solution.

[0043] The method for obtaining the polysilsesquioxane of component (A) is not particularly limited, but a polysilsesquioxane 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.

[0044] 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.

[0045] 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.

[0046] 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)ethylriethoxysilane, 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)tyl methacrylate, 2-(triethoxysilyl)ethyl acrylate, 2-(trimethoxysilyl)tyl acrylate, (triethoxysilyl)methyl methacrylate, (trimethoxysilyl)methyl methacrylate, (triethoxysilyl)methyl acrylate, (trimethoxysilyl)methyl acrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropyl urea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropyl urea, 1-[3-(trimethoxysilyl)propyl]urea, and the like.

[0047] 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.

[0048] In this case, a plurality of types of alkoxysilanes having an organic group containing a thermosetting group may be used.

[0049] 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.

[0050] The polysilsesquioxane of component (A) preferably contains 5 to 50 mol % of alkoxysilanes containing a liquid repellent group based on all alkoxysilanes, and preferably contains 10 to 95 mol % of alkoxysilanes containing a thermosetting group based on all alkoxysilanes, with the remainder being obtained by polycondensation of other alkoxysilanes.

[0051] 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 40 mol %, and the content of the alkoxysilane containing a thermosetting group is more preferably 30 to 80 mol % of the total alkoxysilane.

[0052] Examples of methods for obtaining the polysilsesquioxane of component (A) 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.

[0053] 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 that the polysilsesquioxane-containing solution be heated so that the polysilsesquioxane 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 polysilsesquioxane-containing solution can be obtained.

[0054] 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.

[0055] 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.

[0056] In the present invention, the solution of the specific polysilsesquioxane 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 polysilsesquioxane obtained by the above method may be concentrated, diluted by adding a solvent, or substituted with another solvent before use.

[0057] 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 polysilsesquioxane 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.

[0058] Furthermore, in the present invention, when a polymer other than polysilsesquioxane is used in the photosensitive resin composition, it is preferable to distill off the alcohol generated during the polycondensation reaction of polysilsesquioxane under normal pressure or reduced pressure before mixing the polymer other than polysilsesquioxane.

[0059] In addition to the above-mentioned acrylic polymers and polysilsesquioxanes, examples of the polymer that is component (A) include polyimides, polyamic acids, polyamides, polyureas, polyurethanes, phenols, epoxies, polysiloxanes, polyesters, and polymers in which a quinonediazide group has been introduced into an acrylic polymer.

[0060] 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.

[0061] 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.

[0062] Examples of phenolic resins include novolac resins obtained by polymerizing phenols having a fluoroalkyl group or a fluoroalkoxy group with formaldehyde. Examples of epoxy resins include epoxy resins 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. Examples of polysiloxanes include polymers obtained by polymerizing a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group.

[0063] 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.

[0064] In the present invention, the acrylic polymer of component (A) may be a mixture of a plurality of specific copolymers.

[0065] <Component (B)> The component (B) of the present invention is an alkali-soluble resin having an N-hydroxyphenyl group. The alkali-soluble resin of the component (B) 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.

[0066] The alkali-soluble resin of component (B) preferably has 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.

[0067] Examples of the alkali-soluble resin having an N-hydroxyphenyl group as component (B) include acrylic resins and polymaleimide resins.

[0068] In the present invention, an alkali-soluble resin made of a copolymer obtained by polymerizing multiple types of monomers (hereinafter referred to as a specific copolymer) can also be used as component (B). In this case, the alkali-soluble resin of component (B) may be a blend of multiple types of specific copolymers.

[0069] That is, the specific copolymer is a copolymer formed from a monomer having an N-hydroxyphenyl group and at least one monomer selected from the group of monomers copolymerizable with the monomer as essential structural units, 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.

[0070] The above-mentioned monomer having an N-hydroxyphenyl group is not limited to one having one N-hydroxyphenyl group, and may be one having a plurality of N-hydroxyphenyl groups.

[0071] Specific examples of the above-mentioned monomers are listed below, but are not limited to these. Examples of monomers having an N-hydroxyphenyl group include N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide.

[0072] Examples of monomers copolymerizable with the monomer having an N-hydroxyphenyl 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, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, and 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, 2-propyl-2-adamantyl 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, 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, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxy Propyl 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 N-(2 ...1-(2-(2-(2-(2-(2-(2-(2-(2-(1-(2-(2-(2-(2-(2-(1-(2-(2-(2-(2-(2-(1-(2-(2-(2-(2-(2-(1-(2-(2-(2-(2-(1-(2-(2-(2-(2-(1-(2-(2-(2-(1-(2-(2-(2-(1-(2-(2-(2-(2-(1-(2-(1-(2-(2-(2-(2-(1-(2-(2-(1-(2-(2-(2-(2-(1-(2-(2-(1-(2-(1-(2-(2-(2-(2-(1-(2-(1-(2-(2-(2-(1-(2-(2-(1-(2-(2-(1-(2-(2-(

[0073] The proportion of the monomer having an N-hydroxyphenyl group in the production of the alkali-soluble resin, component (B), is preferably 10 to 90 mol %, more preferably 20 to 85 mol %, and most preferably 30 to 80 mol %, of all the monomers used in the production of the alkali-soluble acrylic polymer, component (B). If the proportion of the monomer having an N-hydroxyphenyl group is less than 10 mol %, the alkali solubility of the polymer will be insufficient.

[0074] In the production of the alkali-soluble resin (B), the proportion of the other monomers 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.

[0075] The method for obtaining the alkali-soluble resin, which is component (B) 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, and optionally other copolymerizable monomers, and optionally a polymerization initiator, etc. The solvent used in this case is not particularly limited as long as it dissolves the monomers that constitute the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include the solvents described below in the section on solvent (E).

[0076] The acrylic polymer thus obtained is usually in the form of a solution dissolved in a solvent.

[0077] Furthermore, 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. This procedure can remove the polymerization initiator and unreacted monomers coexisting with the specific copolymer, resulting in a purified powder of the specific copolymer. If the specific copolymer cannot be sufficiently purified in a single procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated. In the present invention, the powder of the specific copolymer may be used as is, or the powder may be redissolved in, for example, the solvent (E) described below and used in the form of a solution.

[0078] In the present invention, the alkali-soluble resin of component (B) may be a mixture of a plurality of types of alkali-soluble resins.

[0079] The ratio of component (A) to component (B) is 0.1 to 20 parts by mass of component (A) per 100 parts by mass of component (B).

[0080] <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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[0085] The content of component (C) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of component (B). 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.

[0086] <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 (B). 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 compound selected from crosslinkable compounds represented by the following formula (3), 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.

[0087] 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.

[0088] 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.

[0089] 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).

[0090] 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.

[0091] 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.).

[0092] 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.).

[0093] 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.

[0094] 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.

[0095] These crosslinkable compounds may be used alone or in combination of two or more.

[0096] 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 component (B). 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.

[0097] 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 (3). (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)

[0098] Commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (trade names manufactured by Daicel Chemical Industries, Ltd.), alicyclic epoxy resins such as Denacol EX-252 (trade name manufactured by Nagase Chemtex Corporation), CY175, CY177, and CY179 (trade names manufactured by CIBA-GEIGY A.G.), Araldite CY-182, CY-192, and CY-184 (trade names manufactured by CIBA-GEIGY A.G.), Epiclon 200 and 400 (trade names manufactured by DIC Corporation), and Epicoat 871 and 872 (trade names manufactured by Yuka Shell Epoxy Co., Ltd.). ED-5661, ED-5662 (all trade names, manufactured by Celanese Coatings Co., Ltd.) and the like. These crosslinkable compounds may be used alone or in combination of two or more.

[0099] Of these, compounds having a cyclohexene oxide structure, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 are preferred from the viewpoint of process resistance such as heat resistance, solvent resistance, and long-term baking resistance.

[0100] When component (D2) 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 (B). 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.

[0101] <Solvent (E)> The solvent (E) used in the present invention dissolves the components (A), (B), (C), and (D), 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.

[0102] 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.

[0103] 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.

[0104] <Other Additives> Furthermore, the positive photosensitive resin composition of the present invention may contain, as necessary, a rheology modifier, a pigment, a dye, 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.

[0105] <Positive Photosensitive Resin Composition> The positive photosensitive resin composition of the present invention is a positive photosensitive resin composition containing the following components (A), (B), (C), (D), and (E) a solvent, and each of these may further contain one or more of other additives, as desired: Component (A): a polymer having a liquid-repellent group, Component (B): an alkali-soluble resin having an N-hydroxyphenyl group, Component (C): a 1,2-quinonediazide compound, Component (D): a crosslinking agent, and (E): a solvent.

[0106] Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows: A positive photosensitive resin composition containing 0.1 to 20 parts by mass of component (A), 5 to 100 parts by mass of component (C), and 5 to 50 parts by mass of component (D) per 100 parts by mass of component (B), and these components are dissolved in solvent (E).

[0107] 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).

[0108] 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 (A) (specific acrylic copolymer) is dissolved in solvent (E), and the resulting solution is mixed with component (B) alkali-soluble resin, component (C) 1,2-quinonediazide compound, and component (D) crosslinking agent 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.

[0109] In preparing the positive 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, and in this case, when the solution of the component (A) is added with the components (B), (C), and (D) to prepare a homogeneous solution as described above, the solvent (E) may be further added for the purpose of adjusting the concentration. In this case, the solvent (E) used in the process of forming the specific copolymer and the solvent (E) used for adjusting the concentration in preparing the positive photosensitive resin composition may be the same or different.

[0110] 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.

[0111] <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.

[0112] 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.

[0113] 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.

[0114] A mask having a predetermined pattern is attached to the coating film obtained above, and the film is irradiated with light such as ultraviolet light, and then developed with an alkaline developer, whereby the exposed areas are washed out and a sharp relief pattern with sharp edge surfaces is obtained.

[0115] 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.

[0116] Among the above, an aqueous solution of 0.1 to 2.38 mass % tetraethylammonium 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 of 1.0 to 2.38 mass % tetraethylammonium hydroxide.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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 30 to 90 minutes in an oven.

[0121] Thus, by such post-baking, it is possible to obtain a cured film having the desired good pattern shape.

[0122] As described above, the positive photosensitive resin composition of the present invention has high storage stability, sufficiently high sensitivity, and undergoes very little film loss in unexposed areas during development, making it possible to form a coating film having a fine pattern. Furthermore, the coating film (cured film) thus obtained can be suitably used as an image-forming bank for a display device.

[0123] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The number average molecular weight and weight average molecular weight were measured as follows.

[0124] [Measurement of Number Average Molecular Weight and Weight Average Molecular Weight] The number average molecular weight and weight average molecular weight of the copolymers obtained according to the following synthesis examples were measured using a GPC apparatus (Shodex columns KF-804L and 803L) manufactured by Shimadzu Corporation under the condition that elution was performed by flowing tetrahydrofuran, an elution solvent, through the column at a flow rate of 1 ml / min (column temperature 40°C). The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) below are expressed in polystyrene equivalent values.

[0125] The meanings of the abbreviations used in the following examples are as follows: 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 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 MARUKA LINKER CST: a 30 wt % propylene glycol monomethyl ether solution (P2) of a styrene polymer prepared by mixing MARUKA LINKER CST8515 and 7030 manufactured by Maruzen Petrochemical Co., Ltd. in a ratio of 2:8 HMM: Nikallac MW-100LM (hexamethoxymethylmelamine manufactured by Sanwa Chemical Co., Ltd.) PFHMA: 2-(perfluorohexyl)ethyl methacrylate KBM-503: 3-methacryloxypropyltriethoxysilane NHPMA: N-(4-hydroxyphenyl)methacrylamide NHPMI: N-(4-hydroxyphenyl)maleimide St: styrene PFHTMOS: 2-(perfluorohexyl)ethyltrimethoxysilane KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 35 wt% TEA Haq. : 35 wt% tetraethylammonium hydroxide solution PTMOS: Phenyltrimethoxysilane 15JWET: Ion exchange resin manufactured by Organo Corporation PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate THF: Tetrahydrofuran

[0126] Synthesis Example 1: 5.00 g of HPMA, 1.28 g of MMA, 3.93 g of CHMI, and 0.31 g of AIBN were dissolved in 47.88 g of PGME, and the mixture was allowed to react at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass) (P1). The obtained acrylic polymer had an Mn of 6,000 and an Mw of 9,500.

[0127] Synthesis Example 2: 5.00 g of NHPMA, 1.28 g of MMA, 3.93 g of CHMI, and 0.31 g of AIBN were dissolved in 47.88 g of PGME, and the mixture was allowed to react at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass) (P3). The resulting acrylic polymer had an Mn of 5,000 and an Mw of 8,100.

[0128] Synthesis Example 3: 5.00 g of NHPMA, 1.09 g of MMA, 3.00 g of CHMI, and 0.27 g of AIBN were dissolved in 42.66 g of PGME, and the mixture was allowed to react at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass) (P4). The resulting acrylic polymer had an Mn of 4,500 and an Mw of 6,300.

[0129] 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 33.16 g of PGME, and the mixture was reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 18% by mass) (P5). The resulting acrylic polymer had an Mn of 5,600 and an Mw of 9,300.

[0130] Synthesis Example 5: 3.00 g of NHPMA, 0.98 g of HEMA, 2.34 g of CHMI, and 0.12 g of AIBN were dissolved in 29.32 g of PGME, and the mixture was allowed to react at 90° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 18% by mass) (P6). The resulting acrylic polymer had an Mn of 6,200 and an Mw of 9,900.

[0131] 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 PGME, and the mixture was allowed to react at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30% by mass) (P7). The obtained acrylic polymer had an Mn of 4,800 and an Mw of 6,700.

[0132] Synthesis Example 7: 2.34 g of PFHTMOS, 2.46 g of KBM-303, 1.98 g of PTMOS, 0.21 g of 35 wt% TEAH, and 0.68 g of HO were dissolved in 9.21 g of THF and stirred at 40°C for 4 hours. Subsequently, 0.48 g of 15JWET washed with THF was added, and the mixture was stirred at 25°C for 1 hour. The waste 15JWET was then filtered to obtain a siloxane polymer solution (P8). The resulting siloxane polymer had an Mn of 1,900 and an Mw of 2,400.

[0133] Synthesis Example 8: 10.9 g of MAA, 35.3 g of CHMI, 25.5 g of HEMA, and 28.3 g of MMA were used, and 5 g of AIBN was used as a radical polymerization initiator. These were polymerized in 200 g of PGMEA solvent at a temperature of 90° C. to obtain a solution (specific copolymer concentration: 27.5% by mass) of component (B) (specific copolymer) having Mn 4,100 and Mw 7,600 (P9). The resulting specific copolymer had Mn 4,100 and Mw 7,100.

[0134] Synthesis Example 9 3.00 g of NHPMI, 2.06 g of St, 0.71 g of CHMI, and 0.20 g of AIBN were dissolved in 33.16 g of PGME, and the mixture was allowed to react at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration 18% by mass) (P10). The resulting acrylic polymer had an Mn of 6,200 and an Mw of 11,700.

[0135] <Examples 1 to 5 and Comparative Examples 1 to 4> According to the formulations shown in Table 1 below, a solution of component (A), a solution of component (B), component (C), and component (D) were dissolved in solvent (E) in predetermined ratios, and the solution was stirred at room temperature for 3 hours to obtain a homogeneous solution, thereby preparing positive photosensitive resin compositions for each Example and Comparative Example.

[0136]

[0137] [Evaluation of Residues in Openings] The positive photosensitive resin composition was applied to ITO glass using a spin coater, and then prebaked on a hot plate at 80°C for 120 seconds to form a coating film with a thickness of 1.2 µm. This coating film was irradiated with ultraviolet light at 365 nm using a Canon Inc. PLA-600FA ultraviolet irradiation device through a 10 µm line and space pattern mask at a light intensity of 5.5 mW / cm. ２ The coated film was irradiated with ultraviolet light of 0.001 V for a certain period of time. The film was then developed by immersion in a 2.38% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. The coating film on which the line and space pattern was formed was then post-baked and cured by heating at a temperature of 230°C for 30 minutes. The residues in the openings of the cured line and space pattern were observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 2. The pattern was judged to be particularly good (◎), with no residue remaining in the pattern being good (◯), and with residue remaining in the pattern being poor (×).

[0138] [Preparation of substrate for outgassing measurement] The positive photosensitive resin composition was applied to ITO-glass using a spin coater, and then prebaked on a hot plate at 80°C for 120 seconds to form a coating film with a thickness of 1.2 μm. This coating film was developed by immersing it in a 2.38% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating at 230°C for 30 minutes to harden it.

[0139] [Evaluation of outgassing] The prepared outgassing measurement substrates (10 mm x 50 mm, 5 sheets) were heated in a heating furnace at 250°C for 30 minutes, and the outgassing was analyzed using GC / MS (manufactured by Agilent Technologies, GC: 7890A, MS: 5975C), and the sum of the areas of all detected peak components was calculated. Areas less than 8,000,000 were evaluated as ◯, and areas 8,000,000 or more were evaluated as ×. The results are shown in Table 2.

[0140] [Evaluation of Liquid Repellency] The positive photosensitive resin composition was applied to a silicon wafer using a spin coater and then prebaked on a hot plate at 80°C for 120 seconds to form a coating film with a thickness of 1.2 μm. The coating film was developed by immersing it in a 2.38% TMAH aqueous solution for 60 seconds and then washed with running ultrapure water for 30 seconds. The coating film was then postbaked and cured by heating at 230°C for 30 minutes. The contact angle of anisole on the cured film was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. Contact angles of 50° or more were evaluated as ◯, and contact angles of less than 50°C were evaluated as ×. The results are shown in Table 2.

[0141]

[0142] As shown in Table 2, Examples 1 to 5 exhibited good opening residue and low outgassing amounts while maintaining liquid repellency.

Claims

1. A positive photosensitive resin composition containing the following components (A), (B), (C), (D) and (E) solvent. Component (A): A polymer having a liquid-repellent group, Component (B): An alkali-soluble resin having an N-hydroxyphenyl group, Component (C): A 1,2-quinonediazide compound, Component (D): A crosslinking agent (E) Solvent 2. The positive photosensitive resin composition according to claim 1, wherein the component (B) is a polymer containing a structural unit derived from at least one monomer selected from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, or N-(hydroxyphenyl)maleimide.

3. The positive photosensitive resin composition according to claim 1 or claim 2, wherein the liquid-repellent group of the component (A) is at least one group selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, and a polysiloxane group.

4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the monomer unit constituting the polymer of the component (A) is a unit derived from an unsaturated hydrocarbon having the liquid-repellent group.

5. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the monomer unit constituting the polymer of the component (A) is a unit derived from an alkoxysilane compound having the liquid-repellent group.

6. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the component (A) is a polymer having the liquid-repellent group and a thermosetting group.

7. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the crosslinking agent of the component (D) contains an epoxy group or a methoxymethyl group.

8. The positive photosensitive resin composition according to any one of claims 1 to 7, wherein the number average molecular weight of the alkali-soluble resin of the component (B) is 2,000 to 60,000 in terms of polystyrene.

9. The positive photosensitive resin composition according to any one of claims 1 to 8, characterized in that 0.1 to 20 parts by mass of the component (A) is contained per 100 parts by mass of the component (B).

10. The positive photosensitive resin composition according to any one of claims 1 to 9, characterized in that 5 to 100 parts by mass of the component (C) is contained per 100 parts by mass of the component (B).

11. The positive photosensitive resin composition according to any one of claims 1 to 10, characterized in that 5 to 50 parts by mass of component (D) is contained with respect to 100 parts by mass of component (B).

12. A cured film obtained by using the positive photosensitive resin composition according to any one of claims 1 to 11.

13. A display element having the cured film according to claim 12.

14. A display element having the cured film according to claim 12 as an image forming bank.