KR20240025483A - Photosensitive resin composition, resin layer, cured product, partition wall, organic light emitting diode device, display, method for producing cured product, fluororesin and polymer blend - Google Patents

Abstract

(일반식 (1) 중, Ra는, 각각 독립적으로, 탄소수 1∼6의 직쇄상, 탄소수 3∼6의 분기쇄상 혹은 탄소수 3∼6의 환상의 알킬기 또는 불소 원자를 나타내고, 상기 알킬기는 임의의 수의 수소 원자가 불소 원자로 치환되어 있다.)[Problem] To provide a photosensitive resin composition and a cured product thereof having good curability and liquid repellency.
[Solution] Contains an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin (E) having a structure represented by the following general formula (1). A photosensitive resin composition containing 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass.
[Formula 1]

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.)

Description

Photosensitive resin composition, resin film, cured product, partition wall, organic electroluminescent device, display, manufacturing method of cured product, fluorinated resin and polymer blend {PHOTOSENSITIVE RESIN COMPOSITION, RESIN LAYER, CURED PRODUCT, PARTITION WALL, ORGANIC LIGHT EMITTING DIODE DEVICE, DISPLAY, METHOD FOR PRODUCING CURED PRODUCT, FLUORORESIN AND POLYMER BLEND}

The present disclosure relates to photosensitive resin compositions, resin films, cured products, partitions, organic electroluminescent devices, displays, methods for producing cured products, fluorinated resins, and polymer blends.

When manufacturing display elements such as organic EL displays, micro LED displays, and quantum dot displays, the inkjet method is known as a method of forming an organic layer having a function such as light emission. There are several methods in the inkjet method, specifically, a method of solidifying ink dropped from a nozzle into a concave part of a pattern film having irregularities formed on a substrate, or a method of solidifying ink with a lyophilic part that is a part wetted by ink. As a liquid-repellent portion that is a repelling portion, a method of dropping ink droplets on a pattern film previously formed on a substrate and attaching the ink only to the liquid-repellent portion may be used.

In particular, in the method of solidifying ink dropped from a nozzle into the concave portion of the pattern film contained in the former, two methods can be mainly adopted to produce a pattern film having such irregularities. One is a photolithography method in which the surface of a photosensitive resist film applied on a substrate is exposed in a pattern to form exposed and unexposed areas, and either part is removed by dissolving it in a developer, and the other is a method using printing technology. This is the imprint method.

The convex portion of the pattern film having the formed irregularities is called a bank (partition), and the bank acts as a barrier to prevent the inks from mixing when ink is dropped into the concave portion of the pattern film. In order to increase the effect as a barrier, the pattern film recess is required to expose the substrate surface, the substrate surface is required to be lyophilic to ink, and the upper surface of the bank is required to be liquid-repellent to ink.

As a resin for forming such a bank, a fluorinated resin is used as an ink repellent agent. Liquid repellency is improved by using a fluorinated resin.

Patent Document 1 discloses a photosensitive resin containing an ethylenically unsaturated compound, a photopolymerization initiator, an alkali-soluble resin, and a liquid repellent. In addition, it is disclosed that the cured product obtained by curing the photosensitive resin constitutes a partition.

International Publication No. 2021/090836

In order to improve liquid repellency, it is known to add a fluorinated resin with a high fluorine atom content as a liquid repellent to the photosensitive resin composition. However, fluorinated resins with a high fluorine atom content have low compatibility with solvents or compounds that do not contain fluorine, and each component may be omnipresent. Resin cured products of such photosensitive resin compositions sometimes have poor curing or poor liquid repellency, and there is room for improvement. The purpose of this disclosure is to provide a photosensitive resin composition and a cured product thereof having good curability and liquid repellency.

As a result of careful study by the present inventors, the uneven distribution of liquid repellent, ethylenically unsaturated compounds, alkali-soluble resins, etc. partially causes curing failure, making it difficult to retain the liquid repellent in the cured product, making it difficult to achieve liquid repellency. I found this to be difficult. Then, it was discovered that the above problem could be solved by adding a resin having a specific group, which led to the present disclosure.

Means for solving the above problems include the following embodiments.

The first photosensitive resin composition of the present disclosure includes an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin having a structure represented by general formula (1). A photosensitive resin composition containing (E), where the fluorinated resin (D) is 100 parts by mass, contains 30 to 550 parts by mass of the resin (E).

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.)

The second photosensitive resin composition of the present disclosure includes an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin having a structure represented by general formula (1). A photosensitive resin composition containing (E), wherein the resin (E) is a resin having a structural unit having a structure represented by General Formula (1) and a structural unit having a crosslinking site.

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.)

The resin film of the present disclosure is obtained from the first or second photosensitive resin composition.

The cured product of the present disclosure is obtained by curing the above resin film.

The partition wall of the present disclosure is composed of the above-mentioned cured material.

The organic electroluminescent device of the present disclosure includes the partition wall and a light-emitting layer or wavelength conversion layer disposed in a region defined by the partition wall.

The display of the present disclosure includes the partition wall.

The method for producing a cured product of the present disclosure includes a film forming step of obtaining a resin film by applying the first or second photosensitive resin composition to a substrate and then heating it, and an exposure step of exposing the resin film to a high-energy ray. Includes.

The fluorinated resin of the present disclosure has a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site.

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.)

The polymer blend of the present disclosure is characterized by containing the above-described fluorinated resin.

A photosensitive resin composition having good curability and liquid repellency and a cured product thereof can be provided.

Hereinafter, the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be appropriately implemented based on the common knowledge of those skilled in the art, within the scope without impairing the spirit of the present disclosure.

In addition, in this specification, “bank” and “partition wall” are synonyms, and unless otherwise noted, mean a convex portion of a pattern film having irregularities in the inkjet method.

Below, among the photosensitive resin compositions of the present disclosure, the first photosensitive resin composition is explained.

The first photosensitive resin composition of the present disclosure includes an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin having a structure represented by general formula (1). A photosensitive resin composition containing (E), characterized in that it contains 30 to 550 parts by mass of the resin (E), assuming 100 parts by mass of the fluorinated resin (D).

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. (Number of hydrogen atoms is replaced with fluorine atom. Here, any number is 1 or more.)

The first photosensitive resin composition of the present disclosure solves the problem of ubiquitous distribution of each component by including the resin (E) having a structure represented by General Formula (1), and has liquid repellency even when a liquid repellent containing a large fluorine atom content is used. However, cured products or partition walls with improved hardenability can be manufactured. The “liquid repellent” is a fluorinated resin (D) in the first photosensitive resin composition of the present disclosure. Hereinafter, “resin (E) having a structure represented by General Formula (1)” may be referred to as “resin (E).”

<Ethylenically unsaturated compound (A)>

When the first photosensitive resin composition of the present disclosure contains an ethylenically unsaturated compound (A), curing of the first photosensitive resin composition by light irradiation is promoted, and curing in a shorter time becomes possible. As the ethylenically unsaturated compound (A), a compound having two or more ethylenically unsaturated groups can be used. Conjugated stabilized double bonds, such as the double bond of the benzene ring, do not correspond to ethylenically unsaturated groups. From the viewpoint of improving reactivity, the ethylenically unsaturated compound (A) preferably has an ethylenically unsaturated group at its terminal. The ethylenically saturated compound (A) does not contain a fluorine atom.

Specific examples of the ethylenically unsaturated compound (A) include polyfunctional acrylates (e.g., product names: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A manufactured by Shin Nakamura Chemical Co., Ltd. -TMPT, AD-TMP), polyethylene glycol diacrylate (e.g., product name: A-200, A-400, A-600 manufactured by Shinnakamura Chemical Industry Co., Ltd.), urethane acrylate (e.g., Shinnakamura Chemical Co., Ltd. Product name manufactured by Chemical Industry Co., Ltd.: UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200 ), pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.

As a polyfunctional acrylate compound, preferred ones are exemplified below.

In the above example, V ₁ has m1 structural units represented by “-OC(CH ₃ )H-CH ₂ -” and n1 structural units represented by “-O-CH ₂ -C(CH ₃ )H-”. It has a structure of block copolymerization or random copolymerization, and m1 + n1 = 2, 3, 7, 12. V ₂ has m2 structural units represented by “-OC(CH ₃ )H-CH ₂ -”, n2 structural units represented by “-O-CH ₂ -C(CH ₃ )H-”, and is a block copolymer. Alternatively, it has a random copolymerization structure, and m2+n2=7.

The content of the ethylenically unsaturated compound (A) is preferably 10 parts by mass or more and 300 parts by mass or less, with the total of the alkali-soluble resin (C), fluorinated resin (D), and resin (E) described later being 100 parts by mass. , more preferably 50 parts by mass or more and 200 parts by mass or less. If the content of the ethylenically unsaturated compound (A) is less than 10 parts by mass, the crosslinking effect tends not to be sufficiently obtained, and if it exceeds 300 parts by mass, resolution and sensitivity tend to decrease.

< Photopolymerization initiator (B) >

In the first photosensitive resin composition of the present disclosure, the photopolymerization initiator (B) is not particularly limited as long as it polymerizes a monomer having a polymerizable double bond by high-energy rays such as electromagnetic waves or electron beams, and may be any known photopolymerization initiator. can be used.

As the photopolymerization initiator (B), a photo-radical initiator or a photo-acid initiator can be used. These may be used alone, a photo-radical initiator and a photo-acid initiator may be used in combination, two or more types of photo-radical initiators and/or two or more types of photo-acid initiators. You may use a mixture of . Moreover, it is also possible to perform living polymerization in some cases by using additives in addition to the photopolymerization initiator. The additive may be a known additive.

Photoradical initiators include, specifically, the intramolecular cleavage type, which generates radicals by cleaving the bonds within the molecule by absorption of electromagnetic waves or electron beams, or the hydrogen abstraction type, which generates radicals by using a hydrogen donor such as tertiary amine or ether in combination. It can be classified as follows, and any one can be used. Photoradical initiators other than those listed above can also be used.

As a photo radical initiator, benzophenone type, acetophenone type, diketone type, acylphosphine oxide type, quinone type, acyloin type, thioxanthone type, etc. are mentioned specifically.

As benzophenone series, specifically benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino) ) Benzophenone, etc. can be mentioned. Among them, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferable.

Acetophenone series specifically includes acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, and p- Methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- butan-1-one, etc. can be mentioned. Among them, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferable.

Specific examples of the diketone series include 4,4'-dimethoxybenzyl, methyl benzoyl formate, and 9,10-phenanthrenequinone. Among them, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferable.

Specific examples of the acylphosphine oxide series include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

Specific examples of the quinone series include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among them, camphorquinone and 1,4-naphthoquinone are preferable.

Specific examples of acyloin include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among them, benzoin and benzoin methyl ether are preferable.

As thioxanthone series, specific examples include 2,4-diethylthioxanthone.

As a radical photoinitiator, benzophenone series, acetophenone series, and diketone series are preferred, and benzophenone series are more preferred.

Among commercially available optical radical initiators, preferred ones are those manufactured by BASF Co., Ltd., product names: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Irga Cure 2959, Irgacure OXE-01, Irgacure OXE-04, Darocure 1173, Lucirin TPO, product name manufactured by Nihon Kayaku Co., Ltd.: DETXs, etc. Among them, Irgacure 651 and Irgacure 369 are more preferable.

The photoacid initiator is specifically aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrenium, thioxanthonium, (2,4-cyclopentadien-1-yl)(1-methylethylbenzene) A pair of at least one cation selected from the group consisting of iron and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenyl borate It is an onium salt consisting of.

Among them, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, diphenyl Iodonium hexafluorophosphate is particularly preferred.

Commercially available mineral initiators include, for example, product names manufactured by San-Apro Co., Ltd.: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S, and product names manufactured by Dow Chemical Japan Co., Ltd.: Cyracure Kyonggyeong. Curing initiator UVI-6990, Cyracure photocuring initiator UVI-6992, Cyracure photocuring initiator UVI-6976, manufactured by ADEKA Co., Ltd. Product names: Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, Adeka Optomer SP-300, manufactured by Nippon Soda Co., Ltd. Product name: CI-5102, CI-2855, manufactured by Sanshin Chemical Industry Co., Ltd. Product name: San-Aid SI-60L , San Aid SI-80L, San Aid SI-100L, San Aid SI-110L, San Aid SI-180L, San Aid SI-110, San Aid SI-180, product names made by Lamberti: Esacure 1064, Esacure 1187 , product name: Irgacure 250 manufactured by Chiba Specialty Chemicals Co., Ltd., etc.

The content of the photopolymerization initiator (B) in the first photosensitive resin composition of the present disclosure is the total of the ethylenically unsaturated compound (A), alkali-soluble resin (C), fluorinated resin (D), and resin (E) of 100. It is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less. If the content of the photopolymerization initiator (B) is less than 0.1 parts by mass, the crosslinking effect tends not to be sufficiently obtained, and if it exceeds 30 parts by mass, resolution and sensitivity tend to decrease.

<Alkali-soluble resin (C)>

When the first photosensitive resin composition of the present disclosure contains an alkali-soluble resin (C), the shape of the bank obtained from the first photosensitive resin composition of the present disclosure can be improved. The alkali-soluble resin (C) may or may not contain a fluorine atom, but the alkali-soluble resin (C) is preferably a resin that does not contain a fluorine atom. The type of the alkali-soluble resin (C) is not particularly limited as long as it is alkali-soluble, but it is a resin other than the fluorinated resin (D) described later and the resin (E) having a structure represented by General Formula (1).

Examples of the alkali-soluble resin (C) include alkali-soluble novolac resin.

Alkali-soluble novolak resin can be obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

Specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, and 3,5-dimethylphenol. -Dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, Examples include 4-methyl-catechol, pyrogallol, phloroglucinol, thymol, and isothymol. These phenols may be used individually or in combination of two or more types.

Aldehydes include, specifically, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, and m-hydroxybenzaldehyde. Examples include benzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthaldehyde, and isophthalaldehyde.

Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethyl sulfuric acid, and p-toluenesulfonic acid. These acid catalysts may be used individually, or two or more types may be used in combination.

In addition, examples of the alkali-soluble resin (C) include acid-modified epoxy acrylate-based resins. Commercially available acid-modified epoxy acrylate systems include, for example, product names manufactured by Nihon Kayaku Co., Ltd.: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZAR-2050H, ZAR-2051H, ZFR-1185 and ZCR-1569H are available.

The mass average molecular weight of the alkali-soluble resin (C) component is preferably 1,000 to 50,000 from the viewpoint of developability and resolution of the first photosensitive resin composition.

The content of the alkali-soluble resin (C) relative to the total solid content of the first photosensitive resin composition of the present disclosure is preferably 10 to 70% by mass. If the content of the alkali-soluble resin (C) exceeds 70% by mass, the liquid repellency for ink of the fluorinated resin (D) described later tends not to be sufficiently obtained.

<Fluorinated resin (D)>

In the first photosensitive resin composition of the present disclosure, the fluorinated resin (D) has a structural unit made of a hydrocarbon having a fluorine atom. The fluorinated resin (D) does not contain the structure of general formula (1) described later. The fluorinated resin (D) does not contain a radical generator. In this specification, a radical generator is a group that generates radicals when exposed to light.

In the first photosensitive resin composition of the present disclosure, the fluorinated resin (D) may have a structure represented by the following general formula (2), or may have a structure represented by the following general formula (3).

(In the general formula (2), Rb each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and any of the alkyl groups Numerous hydrogen atoms are replaced by fluorine atoms. Here, the arbitrary number is 1 or more. R ² is a hydrogen atom, linear with 1 to 6 carbon atoms, branched with 3 to 6 carbon atoms, or cyclic with 3 to 6 carbon atoms. represents an alkyl group.)

(In the general formula (3), Rb each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and any of the alkyl groups Numerous hydrogen atoms are replaced by fluorine atoms. Here, the arbitrary number is 1 or more. R ¹ represents a hydrogen atom, a fluorine atom, or a methyl group. R ² represents a hydrogen atom, a straight chain with 1 to 6 carbon atoms, and a carbon number. It represents a branched chain of 3 to 6 carbon atoms or a cyclic alkyl group of 3 to 6 carbon atoms.)

In general formula (3), R ¹ is preferably a hydrogen atom or a methyl group. Additionally, R ² is, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n-phene. Examples include ethyl group, isopentyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc., and hydrogen atom and methyl group. , an ethyl group, n-propyl group, and isopropyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Moreover, Rb in general formula (2) or (3) is a fluorine atom, trifluoromethyl group, difluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, or n-heptafluoro. Lopropyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,3-trifluoropropyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, n-nonafluo Lobutyl group, isononafluorobutyl group, and tert-nonafluorobutyl group are preferred, and fluorine atom, trifluoromethyl group, difluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-heptafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,3-trifluoropropyl group, and hexafluoroisopropyl group are more preferable, and a fluorine atom, di Fluoromethyl group and trifluoromethyl group are particularly preferable.

With respect to the structural unit represented by general formula (3) contained in the fluorinated resin (D) in the first photosensitive resin composition of the present disclosure, the following structure can be exemplified as a preferable one.

The content of the structural unit represented by the general formula (3) in the fluorinated resin (D) is preferably 5 mol% or more and 70 mol% or less, based on 100 mol% of all structural units constituting the fluorinated resin (D). , 10 mol% or more and 50 mol% or less is more preferable, and 10 mol% or more and 30 mol% or less is particularly preferable.

If the content of the structural unit of general formula (3) is more than 70 mol%, the fluorinated resin (D) tends to become difficult to dissolve in the solvent. On the other hand, when the content of the structural unit of general formula (3) is less than 5 mol%, when the cured product manufactured from the first photosensitive resin composition is subjected to UV ozone treatment or oxygen plasma treatment, resistance tends to decrease. .

If the fluorinated resin (D) has a structural unit represented by general formula (3), it is one of the preferred embodiments because it has resistance to UV ozone treatment or oxygen plasma treatment.

Moreover, in the first photosensitive resin composition of the present disclosure, the fluorinated resin (D) may contain a structure represented by the following general formula (4).

In General Formula (4), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.

In general formula (4), W ¹ represents a divalent linking group, -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, - It represents C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among them, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- are preferable.

When W ¹ is -OC(=O)-NH-, it is one of the preferred embodiments because the ink has better liquid repellency after UV ozone treatment or oxygen plasma treatment.

In the general formula (4), A ¹ represents a 2- to 4-valent linking group, a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and Any number of hydrogen atoms may be substituted by hydroxyl groups or -OC(=O)-CH ₃ .

When the divalent linking group A ¹ is a linear alkylene group having 1 to 10 carbon atoms, for example, methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexylene group, n- Heptylene group, n-octylene group, n-nonylene group, and n-decanylene group can be mentioned.

When the divalent linking group A ¹ is a branched alkylene group having 3 to 10 carbon atoms, for example, isopropylene group, isobutylene group, sec-butylene group, tert-butylene group, isopentylene group, isohexylene group, etc. can be mentioned.

When the divalent linking group A ¹ is a cyclic alkylene group having 3 to 10 carbon atoms, for example, di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted Cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-tert-butylcyclohexane, etc. can be mentioned.

When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl group-substituted alkylene groups include hydroxyethylene group, 1-hydroxy-n-propylene group, and 2-hydroxy-n group. -Propylene group, hydroxy-isopropylene group (-CH(CH ₂ OH)CH ₂ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ₂ OH)CH ₂ CH ₂ -), hydroxy-isobutylene group (-CH ₂ CH(CH ₂ OH)CH ₂ -), hydroxy-tert-butylene group (-C(CH ₂ OH )(CH ₃ )CH ₂ -) and the like.

In addition, when any number of hydrogen atoms in these alkylene groups are substituted by -OC(=O)-CH ₃ , the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above as the substituted alkylene group is -OC(= O)-CH ₃ may be substituted.

Among them, the divalent linking group A ¹ is methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, 2-hydroxy-n-propylene group, and hydroxy-iso Propylene group (-CH(CH ₂ OH)CH ₂ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ₂ OH)CH ₂ CH ₂ -) are preferred, Ethylene group, propylene group, 2-hydroxy-n-propylene group, and hydroxy-isopropylene group (-CH(CH ₂ OH)CH ₂ -) are more preferable, and ethylene group and 2-hydroxy-n-propylene are more preferable. group is particularly preferable.

Examples of the trivalent linking group A ¹ include -C(CH ₂ -) ₂ CH ₃ , and examples of the tetravalent linking group A ¹ include C(CH ₂ -) ₄ .

In General Formula (4), Y ¹ represents a divalent linking group, represents -O- or -NH-, and is more preferably -O-.

In General Formula (4), u represents an integer of 1 to 3, and it is particularly preferable that u is 1.

In General Formula (4), n represents an integer of 1 to 3, and n is particularly preferably 1.

The substitution positions of the aromatic ring each independently represent an ortho position, a meta position, and a para position, and the para position is preferred.

Regarding the structural unit represented by general formula (4), the following structures can be exemplified as preferable ones. In addition, the substitution position of the aromatic ring is exemplified as the para position, but the substitution position may each independently be an ortho position or a meta position.

The content of the structural unit represented by the general formula (4) in the fluorinated resin (D) is preferably 5 mol% or more and 70 mol% or less, based on 100 mol% of all structural units constituting the fluorinated resin (D). , 10 mol% or more and 50 mol% or less is more preferable, and 10 mol% or more and 30 mol% or less is particularly preferable.

If the content of the structural unit of general formula (4) is more than 70 mol%, the fluorinated resin (D) tends to become difficult to dissolve in the solvent. On the other hand, when the content of the structural unit of general formula (4) is less than 5 mol%, resistance tends to decrease when subjected to UV ozone treatment or oxygen plasma treatment.

Although the effect of the structural unit represented by general formula (4) of the present disclosure is not clear, it is speculated that the cured product manufactured from the first photosensitive resin composition has resistance to UV ozone treatment or oxygen plasma treatment. do. However, the effects of the present disclosure are not limited to the effects described here.

As described above, the fluorinated resin (D) is a copolymer containing a structural unit represented by the general formula (3) and a structural unit represented by the general formula (4), and a copolymer containing the structural unit represented by the general formula (3) It may be a mixture (blend) of a different type of copolymer containing a structural unit and a structural unit represented by the above general formula (4). In particular, the fluorinated resin (D) is a fluorinated resin containing a structural unit wherein W ¹ in general formula (4) is -OC(=O)-NH-, and W in general formula (4) One of the preferred embodiments of the present disclosure is that ¹ is a mixture with a fluorinated resin containing the structural unit -C(=O)-NH-.

Moreover, in the first photosensitive resin composition of the present disclosure, the fluorinated resin (D) may contain a structure represented by the following general formula (5).

In General Formula (5), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group.

In general formula (5), W ² represents a divalent linking group, -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, - It represents C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among them, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- are preferable.

When W ² is -OC(=O)-NH-, the liquid repellency of the fluorinated resin (D) of the present disclosure to ink after UV ozone treatment or oxygen plasma treatment is more excellent, and is therefore a particularly preferred embodiment. It is one.

In general formula (5), A ² represents a divalent linking group, a linear alkylene group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, and any of the alkylene groups. The number of hydrogen atoms may be substituted by a hydroxyl group or -OC(=O)-CH ₃ .

In general formula (5), A ³ represents a 2 to 4 valent linking group, a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and the hydrocarbon group Any number of hydrogen atoms may be substituted by hydroxyl group or -OC(=O)-CH ₃ .

When the divalent linking groups A ² and A ³ are each independently a linear alkylene group having 1 to 10 carbon atoms, for example, methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, and n-decanylene group.

When the divalent linking groups A ² and A ³ are each independently a branched alkylene group having 3 to 10 carbon atoms, for example, isopropylene group, isobutylene group, sec-butylene group, tert-butylene group, iso Pentylene group, isohexylene group, etc. are mentioned.

When the divalent linking groups A ² and A ³ are each independently a cyclic alkylene group having 3 to 10 carbon atoms, for example, disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, or disubstituted cyclopropane. cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-tert-butylcyclohexane, etc.

When any number of hydrogen atoms in these alkylene groups are substituted with a hydroxyl group, the hydroxyl group-substituted alkylene group is, for example, 1-hydroxyethylene group (-CH(OH)CH ₂ -), 2-hydroxy Ethylene group (-CH ₂ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ₂ OH)CH ₂ - ), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ₂ OH)CH ₂ CH ₂ -), hydroxy-isobutylene group (-CH ₂ CH(CH ₂ OH)CH ₂ -), hydroxy-tert-butylene group (-C(CH ₂ OH)(CH ₃ )CH ₂ -), and the like.

In addition, when any number of hydrogen atoms in these alkylene groups are substituted by -OC(=O)-CH ₃ , the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above as the substituted alkylene group is -OC(= O)-CH ₃ may be substituted.

Among them, the divalent linking groups A ² and A ³ are each independently a methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, and 1-hydroxyethylene group ( -CH(OH)CH ₂ -), 2-hydroxyethylene group (-CH ₂ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ₂ OH )CH ₂ -), 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ₂ OH)CH ₂ CH ₂ -) is preferable, ethylene group, propylene group, 1-hyde Oxyethylene group (-CH(OH)CH ₂ -), 2-hydroxyethylene group (-CH ₂ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH (CH ₂ OH)CH ₂ -) is more preferable, and ethylene group, 1-hydroxyethylene group (-CH(OH)CH ₂ -), 2-hydroxyethylene group (-CH ₂ CH(OH)-) is particularly preferable.

Examples of the trivalent linking group A ³ include -C(CH ₂ -) ₂ CH ₃ , and examples of the tetravalent linking group A ³ include C(CH ₂ -) ₄ .

In General Formula (5), Y ² and Y ³ represent a divalent linking group and each independently represents -O- or -NH-, and -O- is more preferable.

In General Formula (5), n represents an integer of 1 to 3, and n is particularly preferably 1.

In General Formula (5), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

Regarding the structural unit represented by general formula (5), the following structure can be exemplified as a preferable one.

The content of the structural unit represented by the general formula (5) in the fluorinated resin (D) is preferably 5 mol% or more and 70 mol% or less, based on 100 mol% of all structural units constituting the fluorinated resin (D). , 10 mol% or more and 50 mol% or less is more preferable, and 10 mol% or more and 30 mol% or less is particularly preferable.

If the content of the structural unit of general formula (5) is more than 70 mol%, the fluorinated resin (D) tends to become difficult to dissolve in the solvent. On the other hand, if the content of the structural unit of general formula (5) is less than 5 mol%, the adhesion of the resin film or bank obtained from the fluorinated resin (D) to the substrate tends to decrease.

Although the effect of the structural unit represented by General Formula (5) is not clear, when the fluorinated resin (D) contains the structural unit represented by General Formula (5), the resulting resin film or bank has an effect on the substrate. It is speculated that it improves adhesion. However, the effects of the present disclosure are not limited to the effects described here.

The fluorinated resin (D) is a copolymer containing a structural unit represented by the general formula (3) and a structural unit represented by the general formula (5), a structural unit represented by the general formula (3), and It may be a mixture (blend) with a different type of copolymer containing the structural unit represented by the general formula (5). In particular, the fluorinated resin (D) is a fluorinated resin containing a structural unit wherein W ² in general formula (5) is -OC(=O)-NH-, and W in general formula (5) ^One of the preferred embodiments of the present disclosure is a mixture with a fluorinated resin containing a divalent -C(=O)-NH- structural unit.

Moreover, in the first photosensitive resin composition of the present disclosure, the fluorinated resin (D) may contain a structure represented by the following general formula (6).

In General Formula (6), R ⁷ represents a hydrogen atom or a methyl group.

In general formula (6), R ⁸ represents a linear alkyl group with 1 to 15 carbon atoms, a branched chain with 3 to 15 carbon atoms, or a cyclic alkyl group with 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkyl group are atomized by a fluorine atom. It is substituted, and the fluorine atom content in the structural unit is 30% by mass or more. Here, the arbitrary number is 1 or more.

When R ⁸ is a linear alkyl group, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or any number of linear alkyl groups having 10 to 14 carbon atoms. An example is that the hydrogen atom of is replaced by a fluorine atom.

When R ⁸ is a linear alkyl group, the structural unit represented by the general formula (6) is preferably a structural unit represented by the following general formula (6-1).

In general formula (6-1), R ⁹ is the same as R ⁷ in general formula (6).

In general formula (6-1), X is a hydrogen atom or a fluorine atom.

In general formula (6-1), p is an integer of 1 to 4. q is an integer from 1 to 14. It is particularly preferable that p is an integer of 1 to 2, q is an integer of 2 to 8, and X is a fluorine atom.

Regarding the structural unit represented by general formula (6), the following structure can be exemplified as a preferable one.

The content of the structural unit represented by the general formula (6) is preferably 5 mol% or more and 70 mol% or less, and 10 mol% or more and 50 mol%, based on 100 mol% of all structural units constituting the fluorinated resin (D). % or less is more preferable, and 10 mol% or more and 30 mol% or less is particularly preferable.

If the content of the structural unit of general formula (6) is more than 70 mol%, the fluorinated resin (D) tends to become difficult to dissolve in the solvent.

The structural unit represented by general formula (6) is a structural unit that provides liquid repellency to ink after UV ozone treatment or oxygen plasma treatment. Therefore, when it is desired to pursue high liquid properties for ink, it is preferable that the fluorinated resin (D) contains a structural unit represented by general formula (6).

Moreover, in the first photosensitive resin composition of the present disclosure, the fluorinated resin (D) may contain a structure represented by the following general formula (7).

In General Formula (7), R ¹⁰ represents a hydrogen atom or a methyl group.

In the general formula (7), B is each independently a hydroxyl group, a carboxyl group, -C(=O)-OR ¹¹ (R ¹¹ is a straight chain having 1 to 15 carbon atoms, a branched chain having 3 to 15 carbon atoms, or a branched chain having 3 to 15 carbon atoms. represents a cyclic alkyl group, any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and the fluorine atom content in R ¹¹ is 30% by mass or more) or -OC(=O)-R ¹² (R ¹² is It represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms. Additionally, m represents an integer from 0 to 3. Here, the arbitrary number is 1 or more.

Regarding the structural unit represented by general formula (7), the following structure can be exemplified as a preferable one.

The content of the structural unit represented by general formula (7) is preferably 5 mol% or more and 70 mol% or less, and 10 mol% or more and 50 mol%, based on 100 mol% of all structural units constituting the fluorinated resin (D). % or less is more preferable, and 20 mol% or more and 40 mol% or less is particularly preferable.

If the content of the structural unit of general formula (7) is more than 70 mol%, the fluorinated resin (D) tends to become difficult to dissolve in the solvent.

In General Formula (7), when B is a hydroxyl group or a carboxyl group, the structural unit represented by General Formula (7) has solubility in an alkaline developer. Therefore, it is preferable that the fluorinated resin (D) contains a structural unit represented by general formula (7) where B is a hydroxyl group or a carboxyl group.

Moreover, in the first photosensitive resin composition of the present disclosure, the fluorinated resin (D) may contain a structure represented by the following general formula (8).

In General Formula (8), R ¹³ represents a hydrogen atom or a methyl group.

In general formula (8), A ⁴ represents a divalent linking group, a linear alkylene group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic alkylene group with 3 to 10 carbon atoms, and is selected from the alkylene group. Any number of hydrogen atoms may be substituted by hydroxyl groups or -OC(=O)-CH ₃ .

When the divalent linking group A ⁴ is a linear alkylene group having 1 to 10 carbon atoms, for example, methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexylene group, n -Heptylene group, n-octylene group, n-nonylene group, and n-decanylene group.

When the divalent linking group A ⁴ is a branched alkylene group having 3 to 10 carbon atoms, for example, isopropylene group, isobutylene group, sec-butylene group, tert-butylene group, isopentylene group, isohexylene group. etc. can be mentioned.

When the divalent linking group A ⁴ is a cyclic alkylene group having 3 to 10 carbon atoms, for example, di-substituted cyclopropane, di-substituted cyclobutane, di-substituted cyclopentane, di-substituted cyclohexane, di-substituted Cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-tert-butylcyclohexane, etc. can be mentioned.

When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl group-substituted alkylene group include, for example, 1-hydroxyethylene group (-CH(OH)CH ₂ -), 2-hyde Oxyethylene group (-CH ₂ CH(OH)-), 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ₂ OH)CH ₂ -), 1-hydroxy-n-butylene group, 2-hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ₂ OH)CH ₂ CH ₂ -), hydroxy-isobutyl Examples include lene group (-CH ₂ CH(CH ₂ OH)CH ₂ -) and hydroxy-tert-butylene group (-C(CH ₂ OH)(CH ₃ )CH ₂ -).

In addition, when any number of hydrogen atoms in these alkylene groups are substituted by -OC(=O)-CH ₃ , the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above as the substituted alkylene group is -OC(= O)-CH ₃ may be substituted.

Among them, the divalent linking group A ⁴ is methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, and 1-hydroxyethylene group (-CH(OH)CH ₂ -), 2-hydroxyethylene group (-CH ₂ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ₂ OH)CH ₂ -), 2 -Hydroxy-n-butylene group, hydroxy-sec-butylene group (-CH(CH ₂ OH)CH ₂ CH ₂ -) is preferable, and ethylene group, propylene group, 1-hydroxyethylene group (-CH( OH)CH ₂ -), 2-hydroxyethylene group (-CH ₂ CH(OH)-), 2-hydroxy-n-propylene group, hydroxy-isopropylene group (-CH(CH ₂ OH)CH ₂ -) is more preferable, and ethylene group, 1-hydroxyethylene group (-CH(OH)CH ₂ -), and 2-hydroxyethylene group (-CH ₂ CH(OH)-) are particularly preferable.

In General Formula (8), Y ⁴ represents a divalent linking group, represents -O- or -NH-, and is more preferably -O-.

In General Formula (8), r represents 0 or 1. When r is 0, (-C(=O)-) represents a single bond.

In general formula (8), E ¹ represents a hydroxyl group, a carboxyl group, or an oxirane group.

When E ¹ is an oxirane group, examples include ethylene oxide group, 1,2-propylene oxide group, and 1,3-propylene oxide group. Among these, ethylene oxide group is preferable.

In General Formula (8), s represents 0 or 1. When s is 0, (-Y ⁴ -A ⁴ -) represents a single bond. When r is 0 and s is 0, it has a structure in which E ¹ is bonded to the main chain of the structural unit.

Regarding the structural unit represented by general formula (8), the following structure can be exemplified as a preferable one.

In the general formula (8), when E ¹ is a hydroxyl group or a carboxyl group, the structural unit represented by the general formula (8) gives the fluorinated resin (D) solubility in an alkaline developer. Therefore, it is preferable that the fluorinated resin (D) of the present disclosure contains a structural unit represented by general formula (8) in which E ¹ is a hydroxyl group or a carboxyl group.

The fluorinated resin (D) may have a crosslinking site. In the present disclosure, “crosslinking site” means a site capable of polymerization reaction with another monomer. Examples of the crosslinking site include a photopolymerizable group, and it is preferably introduced into the side chain of the polymer. The fluorinated resin (D) is obtained by, for example, polymerizing monomers to obtain a fluorinated resin precursor having structural units having the structures shown in the above-mentioned general formulas (3), (6) to (8), and then fluorinated resin. By reacting the precursor with a photopolymerizable group derivative, a photopolymerizable group is introduced into the side chain of the polymer, and a fluorinated resin (D) having a structural unit having the structure shown in the above-mentioned general formulas (4) and (5) can be synthesized.

As the photopolymerizable group introduced into the fluorinated resin precursor, an acrylic group, a methacrylic group, a vinyl group, and an allyl group are preferable, and an acrylic group is more preferable.

When introducing an acrylic group as a photopolymerizable group, examples of the photopolymerizable group derivative include acrylic acid derivatives such as isocyanate monomers having an acrylic group and epoxy monomers having an acrylic group.

Isocyanate monomers having an acrylic group include, for example, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1- (bisacryloyloxymethyl)ethyl isocyanate, etc. are mentioned. Preferably it is 2-isocyanatoethyl acrylate.

Examples of the epoxy monomer having an acrylic group include glycidyl acrylate, 4-hydroxybutylacrylate glycidyl ether (4HBAGE, manufactured by Mitsubishi Chemical Corporation), and the like.

A photopolymerizable group is introduced into the fluorinated resin precursor through an addition reaction between the hydroxyl group of the fluorinated resin precursor and the photopolymerizable group derivative.

The proportion of photopolymerizable groups in the fluorinated resin (D) is preferably 10 mol% or more and 70 mol% or less, assuming that the total amount of structural units constituting the fluorinated resin (D) is 100 mol%. When the fluorinated resin (D) is formed only of structural units having one photopolymerizable group, the content of the photopolymerizable group in the fluorinated resin (D) is 100 mol%. If the ratio of the photopolymerizable group is less than 10 mol%, the strength of the resin film or partition tends to decrease. If the ratio of photopolymerizable groups exceeds 70 mol%, formation of a resin film by application may become difficult. More preferably, it is 15 to 60 mol%.

In the first photosensitive resin composition of the present disclosure, the molecular weight of the fluorinated resin (D) is the mass average molecular weight measured by high-performance gel permeation chromatography (GPC) using polystyrene as a standard material, and is preferably 1,000 or more. , 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and particularly preferably 3,000 or more and 100,000 or less. If the molecular weight is less than 1,000, the strength of the formed resin film or bank tends to decrease, and if the molecular weight is greater than 1,000,000, the solubility in the solvent may be insufficient, making it difficult to form a resin film by application.

The dispersion degree (Mw/Mn) of the fluorinated resin (D) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and especially preferably 1.01 to 3.00.

The fluorinated resin (D) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. From the viewpoint of dispersing each characteristic to an appropriate degree rather than locally, it is preferable that it is a random copolymer.

Preferred aspects of the fluorinated resin (D) in the first photosensitive resin composition of the present disclosure are as follows.

<Sun 1>

Containing the structural unit represented by the following general formula (3), the structural unit represented by the general formula (5), the structural unit represented by the general formula (6-1), and the structural unit represented by the general formula (7) Fluorinated resin (D)

General formula (3): R ¹ and R ² are hydrogen atoms, and Rb is each independently a fluorine atom, a difluoromethyl group, or a trifluoromethyl group.

General formula (5): R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, W ² is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A ² and A ³ are each independently an ethylene group, Y ² and Y ³ are -O-, n is 1, r is 1

General formula (6-1): R ⁹ is a methyl group, p is an integer of 2, q is an integer of 4 to 8, and X is a fluorine atom

General formula (7): R ¹⁰ is a hydrogen atom, B is an acetoxy group, hydroxyl group or carboxyl group, and m is 1

<Sun 2>

Containing the structural unit represented by the following general formula (5), the structural unit represented by the general formula (6), the structural unit represented by the general formula (6-1), and the structural unit represented by the general formula (8) Fluorinated resin (D)

General formula (5): R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, W ² is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A ² and A ³ are each independently an ethylene group, Y ² and Y ³ are -O-, n is 1, r is 1

General formula (6): R ⁷ is a methyl group, and R ⁸ is a branched perfluoroalkyl group having 3 to 15 carbon atoms.

General formula (6-1): R ⁹ is a methyl group, p is an integer of 2, q is an integer of 4 to 8, and X is a fluorine atom

General formula (8): R ¹³ is a methyl group, A ⁴ is an ethylene group, Y ⁴ is -O-, r is 1, s is 0 or 1, E ¹ is a hydroxyl group or a carboxyl group

<Sun 3>

Fluorinated resin (D) containing a structural unit represented by the following general formula (5) and a structural unit represented by the general formula (6-1)

General formula (5): R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, W ² is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A ² and A ³ are each independently an ethylene group, Y ² and Y ³ are -O-, n is 1, r is 1

General formula (6-1): R ⁹ is a methyl group, p is an integer of 2, q is an integer of 4 to 8, and X is a fluorine atom

In the first photosensitive resin composition of the present disclosure, the fluorine atom content of the fluorinated resin (D) is preferably 20 to 60% by mass, and more preferably 25 to 60% by mass.

If the fluorine atom content is within this range, it is easy to dissolve in the solvent. When the fluorinated resin (D) contains a fluorine atom, a resin film or bank with excellent liquid repellency can be obtained.

In addition, in this specification, “fluorine atom content of the resin” refers to the molar ratio of the monomer constituting the resin measured by NMR (nuclear magnetic resonance spectroscopy), the molecular weight of the monomer constituting the resin, and the fluorine contained in the monomer. It means the value calculated from the content.

Here, as an example, fluorine in the case where the fluorinated resin (D) is a resin obtained by polymerizing 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate. Explain how to measure atomic content.

(i) First, the fluorinated resin (D) is subjected to NMR measurement to calculate the ratio of each composition (molar ratio).

(ii) The molecular weight (Mw) of the monomer of each composition of the fluorinated resin (D) is multiplied by the molar ratio, and the obtained values are added together to obtain the total value. From the total value, the weight ratio (wt%) of each composition is calculated. Additionally, the molecular weight of 1,1-bistrifluoromethylbutadiene is 190, the molecular weight of 4-hydroxystyrene is 120, and the molecular weight of 2-(perfluorohexyl)ethyl methacrylate is 432.

(iii) Next, in the composition containing fluorine, the fluorine atom content in the monomer is calculated.

(iv) Calculate the value of “fluorine atom content in monomer ÷ monomer molecular weight (Mw) × weight ratio (wt%)” for each component, and add up the obtained values.

(v) Calculate “value obtained in (iv) above”/“total value obtained in (ii) above” to calculate the fluorine atom content of the fluorinated resin (D).

In the first photosensitive resin composition of the present disclosure, the difference in fluorine atom content between the alkali-soluble resin (C) and the fluorinated resin (D) is preferably 15 to 60% by mass, and more preferably 20 to 55% by mass. , it is more preferable that it is 25 to 45 mass%. If the difference in fluorine atom content is within the above range, uneven distribution of the alkali-soluble resin (C) and the fluorinated resin (D) is eliminated.

In the first photosensitive resin composition of the present disclosure, one type or two or more types of fluorinated resin (D) can be used.

The content of the fluorinated resin (D) relative to the total solid content of the first photosensitive resin composition of the present disclosure is preferably 0.01 to 40% by mass, and more preferably 0.01 to 10% by mass. Within this range, the water and oil repellency and substrate adhesion of the resin film become good.

<Resin (E)>

The first photosensitive resin composition of the present disclosure contains a resin (E) having a structure represented by the following general formula (1). In addition, the resin (E) is a fluorine-containing resin, but it is a different resin from the above-mentioned fluorine-containing resin (D). Resin (E) does not contain radical generators. In this specification, a radical generator is a group that generates radicals when exposed to light.

In general formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is any number. The hydrogen atom of is replaced with a fluorine atom. Here, the arbitrary number is 1 or more.

Straight-chain alkyl groups having 1 to 6 carbon atoms include trifluoromethyl group, difluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, and 3,3,3-trifluoro group. Examples include lopropyl group and nonafluorobutyl group. Examples of the branched alkyl group having 3 to 6 carbon atoms include heptafluoroisopropyl group, hexafluoroisopropyl group, nonafluoroisobutyl group, and nonafluoro-tert-butyl group. Examples of cyclic alkyl groups having 3 to 6 carbon atoms include pentafluorocyclopropyl group. Ra is preferably a linear alkyl group having 1 to 6 carbon atoms, and more preferably a trifluoromethyl group.

Specific examples of the structure represented by General Formula (1) include difluoromethanol group, tetrafluoroethanol group, hexafluoroisopropanol group, trifluoropropanol group, etc., with hexafluoroisopropanol group being preferable.

The resin (E) preferably contains a structural unit having a structure represented by General Formula (1). The structure represented by General Formula (1) is preferably contained in the side chain of the resin (E). Examples of the structural unit having the structure represented by General Formula (1) include the structural unit represented by the following General Formula (1-1).

In general formula (1-1), Ra is the same as Ra in general formula (1).

Rc represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorinated alkyl group (the hydrocarbon group and the fluorinated alkyl group are straight chain or branched and may include a cyclic structure). Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. Examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms (the alkyl group may have a straight chain, branched chain, or cyclic structure), a phenyl group, and a toluyl group, with a methyl group being particularly preferable. Examples of the fluorinated alkyl group include fluorinated alkyl groups having 1 to 6 carbon atoms, and trifluoromethyl group is preferable. Among these, when Rc is hydrogen or a methyl group, the raw materials for the polymerizable monomer to obtain the structure represented by general formula (1-1) are acrylic acid derivatives and methacrylic acid derivatives, and they are easy to obtain in large quantities. , is particularly preferable.

Rd is a divalent (when t = 1) or trivalent (when t = 2) organic group, and the organic group is a straight-chain or branched aliphatic hydrocarbon group that may contain a cyclic structure, an aromatic ring group, or As a group selected from these complex substituents, part or all of the hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group. Examples of aliphatic hydrocarbon groups include those having 1 to 20 carbon atoms. Examples of the aromatic ring group include those having two or three bonding hands attached to the benzene ring. “Complex substituent” means that in one Rd, an aliphatic hydrocarbon unit and an aromatic ring unit are included in series or parallel relationship. Among them, as Rd, those having the following functional groups are preferable because they can serve as raw materials for polymers with excellent physical properties (the dotted lines in the formula represent bond hands).

t represents 1 or 2.

In the resin (E), it is preferable that the structure represented by General Formula (1) is not directly bonded to the aromatic ring. The structure represented by General Formula (1) is preferably directly bonded to a linear, branched, or cyclic alkylene group.

Resin (E) preferably has a crosslinking site. This is because when the resin (E) has a crosslinking site, the uneven distribution of each component of the first photosensitive resin composition is further eliminated.

Examples of the crosslinking site include the photopolymerizable group exemplified as the crosslinking site of the above-described fluorinated resin (D), and it is preferable that it is introduced into the side chain of the polymer. The resin (E) preferably contains a structural unit represented by the following general formula (5).

The above general formula (5) is the same as that exemplified for the fluorinated resin (D).

The resin (E) is preferably a resin containing a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (5).

Resin (E), in addition to the structural unit represented by the following general formula (1-1) and the structural unit represented by the following general formula (5), further contains a structural unit represented by the following general formula (6) It is desirable.

The above general formula (6) is the same as that exemplified for the fluorinated resin (D).

The resin (E) may further contain a structural unit represented by the general formula (3) exemplified for the fluorinated resin (D), a structural unit represented by the general formula (7), etc.

The resin (E) preferably has a content of the structure represented by General Formula (1) of 0.1 mol% or more and less than 50 mol%, assuming that the total amount of structural units constituting the resin (E) is 100 mol%. When the resin (E) is formed only of structural units having one structure represented by general formula (1), the content of the structure represented by general formula (1) in the resin (E) is 100 mol%. If the content of the structure represented by General Formula (1) is less than 0.1 mol%, the effect of making each component sufficiently compatible in the first photosensitive resin composition of the present disclosure may not be sufficiently obtained. If it is 50 mol% or more, the liquid repellency may decrease. If the content of the structure represented by General Formula (1) is 0.1 mol% or more but less than 50 mol%, it is possible to provide other physical properties such as adhesion, heat resistance, and alkali solubility while maintaining sufficient liquid repellency and compatibility. I do it. More preferably, it is 1 mol% or more and less than 50 mol%.

In the resin (E), the content of structural units other than the structural unit having the structure represented by General Formula (1) (hereinafter also referred to as other monomers) is 99.9 mol% or less in the resin (E). It is desirable. When the amount of structural units derived from other monomers exceeds 99.9 mol%, uneven distribution of each component may not be resolved in the first photosensitive resin composition of the present disclosure. More preferably, it is 99 mol% or less. Moreover, the structural unit derived from other monomers in the resin (E) is preferably 50 mol% or more. The molar ratio of the structural units derived from each monomer in the resin (E) can be determined from the measured value of NMR (nuclear magnetic resonance spectroscopy).

Resin (E) preferably has a weight average molecular weight of 1,000 or more and 50,000 or less. If the weight average molecular weight of the resin (E) is outside the above range, the distribution of each component may not be sufficiently improved. More preferably, it is 5,000 or more and 40,000 or less, and even more preferably 5,000 or more and 30,000 or less.

The dispersion degree (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn); Mw/Mn) of the resin (E) is preferably 1.01 to 5.00, more preferably 1.10 to 4.00, and especially preferably 1.30 to 3.00. do.

In the present disclosure, the weight average molecular weight and dispersion degree of resin (E) are values obtained by high-speed gel permeation chromatography using polystyrene as a standard material.

The resin (E) preferably has a fluorine atom content of 15 to 60 mass%. If the fluorine atom content of the resin (E) is within the above range, uneven distribution of each component can be eliminated in the first photosensitive resin composition of the present disclosure. More preferably, it is 15 to 40 mass%, and even more preferably, it is 18 to 36 mass%.

Resin (E) can be obtained by polymerizing a monomer or the like having a structure represented by General Formula (1).

Monomers having a structure represented by general formula (1) include, for example, methacrylic acid-5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl; 4-(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)styrene (4-HFA-ST), 3,5-bis(1,1,1, 3,3,3-hexafluoro-2-hydroxy-2-propanyl)styrene (3,5-HFA-ST), 2,4-bis(1,1,1,3,3,3-hexa Fluoro-2-hydroxy-2-propanyl)cyclohexyl methacrylate, 3,5-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl ) Cyclohexyl methacrylate, 2,4,6-tris (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl) cyclohexyl methacrylate, 1,3 -Bis(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propanyl)isopropyl methacrylate, etc. These monomers can be used one type or two or more types. Preferably methacrylic acid-5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl, 3,5-bis(1,1,1,3, 3,3-hexafluoro-2-hydroxy-2-propanyl)cyclohexyl methacrylate, 1,3-bis(1,1,1,3,3,3-hexafluoro-2-hydroxy -2-Propanyl) isopropyl methacrylate.

Resin (E) can be synthesized, for example, by dissolving a monomer in a solvent, adding a polymerization initiator, and heating as necessary to cause a reaction. In this reaction, it is preferable to include a chain transfer agent as needed. The monomer, solvent, polymerization initiator, and chain transfer agent may be added in their entirety at the start of the reaction, or may be added continuously.

The solvent in the above synthesis method is not particularly limited and includes ketones, alcohols, polyhydric alcohols and their derivatives, ethers, esters, aromatic solvents, and fluorine-based solvents. These may be used individually, or two or more types may be mixed and used.

Ketones include, specifically, acetone, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptyl cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, 2-heptanone, etc. can be mentioned.

Alcohols specifically include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, and 2,3-dimethyl. -2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1 - Examples include butanol, lauryl alcohol, hexyldecanol, and oleyl alcohol.

Polyhydric alcohols and their derivatives specifically include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, and propylene glycol mono. Methyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), monomethyl ether of dipropylene glycol or dipropylene glycol monoacetate, monoethyl Ether, monopropyl ether, monobutyl ether, monophenyl ether, etc. are mentioned.

Specific examples of ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and anisole.

Specific examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and γ-butyrolactone. .

Examples of aromatic solvents include xylene and toluene.

Examples of fluorine-based solvents include freon, substitute freon, perfluoro compounds, and hexafluoroisopropyl alcohol.

Polymerization initiators include known organic peroxides, inorganic peroxides, and azo compounds. Organic peroxides and inorganic peroxides can also be used as a redox-based catalyst in combination with a reducing agent.

Examples of chain transfer agents include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolic acid, 2-ethylhexyl thioglycolic acid, and 2-mercaptoethanol; and halogenated alkyls such as chloroform, carbon tetrachloride, and carbon tetrabromide.

When the resin (E) has a crosslinking site, a method of polymerizing a monomer whose crosslinking site is introduced into the side chain of the polymer by polymerization together with a monomer having a structure represented by General Formula (1) is exemplified. In addition, similar to the synthesis of the fluorinated resin (D) having a crosslinking site, monomers are polymerized to obtain a resin (E) having a structural unit having a structure represented by general formula (1) and a structural unit represented by general formula (8) ), and then reacting the precursor of resin (E) with a photopolymerizable group derivative to introduce a photopolymerizable group into the side chain of the polymer.

Resin (E) may be used singly or in a mixture of two or more types.

In the first photosensitive resin composition of the present disclosure, the content of resin (E) is preferably 0.01 to 10% by mass based on the total solid content of the first photosensitive resin composition. If the content of the resin (E) is within the above range, uneven distribution of each component can be eliminated in the first photosensitive resin composition of the present disclosure. More preferably, it is 0.03 to 5 mass%, and even more preferably, it is 0.03 to 1.0 mass%.

The first photosensitive resin composition of the present disclosure contains 30 to 550 parts by mass of the resin (E), based on 100 parts by mass of the fluorinated resin (D), and preferably 40 to 520 parts by mass. If the content of the resin (E) is within the above range, uneven distribution of each component can be eliminated in the first photosensitive resin composition of the present disclosure.

<Solvent>

It is preferable that the first photosensitive resin composition of the present disclosure contains a solvent. The solvent is not particularly limited as long as the fluorinated resin (D) is soluble, and examples include the same solvents as those exemplified in the synthesis of the resin (E) above. Preferred are methyl ethyl ketone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone.

The amount of solvent in the first photosensitive resin composition of the present disclosure is in the range of 50 parts by mass or more and 2,000 parts by mass or less, with the total of the alkali-soluble resin (C) and the fluorinated resin (D) being 100 parts by mass. desirable. More preferably, it is 100 parts by mass or more and 1,000 parts by mass or less. By adjusting the amount of solvent, the film thickness of the resin film formed can be adjusted, and if it is within the above range, a resin film film thickness suitable for obtaining a bank can be obtained.

The first photosensitive resin composition of the present disclosure preferably further contains at least one member selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor.

<Optical radical sensitizer>

When the first photosensitive resin composition of the present disclosure contains a photoradical sensitizer, the exposure sensitivity of the first photosensitive resin composition of the present disclosure can be further improved. The photoradical sensitizer is preferably a compound that absorbs light or radiation and enters an excited state. By being in an excited state, the photo-radical sensitizer generates electron transfer, energy transfer, or heat generation when it comes into contact with the photo-polymerization initiator, and as a result, the photo-polymerization initiator is easily decomposed to produce acid. The photoradical sensitizer should have an absorption wavelength in the range of 350 nm to 450 nm, and may include polynuclear aromatics, xanthenes, xanthons, cyanines, merocyanines, thiazines, acridines, acridones, and anthracis. Quinones, squarylliums, styryls, basestyryls, or coumarins can be mentioned.

Examples of polynuclear aromatics include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, or 9,10-dipropyloxyanthracene. can do.

Examples of xanthenes include fluorescein, eosin, erythrosine, rhodamine B, and rose bengal.

Examples of xanthone include xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, or isopropylthioxanthone.

Examples of cyanines include thiacarbocyanine and oxacarbocyanine.

Examples of merocyanines include merocyanine and carbomerocyanine.

Examples of thiazines include thionine, methylene blue, and toluidine blue.

Examples of acridine include acridine orange, chloroflavin, and acriflavin.

Examples of acridones include acridone and 10-butyl-2-chloroacridone.

Examples of anthraquinones include anthraquinone.

Examples of squaryllium include squaryllium.

Examples of base styryls include 2-[2-[4-(dimethylamino)phenyl]ethenyl]benzoxazole.

Examples of coumarins include 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, or 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[l]benzopyrano[ 6,7,8-ij]quinolizin-11-one can be exemplified.

These photoradical sensitizers may be used individually or in combination of two or more types.

The photoradical sensitizer used in the first photosensitive resin composition of the present disclosure is preferably polynuclear aromatics, acridones, styryls, basestyryls, coumarins, or xanes, since they have a large effect in improving exposure sensitivity. They are tones, and xanthons are particularly preferable. Among xanthone, diethylthioxanthone and isopropylthioxanthone are preferable.

The content of the photoradical sensitizer is preferably 0.1 parts by mass to 8 parts by mass, more preferably 1 part by mass to 4 parts by mass, based on 100 parts by mass of the fluorinated resin (D). By setting the content of the photoradical sensitizer within the above-mentioned range, the exposure sensitivity of the photosensitive resin composition is improved, and the boundary between the liquid-repellent portion and the lyophilic portion in the pattern forming film after exposure of the first photosensitive resin composition of the present disclosure is made clear. The contrast of the ink pattern after ink application is improved, and a fine pattern is obtained.

< Chain transfer system >

In the first photosensitive resin composition of the present disclosure, it is preferable to use a chain transfer agent as needed.

Examples of the chain transfer agent include the same compounds that can be used in the synthesis of the above-mentioned resin (E).

<UV absorbent>

In the first photosensitive resin composition of the present disclosure, it is preferable to use an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylic acid-based, benzophenone-based, triazole-based, etc. The content of the ultraviolet absorber is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, in the first photosensitive resin composition.

<Polymerization inhibitor>

The polymerization inhibitor used in the first photosensitive resin composition of the present disclosure is not particularly limited, and includes o-cresol, m-cresol, p-cresol, 6-t-butyl-2,4-xylenol, 2,6- Di-t-butyl-p-cresol, hydroquinone, catechol, 4-t-butylpyrocatechol, 2,5-bistetramethylbutylhydroquinone, 2,5-di-t-butylhydroquinone, p- Methoxyphenol, 1,2,4-trihydroxybenzene, 1,2-benzoquinone, 1,3-benzoquinone, 1,4-benzoquinone, leucoquinizarin, phenothiazine, 2-methoxyphenothiazine Azine, tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl or 1,1-diphenyl-2-picrylhydrazine can be exemplified.

Commercially available polymerization inhibitors include N,N'-di-2-naphthyl-p-phenylenediamine (brand name, Nonflex F) manufactured by Seiko Chemical Co., Ltd., N,N-diphenyl-p-phenylenediamine ( Product name, Nonflex H), 4,4'-bis(a,a-dimethylbenzyl)diphenylamine (Product name, Nonflex DCD), 2,2'-methylene-bis(4-methyl-6-tert-butyl) Phenol) (brand name, Nonflex MBP), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (brand name, Ozonon 35) or ammonium N-nitro manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Examples include sophenylhydroxyamine (brand name, Q-1300) or N-nitrosophenylhydroxyamine aluminum salt (brand name, Q-1301).

The content ratio of the polymerization inhibitor in the total solid content in the first photosensitive resin composition of the present disclosure is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, and especially preferably 0.01 to 5% by mass. If the content ratio is within the above range, the development residue of the photosensitive resin composition is reduced and pattern linearity is good.

The first photosensitive resin composition of this disclosure may contain other additives as needed. Other additives include various additives commonly used in photosensitive resin compositions, such as dissolution inhibitors, plasticizers, stabilizers, colorants, thickeners, adhesives, and antioxidants. These other additives may be known.

Next, among the photosensitive resin compositions of the present disclosure, the second photosensitive resin composition is explained. About the second photosensitive resin composition, only the differences from the first photosensitive resin composition will be explained.

The second photosensitive resin composition of the present disclosure includes an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin having a structure represented by general formula (1). A photosensitive resin composition containing (E), wherein the resin (E) is a resin having a structural unit having a structure represented by the general formula (1) and a structural unit having a crosslinking site.

The second photosensitive resin composition preferably contains 30 to 550 parts by mass of the resin (E), based on 100 parts by mass of the fluorinated resin (D).

Specific details of the ethylenically unsaturated compound (A), photopolymerization initiator (B), alkali-soluble resin (C), fluorinated resin (D), resin (E) and other usable compounds contained in the second photosensitive resin composition. The type and mixing amount are the same as those described for the first photosensitive resin composition.

The first photosensitive resin composition or the second photosensitive resin composition of the present disclosure is preferably used for forming a partition.

The resin film of the present disclosure is obtained from the first photosensitive resin composition or the second photosensitive resin composition. The resin film of the present disclosure can be produced by forming the first photosensitive resin composition or the second photosensitive resin composition into a film by a known method.

The cured product of the present disclosure is obtained by curing the above resin film. The cured product of the present disclosure includes a film forming step of obtaining a resin film by applying the first or second photosensitive resin composition to a substrate and then heating it, and an exposure step of exposing the resin film to high energy rays. It can be obtained by the manufacturing method of the cured product. The specific operations in the film formation process and exposure process are the same as the method of forming the partition described later. The method for producing the above-mentioned cured product is also one of the present disclosure.

The cured product obtained from the first photosensitive resin composition or the second photosensitive resin composition of the present disclosure has good curability and liquid repellency by containing the above-mentioned resin (E). The cured product of the present disclosure is preferably used as a partition wall, and is particularly preferably used as a partition wall in an organic EL display or quantum dot display.

A partition wall composed of the cured material of the present disclosure is also one of the present disclosure.

Additionally, an organic electroluminescent device including a barrier rib of the present disclosure and a light-emitting layer or wavelength conversion layer disposed in a region defined by the barrier rib is also one of the present disclosure.

In addition, the wavelength conversion layer provided with the barrier rib of the present disclosure is also one of the present disclosure.

Additionally, a display provided with a partition of the present disclosure is also one of the present disclosure.

Next, a method of forming a partition using the first or second photosensitive resin composition of the present disclosure will be described.

The method of forming the partition may include (1) a film forming process, (2) an exposure process, and (3) a developing process.

Each process is explained below.

(1) Film forming process

First, the first photosensitive resin composition or the second photosensitive resin composition of the present disclosure is applied to a substrate and then heated to form a fluorinated resin film.

Heating conditions are not particularly limited, but are preferably 80 to 100°C and 60 to 200 seconds.

Thereby, the solvent etc. contained in the 1st photosensitive resin composition or the 2nd photosensitive resin composition can be removed.

The substrate can be a silicon wafer, metal, glass, ITO substrate, etc.

Additionally, an organic or inorganic film may be provided in advance on the substrate. For example, there may be an antireflection film or a lower layer of a multilayer resist, and a pattern may be formed on it. Additionally, the substrate may be cleaned in advance. For example, it can be cleaned using ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), etc.

As a method for applying the first photosensitive resin composition or the second photosensitive resin composition of the present disclosure to the substrate, a known method such as a spin coater can be used.

(2) Exposure process

Next, the desired photomask is set in the exposure apparatus, and the fluorinated resin film is exposed to high-energy rays through the photomask.

The high-energy ray is preferably at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and α-rays.

The exposure amount of high-energy rays is preferably 1 mJ/cm2 or more and 200 mJ/cm2 or less, and more preferably 10 mJ/cm2 or more and 100 mJ/cm2 or less.

(3) Development process

Next, the fluorinated resin film after the exposure process is developed with an aqueous alkaline solution to form a fluorinated resin pattern film.

That is, either the exposed portion of the fluorinated resin film or the unexposed portion of the film is dissolved in an aqueous alkaline solution to form a fluorinated resin pattern film.

As an aqueous alkaline solution, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), etc. can be used.

When the aqueous alkaline solution is an aqueous solution of tetramethylammonium hydroxide (TMAH), the concentration is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 2% by mass or more and 3% by mass or less.

As the development method, a known method can be used, and examples include the dip method, paddle method, and spray method.

The development time (the time the developer is in contact with the fluorinated resin film) is preferably 10 seconds or more and 3 minutes or less, and more preferably 30 seconds or more and 2 minutes or less.

After development, if necessary, a step of cleaning the fluorinated resin pattern film using deionized water or the like may be provided. Regarding the cleaning method and cleaning time, it is preferably 10 seconds or more and 3 minutes or less, and more preferably 30 seconds or more and 2 minutes or less.

The partition wall manufactured in this way can be used as a bank for a display.

The fluorinated resin of the present disclosure has a structural unit having a structure represented by the general formula (1) and a structural unit having a crosslinking site. The fluorinated resin of the present disclosure is a type of resin (E) having a structure represented by general formula (1) and contained in the first or second photosensitive resin composition.

The fluorinated resin of the present disclosure preferably contains a structural unit represented by the above general formula (5) as a structural unit having a crosslinking site.

The fluorinated resin of the present disclosure preferably has a fluorine atom content of 15 to 60 mass%.

In the fluorinated resin of the present disclosure, the content of the structure represented by General Formula (1) is preferably 0.1 mol% or more and less than 50 mol%, assuming the total amount of structural units constituting the resin is 100 mol%.

The fluorinated resin of the present disclosure preferably has a weight average molecular weight of 5,000 or more and 40,000 or less.

The fluorinated resin of the present disclosure is believed to function as a commercial agent that eliminates uneven distribution of each component in the composition by having a structural unit having a structure represented by general formula (1) and a structural unit having a crosslinking site. . For example, by introducing and using the fluorinated resin of the present disclosure into a resin composition, molded articles such as resin films and partitions (banks) with improved localization of each component can be produced. The fluorinated resin of the present disclosure can be particularly suitably used in a composition containing two or more types of resins having a difference in fluorine atom content of 15 to 60% by mass.

Since the fluorinated resin of the present disclosure also functions as a surfactant, it can also be used as a surfactant.

A polymer blend containing the fluorinated resin of the present disclosure is also one of the present disclosure. The type of resin included in the polymer blend together with the fluorinated resin of the present disclosure is not particularly limited, and for example, one or two types of olefin resin, epoxy resin, (meth)acrylic resin, urethane resin, fluorine resin, etc. A combination of the above can be mentioned.

In this specification, the following invention is disclosed.

[1] An ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin (E) having a structure represented by the following general formula (1): A photosensitive resin composition containing 30 to 550 parts by mass of the resin (E), assuming 100 parts by mass of the fluorinated resin (D).

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.)

[2] The photosensitive resin composition according to [1], wherein the resin (E) has a crosslinking site.

[3] A photosensitive product comprising an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin (E) having a structure represented by general formula (1). A photosensitive resin composition, wherein the resin (E) is a resin having a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site.

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.)

[4] The photosensitive resin composition according to [3], which contains 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass.

[5] The photosensitive resin composition described in [3] above, comprising a structural unit having the crosslinking site, and a structural unit represented by the following general formula (5).

(In General Formula (5), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, W ² represents a divalent linking group, -O-, -OC(=O)-, -C(= O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-, and A ² is a divalent linking group. represents a linear alkylene group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group is a hydroxyl group or -OC (=O) It may be substituted by -CH ₃ , and A ³ represents a 2 to 4 valent linking group, a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and the hydrocarbon group Any number of hydrogen atoms in the group may be substituted by hydroxyl group or -OC(=O)-CH 3 , Y ² and ^{Y 3} _represent a divalent linking group, and are each independently -O- or -NH- , n represents an integer from 1 to 3, and r represents 0 or 1.)

[6] The photosensitive resin composition according to [5], which contains 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass.

[7] The photosensitive resin composition according to [3] above, wherein the resin (E) is a resin containing a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (5) .

(In General Formula (1-1), Ra each independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched chain having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is Any number of hydrogen atoms are replaced with fluorine atoms. Rc is a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorinated alkyl group (the hydrocarbon group and the fluorinated alkyl group are straight or branched and may include a cyclic structure). Rd is a divalent or trivalent organic group, and the organic group is selected from a straight or branched aliphatic hydrocarbon group that may contain a cyclic structure, an aromatic ring group, or a complex substituent thereof. As the selected group, part or all of the hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group, and t represents 1 or 2. In General Formula (5), R ⁵ and R ⁶ are each independently a hydrogen atom. Or represents a methyl group, and W ² represents a divalent linking group, -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(= O)-OC(=O)-NH- or -C(=O)-NH-, and A ² represents a divalent linking group, linear with 1 to 10 carbon atoms, branched chain with 3 to 10 carbon atoms, or carbon atoms. It represents a 3-10 cyclic alkylene group, any number of hydrogen atoms in the alkylene group may be substituted by hydroxyl group or -OC(=O)-CH ₃ , and A ³ represents a 2-4 valent linking group. , a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group, a hydroxyl group, or -OC(=O)-CH ₃ may be substituted, Y ² and Y ³ represent a divalent linking group, each independently represents -O- or -NH-, n represents an integer of 1 to 3, and r represents 0 or 1. .)

[8] The photosensitive resin composition according to [7], which contains 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass.

[9] The above resin (E) has a structural unit represented by the following general formula (1-1), a structural unit represented by the following general formula (5), and a structural unit represented by the following general formula (6), The photosensitive resin composition according to [3] above, which is a resin containing.

(In General Formula (1-1), Ra each independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched chain having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is Any number of hydrogen atoms are replaced with fluorine atoms. Rc is a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorinated alkyl group (the hydrocarbon group and the fluorinated alkyl group are straight or branched and may include a cyclic structure). Rd is a divalent or trivalent organic group, and the organic group is selected from a straight or branched aliphatic hydrocarbon group that may contain a cyclic structure, an aromatic ring group, or a complex substituent thereof. As the selected group, part or all of the hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group, and t represents 1 or 2. In General Formula (5), R ⁵ and R ⁶ are each independently a hydrogen atom. Or represents a methyl group, and W ² represents a divalent linking group, -O-, -OC(=O)-, -C(=O)-O-, -OC(=O)-NH-, -C(= O)-OC(=O)-NH- or -C(=O)-NH-, and A ² represents a divalent linking group, linear with 1 to 10 carbon atoms, branched chain with 3 to 10 carbon atoms, or carbon atoms. It represents a 3-10 cyclic alkylene group, any number of hydrogen atoms in the alkylene group may be substituted by hydroxyl group or -OC(=O)-CH ₃ , and A ³ represents a 2-4 valent linking group. , a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group, a hydroxyl group, or -OC(=O)-CH ₃ may be substituted, Y ² and Y ³ represent a divalent linking group, each independently represents -O- or -NH-, n represents an integer of 1 to 3, and r represents 0 or 1. In general formula (6), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a linear alkyl group with 1 to 15 carbon atoms, a branched chain with 3 to 15 carbon atoms, or a cyclic alkyl group with 3 to 15 carbon atoms, and the alkyl group Any number of hydrogen atoms in are replaced by fluorine atoms.)

[10] The photosensitive resin composition according to [9], which contains 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass.

[11] The photosensitive resin composition according to any one of [1] to [10], wherein the resin (E) has a fluorine atom content of 15 to 60% by mass.

[12] The photosensitive resin composition according to any one of [1] to [11] above, wherein the content of the alkali-soluble resin (C) relative to the total solid content of the photosensitive resin composition is 10 to 70% by mass.

[13] The photosensitive resin composition according to any one of [1] to [12] above, wherein the content of the fluorinated resin (D) relative to the total solid content of the photosensitive resin composition is 0.01 to 10% by mass.

[14] The photosensitive resin composition according to any one of [1] to [13] above, wherein the content of the resin (E) relative to the total solid content of the photosensitive resin composition is 0.01 to 10% by mass.

[15] The photosensitive resin composition according to any one of [1] to [14] above, wherein the difference in fluorine atom content between the alkali-soluble resin (C) and the fluorinated resin (D) is 15 to 60% by mass.

[16] The content of the structure represented by the general formula (1) contained in the resin (E) is 0.1 mol% or more, 50%, assuming that the total amount of structural units constituting the resin (E) is 100 mol%. The photosensitive resin composition according to any one of [1] to [15] above, which is less than mol%.

[17] The photosensitive resin composition according to any one of [1] to [16] above, wherein the structure represented by the general formula (1) is a hexafluoroisopropanol group.

[18] The photosensitive resin composition according to any one of [1] to [17], wherein the resin (E) has a weight average molecular weight of 5,000 or more and 40,000 or less.

[19] The photosensitive resin composition according to any one of [1] to [18] above, further comprising at least one member selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor.

[20] The photosensitive resin composition according to any one of [1] to [19] above, which is used for forming a partition.

[21] A resin film obtained from the photosensitive resin composition according to any one of [1] to [20] above.

[22] A cured product obtained by curing the resin film described in [21] above.

[23] A partition wall composed of the cured material described in [22] above.

[24] An organic electroluminescent device comprising the partition wall described in [23] above, and a light-emitting layer or wavelength conversion layer disposed in a region defined by the partition wall.

[25] A display provided with the partition described in [23] above.

[26] A method for producing a cured product, comprising the steps of applying the photosensitive resin composition according to any of [1] to [20] above to a substrate and then heating it to obtain a resin film, and exposing the resin film to a high-energy ray. A method for producing a cured product including an exposure process.

[27] A fluorinated resin comprising a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site.

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.)

[28] The fluorinated resin described in [27] above, which contains a structural unit having a crosslinking site and a structural unit represented by the following general formula (5).

(In General Formula (5), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, W ² represents a divalent linking group, -O-, -OC(=O)-, -C(= O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-, and A ² is a divalent linking group. represents a linear alkylene group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group is a hydroxyl group or -OC (=O) It may be substituted by -CH ₃ , and A ³ represents a 2 to 4 valent linking group, a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and the hydrocarbon group Any number of hydrogen atoms in the group may be substituted by hydroxyl group or -OC(=O)-CH 3 , Y ² and ^{Y 3} _represent a divalent linking group, and are each independently -O- or -NH- , n represents an integer from 1 to 3, and r represents 0 or 1.)

[29] The fluorinated resin according to [27] or [28] above, wherein the fluorine atom content is 15 to 60% by mass.

[30] The above [27] to [29] in which the content of the structure represented by the general formula (1) is 0.1 mol% or more and less than 50 mol%, assuming that the total amount of structural units constituting the resin is 100 mol%. The fluorinated resin according to any of the above.

[31] The fluorinated resin according to any of [27] to [30] above, wherein the weight average molecular weight is 5,000 or more and 40,000 or less.

[32] A polymer blend containing the fluorinated resin according to any of [27] to [31] above.

[Example]

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited to these examples.

[Measurement of molar ratio of each constituent unit of polymer]

The molar ratio of each structural unit in the polymer was determined from the measured values of ¹ H-NMR, ¹⁹ F-NMR, or ¹³ C-NMR.

[Measurement of molecular weight of polymer]

The weight average molecular weight (Mw) and molecular weight dispersion (ratio of number average molecular weight (Mn) and weight average molecular weight (Mw); Mw/Mn) of the polymer can be measured using high-speed gel permeation chromatography (hereinafter sometimes referred to as GPC). Measurement was performed using a Tosoh Co., Ltd. model (HLC-8320GPC), connecting one ALPHA-M column and an ALPHA-2500 column (both manufactured by Tosoh Co., Ltd.) in series, and using tetrahydrofuran (THF) as a developing solvent. did. A refractive index difference measurement detector was used as the detector.

1. Synthesis of fluorinated resin (D) (liquid repellent)

[Synthesis of liquid release agent precursor 1]

In a 500 ml glass flask equipped with a stirrer, 2.7 g (hereinafter referred to as BTFBE) of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd.) at room temperature (about 20°C). 0.014 mol), 4-acetoxystyrene (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St), 2.3 g (0.014 mol), 2-(perfluorohexyl)ethyl methacrylate (Tokyo) 18.2 g (0.042 mol) of Kasei Kogyo Co., Ltd. (hereinafter referred to as MA-C6F) and 3.9 g (0.03 mol) of hydroxyethyl methacrylate (product of Tokyo Kasei Kogyo Co., Ltd., hereinafter referred to as HEMA). ), 47.2 g of methyl ethyl ketone (hereinafter referred to as MEK) was collected, and 0.84 g (0.005 mol) of azobis(2-methylbutyronitrile) (manufactured by Tokyo Kasei Industry Co., Ltd., hereinafter referred to as AIBN). ) was added, and after degassing with stirring, the inside of the flask was replaced with nitrogen gas, the temperature was raised to an internal temperature of 79°C, and the reaction was allowed to occur overnight. When 200 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 24.0 g of liquid repellent precursor 1 as a white solid with a yield of 89%.

< NMR measurement results >

The composition ratio of each structural unit of liquid repellent precursor 1 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C6F: structural unit by HEMA = 14:14: It was 42:30.

< GPC measurement results >

Mw=9,200, Mw/Mn=1.5

[Synthesis of liquid repellent 1]

In a 500 ml glass flask equipped with a stirrer, 20 g of liquid repellent precursor 1 (hydroxyl equivalent weight 0.03 mol), 0.21 g triethylamine (hydroxyl equivalent weight 0.0021 mol), and propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) 60 g, 4.26 g (hydroxyl equivalent weight 0.030 mol) of 2-isocyanatoethyl acrylate (manufactured by Showa Denko Co., Ltd., product name: Karenz AOI) was added, and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 21.6 g of liquid repellent 1 as a white solid with a yield of 90%.

< ¹³ C-NMR measurement results >

In liquid repellent 1, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, the composition ratio of each structural unit (BTFBE structural unit, p-AcO-St structural unit, MA-C6F structural unit) that does not react with the crosslinking site is unchanged from the liquid repellent precursor 1 used ( It was confirmed that it was the same as before the introduction of the cross-linker. From the structural units, the fluorine atom content in liquid repellent 1 was 38.6% by mass.

< GPC measurement results >

Mw=13,100, Mw/Mn=1.7

[Synthesis of liquid release agent precursor 2]

In a 300 ml glass flask equipped with a stirrer, at room temperature (about 20°C), 3.8 g (0.02 mol) of BTFBE, 3.2 g (0.02 mol) of p-AcO-St, and 2-(perfluorobutyl)ethyl methacrylate ( 16.6 g (0.05 mol) of Tokyo Kasei Kogyo Co., Ltd. (hereinafter referred to as MA-C4F), 5.2 g (0.04 mol) of HEMA (Tokyo Kasei Kogyo Co., Ltd.), 60 g of MEK, and AIBN were collected. After adding 0.84 g (0.005 mol) and degassing with stirring, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 79°C, and the reaction was allowed to occur overnight. When 250 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 26.0 g of liquid repellent precursor 2 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of liquid repellent precursor 2 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C4F: structural unit by HEMA = 15:16: It was 38:31.

< GPC measurement results >

Mw=9,200, Mw/Mn=1.4

[Synthesis of liquid repellent 2]

In a 100 ml glass flask equipped with a stirrer, 26 g of liquid repellent precursor 2 (hydroxyl equivalent 0.038 mol), 0.21 g of triethylamine (hydroxyl equivalent 0.0021 mol), and 20 g of PGMEA were collected, and 5.4 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.038 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 100 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 26.7 g of liquid repellent 2 as a white solid with a yield of 85%.

< ¹³ C-NMR measurement results >

In liquid repellent 2, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, the composition ratio of each structural unit (BTFBE structural unit, p-AcO-St structural unit, MA-C4F structural unit) that does not react with the crosslinking site is unchanged from the liquid repellent precursor 2 used ( It was confirmed that it was the same as before the introduction of the cross-linker. From the structural units, the fluorine atom content in liquid repellent 2 was 31.6% by mass.

< GPC measurement results >

Mw=13,100, Mw/Mn=1.5

[Synthesis of liquid release agent precursor 3]

In a 500 ml glass flask equipped with a stirrer at room temperature (about 20°C), 25.9 g (0.06 mol) of MA-C6F, 5.2 g (0.04 mol) of HEMA (manufactured by Tokyo Chemical Industry Co., Ltd.), and 62 g of MEK were collected. After adding 0.84 g (0.005 mol) of AIBN and degassing with stirring, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 79°C, and the reaction was allowed to occur overnight. When 250 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 28 g of liquid repellent precursor 3 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of liquid repellent precursor 3 was expressed in mole ratio, and the structural unit by MA-C6F: structural unit by HEMA = 60:40.

< GPC measurement results >

Mw=10,800, Mw/Mn=1.6

[Synthesis of liquid repellent 3]

In a 500 ml glass flask equipped with a stirrer, 28 g of liquid repellent precursor 3 (hydroxyl equivalent 0.05 mol), 0.45 g of triethylamine (hydroxyl equivalent 0.0045 mol), and 60 g of PGMEA were collected, and 7.1 g of Karenz AOI (hydroxyl equivalent) was collected. Equivalent of 0.050 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 30 g of liquid repellent 3 as a white solid with a yield of 85%.

< ¹³ C-NMR measurement results >

In liquid repellent 3, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, it was confirmed that the composition ratio of each structural unit (unit of MA-C6F) that does not react with the crosslinking site did not change from the liquid repellent precursor 3 used (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in liquid repellent 3 was 40.6% by mass.

< GPC measurement results >

Mw=14,300, Mw/Mn=1.7

[Liquid remover 4]

“RS-72A” manufactured by DIC (fluorine atom content 8% by mass)

[Liquid remover 5]

“Ftergent 601ADH2” manufactured by Neos (fluorine atom content 19% by mass)

2. Synthesis of Resin (E)

[Synthesis of fluororesin precursor 1]

In a 500 ml glass flask equipped with a stirrer, at room temperature (about 20°C), 2.9 g (0.015 mol) of BTFBE, 2.4 g (0.015 mol) of p-AcO-St, 13.0 g (0.03 mol) of MA-C6F, and HEMA were added. 3.9 g (0.03 mol), methacrylic acid-5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl (Central Glass Co., Ltd., hereinafter referred to as MA- 3.0 g (0.01 mol) of (denoted as BTHB-OH) and 50.0 g of MEK were collected, 0.84 g (0.005 mol) of AIBN was added, and after degassing with stirring, the inside of the flask was replaced with nitrogen gas, and the internal temperature was adjusted to The temperature was raised to 79°C and reaction was performed overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 22.6 g of fluororesin precursor 1 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of fluororesin precursor 1 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C6F: structural unit by HEMA: MA-BTHB- The structural unit by OH was 15:15:30:30:10. From the structural units, the fluorine atom content in the fluororesin precursor 1 was 40.9% by mass.

< GPC measurement results >

Mw=7,800, Mw/Mn=1.4

[Synthesis of fluororesin 1]

In a 500 ml glass flask equipped with a stirrer, 22 g of fluororesin precursor 1 (hydroxyl equivalent 0.03 mol), 0.21 g of triethylamine (hydroxyl equivalent 0.0021 mol), and 60 g of PGMEA were collected, and 4.26 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.03 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 22.3 g of fluororesin 1 as a white solid with a yield of 85%.

< ¹³ C-NMR measurement results >

In fluororesin 1, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, the composition ratio of each structural unit (unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C6F, structural unit by MA-BTHB-OH) that does not react with the crosslinking site is, It was confirmed that there was no change from the fluororesin precursor 1 used (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in fluororesin 1 was 35.2% by mass.

< GPC measurement results >

Mw=10,100, Mw/Mn=1.5

[Synthesis of fluororesin precursor 2]

In a 500 ml glass flask equipped with a stirrer, at room temperature (about 20°C), 2.9 g (0.015 mol) of BTFBE, 2.4 g (0.015 mol) of p-AcO-St, 10.0 g (0.03 mol) of MA-C4F, and HEMA were added. 3.9 g (0.03 mol), 3.0 g (0.01 mol) of MA-BTHB-OH, and 44.0 g of MEK were collected, 0.84 g (0.005 mol) of AIBN was added, and after degassing with stirring, the inside of the flask was filled with nitrogen gas. , the temperature was raised to 79°C, and the reaction was allowed to occur overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered off and dried under reduced pressure at a temperature of 45°C to obtain 20.1 g of fluororesin precursor 2 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of the fluororesin precursor 2 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C4F: structural unit by HEMA: MA-BTHB- The structural unit by OH was 15:15:30:30:10. From the structural units, the fluorine atom content in the fluororesin precursor 2 was 36.1% by mass.

< GPC measurement results >

Mw=7,700, Mw/Mn=1.4

[Synthesis of fluororesin 2]

In a 500 ml glass flask equipped with a stirrer, 20 g of fluororesin precursor 2 (hydroxyl equivalent 0.03 mol), 0.21 g of triethylamine (hydroxyl equivalent 0.0021 mol), and 60 g of PGMEA were collected, and 4.26 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.03 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 21.3 g of fluororesin 2 as a white solid with a yield of 87%.

< ¹³ C-NMR measurement results >

In fluororesin 2, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate), expressed in mol ratio, were 98:2. In addition, the composition ratio of each structural unit (unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C4F, structural unit by MA-BTHB-OH) that does not react with the crosslinking site is, It was confirmed that there was no change from the fluororesin precursor 2 used (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in fluororesin 2 was 30.5% by mass.

< GPC measurement results >

Mw=9,100, Mw/Mn=1.4

[Synthesis of fluororesin precursor 3]

In a 500 ml glass flask equipped with a stirrer at room temperature (about 20°C), 7.2 g (0.055 mol) of HEMA, 13.3 g (0.045 mol) of MA-BTHB-OH, and 40.0 g of MEK were collected, and 0.84 g (0.005 mol) of AIBN. mol), and after degassing with stirring, the inside of the flask was replaced with nitrogen gas, the temperature was raised to 79°C, and the reaction was allowed to occur overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered off and dried under reduced pressure at a temperature of 45°C to obtain 18.1 g of fluororesin precursor 3 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of the fluororesin precursor 3 was expressed in mol ratio, and was: structural unit by HEMA: structural unit by MA-BTHB-OH = 55:45. From the structural units, the fluorine atom content in the fluororesin precursor 3 was 25.1% by mass.

< GPC measurement results >

Mw=6,700, Mw/Mn=1.3

[Synthesis of fluororesin 3]

In a 500 ml glass flask equipped with a stirrer, 18 g of fluororesin precursor 3 (hydroxyl equivalent 0.055 mol), 0.30 g of triethylamine (hydroxyl equivalent 0.0050 mol), and 60 g of PGMEA were collected, and 7.42 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.055 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 21 g of fluororesin 3 as a white solid with a yield of 84%.

< ¹³ C-NMR measurement results >

In fluororesin 3, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 98:2. In addition, it was confirmed that the composition ratio of each structural unit (unit of MA-BTHB-OH) that does not react with the crosslinking site did not change from the used fluororesin precursor 3 (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in fluororesin 3 was 18.4% by mass.

< GPC measurement results >

Mw=8,100, Mw/Mn=1.4

[Fluororesin 4]

The above fluororesin precursor 1 was called fluororesin 4. From the structural units, the fluorine atom content in fluororesin 4 (fluororesin precursor 1) was 40.9% by mass.

[Fluororesin 5]

The above fluororesin precursor 2 was referred to as fluororesin 5. From the structural units, the fluorine atom content in fluororesin 5 (fluororesin precursor 2) was 36.1% by mass.

[Synthesis of fluororesin precursor 6]

In a 500 ml glass flask equipped with a stirrer, at room temperature (about 20°C), 1.0 g (0.005 mol) of BTFBE, 8.0 g (0.015 mol) of p-AcO-St, 4.3 g (0.01 mol) of MA-C6F, and HEMA were added. 3.9 g (0.03 mol), 1.5 g (0.005 mol) of MA-BTHB-OH, and 50.0 g of MEK were collected, 0.84 g (0.005 mol) of AIBN was added, and after degassing with stirring, the inside of the flask was poured into nitrogen gas. was substituted, the temperature was raised to an internal temperature of 79°C, and the reaction was allowed to occur overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 16.06 g of fluororesin precursor 6 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of the fluororesin precursor 6 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C6F: structural unit by HEMA: MA-BTHB- The structural unit by OH was 5:50:10:30:5. From the structural units, the fluorine atom content in the fluororesin precursor 6 was 19.3% by mass.

< GPC measurement results >

Mw=8,900, Mw/Mn=1.5

[Synthesis of fluororesin 6]

In a 500 ml glass flask equipped with a stirrer, 11 g of fluororesin precursor 6 (hydroxyl equivalent 0.015 mol), 0.11 g of triethylamine (hydroxyl equivalent 0.001 mol), and 60 g of PGMEA were collected, and 2.13 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.015 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 11.2 g of fluororesin 6 as a white solid with a yield of 90%.

< ¹³ C-NMR measurement results >

In fluororesin 6, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, the composition ratio of each structural unit (unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C6F, structural unit by MA-BTHB-OH) that does not react with the crosslinking site is, It was confirmed that there was no change from the fluororesin precursor 6 used (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in fluororesin 6 was 14.4% by mass.

< GPC measurement results >

Mw=10,500, Mw/Mn=1.5

[Synthesis of fluororesin precursor 7]

In a 500 ml glass flask equipped with a stirrer, at room temperature (about 20°C), 2.0 g (0.010 mol) of BTFBE, 0.5 g (0.003 mol) of p-AcO-St, 34.5 g (0.079 mol) of MA-C6F, and HEMA were added. 0.39 g (0.003 mol), 1.5 g (0.005 mol) of MA-BTHB-OH, and 100.0 g of MEK were collected, 0.84 g (0.005 mol) of AIBN was added, and after degassing with stirring, the inside of the flask was filled with nitrogen gas. was substituted, the temperature was raised to an internal temperature of 79°C, and the reaction was allowed to occur overnight. When 500 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 35.2 g of fluororesin precursor 7 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of the fluororesin precursor 7 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C6F: structural unit by HEMA: MA-BTHB- Constituent unit by OH = 10:3:79:3:5. From the structural units, the fluorine atom content in the fluororesin precursor 7 was 56.1% by mass.

< GPC measurement results >

Mw=8,800, Mw/Mn=1.5

[Synthesis of fluororesin 7]

In a 500 ml glass flask equipped with a stirrer, 30 g of fluororesin precursor 7 (hydroxyl equivalent 0.003 mol), 0.21 g of triethylamine (hydroxyl equivalent 0.00021 mol), and 100 g of PGMEA were collected, and 0.42 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.03 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 500 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 28.5 g of fluororesin 7 as a white solid with a yield of 95%.

< ¹³ C-NMR measurement results >

In fluororesin 7, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, the composition ratio of each structural unit (unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C6F, structural unit by MA-BTHB-OH) that does not react with the crosslinking site is, It was confirmed that there was no change from the used fluororesin precursor 7 (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in fluororesin 7 was 55.2% by mass.

< GPC measurement results >

Mw=9,100, Mw/Mn=1.5

[Synthesis of fluororesin precursor 8]

In a 500 ml glass flask equipped with a stirrer, at room temperature (about 20°C), 2.9 g (0.015 mol) of BTFBE, 2.4 g (0.015 mol) of p-AcO-St, 13.0 g (0.03 mol) of MA-C6F, and HEMA were added. 3.9 g (0.03 mol), 3.0 g (0.01 mol) of MA-BTHB-OH, and 100.0 g of MEK were collected, 3.41 g (0.020 mol) of AIBN was added, and after degassing with stirring, the inside of the flask was filled with nitrogen gas. was substituted, the temperature was raised to an internal temperature of 81°C, and the reaction was allowed to occur overnight. When 400 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 20.1 g of fluororesin precursor 8 as a white solid with a yield of 80%.

< NMR measurement results >

The composition ratio of each structural unit of the fluororesin precursor 8 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C6F: structural unit by HEMA: MA-BTHB- The structural unit by OH was 15:15:30:30:10. From the structural units, the fluorine atom content in the fluororesin precursor 8 was 40.9% by mass.

< GPC measurement results >

Mw=4,100, Mw/Mn=1.3

[Synthesis of fluororesin 8]

In a 500 ml glass flask equipped with a stirrer, 11 g of fluororesin precursor 8 (hydroxyl equivalent 0.03 mol), 0.11 g of triethylamine (hydroxyl equivalent 0.0021 mol), and 30 g of PGMEA were collected, and 2.13 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.03 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 11.2 g of fluororesin 8 as a white solid with a yield of 85%.

< ¹³ C-NMR measurement results >

In fluororesin 8, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, the composition ratio of each structural unit (unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C6F, structural unit by MA-BTHB-OH) that does not react with the crosslinking site is, It was confirmed that there was no change from the used fluororesin precursor 8 (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in fluororesin 8 was 35.2% by mass.

< GPC measurement results >

Mw=4,500, Mw/Mn=1.4

[Synthesis of fluororesin precursor 9]

In a 500 ml glass flask equipped with a stirrer, at room temperature (about 20°C), 2.9 g (0.015 mol) of BTFBE, 2.4 g (0.015 mol) of p-AcO-St, 13.0 g (0.03 mol) of MA-C6F, and HEMA were added. 3.9 g (0.03 mol), 3.0 g (0.01 mol) of MA-BTHB-OH, and 40.0 g of MEK were collected, 0.21 g (0.00125 mol) of AIBN was added, and after degassing with stirring, the inside of the flask was filled with nitrogen gas. was substituted, the temperature was raised to 70°C, and the reaction was allowed to occur overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was separated by filtration and dried under reduced pressure at a temperature of 45°C to obtain 22.1 g of fluororesin precursor 9 as a white solid with a yield of 90%.

< NMR measurement results >

The composition ratio of each structural unit of the fluororesin precursor 9 is expressed in mol ratio, structural unit by BTFBE: structural unit by p-AcO-St: structural unit by MA-C6F: structural unit by HEMA: MA-BTHB- The structural unit by OH was 15:15:30:30:10. From the structural units, the fluorine atom content in the fluororesin precursor 9 was 40.9% by mass.

< GPC measurement results >

Mw=38,200, Mw/Mn=1.8

[Synthesis of fluororesin 9]

In a 500 ml glass flask equipped with a stirrer, 22 g of fluororesin precursor 9 (hydroxyl equivalent 0.03 mol), 0.21 g of triethylamine (hydroxyl equivalent 0.0021 mol), and 60 g of PGMEA were collected, and 4.26 g of Karen's AOI (hydroxyl equivalent) was collected. Equivalent of 0.03 mol) was added and reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, 200 g of n-heptane was added, and the precipitate was deposited. This precipitate was separated by filtration and dried under reduced pressure at 40°C to obtain 21.1 g of fluororesin 9 as a white solid with a yield of 80%.

< ¹³ C-NMR measurement results >

In fluororesin 9, the amount of acrylic acid derivative derived from Karen's AOI introduced (reaction rate) and the amount of residual hydroxyl group (unreacted rate) expressed in mol ratio were 99:1. In addition, the composition ratio of each structural unit (unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C6F, structural unit by MA-BTHB-OH) that does not react with the crosslinking site is, It was confirmed that there was no change from the used fluororesin precursor 9 (same as before introduction of the crosslinking group). From the structural units, the fluorine atom content in fluororesin 9 was 35.2% by mass.

< GPC measurement results >

Mw=45,300, Mw/Mn=1.9

3. Preparation of photosensitive resin composition

Below, each component used in preparation of the photosensitive resin composition of Examples and Comparative Examples is shown.

<Ethylenically unsaturated compound (A)>

Ethylenically unsaturated compound: “DPHA” (dipentaerythritol hexaacrylate) manufactured by Nihon Kayaku Co., Ltd.

< Photopolymerization initiator (B) >

Light polymerization initiator 1: “Irgacure OXE-01” manufactured by BASF

Light polymerization initiator 2: “DETXs” (2,4-diethylthioxanthone) manufactured by Nihon Kayaku Co., Ltd.

Light polymerization initiator 3: “Irgacure OXE-04” manufactured by BASF

<Alkali-soluble resin (C)>

Alkali-soluble resin: “ZAR-2050H” manufactured by Nihon Kayaku Co., Ltd. (special BIS-A type epoxy acrylate, does not contain fluorine atoms)

< Additives >

Adhesive: “KAYAMER PM-21” manufactured by Nihon Kayakusa.

< Chain transfer system >

Chain transfer agent: “Carens MT-PE1” manufactured by Showa Denko Co., Ltd.

[Preparation of photosensitive resin basic composition liquid]

2.0 parts by mass of Karen's MT-PE1 as a chain transfer agent, 27.0 parts by mass of DPHA as an ethylenically unsaturated compound (A), 18.0 parts by mass of ZAR-2050H as an alkali-soluble resin (C), and 1.0 parts by mass of PM-21 as an adhesive. A photosensitive resin base composition liquid was prepared by mixing 50 parts by mass of PGMEA as a solvent and filtering the resulting solution through a 0.2 µm membrane filter.

[Preparation of photosensitive resin composition]

The photosensitive resin base composition liquid and each of the above-mentioned components were added so that the ratios of the photosensitive resin base composition liquid and other materials were the values shown in Tables 1 to 4, and stirred and dissolved to produce Examples 1 to 26 and Comparative Examples 1 to 16. A photosensitive resin composition was prepared. Evaluation was performed by the method described later using the obtained photosensitive resin composition.

4. Amount of fluorine content on the surface

Coating films were produced using the photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 16, and the amount of fluorine component on the surface of the coating film was calculated, evaluated, and compared. The results are shown in Tables 1 and 2.

[Formation of coating film]

An alkali-free substrate measuring 10 cm square was washed with ultrapure water and then with acetone, and then UV ozone treatment was performed on the substrate for 5 minutes using a UV ozone treatment device. Next, the photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 16 were applied to the obtained UV ozone-treated substrate using a spin coater at a rotation speed of 1,000 rpm, and applied on a hot plate at 100°C for 150 seconds. By heating, a coating film with a film thickness of 1 μm was produced.

[Evaluation and comparison of fluorine content]

The F1s spectrum of the surface of the coating film was measured using X-ray photoelectron spectroscopy (abbreviated as XPS), and the intensity was compared. XPS measurement was performed using JPS-9000MC manufactured by Japan Electronics. In order to check the unevenness of the coating film, measurements were made at 10 different locations, and the average, maximum value, minimum value, and difference between the maximum and minimum values were shown. The larger the value of the spectrum measured under the described conditions, the more covalent bonds containing fluorine are contained on the film surface. From this, it can be said that a film with a larger measured spectrum contains more fluorine atoms on the film surface than a film with a smaller measured spectrum value.

Peaks derived from fluorine were observed on the surfaces of the coating films of Examples 1 to 26 and Comparative Examples 1 to 16, and the intensity was 1600 to 3300 cps. In Examples 1 to 26 containing fluororesins 1 to 9, the difference between the maximum and minimum values of the fluorine-derived peak observed on the surface of the coating film is 400, and the maximum value is 400 compared to Comparative Examples 1 to 10 and 14 to 16. It was confirmed that the difference between and the minimum value was small. From this, it was found that by including fluorine resins 1 to 9, the amount of fluorine component on the surface of the coating film became more uniform. Comparative Examples 11 to 13, which do not contain a fluorinated resin (D), compared with Examples 1 to 26, Comparative Examples 1 to 10, and Comparative Examples 14 to 16 that contain a fluorinated resin (D), the surface of the coating film The fluorine-derived peak intensity observed in was small. It was found that the fluorine-containing resin (D) influences the amount of fluorine component on the surface of the coating film. Examples 1 to 20 and 23 to 26 using fluororesins 1 to 3 and 6 to 9 having a crosslinking site are compared with Examples 21 and 22 using fluororesin 4 or fluororesin 5 not containing a crosslinking site, The difference between the maximum and minimum values of the fluorine-derived peak observed on the surface of the coating film was smaller.

5. Bank evaluation

[Formation of a bank]

An ITO substrate measuring 10 cm square was washed with ultrapure water and then with acetone, and then UV ozone treatment was performed on the substrate for 5 minutes using the UV ozone treatment device described above. Next, the photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 16 were applied to the obtained UV ozone-treated substrate using a spin coater at a rotation speed of 1,000 rpm, and heated on a hot plate at 80°C for 150 seconds. Thus, a fluorinated resin film and a comparative fluorinated resin film with a film thickness of 1 μm were formed. Using a mask aligner (manufactured by Suss Microtech Co., Ltd.), i-line (wavelength 365 nm) was irradiated to the obtained resin film through a mask with a line and space of 5 μm, and exposure was performed.

The obtained cured film after exposure was subjected to evaluation of developer solubility, bank performance (sensitivity, resolution), and measurement of contact angle.

[Developer solubility]

The cured film after exposure on the ITO substrate was immersed in an alkaline developer at room temperature for 80 seconds, and its solubility in the alkaline developer was evaluated. As the alkaline developer, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) was used. The solubility of the bank was evaluated by measuring the film thickness of the bank after immersion using a contact film thickness meter. The case where the bank was completely dissolved was referred to as “soluble”, and the case where the resist film remained undissolved was referred to as “insoluble.”

[Bank performance (sensitivity, resolution)]

The optimal exposure amount Eop (mJ/cm2) when forming the bank, which is the line and space pattern, was determined and used as an index of sensitivity.

Additionally, the obtained bank pattern was observed with a laser microscope (VX-1100, manufactured by Keyence) (3000x) to evaluate the resolution. The line edge roughness that could not be confirmed was called “good”, the line edge roughness that could not be confirmed was called “good”, and the line edge roughness that was noticeable was called “impossible.”

[Contact angle]

After heating the substrate with the cured film obtained by the above process at 230°C for 60 minutes, the contact angle of the surface of the cured film to water and propylene glycol monomethyl ether acetate (PGMEA) was measured using a contact angle meter (manufactured by Kyowa Interface Chemicals Co., Ltd.) GMs-601) was used to measure at 20 locations on the coating film.

As a result of comparing the developer solubility, bank performance, and contact angle of the banks (cured films) produced from the photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 16, the developer solubility was Mino in all Examples and Comparative Examples. Since the light portion was soluble and the exposed portion was insoluble, the photosensitive resin composition of the present disclosure had excellent curability. Among the bank performances, the sensitivity was 150 to 200 mJ/cm2 in both Examples and Comparative Examples, and the resolution was "positive" or "right". Regarding the resolution of the banks, it was found that Examples 1 to 26 were equivalent or superior to Comparative Examples 1 to 16. Regarding liquid repellency, in Examples 1 to 26 containing fluororesins 1 to 9, the difference between the maximum and minimum contact angles was small.

Example 23, which used fluororesin 6 with a low fluorine atom content, had a slightly smaller contact angle than the other examples.

In Example 24, which used fluororesin 7 with a slightly higher fluorine atom content, slightly line edge roughness was observed (“positive”) compared to the other examples, and the difference between the maximum and minimum contact angles was slightly large.

Example 25, which used fluororesin 8 with a slightly smaller molecular weight, had a slightly smaller contact angle than the other examples.

In Example 26, which used fluororesin 9 with a slightly large molecular weight, line edge roughness was confirmed slightly.

Comparative Examples 11 to 13 not containing the fluorinated resin (D) had a small contact angle compared to Examples 1 to 26, Comparative Examples 1 to 10, and Comparative Examples 14 to 16 containing the fluorinated resin (D). all.

In Comparative Examples 14 and 15, which contained a large content of Resin (E), and Comparative Example 16, which contained a small content of Resin (E), the difference between the maximum and minimum values of the contact angle was large compared to the Examples.

Claims (32)

A photosensitive resin composition comprising an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin (E) having a structure represented by the following general formula (1): as,
A photosensitive resin composition containing 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass.

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.) According to claim 1,
A photosensitive resin composition in which the resin (E) has a crosslinking site. A photosensitive resin composition comprising an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorinated resin (D), and a resin (E) having a structure represented by general formula (1). ,
A photosensitive resin composition in which the resin (E) is a resin having a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site.

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.) According to claim 3,
A photosensitive resin composition containing 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass. According to claim 3,
A photosensitive resin composition comprising, as a structural unit having the crosslinking site, a structural unit represented by the following general formula (5).

(In General Formula (5), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, W ² represents a divalent linking group, -O-, -OC(=O)-, -C(= O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-, and A ² is a divalent linking group. represents a linear alkylene group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group is a hydroxyl group or -OC (=O) It may be substituted by -CH ₃ , and A ³ represents a 2 to 4 valent linking group, a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and the hydrocarbon group Any number of hydrogen atoms in the group may be substituted by hydroxyl group or -OC(=O)-CH 3 , Y ² and ^{Y 3} _represent a divalent linking group, and are each independently -O- or -NH- , n represents an integer from 1 to 3, and r represents 0 or 1.) According to claim 5,
A photosensitive resin composition containing 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass. According to claim 3,
A photosensitive resin composition in which the resin (E) is a resin containing a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (5).

(In General Formula (1-1), Ra is the same as Ra in General Formula (1), and Rc is a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorinated alkyl group (the hydrocarbon group and the fluorinated alkyl group are: represents a group selected from the group consisting of (a straight chain or branched chain and may include a cyclic structure. Rd is a divalent or trivalent organic group, and the organic group is a straight chain or branched chain that may include a cyclic structure) A group selected from an aliphatic hydrocarbon group, an aromatic ring group, or a complex substituent group thereof, and some or all of the hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group. t represents 1 or 2. In the general formula (5) , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a methyl group, W ² represents a divalent linking group, -O-, -OC(=O)-, -C(=O)-O-, - Represents OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A ² represents a divalent linking group, and has 1 to 10 carbon atoms. represents a linear, branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group are substituted by a hydroxyl group or -OC(=O)-CH ₃ May be optional, and A ³ represents a divalent to tetravalent linking group, a linear hydrocarbon group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogens in the hydrocarbon group. It may be substituted by valence, hydroxyl group, or -OC(=O)-CH 3 , Y ² and Y ₃ represent ^a divalent linking group, each independently represents -O- or -NH-, and n is 1 to 1. represents the integer of 3, and r represents 0 or 1.) According to claim 7,
A photosensitive resin composition containing 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass. According to claim 3,
The resin (E) contains a structural unit represented by the following general formula (1-1), a structural unit represented by the following general formula (5), and a structural unit represented by the following general formula (6). A photosensitive resin composition that is a resin.

(In General Formula (1-1), Ra is the same as Ra in General Formula (1), and Rc is a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorinated alkyl group (the hydrocarbon group and the fluorinated alkyl group are: represents a group selected from the group consisting of: a straight chain or branched chain and may include a cyclic structure. Rd is a divalent or trivalent organic group, and the organic group is a straight chain or branched group that may include a cyclic structure. It is a group selected from an aliphatic hydrocarbon group, an aromatic ring group, or a complex substituent group thereof, and some or all of the hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group. t represents 1 or 2. In general formula (5), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, W ² represents a divalent linking group, -O-, -OC(=O)-, -C(=O)-O-, -OC (=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A ² represents a divalent linking group, and has 1 to 10 carbon atoms. It represents a linear, branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, even if any number of hydrogen atoms in the alkylene group are substituted by a hydroxyl group or -OC(=O)-CH ₃ and A ³ represents a 2-4 valent linking group, a linear hydrocarbon group with 1-10 carbon atoms, a branched chain with 3-10 carbon atoms, or a cyclic hydrocarbon group with 3-10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group is , may be substituted with a hydroxyl group or -OC(=O)-CH ₃ , Y ² and Y ³ represent a divalent linking group, each independently represents -O- or -NH-, and n is 1 to 3. represents an integer, and r represents 0 or 1. In general formula (6), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a straight chain having 1 to 15 carbon atoms, a branched chain having 3 to 15 carbon atoms, or a carbon number. Represents a 3 to 15 cyclic alkyl group, and any number of hydrogen atoms in the alkyl group are replaced by fluorine atoms.) According to clause 9,
A photosensitive resin composition containing 30 to 550 parts by mass of the resin (E), assuming that the fluorinated resin (D) is 100 parts by mass. According to claim 1 or 3,
A photosensitive resin composition wherein the resin (E) has a fluorine atom content of 15 to 60% by mass. According to claim 1 or 3,
A photosensitive resin composition wherein the content of the alkali-soluble resin (C) relative to the total solid content of the photosensitive resin composition is 10 to 70% by mass. According to claim 1 or 3,
A photosensitive resin composition wherein the content of the fluorinated resin (D) relative to the total solid content of the photosensitive resin composition is 0.01 to 10% by mass. According to claim 1 or 3,
A photosensitive resin composition wherein the content of the resin (E) relative to the total solid content of the photosensitive resin composition is 0.01 to 10% by mass. According to claim 1 or 3,
A photosensitive resin composition wherein the difference in fluorine atom content between the alkali-soluble resin (C) and the fluorinated resin (D) is 15 to 60% by mass. According to claim 1 or 3,
The content of the structure represented by the general formula (1) contained in the resin (E) is 0.1 mol% or more and less than 50 mol%, assuming that the total amount of structural units constituting the resin (E) is 100 mol%. Photosensitive resin composition. According to claim 1 or 3,
A photosensitive resin composition in which the structure represented by the general formula (1) is a hexafluoroisopropanol group. According to claim 1 or 3,
A photosensitive resin composition wherein the resin (E) has a weight average molecular weight of 5,000 or more and 40,000 or less. According to claim 1 or 3,
A photosensitive resin composition further comprising at least one member selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor. According to claim 1 or 3,
A photosensitive resin composition used for forming a partition. A resin film obtained from the photosensitive resin composition according to claim 1 or 3. A cured product obtained by curing the resin film according to claim 21. A partition comprised of the hardened|cured material of Claim 22. An organic electroluminescent device comprising the barrier rib according to claim 23 and a light emitting layer or wavelength conversion layer disposed in a region defined by the barrier rib. A display comprising the partition wall according to claim 23. As a method for producing a cured product,
A film forming step of obtaining a resin film by applying the photosensitive resin composition according to claim 1 or 3 to a substrate and then heating it;
A method of producing a cured product including an exposure process of exposing the resin film to high-energy rays. A fluorinated resin comprising a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site.

(In General Formula (1), Ra each independently represents a linear alkyl group with 1 to 6 carbon atoms, a branched chain with 3 to 6 carbon atoms, or a cyclic alkyl group with 3 to 6 carbon atoms, or a fluorine atom, and the alkyl group is optional. Several hydrogen atoms are replaced with fluorine atoms.) According to clause 27,
A fluorinated resin comprising, as a structural unit having a crosslinking site, a structural unit represented by the following general formula (5).

(In General Formula (5), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, W ² represents a divalent linking group, -O-, -OC(=O)-, -C(= O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH-, or -C(=O)-NH-, and A ² is a divalent linking group. represents a linear alkylene group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group is a hydroxyl group or -OC (=O) It may be substituted by -CH ₃ , and A ³ represents a 2 to 4 valent linking group, a linear hydrocarbon group with 1 to 10 carbon atoms, a branched chain with 3 to 10 carbon atoms, or a cyclic hydrocarbon group with 3 to 10 carbon atoms, and the hydrocarbon group Any number of hydrogen atoms in the group may be substituted by hydroxyl group or -OC(=O)-CH 3 , Y ² and ^{Y 3} _represent a divalent linking group, and are each independently -O- or -NH- , n represents an integer from 1 to 3, and r represents 0 or 1.) According to clause 27,
A fluorinated resin having a fluorine atom content of 15 to 60 mass%. According to clause 27,
A fluorinated resin in which the content of the structure represented by the general formula (1) is 0.1 mol% or more and less than 50 mol%, assuming that the total amount of structural units constituting the resin is 100 mol%. According to clause 27,
Fluorinated resin with a weight average molecular weight of 5,000 or more and 40,000 or less. A polymer blend comprising the fluorinated resin according to any one of claims 27 to 31.