TW202242550A - Positive-acting photosensitive resin composition - Google Patents

Abstract

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. 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

The present invention relates to a positive-type photosensitive resin composition and a cured film obtained therefrom. More specifically, it relates to positive-type photosensitive resins that can form images with high water-repellency and oil-repellency on the surface of the cured film, which are less likely to generate residue during pattern formation and generate less outgassing during high-temperature firing. Composition and its cured film, and various materials using the cured film. This positive-type photosensitive resin composition is particularly suitable for use as an interlayer insulating film of display elements such as liquid crystal displays, EL displays, and micro LED displays, and as a light-shielding material or partition wall material corresponding to inkjet methods.

In general, display elements such as thin film transistor (TFT) liquid crystal display elements and organic EL (electroluminescent) elements are provided with patterned electrode protection films, planarization films, insulating films, and the like. As a material for forming such a film, among the photosensitive resin compositions, the photosensitive resin composition having the characteristics of fewer steps to obtain the necessary pattern shape and sufficient flatness has been conventionally used. widely used.

In addition, in the production steps of display elements, the production technology of full-color display substrates using inkjet has been actively researched in recent years. For example, with regard to the production of color filters for liquid crystal display elements, compared to the conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method, it is proposed that the photosensitive resin layer that blocks light should be patterned in advance. The division of pixels (hereinafter referred to as a bank), the color filter on which ink drops are dropped to surround the opening of the bank, and its manufacturing method (Patent Document 1) and the like. And in the organic EL display element, there is also a proposal to prepare the storage body in advance, and drop the ink that also becomes the light-emitting layer to make the method of the organic EL display element (Patent Document 2). However, when dripping ink droplets surrounding the memory body by the inkjet method, in order to prevent ink droplets from overflowing the adjacent pixels beyond the memory body, it is necessary to have ink affinity (hydrophilicity) in the substrate, and to have ink affinity (hydrophilicity) on the surface of the memory body. It is water repellent.

In order to achieve the above-mentioned purpose, the proposal (Patent Document 3) of a negative photosensitive resin composition in which a photosensitive organic film is mixed with a fluorine-based surfactant or a fluorine-based polymer is difficult to improve the resolution, so it is difficult to improve the resolution of the display element. High-definition is seeking the application of positive-type photosensitive resin.

On the other hand, as a positive type, although there is International Publication No. 2007-132890 (Patent Document 4) that uses a polymer having a carboxyl group as an alkali-soluble polymer, tetraethylammonium hydroxide in the alkali developing solution used When the concentration is high, it is easy to generate residue between patterns, and it is difficult to correspond to all manufacturing lines (Line). Also, even if a high-concentration developer is used, as a positive-type material that can form a pattern, there are Japanese Patent Application Laid-Open No. 2009-251327 or Japanese Patent Laid-Open No. 2015-215449 ( Patent Documents 5 and 6), however, have problems such as low heat resistance and reduced lifetime of display elements due to outgassing during firing. If a high-concentration developer can be used, it can be shared with the developer of the resist for TFT formation, the TFT planarization layer, etc., which can be related to cost reduction and optimization of the manufacturing process, but the current situation is difficult. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-187111 [Patent Document 2] Japanese Patent Application Laid-Open No. 11-54270 [Patent Document 3] Japanese Unexamined Patent Publication No. 2015-172742 [Patent Document 4] Japanese Patent Laid-Open No. 2007-132890 [Patent Document 5] Japanese Patent Laid-Open No. 2009-251327 [Patent Document 6] Japanese Patent Laid-Open No. 2015-215449

[Problem to be solved by the invention]

The present invention was accomplished in view of the above-mentioned matters, and the problem to be solved is to propose a positive-type photosensitive resin composition, which is used in liquid crystal display elements, organic EL display elements, etc., and can be formed on the surface of the cured film with high Water repellency and high oil repellency, even if a high concentration developer is used, there will be less residue after pattern formation, and the image of the cured film with less outgassing during high temperature firing. [Means to solve the problem]

As a result of diligent research by the present inventors in order to achieve the above object, it was found that by using an alkali-soluble resin having an N-hydroxyphenyl group, the developability when a high-concentration methylammonium hydroxide aqueous solution is used as a developing solution is improved, And suppress the occurrence of residues between patterns, and further greatly reduce the outgassing observed in resins containing phenolic hydroxyl groups, and complete the present invention. The first aspect of the present invention is a thermally curable positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, (D) component and (E) solvent, (A) Component: Polymer with a liquid-repellent base, (B) Component: Alkali-soluble resin having N-hydroxyphenyl group, (C) Component: 1,2-quinonediazide compound, (D) Component: Cross-linking agent (E) solvent; The second aspect of the present invention is the positive-type photosensitive resin composition as described in the first aspect, wherein (B) component is a composition derived from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl) base) methacrylamide, or N-(hydroxyphenyl)maleimide, a polymer of constituent units of at least one monomer; A third aspect of the present invention is the positive-type photosensitive resin composition as described in the first aspect or the second aspect, wherein the liquid repellent group of the component (A) is selected from fluorocarbons having 3 to 10 carbon atoms. At least one of the group consisting of a polyfluoroether group and a polysiloxane group; A fourth aspect of the present invention is the positive-type photosensitive resin composition as described in any one of the first to third aspects, wherein the monomer unit of the polymer constituting (A) is derived from the above-mentioned A unit of liquid-based unsaturated hydrocarbons. A fifth aspect of the present invention is the positive-type photosensitive resin composition as described in any one of the first to third aspects, wherein the monomer unit of the polymer constituting (A) is derived from the above-mentioned Units of liquid-based alkoxysilane compounds; A sixth aspect of the present invention is the positive-type photosensitive resin composition as described in any one of the first to fifth aspects, wherein the component (A) is a polymer having the liquid repellent group and the thermosetting group. thing; A seventh aspect of the present invention is the positive-type photosensitive resin composition according to any one of the first to sixth aspects, wherein the crosslinking agent of component (D) contains an epoxy group or a methoxymethyl group ; An eighth aspect of the present invention is the positive-type photosensitive resin composition as described in any one of the first to seventh aspects, wherein the number average molecular weight of the alkali-soluble resin of the component (B) is: 2,000 to 60,000; The ninth form of the present invention is the positive-type photosensitive resin composition described in any one of the first form to the eighth form, which is characterized by containing (A) component 0.1 to 100 parts by mass relative to (B) component. 20 parts by mass; A tenth aspect of the present invention is the positive-type photosensitive resin composition described in any one of the first to ninth aspects, which is characterized by containing (C) component 5 to 100 parts by mass of (B) component. 100 parts by mass; The eleventh aspect of the present invention is the positive-type photosensitive resin composition described in any one of the above-mentioned first aspect to the tenth aspect, which is characterized by containing (D) component 5 with respect to 100 parts by mass of (B) component to 50 parts by mass; A twelfth aspect of the present invention is a cured film obtained by using the positive-type photosensitive resin composition described in any one of the first to eleventh aspects; A thirteenth aspect of the present invention is a display element having the cured film described in the twelfth aspect; A fourteenth aspect of the present invention is a display element comprising the cured film as described in the twelfth aspect as an image forming memory body. [Invention effect]

The positive photosensitive resin composition of the present invention can form a cured film with high water repellency and high oil repellency on the surface of the cured film, less residue after pattern formation, and less outgassing during high-temperature firing.

The photosensitive resin composition of the present invention is a positive-type photosensitive resin composition containing the following (A) component, (B) component, (C) component, (D) component, and (E) solvent. (A) Component: Polymer with a liquid-repellent base, (B) Component: Alkali-soluble resin having N-hydroxyphenyl group, (C) Component: 1,2-quinonediazide compound, (D) Component: Cross-linking agent (E) solvent Hereinafter, details of each component will be described.

＜(A)Ingredient＞ Component (A) is a polymer having a liquid-repellent group.

In the present invention, the so-called polymer refers to the use of polymerizable unsaturated groups such as acrylate, methacrylate, styrene, maleimide, etc. acrylic acid polymers obtained from polymerizable monomers with double bonds), or polysilsesquioxanes obtained by hydrolysis and polycondensation of polyfunctional alkoxysilane monomers.

As said liquid repellent group, the group selected from the group of at least 1 sort(s) chosen from the fluoroalkyl group of 3-10 carbon atoms, a polyfluoroether group, and a polysiloxane group is mentioned, for example.

The above-mentioned fluoroalkyl group preferably has 3 to 10 carbon atoms, preferably a fluoroalkyl group having 4 to 10 carbon atoms. Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 3-perfluorobutyl Fluorobutyl-2-hydroxypropyl, 2-(perfluorohexyl)ethyl, 3-perfluorohexyl-2-hydroxypropyl, 2-(perfluorooctyl)ethyl, 3-perfluorooctyl- 2-Hydroxypropyl, 2-(perfluorodecyl)ethyl, 2-(perfluoro-3-methylbutyl)ethyl, 3-(perfluoro-3-methylbutyl)-2-hydroxy Propyl, 2-(perfluoro-5-methylhexyl)ethyl, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl, 2-(perfluoro-7-methyloctyl) Ethyl, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl, etc.

In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer of component (A) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms can be copolymerized. In addition, a compound having a functional group that reacts with a polymer having a reactive site and a fluoroalkyl group having 3 to 10 carbon atoms may be reacted with the polymer having a reactive site.

Examples of the polyfluoroether group include an Rf group (a) having a polyfluoroether structure represented by the following formula 1. -(XO) _n -Y ･･･Formula 1 In formula 1, X is a divalent saturated hydrocarbon group with 1 to 10 carbons or a fluorinated divalent saturated hydrocarbon group with 1 to 10 carbons. One unit represents the same group or different groups, Y represents a hydrogen atom (only when there is no fluorine atom bonded to the carbon atom adjacent to the oxygen atom adjacent to Y), and the valence of 1 to 20 carbon atoms A saturated hydrocarbon group or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, n represents an integer of 2 to 50. However, the total number of fluorine atoms in Formula 1 is 2 or more.

As an aspect of X and Y in Formula 1, X is preferably a fluorinated alkylene group having 1 to 10 carbon atoms removed by removing one hydrogen atom, or a perfluorinated alkylene group having 1 to 10 carbon atoms. Alkyl, each unit covered by n represents the same group or a different group, Y represents a fluorinated alkyl group with 1 to 20 carbon atoms removed by removing one hydrogen atom, or a perfluorinated group with 1 to 20 carbon atoms The alkyl.

As an aspect of X and Y in Formula 1, X is more preferably a perfluorinated alkylene group with 1 to 10 carbons, and each unit covered by n represents the same group or a different group, Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.

In Formula 1, n represents an integer of 2-50. n is preferably 2-30, more preferably 2-15. When n is 2 or more, liquid repellency is favorable. When n is 50 or less, when the polymer of (A) component is synthesize|combined by the copolymerization of the monomer which has Rf group (a) and another monomer, the compatibility of a monomer will become favorable.

Also, the total number of carbon atoms in the Rf group (a) constituted by the polyfluoroether structure represented by Formula 1 is preferably 2-50, more preferably 2-30. In this range, the polymer of (A) component exhibits favorable liquid repellency.

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 -.

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 .

As a preferred aspect of the Rf group (a) formed by the polyfluoroether structure represented by Formula 1, the Rf group (a) represented by Formula 2 can be mentioned.

-C _p-1 F _2(p-1) -O-(C _p F _2p -O) _n-1 -C _q F _2q+1 ･･･Formula 2 In formula 2, p represents an integer of 2 or 3, On the same base as each unit covered by n, q represents an integer of 1-20, and n represents an integer of 2-50.

As the Rf group (a) represented by Formula 2, specifically, from the viewpoint of ease of synthesis, it is preferable to include: -CF ₂ O(CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2～9), -CF(CF ₃ )O(CF ₂ CF(CF ₃ )O) _n-1 C ₆ F ₁₃ (n is 2～6), -CF(CF ₃ )O(CF ₂ CF(CF ₃ )O) _n-1 C ₃ F ₇ (n is 2 to 6).

The Rf groups (a) in the polymer of the component (A) may all be the same or different.

As said polysiloxane group, the group (b) which has the polysiloxane structure represented by Formula 3 is mentioned. Hereinafter, the group (b) having the polysiloxane structure represented by Formula 3 is called pSi group (b). -(SiR ¹ R ² -O) _n -SiR ¹ R ² R ³ ･･･Formula 3 (except that R ¹ and R ² independently represent hydrogen, alkyl, cycloalkyl or aryl, and R ³ represents hydrogen or carbon an organic group of the number 1 to 10, n represents an integer of 1 to 200).

R ¹ and R ² independently represent hydrogen, alkyl, cycloalkyl or aryl, and each siloxy unit may be the same or different. Since the polymer of component (A) exhibits good liquid repellency, R ¹ and R ² are preferably hydrogen, methyl or phenyl, more preferably R ¹ and R ² of all siloxy units are The case of methyl. In addition, R ³ may contain a nitrogen atom, an oxygen atom, or the like.

Examples of the method of introducing pSi group (b) into the polymer of component (A) include a method of copolymerizing a monomer having a pSi group (b), and adding a pSi group (b) to a polymer having a reaction site. Various modification methods of reacting the compound of the compound, the method of using the polymerization initiator having pSi group (b), etc.

As a monomer which has a pSi group (b), _CH2 =CHCOO(pSi), _CH2 =C( _CH3 )COO(pSi), etc. are mentioned. However, pSi represents a pSi group (b). The monomer having a pSi group (b) may be used alone or in combination of two or more.

Examples of various modification methods for reacting a compound having a pSi group (b) in a polymer having a reaction site include the following methods.

There are: pre-copolymerization of monomers with epoxy groups, and then reacting compounds with carboxyl groups at one end and pSi groups at the other single end; pre-copolymerization of monomers with epoxy groups, A method of reacting a compound having an amine group at one end and a pSi group at the other end; copolymerizing a monomer having an epoxy group in advance, and then making a mercapto group at one end and a pSi group at the other end A method of reacting a pSi-based compound; and a method of copolymerizing a monomer having an amine group in advance, and then reacting a compound having a carboxyl group at one end and a pSi group at the other single end.

Also, there is a method of pre-copolymerizing a monomer having an amine group, and then reacting a compound having an epoxy group at one end and a pSi group at the other end; copolymerizing a monomer having a carboxyl group in advance , a method of reacting a compound having an epoxy group at one end and a pSi group at the other end; copolymerizing a monomer having a carboxyl group in advance, and then making an amine group at one end and a pSi group at the other end A method of reacting a compound having a pSi group; a method of pre-copolymerizing a monomer having a carboxyl group, and then reacting a compound having a silyl chloride group at one end and a pSi group at the other end; and using A method of copolymerizing a monomer having a hydroxyl group, and then reacting a compound having a silyl chloride group at one end and a pSi group at the other end.

As a polymerization initiator having a pSi group (b), it may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or it may be included in the terminal part or side chain of the initiator molecule. The base of monovalent polysiloxane structure. Examples of the initiator containing a group having a divalent polysiloxane structure in the molecular main chain of the initiator include compounds having a group having a divalent polysiloxane structure and an azo group alternately. Examples of commercially available products include VPS-1001 and VPS-0501 (the above are manufactured by Wako Pure Chemical Industries, Ltd.).

In the polymer of the above-mentioned (A) component, the introduction amount of the above-mentioned liquid-repellent group is preferably 5 to 60 mol% with respect to the total repeating unit. When it is less than 5 mol%, the effect of liquid repellency may not be exhibited. When it is too large than 60 mol%, problems such as aggregation may occur.

The polymer of the component (A) can suppress bleeding or decomposition of the opening of the component (A) during thermal curing by copolymerizing a functional group having thermosetting properties. The thermosetting functional group is not particularly limited as long as it is a group that forms a covalent bond by heating, and it may be a functional group that reacts with (B) component or (D) component, or may be based on (A) Functional groups for self-crosslinking between components. Such thermosetting functional groups (thermosetting groups) include hydroxyl group, carboxyl group, amido group, amino group, N-alkoxymethyl group, N-hydroxymethyl group, and alkoxysilyl group. , epoxy group, oxetanyl group, vinyl group, mercapto group and blocked isocyanate group, etc.

The production method of the acrylic polymer as the above-mentioned (A) component is not particularly limited, but the monomer having a liquid repellent group, for example, is obtained by adding a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, At least one of a monomer having a polyfluoroether group and a monomer having a polysiloxane group, the above-mentioned monomer having a thermosetting group, and optionally other monomers (hereinafter also referred to as other monomers A) , In a solvent in the presence of a polymerization initiator, it is obtained by performing a polymerization reaction at a temperature of 50 to 110°C. At this time, the solvent to be used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. As a specific example, the solvent described in (E) solvent mentioned later is mentioned.

Specific examples of the radically polymerizable monomer 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, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-(perfluorobutyl) Fluorohexyl) ethyl acrylate, 2-(perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate ester, 2-(perfluorooctyl) ethyl acrylate, 2-(perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorooctyl Base-2-hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-methyl Butyl) 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-methyl 2-(perfluoro-5-methylhexyl)ethyl methacrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropylmethacrylate 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, etc.

Specific examples of radically polymerizable monomers having thermosetting groups include acrylic acid, methacrylic acid, crotonic acid, and mono-(2-(acryloxy)ethyl)phthalic acid. Esters, Mono-(2-(methacryloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide , N-(carboxyphenyl)acrylamide, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide Imine, 2-Hydroxyethyl Acrylate, 2-Hydroxypropyl Acrylate, 5-Acryloxy-6-Hydroxynorcamphene-2-Carboxylic-6-Lactone, 2-Hydroxyethyl Methacrylate, 2-Hydroxypropyl Methacrylate, 5-Methacryloxy-6-Hydroxynorcamphene-2-Carboxylic-6-Lactone, 2-Aminoethyl Acrylic Acid ester, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethacrylate, glycidyl α-n-propyl acrylate Glycerides, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, methyl 6,7-epoxyheptyl acrylate, α-6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, 3-(methacryloxymethyl)oxetane, 3-(acryloxymethyl)oxetane, 3-(methacryloxymethyl)oxetane Acyloxymethyl)-3-ethyl-oxetane, 3-(acryloxymethyl)-3-ethyl-oxetane, 3-(methacryloxymethyl base)-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl) -2-Phenyl-oxetane, 3-(acryloxymethyl)-2-phenyl-oxetane, 2-(methacryloxymethyl)oxetane alkane, 2-(acryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, 2-(acryloxy Methyl)-4-trifluoromethyloxetane, N-butoxymethacrylamide, N-isobutoxymethacrylamide, N-methoxymethacrylamide, N-Methoxymethylmethacrylamide, N-Hydroxymethylacrylamide, N-Hydroxymethylacrylamide, N-Hydroxymethylmethacrylamide, N-Hydroxyethylacrylamide , N-hydroxyethyl methacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, methacrylic acid 2-(0-(1'-methyl Propyleneamino) carboxylamino) ethyl ester, 2-(3,5-dimethylpyrazolyl) carbonylamino) ethyl methacrylate, 3-acryloxytrimethoxysilane, 3- Acryloxy Triethoxysilane, 3-methacryloxytrimethoxysilane, 3-methacryloxytriethoxysilane, etc.

Specific examples of other monomers A include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracenyl methyl acrylate methacrylate, anthracenyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol Methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyl Lactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, 8-ethyl-8-tricyclodecanylmethacrylate Acrylate, Methacrylate, Ethacrylate, Isopropylacrylate, Benzylacrylate, Naphthylacrylate, Anthracenylacrylate, Anthracenylmethacrylate, Phenylacrylate, Glycidyl Acrylate, Cyclohexyl Acrylate, Isocamyl Acrylate, Methoxytriethylene Glycol Acrylate, 2-Ethoxyethyl Acrylate, 2-Amino Methacrylate, Tetrahydrofurfuryl Acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecanyl acrylate, 8-ethyl- 8-tricyclodecanyl acrylate, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, styrene, vinylnaphthalene, vinylanthracene, And vinyl biphenyl, etc.

The acrylic polymer having the specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

Also, by pouring the solution of the acrylic acid polymer obtained as above into diethyl ether or water under stirring to reprecipitate, after filtering and washing the generated precipitate, under normal pressure or reduced pressure, It can be dried at room temperature or heated to become a powder of a specific copolymer. By such an operation, the polymerization initiator or unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If the purification cannot be sufficiently performed by one operation, the obtained powder can be redissolved in a solvent, and the above-mentioned operation can be repeated. In the present invention, the powder of the above-mentioned specific copolymer can be used as it is, or the powder can be used as a solution by redissolving the powder in (E) solvent described later, for example.

Although the method for obtaining the polysilsesquioxane of the above-mentioned component (A) is not particularly limited, it is preferably polycondensation of an alkoxysilane with a liquid-repellent group and an alkoxysilane with a thermosetting group and optionally Polysilsesquioxanes derived from alkoxysilanes with other organic groups.

Specific examples of alkoxysilane monomers having a liquid repellent group include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, trifluorooctyltrimethoxysilane, Fluorooctyltriethoxysilane, Heptadecylfluorodecyltrimethoxysilane, Heptadecfluorodecyltriethoxysilane, 2-(perfluorohexyl)ethyltrimethoxysilane, 2-(perfluorohexyl ) ethyltriethoxysilane, 2-(perfluorobutyl)ethyltrimethoxysilane, 2-(perfluorobutyl)ethyltriethoxysilane, etc.

In the present invention, at least one type of alkoxysilane having a liquid-repellent group may be used, but a plurality of types may be used if necessary.

Specific examples of alkoxysilane monomers having thermosetting groups include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxy Methyl vinyl silane, triethoxy vinyl silane, trimethoxy vinyl silane, vinyl ginseng (2-ethoxy) silane, vinyl ginseng (2-methoxy) silane, m-styryl Triethoxysilane, m-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-(N-styrylmethyl-2- Aminoethylamino)propyltrimethoxysilane, Diethoxy(3-glycidoxypropyl)methylsilane, 3-glycidoxypropyl(dimethoxy)methylsilane, 3-glycidoxypropyl(diethoxy)methylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3, 4-Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylethoxysilane, 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)methyl ethacrylate, 2-(trimethoxysilyl ) ethyl acrylate, Ethoxysilyl ) ethyl acrylate, 2-(trimethoxysilyl) methyl ethacrylate, (triethoxysilyl) methyl methacrylate, (trimethoxysilyl) methyl Methacrylate, (triethoxysilyl)methacrylate, (trimethoxysilyl)methacrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxy yl silane, γ-ureidopropyl tripropropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilyl propyl urea, (R)-N-1-phenyl Ethyl-N'-trimethoxysilylpropylurea, 1-[3-(trimethoxysilyl)propyl]urea, etc.

Furthermore, 3-glycidoxypropyl (dimethoxy) methylsilane, 3-glycidoxypropyl (diethoxy) methylsilane, 3-glycidoxypropyl (diethoxy) methylsilane, 3-glycidoxypropyl Glyceryloxypropyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is also preferred.

In this case, plural types of alkoxysilanes having an organic group having a thermosetting group can be used.

Examples of alkoxysilanes having other organic groups include tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , Propyltrimethoxysilane, Propyltriethoxysilane, Butyltrimethoxysilane, Butyltriethoxysilane, Amyltrimethoxysilane, Amyltriethoxysilane, Heptyltrimethoxysilane Hexyltrimethoxysilane, Heptyltriethoxysilane, Octyltrimethoxysilane, Octyltriethoxysilane, Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Hexadecyltrimethoxysilane Alkyl trialkoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, etc., phenyltrimethoxysilane, phenyl Triethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, trialkoxysilane with aromatic group, dimethyldimethoxysilane, dimethyldiethoxysilane Such as dialkoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, etc.

The polysilsesquioxane of the above-mentioned component (A) preferably contains 5 to 50 mole % of the alkoxysilane containing a liquid repellent group in the per-alkoxysilane, preferably contains a per-alkoxy 10-95 mol% of the silanes contain alkoxysilanes containing thermosetting groups, and the residues are obtained by polycondensation of other alkoxysilanes.

When considering the liquid repellency and solvent resistance of the film, the content of the alkoxysilane containing the liquid repellent group is more preferably 10-40 mol%. The content of the alkoxysilane containing thermosetting groups is more preferably 30 to 80 mol% of the peralkoxysilane.

As a method of obtaining the polysilsesquioxane of the above-mentioned (A) component, for example, an alkoxysilane containing a liquid-repellent group, an alkoxysilane having a thermosetting group, and if necessary, other A method of polycondensation by heating alkoxysilane and organic solvent in the presence of tetraethylammonium hydroxide aqueous solution. Specifically, there is a method of mixing the above-mentioned various alkoxysilanes in a state of heating the solution after adding an aqueous solution of tetraethylammonium hydroxide to an organic solvent in advance as a solution of the aqueous solution of tetraethylammonium hydroxide. The amount of the tetraethylammonium hydroxide aqueous solution is preferably 0.01 to 0.2 moles relative to 1 mole of the total alkoxy groups contained in the alkoxysilane used. The above-mentioned heating can be performed at a liquid temperature of preferably 0 to 100°C, and in a manner that does not cause evaporation or volatilization of the solution, it is preferably performed under reflux in a container equipped with a reflux tube for tens of minutes to tens of hours. .

When multiple alkoxysilanes are used, they can be mixed as a premixed alkoxysilane mixture, or multiple alkoxysilanes can be mixed sequentially. When alkoxysilane is polycondensed, it is preferable that the concentration of all silicon atoms of the alkoxysilane to be inserted into an oxide (hereinafter referred to as SiO ₂ conversion concentration) is 40% by mass or less, particularly preferably 10 to 30% by mass. The range of mass % is heated. By selecting an arbitrary concentration within such a concentration range, it is possible to obtain a homogeneous polysilsesquioxane-containing solution that inhibits gel formation.

The organic solvent used for the polycondensation of alkoxysilane (hereinafter, also referred to as the polymerization solvent), if it dissolves the alkoxysilane with a liquid-repellent group and the alkoxysilane with a thermosetting group and if necessary Other alkoxysilanes are not particularly limited, but are preferably used as the solvent (E). Among them, since alcohol is produced by the polycondensation reaction of alkoxysilane, an organic solvent with good compatibility with alcohols or alcohols is used.

Specific examples of the above-mentioned polymerization solvent include alcohols such as methanol, ethanol, propanol, and n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, Glycol ethers such as diethylene glycol monoethyl ether and propylene glycol monomethyl ether, ethers such as tetrahydrofuran. In the present invention, plural kinds of the above-mentioned organic solvents can be mixed and used.

In the present invention, the solution of the specific polysilsesquioxane obtained by the aforementioned method can be directly used in the photosensitive resin composition of the present invention. If necessary, it can also be concentrated in the specific polysilsesquioxane solution obtained by the aforementioned method. The solution of hemioxane can be diluted with a solvent or replaced with other solvents.

The solvent used when adding the aforementioned solvent for dilution (also referred to as added solvent) may be the solvent used in the polycondensation reaction or other solvents. The addition solvent is not particularly limited as long as polysilsesquioxane can be uniformly dissolved, and one type or two or more types can be arbitrarily selected and used. As such an additional solvent, in addition to the solvent used in the aforementioned polycondensation reaction, ketone-based solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, methyl acetate, ethyl acetate, or lactic acid Ester-based solvents such as ethyl ester, etc.

Furthermore, in the present invention, when polymers other than polysilsesquioxane are used in the photosensitive resin composition, it is preferable to mix polysilsesquioxane The alcohol produced during the polycondensation reaction was distilled off under normal or reduced pressure.

In addition, as the polymer of the (A) component, in addition to the above-mentioned acrylic polymer and polysilsesquioxane, polyimide, polyamic acid, polyamide, polyurea, polyamine-based Formate, phenol, epoxy, polysiloxane, polyester and acrylic polymers, polymers with quinonediazide groups introduced.

Examples of polyamic acid, polyimide, polyamide, and polyurea include polyamic acid in which diamine having a fluoroalkyl or fluoroalkoxy group, diamine having a hydroxyl group, and an acid dianhydride are reacted. . Polyimide obtained by imidizing polyamic acid, polyamide obtained by reacting the aforementioned diamine with dicarboxylic anhydride, or polyurea obtained by reacting the aforementioned diamine with diisocyanate.

As the polyurethane, a polyurethane obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group, a diol having an amino group, and a diisocyanate is exemplified.

Examples of the phenol resin include novolac resins obtained by polymerizing phenol having a fluoroalkyl group or a fluoroalkoxy group and formaldehyde. Examples of epoxy resins include those obtained by reacting bisphenol A and/or bisphenol F having a fluoroalkyl group or a fluoroalkoxy group with glycidyl ether when the bisphenol A and/or bisphenol F are present. of epoxy resin. Examples of the polysiloxane include trialkoxysilane with a fluoroalkyl group or dialkoxysilane silane with a fluoroalkyl group, and trialkoxysilane with an amino group or dioxane with an amino group. The polymer obtained by polymerizing the silane monomer mixture of oxysilane silane.

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.

Moreover, in this invention, the acrylic polymer of (A) component may be the mixture of several types of specific copolymers.

＜Component (B)＞ (B) component of this invention is an alkali-soluble resin which has N-hydroxyphenyl group. The alkali-soluble resin of the above-mentioned (B) component may be an alkali-soluble resin having such a structure, and there are no particular limitations on the skeleton of the main chain of the polymer constituting the resin, the type of side chains, and the like.

(B) It is preferable that the alkali-soluble resin of a component exists in the range whose number average molecular weight is 2,000-60,000. When the number average molecular weight exceeds 60,000 and is too large, in addition to easily generating development residues and greatly reducing sensitivity, when the number average molecular weight is less than 2,000 and is too small, when there is development, a considerable amount of film reduction and hardening of the exposed part will occur. Insufficient situation.

As an alkali-soluble resin which has an N-hydroxyphenyl group as a component (B), an acryl type resin, a polymaleimide type resin, etc. are mentioned, for example.

Moreover, in this invention, the alkali-soluble resin which consists of the copolymer (henceforth a specific copolymer) obtained by polymerizing several types of monomers can also be used as (B) component. In this case, the alkali-soluble resin of (B) component may be the mixture of several types of specific copolymers.

That is, the above-mentioned specific copolymer has a monomer having an N-hydroxyphenyl group and at least one monomer selected from the group of monomers copolymerizable with these monomers as essential constituent units. The formed copolymer has a number average molecular weight of 2,000 to 60,000. When the number average molecular weight is too large than 60,000, residues may be generated.

The above-mentioned N-hydroxyphenyl-containing monomers are not limited to those having one N-hydroxyphenyl group, and may have plural ones.

Hereinafter, although the specific example of the said monomer is mentioned, it is not limited to these. Examples of monomers having an N-hydroxyphenyl group include N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide Wait.

Examples of monomers that can be copolymerized with monomers having an N-hydroxyphenyl group include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, Naphthyl methacrylate, anthracenyl methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isocamyl methyl Acrylates, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methylmethacrylate Oxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, 8- Ethyl-8-tricyclodecanyl methacrylate, methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracenyl acrylate, anthracenyl methacrylate ester, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isocamphoryl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl Acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, gamma-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclo Decyl acrylate, 8-ethyl-8-tricyclodecanyl acrylate, styrene, vinylnaphthalene, vinylanthracene, vinylbiphenyl, N-phenylmaleimide, N-cyclohexylmaleimide Laylimide, N-methylmaleimide, N-ethylmaleimide, N-methacrylamide, N-methylmethacrylamide, N,N-dimethyl Acrylamide, N,N-dimethylmethacrylamide, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, mono-( 2-(Methacryloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxy Phenyl)acrylamide, Hydroxystyrene, 2-Hydroxyethylacrylate, 2-Hydroxypropylacrylate, 5-Acryloxy-6-Hydroxynorcamphene-2-Carboxylic-6- Lactone, 2-Hydroxyethyl Methacrylate, 2-Hydroxypropyl Methacrylate, 5-Methacryloxy-6-Hydroxynorbornene-2-Carboxylic-6-Lactone , 2-aminoethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6, 7-epoxyheptyl, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethacrylate, o-vinylbenzyl glycidyl ether, m-vinyl Benzylic Water Glyceryl Ether, p-Vinylbenzyl Glycidyl Ether, 3-(Methacryloxymethyl)oxetane, 3-(Acryloxymethyl)oxetane, 3-(methacryloxymethyl)-3-ethyl-oxetane, 3-(acryloxymethyl)-3-ethyl-oxetane, 3-(methacryloxymethyl) Acryloxymethyl)-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-(methylpropene Acryloxymethyl)-2-phenyl-oxetane, 3-(acryloxymethyl)-2-phenyl-oxetane, 2-(methacryloxymethyl base) oxetane, 2-(acryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, 2 -(Acryloxymethyl)-4-trifluoromethyloxetane, N-butoxymethacrylamide, N-isobutoxymethacrylamide, N-methoxy Methacrylamide, N-methoxymethylmethacrylamide, N-methylolacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N- Hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, methacrylic acid 2-(0- (1'-methylpropyleneamino)carboxyamino)ethyl ester, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, 3-acryloxytrimethyl Oxysilane, 3-acryloxytriethoxysilane, 3-methacryloxytrimethoxysilane, and 3-methacryloxytriethoxysilane, etc.

The ratio of monomers having an N-hydroxyphenyl group used in the production of the alkali-soluble resin of the component (B) among all the monomers used in the production of the alkali-soluble acrylic polymer of the component (B) is preferably 10 to 90 Mole %, more preferably 20-85 mole %, most preferably 30-80 mole %. When the ratio of the monomer having an N-hydroxyphenyl group is less than 10 mol%, the alkali solubility of the polymer is insufficient.

In manufacture of the alkali-soluble resin of (B) component, the ratio of the said other monomer is preferably 80 weight% or less, More preferably, it is 50 weight% or less, More preferably, it is 20 weight% or less. When it is more than 80% by weight, since the essential components are relatively reduced, it becomes difficult to sufficiently obtain the effect of the present invention.

The method of obtaining the alkali-soluble resin used in the (B) component of the present invention is not particularly limited, but for example, by coexisting a monomer having an N-hydroxyphenyl group and, if desired, other copolymerizable monomers It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110° C. in a solvent such as a desired polymerization initiator. At this time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. As a specific example, the solvent described in (E) solvent mentioned later is mentioned.

The acrylic polymer thus obtained is usually in the state of a solution dissolved in a solvent.

Also, by pouring the solution of the specific copolymer obtained as above into diethyl ether or water under stirring to reprecipitate, and filtering and washing the resulting precipitate, the It can be dried at room temperature or heated to become a powder of a specific copolymer. By such an operation, the polymerization initiator or unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If it is not possible to sufficiently purify in one operation, the obtained powder can be redissolved in a solvent, and the above-mentioned operation can be repeated. In the present invention, the powder of the above-mentioned specific copolymer may be used as it is, or the powder may be redissolved in, for example, the (E) solvent described later, and used as a solution.

Moreover, in this invention, the alkali-soluble resin of (B) component may be the mixture of several types of alkali-soluble resins.

The ratio of (A) component and (B) component is 0.1-20 mass parts of (A) components with respect to 100 mass parts of (B) components.

＜(C)Ingredient＞ The 1,2-quinonediazide compound as component (C) is either a hydroxyl group or an amino group, or a compound having both a hydroxyl group and an amino group. These hydroxyl or amino groups (having a hydroxyl group and an amino group When both parties are used, it is the total amount of these), preferably 10 to 100 mol%, particularly preferably 20 to 95 mol%, is sulfonated or amidated with 1,2-quinone diazide compound.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, gallate Ethyl subcatenate, 1,3,3-paraffin(4-hydroxyphenyl)butane, 4,4-isopropylidene diphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1 -Bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylene, 4,4-hexafluoroisopropylidene diphenol, 4,4',4"-parahydroxyphenylethyl Alkane, 1,1,1-paraffinic hydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene ] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4 ,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, etc. Phenol compounds, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2- Aliphatic alcohols such as methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate, etc.

In addition, examples of the aforementioned compound having an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-benzenediphenyl Amines, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether and other anilines, aminocyclohexane.

Furthermore, as a compound containing both a hydroxyl group and an amino group, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diamino Phenol, 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- Aminophenols such as 5-hydroxyphenyl)propane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane, 2-aminoethanol, 3-aminopropane Alkanolamines such as alcohols and 4-aminocyclohexanol.

These 1,2-quinonediazide compounds can be used individually or in combination of 2 or more types.

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, relative to 100 parts by mass of component (B). 10 to 40 parts by mass. When it is less than 5 parts by mass, the difference in the dissolution rate of the developer between the exposed part and the unexposed part of the positive photosensitive resin composition may be reduced, and patterning by development may be difficult. Also, when it exceeds 100 parts by mass, the 1,2-quinonediazide compound cannot be sufficiently decomposed by exposure for a short time, and the sensitivity may be lowered, or residues may be generated between patterns.

＜(D)Ingredient＞ (D) Component is a crosslinking agent, More specifically, it is a compound which has a structure which can form a crosslinked structure by heat-reacting with the N-hydroxyphenyl gene of (B) component. Although specific examples are listed below, it is not limited to these. The thermal cross-linking agent is preferably, for example, (D1) a cross-linking compound having two or more substituents selected from alkoxymethyl and hydroxymethyl groups or (D2) a cross-linking compound selected from the group represented by the following formula (3). A linking compound and (D3) a crosslinking agent having two or more isocyanate groups. These crosslinking agents can be used individually or in combination of 2 or more types.

(D1) A cross-linking compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, which undergoes a cross-linking reaction by dehydration condensation reaction when exposed to high temperature during thermosetting . Examples of such compounds include compounds such as alkoxymethylated glycolurils, alkoxymethylated benzoguanamines, and alkoxymethylated melamines, and phenoplast-based compounds.

Specific examples of alkoxymethylated glycoluril include, for example, 1,3,4,6-tetra(methoxymethyl)glycoluril, 1,3,4,6-tetra(butoxymethyl) ) glycoluril, 1,3,4,6-tetra(hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea , 1,1,3,3-tetra(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis( Methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc. Commercially available products include compounds such as 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) Trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. urea/formaldehyde resin (high condensation type, commercial Name: BECKAMINE (registered trademark) J-300S, same as P-955, same as N), etc.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. Examples of commercially available products include Mitsui Cytec Co., Ltd. (trade name: CYMEL (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: NIKALACK (registered trademark) BX-4000, Tong BX-37, Same as BL-60, same as BX-55H), etc.

As a specific example of alkoxymethylated melamine, hexamethoxymethylmelamine etc. are mentioned, for example. Examples of commercially available products include methoxymethyl melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: CYMEL (registered trademark) 300, TO 301, TO 303, TO 350), and butoxymethyl melamine compounds. (trade name: MYCOAT (registered trademark) 506, same 508), methoxymethyl-type melamine compound manufactured by Sanwa Chemical Co., Ltd. Same as MW-100LM, same as MS-001, same as MX-002, same as MX-730, same as MX-750, same as MX-035), butoxymethyl melamine compound (trade name: NIKALACK (registered trademark) MX- 45. Same as MX-410, same as MX-302), etc.

Moreover, the compound obtained by condensing the melamine compound, the urea compound, the glycoluril compound, and the benzoguanamine compound which substituted the hydrogen atom of such an amino group with a methylol group or an alkoxymethyl group can also be used. For example, high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 can be mentioned. Commercially available products of the above-mentioned melamine compound include trade name: CYMEL (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), etc., and commercially available products of the aforementioned benzoguanamine compound include trade name: CYMEL (registered trademark) Trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.), etc.

Specific examples of phenolic plastic compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4- Methoxyphenol, 3,3',5,5'-tetra(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methyl benzyl alcohol), 4,4'-(1-methylethylene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6- hydroxymethylphenol], 4,4'-(1-methylethylene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis (Hydroxymethyl)phenol], 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl)- 4-methoxyphenol, 3,3',5,5'-tetra(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy base-5-methylbenzyl alcohol), 4,4'-(1-methylethylene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-Methyl-6-methoxymethylphenol], 4,4'-(1-methylethylene)bis[2,6-bis(methoxymethyl)phenol], 4,4 '-methylenebis[2,6-bis(methoxymethyl)phenol], etc. It is also available as a commercial product, and its specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (above Manufactured by Asahi Organic Material Co., Ltd.) etc.

Furthermore, as (D1) component, a polymer can also be used, and this polymer uses N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide Amine, N-butoxymethylmethacrylamide and other acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups.

Examples of such polymers include poly(N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, N-hydroxymethylmethacrylamide Copolymers of amine and methyl methacrylate, copolymers of N-ethoxymethyl methacrylamide and benzyl methacrylate, and copolymers of N-butoxy methacrylamide and benzyl methacrylate Copolymer of acrylate and 2-hydroxypropyl methacrylate, etc. Such polymers have a weight average molecular weight of 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.

These crosslinkable compounds can be used individually or in combination of 2 or more types.

As the crosslinking agent in the positive photosensitive resin composition of the present invention, the content when the component (D1) is selected is relative to 100 parts by mass of the component (B), preferably 5 to 50 parts by mass of the copolymer, more preferably 10 parts by mass. to 40 parts by mass. When the content is less than 5 parts by mass, outgassing may increase in the display element production process, components of the positive photosensitive resin composition may be eluted to other layers, or device characteristics or reliability may deteriorate. Moreover, when it exceeds 50 mass parts, there exists a possibility that storage stability may fall, the adhesiveness at the time of image development may fall, or a sensitivity may fall.

(式中，k表示2～10之整數，m表示0～4之整數，R ¹¹表示k價之有機基)。 And the positive photosensitive resin composition of this invention can contain the crosslinkable compound which has the epoxy group represented by formula (3) as (D2) component.

(In the formula, k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R ¹¹ represents an organic group with a valency of k).

Examples of commercially available products include EPOLEAD GT-401, GT-403, GT-301, GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (trade name of Daicel Chemical Industry Co., Ltd.), cycloaliphatic epoxy resin DENACOL EX-252 (trade names manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (the above are trade names manufactured by CIBA-GEIGY A.G), ARALDITE CY-182, same CY-192, same CY-184 (above are CIBA-GEIGY A.G), EPICLON 200, DON 400 (the above are DIC Co., Ltd. trade names), Epikote 871, TON 872 (the above are Yuka Shell Epoxy Co., Ltd. trade names), ED-5661, ED -5662 (the above are trade names of Celanese Coating Co., Ltd.), etc. Moreover, these crosslinkable compounds can be used individually or in combination of 2 or more types.

Among them, from the viewpoint of process resistance such as heat resistance, solvent resistance, and long-time firing resistance, compounds having a cyclohexene oxide structure, EPOLEAD GT-401, and GT-403 are preferable. , Same as GT-301, same as GT-302, CELLOXIDE 2021, CELLOXIDE 3000.

As said crosslinking agent, when selecting (D2) component, content is 5-50 mass parts with respect to 100 mass parts of (B) components, Preferably it is 7-40 mass parts, More preferably, it is 10-30 mass parts. When the content of the cross-linking compound is less than 5 parts by mass, the density of the cross-links formed by the cross-linking compound is not sufficient, so the outgassing is increased in the manufacturing step of the display device, or the dissolution of other layers is positive. Type photosensitive resin composition components, or deterioration of device characteristics or reliability. On the other hand, when it exceeds 50 parts by mass, there are uncrosslinked crosslinking compounds, and the heat resistance after pattern formation, solvent resistance, and resistance to long-term firing are reduced, and the photosensitivity is deteriorated. The storage stability of the resin composition.

＜(E)Solvent＞ The (E) solvent used in the present invention is one that dissolves (A) component, (B) component, (C) component, and (D) component, and dissolves other additives described later if desired, if it has such The type, structure, etc. of the solvent capable of dissolving are not particularly limited.

Such (E) solvents include, for example, 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, toluene Ethyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate Esters, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate ester, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, etc.

These solvents may 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., It is more preferable from a viewpoint of favorable coating-film property and high safety. These solvents are generally used as solvents for photoresist materials.

＜Other additives＞ Furthermore, as long as the positive-type photosensitive resin composition of the present invention does not impair the effect of the present invention, if necessary, it may contain rheology modifiers, pigments, dyes, storage stabilizers, defoamers, adhesion promoters, or polyphenols, polyhydric Dissolution accelerators for carboxylic acids, etc.

＜Positive Photosensitive Resin Composition＞ The positive-type photosensitive resin composition of the present invention is a positive-type photosensitive resin composition containing the following (A) component, (B) component, (C) component, (D) component and (E) solvent. A composition that may further contain one or more kinds of other additives is desirable. (A) Component: Polymer with a liquid-repellent base, (B) Component: Alkali-soluble resin having N-hydroxyphenyl group, (C) Component: 1,2-quinonediazide compound, (D) Component: Cross-linking agent (E) solvent

Among them, preferred examples of the positive photosensitive resin composition of the present invention are as follows. With respect to 100 parts by mass of component (B), it contains 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), and these components are dissolved in ( E) The positive photosensitive resin composition of the solvent.

The ratio of the solid content of the positive-type photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but it is, for example, 1 to 80% by mass, and for example, 5 to 60% by mass, Or 10 to 50% by mass. Here, solid content means what removed (E) solvent from all components of a positive photosensitive resin composition.

The preparation method of the positive-type photosensitive resin composition of the present invention is not particularly limited, but as its preparation method, for example, dissolving (A) component (specific acrylic acid copolymer) in (E) solvent, and dissolving The method of mixing the alkali-soluble resin of (B) component, the 1,2-quinonediazide compound of (C) component, and the crosslinking agent of (D) component in a specified ratio to form a uniform solution, or here In the appropriate stage of the preparation method, if necessary, further adding other additives for mixing.

In the preparation of the positive photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the (E) solvent can be directly used. In this case, the solution of the component (A) can be the same as the above , (B) components, (C) components, (D) components, etc. are added to form a uniform solution, and the concentration adjustment is used as the purpose, and the (E) solvent is further added. At this time, the (E) solvent used in the formation of the specific copolymer and the (E) solvent used for concentration adjustment when preparing the positive photosensitive resin composition may be the same or different.

Therefore, it is preferable to use the prepared solution of the positive-type photosensitive resin composition after filtration with a filter having a pore size of about 0.2 μm or the like.

＜Coated film and hardened film＞ Apply the positive photosensitive resin composition of the present invention to semiconductor substrates (such as silicon/silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metals such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates, etc. ), by rotary coating, flow coating, roll coating, slit coating, rotary coating followed by slit, inkjet coating, etc., and then pre-drying with a hot plate or an oven, etc., Coating film can be formed. Then, by heat-treating this coating film, a positive photosensitive resin film is formed.

As the conditions of this heat treatment, for example, a heating temperature and a heating time appropriately selected from a range of a temperature of 70° C. to 160° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80° C. to 140° C. and 0.5 to 10 minutes.

Also, the film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and further, for example, 0.3 to 5 μm.

By installing a mask with a specified pattern on the coating film obtained above, irradiating it with light such as ultraviolet rays, developing it with an alkaline developer, washing out the exposed part, and obtaining a relief pattern with a clear end surface.

Examples of alkaline developing solutions that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, methylammonium hydroxide, tetraethylammonium hydroxide, and choline. Aqueous solution of quaternary ammonium hydroxide, alkaline aqueous solution of amine aqueous solution such as ethanolamine, propylamine, ethylenediamine, etc. Furthermore, surfactants and the like can also be added to these developer solutions.

Among the above, tetraethylammonium hydroxide 0.1 to 2.38% by mass aqueous solution is generally used as a photoresist developer. Even in the photosensitive resin composition of the present invention, the use of this alkaline developer will not cause problems such as swelling , can be developed well. By using an aqueous solution of preferably 1.0 to 2.38% by mass, a more effective relief pattern can be obtained.

In addition, as a developing method, any of a liquid filling method, a dipping method, a vibration dipping method, and the like can be used. The developing time at this time is usually 15 to 180 seconds.

After development, for the positive photosensitive resin film, carry out by running water washing for example 20 to 120 seconds, then, by using compressed air or compressed nitrogen, or by rotary air drying, remove the moisture on the substrate, and obtain Film formed by patterning.

Next, by post-baking the patterned film for thermosetting, specifically, by heating using a hot plate, an oven, etc., heat resistance, transparency, planarization, low water absorption, Excellent chemical resistance, etc., with a good embossed pattern film.

As post-baking, generally, the heating temperature is selected from the temperature range of 140°C to 270°C, and it is used for 5 to 30 minutes in the case of a hot plate, and 30 to 90 minutes in the case of an oven. method.

Therefore, by this post-baking, the cured film which has the target favorable pattern shape can be obtained.

As above, with the positive photosensitive resin composition of the present invention, it is possible to form a coating film with high storage stability, sufficiently high sensitivity, and a very small film reduction in unexposed areas during development, and a fine pattern. . And the coating film (cured film) obtained in this way can be suitably used as the memory body for image formation of a display element. [Example]

Hereinafter, although examples are given and the present invention is further described in detail, the present invention is not limited to these examples. Also, the measurement of number average molecular weight and weight average molecular weight is as follows.

[Determination of number average molecular weight and weight average molecular weight] The number-average molecular weight and weight-average molecular weight of the copolymer obtained according to the following synthesis example were used to GPC equipment (Shodex column KF-804L and 803L) manufactured by Shimadzu Corporation, so that the dissolution solvent tetrahydrofuran flowed into the column at a flow rate of 1 ml/min ( The column temperature is 40°C) to determine the conditions for dissolution. Furthermore, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene conversion values.

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: by α, α, α'-paraffin (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene 1mol and 1,2-naphthoquinone-2-diazide-5-sulfonyl The compound synthesized by the condensation reaction of 2 mol of chlorine GT-401: Butanetetracarboxylic acid tetrakis(3,4-epoxycyclohexylmethyl) modified ε-caprolactone MARUKA LYNCUR CST: 30wt% propylene glycol monomethyl ether solution (P2) of styrene polymer made by mixing MARUKA LYNCUR CST8515 and 7030 manufactured by Maruzen Petrochemical Co., Ltd. at a ratio of 2:8 HMM: NIKALACK 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 35wt%TEAHaq.: 35wt% tetraethylammonium hydroxide solution PTMOS: Phenyltrimethoxysilane 15JWET: Ion exchange resin manufactured by ORGANO PGME: Propylene Glycol Monomethyl Ether PGMEA: Propylene Glycol Monomethyl Ether Acetate THF: Tetrahydrofuran

<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 reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 18% by mass) (P1). Mn of the obtained acrylic polymer was 6,000, and Mw was 9,500.

<Synthesis Example 2> NHPMA 5.00g, MMA 1.28g, CHMI 3.93g, and AIBN 0.31g were dissolved in PGME 47.88g and reacted at 90 degreeC for 20 hours to obtain an acrylic acid polymer solution (18 mass % of solid content concentration) (P3). Mn of the obtained acrylic polymer was 5,000, and Mw was 8,100.

＜Synthesis Example 3＞ NHPMA 5.00g, MMA 1.09g, CHMI 3.00g, and AIBN 0.27g were dissolved in PGME 42.66g, and it reacted at 90 degreeC for 20 hours, and obtained the acrylic acid polymer solution (18 mass % of solid content concentration) (P4). Mn of the obtained acrylic polymer was 4,500, and Mw was 6,300.

<Synthesis Example 4> NHPMA 3.00g, HEMA 1.11g, CHMI 3.04g, and AIBN 0.14g were dissolved in PGME 33.16g, and it was made to react at 90 degreeC for 20 hours, and the acrylic polymer solution (18 mass % of solid content concentration) was obtained (P5). Mn of the obtained acrylic polymer was 5,600, and Mw was 9,300.

<Synthesis Example 5> NHPMA 3.00g, HEMA 0.98g, CHMI 2.34g, and AIBN 0.12g were dissolved in PGME 29.32g and reacted at 90 degreeC for 20 hours to obtain an acrylic acid polymer solution (18 mass % of solid content concentration) (P6). Mn of the obtained acrylic polymer was 6,200, and Mw was 9,900.

<Synthesis Example 6> By dissolving 5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN in 25.32 g of PGME, and reacting at 80° C. for 20 hours, an acrylic polymer solution (30% by mass of solid content) was obtained (P7 ). Mn of the obtained acrylic polymer was 4800, and Mw was 6700.

<Synthesis Example 7> By dissolving 2.34g of PFHTMOS, 2.46g of KBM-303, 1.98g of PTMOS, 0.21g of 35wt%TEAH, and 0.68g of H2O in 9.21g of THF, and stirring at 40°C for 4 hours. Next, 0.48 g of 15JWET washed with THF was added, followed by stirring at 25° C. for 1 hour. Next, the spent 15JWET was filtered to obtain a siloxane polymer solution (P8). Mn of the obtained siloxane polymer was 1,900, and Mw was 2,400.

<Synthesis Example 8> By using MAA 10.9g, CHMI 35.3g, HEMA 25.5g, MMA 28.3g, and using AIBN 5g as a radical polymerization initiator, these are polymerized in a solvent PGMEA 200g at a temperature of 90°C to obtain Solution of (B) component (specific copolymer) of Mn4,100 and Mw7,600 (specific copolymer concentration: 27.5% by mass) (P9). The obtained specific copolymer had Mn of 4,100 and Mw of 7,100.

<Synthesis Example 9> NHPMI 3.00g, St 2.06g, CHMI 0.71g, and AIBN 0.20g were dissolved in PGME 33.16g, and it was made to react at 90 degreeC for 20 hours, and the acrylic acid polymer solution (18 mass % of solid content concentration) was obtained (P10). Mn of the obtained acrylic polymer was 6,200, and Mw was 11,700.

<Examples 1 to 5 and Comparative Examples 1 to 4> According to the composition shown in the following Table 1, the solution of (A) component, the solution of (B) component, (C) component, and (D) component were dissolved in the (E) solvent at a specified ratio, and the Warm stirring was carried out for 3 hours to form a uniform solution, and the positive-type photosensitive resin compositions of each example and each comparative example were prepared.

[Evaluation of Residue at the Opening] After coating the positive-tone photosensitive resin composition on ITO-glass using a spin coater, pre-baked it on a hot plate at a temperature of 80°C for 120 seconds to form a coating with a film thickness of 1.2 μm. membrane. Here, the coating film was irradiated with ultraviolet light at 365nm with a light intensity of 5.5mW/cm ² for a certain period of time through a mask of 10μm line and space pattern by Canon Co., Ltd. ultraviolet irradiation device PLA-600FA. Then, after image development was performed by immersing in 2.38% TMAH aqueous solution for 60 seconds, it wash|cleaned with running water for 30 seconds with ultrapure water. Next, the coating film formed by this line-and-space pattern was heated at a temperature of 230° C. for 30 minutes, and post-baked to harden it. The hardened line and space pattern opening residues were observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technology Co., Ltd. The obtained results are shown in Table 2. At this time, the case where no residue remained in the pattern was judged to be particularly good (⊚), the case where no residue remained in the pattern was judged to be good (◯), and the case where residue remained was judged to be poor (×).

[Fabrication of substrate for outgassing measurement] After coating the positive-type photosensitive resin composition on ITO-glass using a spin coater, pre-baked it on a hot plate at a temperature of 80°C for 120 seconds to form a coating film with a film thickness of 1.2 μm. This coating film was immersed in a 2.38% TMAH aqueous solution for 60 seconds, developed, and washed with ultrapure water for 30 seconds. Next, by heating this coating film at a temperature of 230° C. for 30 minutes, post-baking was performed to harden it.

[Evaluation of outgassing] The prepared substrates for degassing measurement (10mm×50mm, 5 pieces) were analyzed by GC/MS (manufactured by Agilent Technologies, GC: 7890A, MS: 5975C) at 250°C for 30 minutes in a heating furnace. For gases, calculate the sum of the areas of all detected peak components. Those with an area of less than 8,000,000 were judged as 〇, and those with an area of more than 8,000,000 were judged as x. The results are shown in Table 2.

[Evaluation of liquid repellency] After coating the positive-type photosensitive resin composition on the silicon wafer with a spin coater, pre-bake it on a hot plate at a temperature of 80°C for 120 seconds to form a coating film with a film thickness of 1.2 μm. This coating film was immersed in a 2.38% TMAH aqueous solution for 60 seconds, developed, and washed with ultrapure water for 30 seconds. Next, by heating this coating film at a temperature of 230° C. for 30 minutes, post-baking was performed to harden it. The contact angle of anisole on this cured film was measured using the Drop Master made from Kyowa Interface Science Co., Ltd. The case where the contact angle was 50 degrees or more was judged as 0, and the case where the contact angle was less than 50° C. was judged as x. The obtained results are shown in Table 2.

As shown in Table 2, in Examples 1 to 5, the liquid repellency was maintained, and good opening residue and low outgassing amount were shown.

Claims (14)

A thermally curable positive-type photosensitive resin composition, which contains the following components (A), component (B), component (C), component (D) and solvent (E); (A) Component: Polymer with liquid-repellent base, (B) Component: Alkali-soluble resin having N-hydroxyphenyl group, (C) Component: 1,2-quinonediazide compound, (D) Component: Cross-linking agent (E) Solvent. The positive-type photosensitive resin composition as claimed in claim 1, wherein, (B) component is a composition derived from N-(hydroxyphenyl) acrylamide, N-(hydroxyphenyl)methacrylamide, or A polymer of constituent units of at least one monomer of N-(hydroxyphenyl)maleimide. The positive-type photosensitive resin composition according to claim 1 or claim 2, wherein the liquid repellent group of component (A) is selected from fluoroalkyl groups with 3 to 10 carbon atoms, polyfluoroether groups, and polysilicon At least one group of the group consisting of oxyalkyl groups. The positive-type photosensitive resin composition according to any one of claim 1 to claim 3, wherein the monomer unit of the polymer constituting the component (A) is a unit derived from the above-mentioned unsaturated hydrocarbon having a liquid-repellent group . The positive-type photosensitive resin composition according to any one of claim 1 to claim 3, wherein the monomer unit of the polymer constituting component (A) is derived from the above-mentioned alkoxysilane compound having a liquid-repellent group The unit. The positive-type photosensitive resin composition according to any one of claim 1 to claim 5, wherein component (A) is a polymer having the above-mentioned liquid repellent group and thermosetting group. The positive photosensitive resin composition according to any one of claim 1 to claim 6, wherein the crosslinking agent of component (D) contains an epoxy group or a methoxymethyl group. The positive-type 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. The positive-type photosensitive resin composition according to any one of claims 1 to 8, which contains 0.1 to 20 parts by mass of the component (A) relative to 100 parts by mass of the component (B). The positive-type photosensitive resin composition according to any one of claims 1 to 9, which contains 5 to 100 parts by mass of component (C) relative to 100 parts by mass of component (B). The positive-type photosensitive resin composition according to any one of claims 1 to 10, which contains 5 to 50 parts by mass of component (D) relative to 100 parts by mass of component (B). A cured film obtained by using the positive photosensitive resin composition according to any one of claim 1 to claim 11. A display element having the cured film according to claim 12. A display element having the cured film according to claim 12 as a bank for image formation.