JP2024028150A - Photosensitive resin composition, resin film, cured product, partition wall, organic electroluminescent element, display, production method of cured product, fluorine-containing resin, and polymer blend - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has good curability and water-repellent property, and a cured product of the same.

SOLUTION: A photosensitive resin composition contains an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D), and a resin (E) having a structure represented by the following general formula (1), wherein when the fluorine-containing resin (D) is 100 pts.mass, 30-550 pts.mass of the resin (E) is contained. (In the general formula (1), Ra each independently represents 1-6C linear, 3-6C branched, or 3-6C cyclic alkyl group or a fluorine atom, and in the alkyl group, an arbitrary number of hydrogen atoms are substituted with a fluorine atom.)

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present disclosure relates to a photosensitive resin composition, a resin film, a cured product, a partition wall, an organic electroluminescent device, a display, a method for producing a cured product, a fluororesin, and a polymer blend.

When manufacturing display elements such as organic EL displays, micro LED displays, and quantum dot displays, an inkjet method is known as a method for forming an organic layer having functions such as light emission. There are several methods for the inkjet method.Specifically, there is a method in which ink is dropped from a nozzle into the recesses of a patterned film formed on a substrate and is solidified, or a method in which ink is solidified between a lyophilic area that is a part that gets wet with ink and ink. As the liquid-repellent part, which is the part that repels liquid, a method may be used in which droplets of ink are dropped onto a patterned film formed in advance on the substrate, and the ink is applied only to the lyophilic part.

In particular, in the former method of solidifying ink dropped from a nozzle into the concave portions of a patterned film, two main methods can be employed to produce a patterned film having such unevenness. One is a photolithography method in which the surface of a photosensitive resist film coated on a substrate is exposed in a pattern to form exposed and unexposed areas, and either area is dissolved and removed using a developer. , the other is an imprint method that uses printing technology.

The convex portions of the patterned film having the formed irregularities are called banks (partition walls), and the banks act as a barrier to prevent the inks from mixing with each other when ink is dropped into the concave portions of the patterned film. In order to enhance this barrier effect, the substrate surface of the patterned film recesses is exposed, and the substrate surface is required to be lyophilic to ink, and the bank top surface is required to be lyophobic to ink. .

As a resin for forming such banks, a fluororesin is used as an ink repellent. Liquid repellency is improved by using a fluororesin.

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

International Publication No. 2021/090836

In order to improve liquid repellency, it is known to add a fluorine-containing resin with a high fluorine atom content to a photosensitive resin composition as a liquid repellent. However, fluororesins with a high fluorine atom content have low compatibility with solvents and compounds that do not contain fluorine, and each component may be unevenly distributed. Cured resin products of such photosensitive resin compositions may suffer from poor curing or poor liquid repellency, and there is room for improvement. An object of the present disclosure is to provide a photosensitive resin composition having good curability and liquid repellency, and a cured product thereof.

As a result of intensive studies by the present inventors, the uneven distribution of the liquid repellent, ethylenically unsaturated compound, alkali-soluble resin, etc. causes partial curing failure, making it difficult to retain the liquid repellent in the cured product. It has been found that it becomes difficult to achieve liquid repellency. Then, they discovered that the above problems can be solved by adding a resin having a specific group, leading to the present disclosure.

Means for solving the above problems include the following embodiments.
The first photosensitive resin composition of the present disclosure comprises an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluororesin (D), and general formula (1). A photosensitive resin composition containing a resin (E) having the structure shown above, containing 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass. .

(In general formula (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. , the above alkyl group has any number of hydrogen atoms substituted with fluorine atoms.)

The second photosensitive resin composition of the present disclosure comprises an ethylenically unsaturated compound (A), a photoinitiator (B), an alkali-soluble resin (C), a fluororesin (D), and general formula (1). A photosensitive resin composition comprising a resin (E) having the structure represented by the above structure, wherein the resin (E) includes a structural unit having a structure represented by general formula (1) and a structural unit having a crosslinking site. It is a resin having the following.

（一般式（１）中、Ｒａは、それぞれ独立に、炭素数１～６の直鎖状、炭素数３～６の分岐鎖状若しくは炭素数３～６の環状のアルキル基又はフッ素原子を表し、前記アルキル基は任意の数の水素原子がフッ素原子に置換されている。）

(In general formula (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. , in the alkyl group, any number of hydrogen atoms are substituted with fluorine atoms.)

The resin film of the present disclosure is obtained from the first photosensitive resin composition or the second photosensitive resin composition.
The cured product of the present disclosure is obtained by curing the resin film described above.
The partition wall of the present disclosure is composed of the above-mentioned cured product.

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

The method for producing a cured product of the present disclosure includes a film forming step of applying the first photosensitive resin composition or the second photosensitive resin composition to a substrate and then heating it to obtain a resin film; and an exposure step of exposing the resin film to high energy rays.

The fluororesin of the present disclosure includes 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 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. , the above alkyl group has any number of hydrogen atoms substituted with fluorine atoms.)

The polymer blend of the present disclosure is characterized by containing the above-mentioned fluororesin.

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

The present disclosure will be described in detail below. The present disclosure is not limited to the following embodiments, and can be implemented as appropriate based on the common knowledge of those skilled in the art without departing from the spirit of the present disclosure.
Note that in this specification, "bank" and "partition wall" are synonymous, and unless otherwise noted, mean a convex portion of a patterned film having concavities and convexities in an inkjet method.

Below, the first photosensitive resin composition among the photosensitive resin compositions of the present disclosure will be explained.
The first photosensitive resin composition of the present disclosure comprises an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluororesin (D), and general formula (1). A photosensitive resin composition containing a resin (E) having the structure shown above, containing 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass. It is characterized by

(In general formula (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. , the above alkyl group has an arbitrary number of hydrogen atoms substituted with fluorine atoms. Here, the arbitrary number is 1 or more.)

The first photosensitive resin composition of the present disclosure solves the problem of uneven distribution of each component by containing the resin (E) having a structure represented by general formula (1), and is a repellent with a high fluorine atom content. Even by using a liquid agent, it is possible to produce a cured product or partition wall with improved liquid repellency and curability. The above-mentioned "liquid repellent" is the fluororesin (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 the ethylenically unsaturated compound (A), curing of the first photosensitive resin composition by light irradiation is promoted, and curing can be performed in a shorter time. Become. As the ethylenically unsaturated compound (A), a compound having two or more ethylenically unsaturated groups can be used. Conjugation-stabilized double bonds, such as the double bond of a benzene ring, do not qualify as ethylenically unsaturated groups. From the viewpoint of improving reactivity, the ethylenically unsaturated compound (A) preferably has an ethylenically unsaturated group at its terminal. The ethylenic saturated compound (A) does not contain a fluorine atom.
Specific examples of the ethylenically unsaturated compound (A) include polyfunctional acrylates (for example, product names manufactured by Shin Nakamura Chemical Co., Ltd.: A-TMM-3, A-TMM-3L, A-TMM-3LM-N). , A-TMPT, AD-TMP), polyethylene glycol diacrylate (for example, Shin Nakamura Chemical Co., Ltd. product name: A-200, A-400, A-600), urethane acrylate (for example, Shin Nakamura Chemical Co., Ltd. product name: A-200, A-400, A-600), Product names manufactured by 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, and the like.

Preferred examples of the polyfunctional acrylate compound are listed below.

Among the above examples, V ₁ has m1 structural units represented by "-OC(CH ₃ )H-CH ₂ --" and a structure represented by "-O-CH ₂ --C(CH ₃ )H-" It has a structure in which n1 units are block copolymerized or randomly copolymerized, and m1+n1=2, 3, 7, 12. V ₂ has m2 constituent units represented by "-OC(CH ₃ )H-CH ₂ -", n2 constituent units indicated by "-O-CH ₂ -C(CH ₃ )H-", It has a block copolymerized or random copolymerized structure, and m2+n2=7.

The content of the ethylenically unsaturated compound (A) is 10 parts by mass or more and 300 parts by mass or less, with the total of the alkali-soluble resin (C), fluororesin (D), and resin (E) described below being 100 parts by mass. The content is preferably 50 parts by mass or more and 200 parts by mass or less. When the content of the ethylenically unsaturated compound (A) is less than 10 parts by mass, a sufficient crosslinking effect tends to be insufficient, and when 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 one that polymerizes a monomer having a polymerizable double bond with high energy rays such as electromagnetic waves or electron beams. There are no particular limitations, and any known photopolymerization initiator can be used.
As the photopolymerization initiator (B), a photoradical initiator or a photoacid initiator can be used, and these may be used alone, or a photoradical initiator and a photoacid initiator may be used in combination. , two or more types of photoradical initiators and/or two or more types of photoacid initiators may be used in combination. Furthermore, by using additives together with a photopolymerization initiator, it is also possible to carry out living polymerization in some cases. Known additives can be used as the additive.

As a photo radical initiator, specifically, an intramolecular cleavage type in which the bonds within the molecule are cleaved by absorption of electromagnetic waves or electron beams to generate radicals, and a hydrogen donor such as a tertiary amine or ether are used in combination. It can be classified as a hydrogen abstraction type that generates radicals by doing so, and either type may be used. Photoradical initiators other than the types listed above can also be used.

Specific examples of the photoradical initiator include benzophenone, acetophenone, diketone, acylphosphine oxide, quinone, acyloin, and thioxanthone.

Specific examples of benzophenone include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone. Examples include. Among these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis(diethylamino)benzophenone are preferred.

Specific examples of acetophenone include acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, -Methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like. Among these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferred.

Specific examples of diketones include 4,4'-dimethoxybenzyl, methyl benzoylformate, and 9,10-phenanthrenequinone. Among these, 4,4'-dimethoxybenzyl and methyl benzoylformate are preferred.

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

Specific examples of quinones include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Among them, camphorquinone and 1,4-naphthoquinone are preferred.

Specific examples of the acyloin type include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Among these, benzoin and benzoin methyl ether are preferred.

Specific examples of thioxanthone include 2,4-diethylthioxanthone.

As the photoradical initiator, benzophenone type, acetophenone type, and diketone type are preferable, and benzophenone type is more preferable.

Among the commercially available photoradical initiators, preferred are those manufactured by BFA Co., Ltd. under the product names: IRGACURE 127, IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE-01, IRGACURE Examples include OXE-04, Darocure 1173, Lucirin TPO, and DETXs manufactured by Nippon Kayaku Co., Ltd. Among them, Irgacure 651 and Irgacure 369 are more preferred.

Photoacid initiators include aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrenium, thioxanthonium, (2,4-cyclopentadien-1-yl)(1- Onium consisting of a pair of at least one cation selected from the group consisting of iron (methylethylbenzene) and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and pentafluorophenylborate. It's salt.
Among these, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and diphenyliodonium hexafluorophosphate are particularly preferred.

Commercially available photoacid initiators include, for example, product names manufactured by Sun-Apro Co., Ltd.: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S, and product names manufactured by Dow Chemical Japan Co., Ltd.: Cylacure Photocuring Initiator UVI-6990, Cylacure Photocuring Initiator UVI-6992, Cylacure Photocuring Initiator UVI-6976, Product name manufactured by ADEKA Co., Ltd.: ADEKA Optomer SP-150, ADEKA Optomer SP-152, ADEKA Optomer SP-170, ADEKA OPTOMER SP-172, ADEKA OPTOMER SP-300, Nippon Soda Co., Ltd. product name: CI-5102, CI-2855, Sanshin Chemical Industry Co., Ltd. product name: SUN-AID SI -60L, SunAid SI-80L, SunAid SI-100L, SunAid SI-110L, SunAid SI-180L, SunAid SI-110, SunAid SI-180, Lamberti product names: Esacure 1064, Esacure 1187, Ciba Specialty -Product name manufactured by Chemicals Co., Ltd.: Irgacure 250, etc.

The content of the photopolymerization initiator (B) in the first photosensitive resin composition of the present disclosure includes the ethylenically unsaturated compound (A), the alkali-soluble resin (C), the fluororesin (D), and the resin (E ) 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, based on 100 parts by mass. When the content of the photopolymerization initiator (B) is less than 0.1 parts by mass, a sufficient crosslinking effect tends to be insufficient, and when 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 the 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 it is preferable that the alkali-soluble resin (C) is a resin that does not contain a fluorine atom. The type of alkali-soluble resin (C) is not particularly limited as long as it is alkali-soluble, but it may be a resin other than the fluororesin (D) described below or the resin (E) having a structure represented by general formula (1). be.
Examples of the alkali-soluble resin (C) include alkali-soluble novolac resins.
Alkali-soluble novolak resins 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, and 3,4-dimethylphenol. , 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl-catechol , pyrogallol, phloroglucinol, thymol, isothymol, and the like. These phenols may be used alone or in combination of two or more.

Specific examples of aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p- Examples include hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, 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 sulfate, and p-toluenesulfonic acid. These acid catalysts may be used alone or in combination of two or more.

Other examples of the alkali-soluble resin (C) include acid-modified epoxy acrylate resins. Commercially available acid-modified epoxy acrylates include, for example, Nippon Kayaku Co., Ltd. product names: 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, ZCR-1569H, etc. can be used.

The weight 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) based on the total solid content of the first photosensitive resin composition of the present disclosure is preferably 10 to 70% by mass. When the content of the alkali-soluble resin (C) exceeds 70% by mass, there is a tendency that the fluororesin (D) described below has insufficient liquid repellency to ink.

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

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

（一般式（２）中、Ｒｂは、それぞれ独立に、炭素数１～６の直鎖状、炭素数３～６の分岐鎖状若しくは炭素数３～６の環状のアルキル基又はフッ素原子を表し、該アルキル基中の任意の数の水素原子がフッ素原子で置換されている。ここで任意の数は１以上である。Ｒ^２は水素原子、炭素数１～６の直鎖状、炭素数３～６の分岐鎖状又は炭素数３～６の環状のアルキル基を表す。）

(In general formula (2), Rb 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. , an arbitrary number of hydrogen atoms in the alkyl group is substituted with a fluorine atom. Here, the arbitrary number is 1 or more. R ² is a hydrogen atom, a linear chain having 1 to 6 carbon atoms, a carbon number Represents a 3-6 branched or cyclic alkyl group having 3-6 carbon atoms.)

（一般式（３）中、Ｒｂは、それぞれ独立に、炭素数１～６の直鎖状、炭素数３～６の分岐鎖状若しくは炭素数３～６の環状のアルキル基又はフッ素原子を表し、該アルキル基中の任意の数の水素原子がフッ素原子で置換されている。ここで任意の数は１以上である。Ｒ^１は、水素原子、フッ素原子又はメチル基を表す。Ｒ^２は水素原子、炭素数１～６の直鎖状、炭素数３～６の分岐鎖状又は炭素数３～６の環状のアルキル基を表す。）

(In general formula (3), Rb 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. , an arbitrary number of hydrogen atoms in the alkyl group are substituted with 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 is Represents a hydrogen atom, 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.)

In general formula (3), R ¹ is preferably a hydrogen atom or a methyl group. Further, R ² is, for example, a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n- Examples include pentyl group, isopentyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Hydrogen atom, methyl group, Ethyl group, n-propyl group, and isopropyl group are preferred, and hydrogen atom and methyl group are more preferred.
Furthermore, Rb in general formula (2) or general formula (3) is a fluorine atom, trifluoromethyl group, difluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-heptafluoroethyl group, Propyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,3-trifluoropropyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, n-nonafluorobutyl group, isononafluorobutyl group group, tert-nonafluorobutyl group is preferred, fluorine atom, trifluoromethyl group, difluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-heptafluoropropyl group, 2,2, A 3,3,3-pentafluoropropyl group, a 3,3,3-trifluoropropyl group, and a hexafluoroisopropyl group are more preferred, and a fluorine atom, a difluoromethyl group, and a trifluoromethyl group are particularly preferred.

The following structures can be exemplified as preferable structural units represented by the general formula (3) contained in the fluororesin (D) in the first photosensitive resin composition of the present disclosure.

The content of the structural unit represented by the general formula (3) in the fluororesin (D) is 5 mol% or more and 70 mol% with respect to 100 mol% of all the structural units constituting the fluororesin (D). The following is preferable, 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.

When the content of the structural unit of general formula (3) is more than 70 mol%, the fluororesin (D) tends to be difficult to dissolve in a solvent. On the other hand, if the content of the structural unit of general formula (3) is less than 5 mol%, the resistance will decrease when the cured product prepared from the first photosensitive resin composition is subjected to UV ozone treatment or oxygen plasma treatment. There is a tendency to

When the fluororesin (D) has a structural unit represented by the 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 fluororesin (D) may include 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-, -O-C(=O) -NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

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

In the general formula (4), A ¹ represents a divalent to tetravalent linking group, which is a linear hydrocarbon having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic hydrocarbon having 3 to 10 carbon atoms. represents a group, and any number of hydrogen atoms in the hydrocarbon group may be substituted with a hydroxyl group 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.

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, 2-substituted cyclopropane, 2-substituted cyclobutane, 2-substituted cyclopentane, 2-substituted cyclohexane, 2-substituted Examples include cycloheptane, 2-substituted cyclooctane, 2-substituted cyclodecane, and 2-substituted 4-tert-butylcyclohexane.

When any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene groups include hydroxyethylene group, 1-hydroxy-n-propylene group, 2-hydroxy-n-propylene group. 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 -) etc. can be mentioned.

In addition, when an arbitrary number of hydrogen atoms in these alkylene groups are substituted with -OC(=O) _-CH3 , the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is used as the substituted alkylene group. Those substituted with -OC(=O)-CH ₃ can be mentioned.

Among them, the divalent linking group ^A1 is a methylene group, ethylene group, propylene group, n-butylene group, isobutylene group, sec-butylene group, cyclohexyl group, 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 -) are preferred, and ethylene group, propylene group , 2-hydroxy-n-propylene group, and hydroxy-isopropylene group (-CH(CH ₂ OH)CH ₂ -) are more preferred, and ethylene group and 2-hydroxy-n-propylene group are particularly preferred.
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, and represents -O- or -NH-, and -O- is more preferable.

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 on the aromatic ring each independently represent the ortho position, the meta position, and the para position, with the para position being preferred.

The following structures can be exemplified as preferable structural units represented by the general formula (4). In addition, although the substitution position of the aromatic ring is exemplified as the para position, the substitution position may be independently the ortho position or the meta position.

The content of the structural unit represented by general formula (4) in the fluororesin (D) is 5 mol% or more and 70 mol% with respect to 100 mol% of all the structural units constituting the fluororesin (D). The following is preferable, 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.

When the content of the structural unit of general formula (4) is more than 70 mol%, the fluororesin (D) tends to be difficult to dissolve in a solvent. On the other hand, if the content of the structural unit of general formula (4) is less than 5 mol %, resistance to UV ozone treatment or oxygen plasma treatment tends to decrease.

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

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

Moreover, in the first photosensitive resin composition of the present disclosure, the fluororesin (D) may include 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-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-. Among these, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- is preferred.

When W ² is -OC(=O)-NH-, the fluorine-containing resin (D) of the present disclosure has better liquid repellency to ink after UV ozone treatment or oxygen plasma treatment. This is one of the preferred embodiments.

In the general formula (5), A ² represents a divalent linking group, and 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. , any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -OC(=O)-CH ₃ .
In the general formula (5), A ³ represents a divalent to tetravalent linking group, which is a straight chain having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic carbonized group having 3 to 10 carbon atoms. It represents a hydrogen group, and any number of hydrogen atoms in the hydrocarbon group may be substituted with a 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, a methylene group, an ethylene group, a propylene group, an n-butylene group, an n- Examples include 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, an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group. , isopentylene group, isohexylene group, etc.

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, 2-substituted cyclopropane, 2-substituted cyclobutane, 2-substituted cyclopentane, 2 Examples include substituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, and disubstituted 4-tert-butylcyclohexane.

When an arbitrary number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene groups include 1-hydroxyethylene group (-CH(OH)CH ₂ -), 2-hydroxyethylene 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 an arbitrary number of hydrogen atoms in these alkylene groups are substituted with -OC(=O) _-CH3 , the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is used as the substituted alkylene group. Those substituted with -OC(=O)-CH ₃ can be mentioned.

Among them, the divalent linking groups A ² and A ³ each independently include a methylene group, an ethylene group, a propylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a cyclohexyl group, and a 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 -) are 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 -) are more Ethylene group, 1-hydroxyethylene group (-CH(OH)CH ₂ -), and 2-hydroxyethylene group (-CH ₂ CH(OH)-) are particularly preferred.
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, each independently representing -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.

As for the structural unit represented by the general formula (5), the following structures can be exemplified as preferable ones.

The content of the structural unit represented by general formula (5) in the fluororesin (D) is 5 mol% or more and 70 mol% with respect to 100 mol% of all the structural units constituting the fluororesin (D). The following is preferable, 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.

When the content of the structural unit of general formula (5) is more than 70 mol%, the fluororesin (D) tends to be difficult to dissolve in a 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 fluororesin (D) to the substrate tends to decrease.

Although the effect of the structural unit represented by the general formula (5) is not clear, the resin film or bank obtained by the fluororesin (D) containing the structural unit represented by the general formula (5) It is inferred that this improves the adhesion to the substrate. However, the effects of the present disclosure are not limited to the effects described here.

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

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

In general formula (6), R ⁷ represents a hydrogen atom or a methyl group.

In the general formula (6), R ⁸ represents a linear alkyl group having 1 to 15 carbon atoms, a branched chain having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms; Several hydrogen atoms are replaced with fluorine atoms, 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, a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or a group having 10 to 14 carbon atoms. Examples include straight-chain alkyl groups in which any number of hydrogen atoms are substituted with fluorine atoms.

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

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

In the 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 preferred that p is an integer of 1 to 2, q is an integer of 2 to 8, and X is a fluorine atom.

The following structures can be exemplified as preferable structural units represented by the general formula (6).

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

When the content of the structural unit of general formula (6) is more than 70 mol %, the fluororesin (D) tends to be difficult to dissolve in a 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 repellency to ink, it is preferable that the fluororesin (D) contains a structural unit represented by the general formula (6).

Further, in the first photosensitive resin composition of the present disclosure, the fluororesin (D) may include a structure represented by the following general formula (7).

In general formula (7), R ¹⁰ represents a hydrogen atom or a methyl group.

In general formula (7), B each independently represents a hydroxyl group, a carboxyl group, -C(=O)-O-R ¹¹ (R ¹¹ is a linear chain having 1 to 15 carbon atoms, a branched chain having 3 to 15 carbon atoms) Represents a chain or cyclic alkyl group having 3 to 15 carbon atoms, 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 -O-C(=O)-R ¹² (R ¹² 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 ). Further, m represents an integer from 0 to 3. Here, the arbitrary number is 1 or more.

As for the structural unit represented by the general formula (7), the following structures can be exemplified as preferable ones.

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, based on 100 mol% of all the structural units constituting the fluororesin (D). It is more preferably 50 mol% or less, and particularly preferably 20 mol% or more and 40 mol% or less.

When the content of the structural unit of general formula (7) is more than 70 mol%, the fluororesin (D) tends to be difficult to dissolve in a 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 fluororesin (D) contains a structural unit represented by the general formula (7) in which B is a hydroxyl group or a carboxyl group.

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

In general formula (8), R ¹³ represents a hydrogen atom or a methyl group.

In the general formula (8), A ⁴ represents a divalent linking group, which is 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 may be substituted with a hydroxyl group 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, a 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, 2-substituted cyclopropane, 2-substituted cyclobutane, 2-substituted cyclopentane, 2-substituted cyclohexane, 2-substituted Examples include cycloheptane, 2-substituted cyclooctane, 2-substituted cyclodecane, and 2-substituted 4-tert-butylcyclohexane.

When an arbitrary number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene groups include 1-hydroxyethylene group (-CH(OH)CH ₂ -), 2-hydroxyethylene 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 an arbitrary number of hydrogen atoms in these alkylene groups are substituted with -OC(=O) _-CH3 , the hydroxyl group of the hydroxyl group-substituted alkylene group exemplified above is used as the substituted alkylene group. Those substituted with -OC(=O)-CH ₃ can be mentioned.

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

In general formula (8), Y ⁴ represents a divalent linking group, and represents -O- or -NH-, and -O- is more preferable.

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 thereof include ethylene oxide group, 1,2-propylene oxide group, and 1,3-propylene oxide group. Among these, an ethylene oxide group is preferred.

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, the structure is such that E ¹ is bonded to the main chain of the structural unit.

As for the structural unit represented by the general formula (8), the following structures can be exemplified as preferable ones.

In general formula (8), when E ¹ is a hydroxyl group or a carboxyl group, the structural unit represented by general formula (8) provides solubility of the fluororesin (D) in an alkaline developer. Therefore, it is preferable that the fluororesin (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 fluororesin (D) may have a crosslinking site. In the present disclosure, "crosslinking site" means a site capable of polymerization reaction with other monomers. Examples of the crosslinking site include a photopolymerizable group, which is preferably introduced into the side chain of the polymer. The fluororesin (D) can be obtained, for example, by polymerizing monomers to obtain a fluororesin precursor having structural units having the structures shown in the above general formulas (3), (6) to (8), and then adding the fluororesin to the fluororesin precursor. By reacting a precursor with a photopolymerizable group derivative, a photopolymerizable group is introduced into the side chain of the polymer, and a polymer having a structural unit having the structure shown in the above general formulas (4) and (5) is produced. Fluororesin (D) can be synthesized.
The photopolymerizable group introduced into the fluororesin precursor is preferably an acrylic group, a methacryl group, a vinyl group, or an allyl group, and more preferably an acrylic group.
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.
Examples of isocyanate monomers having an acrylic group include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl. Examples include isocyanates. Preferably it is 2-isocyanatoethyl acrylate.
Examples of the epoxy monomer having an acrylic group include glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether (4HBAGE, manufactured by Mitsubishi Chemical Corporation), and the like.

A photopolymerizable group is introduced into the fluororesin precursor through an addition reaction between the hydroxyl group of the fluororesin precursor and the photopolymerizable group derivative.
The proportion of photopolymerizable groups in the fluororesin (D) is preferably 10 mol% or more and 70 mol% or less, based on 100 mol% of the total amount of structural units constituting the fluororesin (D). When the fluororesin (D) is formed only from a structural unit having one photopolymerizable group, the content of the photopolymerizable group in the fluororesin (D) is 100 mol%. If the proportion of photopolymerizable groups is less than 10 mol %, the strength of the resin film and partition walls tends to decrease. If the proportion of photopolymerizable groups exceeds 70 mol%, it may become difficult to form a resin film by coating. More preferably it is 15 to 60 mol%.

In the first photosensitive resin composition of the present disclosure, the molecular weight of the fluororesin (D) is a mass average molecular weight measured by high performance gel permeation chromatography (GPC) using polystyrene as a standard substance, and is preferably 1,000. 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, particularly preferably 3,000 or more and 100,000 or less. When the molecular weight is less than 1,000, the strength of the resin film or bank formed tends to decrease, and when the molecular weight is more than 1,000,000, the solubility in solvents is insufficient, making it difficult to form a resin film by coating. It may happen.

The degree of dispersion (Mw/Mn) of the fluororesin (D) is preferably from 1.01 to 5.00, more preferably from 1.01 to 4.00, particularly preferably from 1.01 to 3.00.

The fluororesin (D) may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. . A random copolymer is preferable from the viewpoint of dispersing each characteristic appropriately rather than locally.

Preferred embodiments of the fluororesin (D) in the first photosensitive resin composition of the present disclosure are as follows.
<Aspect 1>
A structural unit represented by the following general formula (3), a structural unit represented by general formula (5), a structural unit represented by general formula (6-1), and a structure represented by general formula (7) Fluororesin containing units (D)
General formula (3): R ¹ and R ² are each independently a hydrogen atom, Rb is each independently a fluorine atom, difluoromethyl group, or trifluoromethyl group General formula (5): R ⁵ and R ⁶ are each independently a hydrogen atom or methyl group, W ² is -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH-, A ² , A ³ is each independently an ethylene group, Y ² and Y ³ are -O-, n is 1, and 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, X is a fluorine atom General formula (7): R ¹⁰ is a hydrogen atom, B is an acetoxy group, a hydroxyl group or carboxyl group, m is 1

<Aspect 2>
A structural unit represented by the following general formula (5), a structural unit represented by general formula (6), a structural unit represented by general formula (6-1), and a structure represented by general formula (8) Fluororesin containing units (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, and r is 1
General formula (6): R ⁷ is a methyl group, 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 from 4 to 8, 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 carboxyl group

<Aspect 3>
Fluororesin (D) containing a structural unit represented by the following general formula (5) and a structural unit represented by 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, and 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, X is a fluorine atom

In the first photosensitive resin composition of the present disclosure, the fluorine atom content of the fluororesin (D) is preferably 20 to 60% by mass, 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 fluorine-containing resin (D) contains fluorine atoms, a resin film or bank having excellent liquid repellency can be obtained.

In this specification, the "fluorine atom content of the resin" refers to the molar ratio of the monomers constituting the resin measured by NMR (nuclear magnetic resonance spectroscopy), the molecular weight of the monomers constituting the resin, and the amount contained in the monomers. It means the value calculated from the fluorine content.
Here, as an example, the content of fluorine atoms when the fluororesin (D) is a resin obtained by polymerizing 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene, and 2-(perfluorohexyl)ethyl methacrylate. Explain how to measure quantities.
(i) First, the fluororesin (D) is subjected to NMR measurement to calculate the ratio of each composition (molar ratio).
(ii) Multiply the molecular weight (Mw) of the monomer of each composition of the fluororesin (D) by the molar ratio, and add the obtained values to determine the total value. The weight percentage (wt%) of each composition is calculated from the total value.
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 a 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) x weight ratio (wt%)" for each component, and add up the obtained values.
(v) Calculate "the numerical value obtained in the above (iv)"/"the total value obtained in the above (ii)" to calculate the fluorine atom content of the fluororesin (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 fluororesin (D) is preferably 15 to 60% by mass, and preferably 20 to 55% by mass. It is more preferable that it is, and even more preferably that it is 25 to 45% by mass. When the difference in fluorine atom content is within the above range, uneven distribution of the alkali-soluble resin (C) and the fluororesin (D) is eliminated.

In the first photosensitive resin composition of the present disclosure, one type or two or more types of fluororesins (D) can be used.
The content of the fluororesin (D) based on the total solid content of the first photosensitive resin composition of the present disclosure is preferably 0.01 to 40% by mass, more preferably 0.01 to 10% by mass. Within this range, the water and oil repellency and adhesion of the resin film to the substrate will be good.

<Resin (E)>
The first photosensitive resin composition of the present disclosure includes a resin (E) having a structure represented by the following general formula (1). Although the resin (E) is a fluororesin, it is a different resin from the above-mentioned fluororesin (D). Resin (E) does not contain a radical generating group. In this specification, a radical-generating group is a group that generates radicals when exposed to light.

In the general formula (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; In the above alkyl group, any number of hydrogen atoms are substituted with fluorine atoms. Here, the arbitrary number is 1 or more.
Examples of linear alkyl groups having 1 to 6 carbon atoms include trifluoromethyl group, difluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 3,3, Examples include 3-trifluoropropyl group and nonafluorobutyl group. Examples of the branched alkyl group having 3 to 6 carbon atoms include heptafluoroisopropyl group, hexafluoroisopropyl group, nonafluoroisobutyl group, nonafluoro-tert-butyl group, and the like. Examples of the cyclic alkyl group having 3 to 6 carbon atoms include a pentafluorocyclopropyl group. Ra is preferably a linear alkyl group having 1 to 6 carbon atoms, more preferably a trifluoromethyl group.
Specific examples of the structure represented by general formula (1) include a difluoromethanol group, a tetrafluoroethanol group, a hexafluoroisopropanol group, a trifluoropropanol group, and a hexafluoroisopropanol group is preferred.

It is preferable that the resin (E) contains a structural unit having a structure represented by general formula (1). The structure represented by general formula (1) is preferably included in the side chain of resin (E). Examples of the structural unit having the structure represented by the 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 is from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorine-containing alkyl group (the hydrocarbon group and the fluorine-containing alkyl group are linear or branched and can include a cyclic structure); Represents the selected group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being particularly preferred. Examples of the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms (the alkyl group may have a linear, branched or cyclic structure), a phenyl group, and a tolyl group, with a methyl group being particularly preferred. Examples of the fluorine-containing alkyl group include fluorine-containing alkyl groups having 1 to 6 carbon atoms, with a trifluoromethyl group being preferred. 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 large-scale production is required. It is particularly preferred because it is easily available.
Rd is a divalent (when t=1) or trivalent (when t=2) organic group, and the organic group is a linear or branched aliphatic group that may include a cyclic structure. A group selected from a hydrocarbon group, an aromatic ring group, or a composite substituent thereof, in which some 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 bonds attached to a benzene ring. "Composite substituent" refers to one in which an aliphatic hydrocarbon unit and an aromatic ring unit are contained in a series or parallel relationship in one Rd. Among these, as Rd, the following functional groups are preferable because they can serve as raw materials for polymers with excellent physical properties (the dotted line in the formula represents a bond).

t represents 1 or 2.
In resin (E), the structure represented by general formula (1) is preferably not directly bonded to an aromatic ring. The structure represented by general formula (1) is preferably directly bonded to a linear, branched, or cyclic alkylene group.

It is preferable that the resin (E) has a crosslinking site. This is because when the resin (E) has a crosslinking site, uneven distribution of each component of the first photosensitive resin composition is further eliminated.
Examples of the crosslinking site include the photopolymerizable groups exemplified as the crosslinking site of the above-mentioned fluororesin (D), and it is preferable that the crosslinking site is introduced into the side chain of the polymer. It is preferable that the resin (E) contains a structural unit represented by the following general formula (5).

The above general formula (5) is the same as that exemplified for the fluororesin (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).

In addition to the structural units represented by the following general formula (1-1) and the structural units represented by the following general formula (5), the resin (E) further contains a structural unit represented by the following general formula (6). It is preferable to include units.

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

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

The content of the structure represented by general formula (1) in the resin (E) is 0.1 mol% or more and less than 50 mol%, based on the total amount of structural units constituting the resin (E) as 100 mol%. It is preferable that When the resin (E) is formed only from structural units having one structure represented by the general formula (1), the content of the structure represented by the general formula (1) in the resin (E) is 100 It is mole%. If the content of the structure represented by general formula (1) is less than 0.1 mol%, the effect of sufficiently dissolving each component in the first photosensitive resin composition of the present disclosure cannot be obtained. There are cases. If it is 50 mol% or more, the liquid repellency may decrease. When the content of the structure represented by general formula (1) is 0.1 mol% or more and less than 50 mol%, sufficient liquid repellency and compatibility can be maintained, and adhesion, heat resistance, and alkali properties can be improved. It is also possible to impart other physical properties such as solubility. More preferably, it is 1 mol% or more and less than 50 mol%.

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) in the resin (E) is 99. It is preferably 9 mol% or less. If the content 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. Furthermore, the content of structural units 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 values of NMR (nuclear magnetic resonance spectroscopy).

It is preferable that the resin (E) 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 uneven distribution of each component may not be sufficiently improved. More preferably, it is 5,000 or more and 40,000 or less, still more preferably 5,000 or more and 30,000 or less.
The dispersity (ratio of weight average molecular weight Mw to 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 1.30. ~3.00 is particularly preferred.
In the present disclosure, the weight average molecular weight and dispersity of the resin (E) are values obtained by high-speed gel permeation chromatography using polystyrene as a standard substance.

The resin (E) preferably has a fluorine atom content of 15 to 60% by mass. When 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. It is more preferably 15 to 40% by weight, and even more preferably 18 to 36% by weight.

Resin (E) can be obtained by polymerizing monomers having a structure represented by general formula (1).
Examples of the monomer having the structure represented by general formula (1) include 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-hexafluoro-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) Examples include isopropyl methacrylate. These monomers can be used alone or in combination of two or more. Preferably methacrylic acid-5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl, 3,5-bis(1,1,1,3,3,3-hex These are fluoro-2-hydroxy-2-propanyl) cyclohexyl methacrylate and 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 monomers in a solvent, adding a polymerization initiator, and reacting by heating if necessary. In this reaction, it is preferable to include a chain transfer agent if necessary. 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 examples include ketones, alcohols, polyhydric alcohols and derivatives thereof, ethers, esters, aromatic solvents, fluorine solvents, and the like. These may be used alone or in combination of two or more.

Specific examples of ketones include acetone, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptyl cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, 2-heptanone, etc. can.
Examples of alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 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-butanol, Examples include lauryl alcohol, hexyldecanol, and oleyl alcohol.

Specific examples of polyhydric alcohols and derivatives thereof 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 monomethyl 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.

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. can be mentioned.
Examples of aromatic solvents include xylene and toluene.

Examples of the fluorine-based solvent include fluorocarbons, fluorocarbon substitutes, perfluoro compounds, hexafluoroisopropyl alcohol, and the like.

Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, azo compounds, and the like. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with reducing agents.

Examples of chain transfer agents include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol; chloroform, carbon tetrachloride, and tetraodor. Examples include alkyl halides such as carbon dioxide.

When the resin (E) has a crosslinking site, there is a method of polymerizing a monomer that introduces a crosslinking site into the side chain of the polymer together with a monomer having a structure represented by general formula (1). Can be mentioned. In addition, similarly to the synthesis of the fluororesin (D) having a crosslinking site, monomers are polymerized to form a structural unit having a structure represented by general formula (1) and a structure represented by general formula (8). Examples include a method in which a photopolymerizable group is introduced into the side chain of the polymer by obtaining a precursor of the resin (E) having the unit and then reacting the precursor of the resin (E) with a photopolymerizable group derivative. It will be done.

The resin (E) may be used alone or in a mixture of two or more.

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. When 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. It is more preferably 0.03 to 5% by weight, and even more preferably 0.03 to 1.0% by weight.

The first photosensitive resin composition of the present disclosure contains 30 to 550 parts by mass of resin (E), preferably 40 to 520 parts by mass, based on 100 parts by mass of fluororesin (D). . When 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>
The first photosensitive resin composition of the present disclosure preferably contains a solvent. The solvent is not particularly limited as long as the fluorine-containing 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 the solvent in the first photosensitive resin composition of the present disclosure is 50 parts by mass or more and 2,000 parts by mass or less, with the total of the alkali-soluble resin (C) and fluororesin (D) being 100 parts by mass. It is preferable that the range is as follows. 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 thickness of the resin film formed can be adjusted, and within the above range, the thickness of the resin film particularly suitable for obtaining banks can be obtained.

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

<Photoradical 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 becomes excited. When the photoradical sensitizer becomes excited, it causes electron transfer, energy transfer, heat generation, etc. when it comes into contact with the photopolymerization initiator, and as a result, the photopolymerization initiator easily decomposes and generates acid. The photoradical sensitizer may have an absorption wavelength in the range of 350 nm to 450 nm, and may include polynuclear aromatics, xanthenes, xanthones, cyanines, merocyanines, thiazines, acridines, acridones, anthraquinones, Mention may be made of squaliums, styryls, base styryls or coumarins.

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

Examples of xanthenes include fluorescein, eosin, erythrosin, rhodamine B, and rose bengal.
Examples of xanthones include xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and 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 acridines include acridine orange, chloroflavin, and acriflavin.
Examples of acridones include acridone and 10-butyl-2-chloroacridone.

As the anthraquinones, anthraquinone can be exemplified.
Examples of squaliums include squalium.
Examples of base styryls include 2-[2-[4-(dimethylamino)phenyl]ethenyl]benzoxazole.

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]quinolidin-11-one can be exemplified.
These photoradical sensitizers may be used alone or in combination of two or more.

As the photoradical sensitizer used in the first photosensitive resin composition of the present disclosure, polynuclear aromatics, acridones, styryls, base styryls, Coumarins or xanthones, particularly preferably xanthones. Among the xanthones, diethylthioxanthone and isopropylthioxanthone are preferred.

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 fluororesin (D). By setting the content of the photoradical sensitizer within the above range, the exposure sensitivity of the photosensitive resin composition is improved and the pattern forming film after exposing the first photosensitive resin composition of the present disclosure is repelled. The boundary between the liquid region and the lyophilic region becomes clear, the contrast of the ink pattern after ink application improves, and a precise pattern can be obtained.

<Chain transfer agent>
It is preferable that the first photosensitive resin composition of the present disclosure uses a chain transfer agent as necessary.
Examples of the chain transfer agent include the same compounds that can be used in the synthesis of the resin (E) described above.

<Ultraviolet absorber>
It is preferable that the first photosensitive resin composition of the present disclosure uses an ultraviolet absorber if necessary, and examples of the ultraviolet absorber include salicylic acid-based, benzophenone-based, triazole-based, and the like.
The content of the ultraviolet absorber in the first photosensitive resin composition is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass.

<Polymerization inhibitor>
Polymerization inhibitors used in the first photosensitive resin composition of the present disclosure are not particularly limited, but include 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, tetraethylthiuram disulfide, 1,1-diphenyl-2-picri Examples include hydrazyl and 1,1-diphenyl-2-picrylhydrazine.

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

The content ratio of the polymerization inhibitor in the total solid content of 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 0.01 to 5% by mass. % by weight is particularly preferred. When the content ratio is within the above range, development residues of the photosensitive resin composition are reduced and pattern linearity is good.

The first photosensitive resin composition of the present disclosure may contain other additives as necessary. 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 ones.

Next, a second photosensitive resin composition among the photosensitive resin compositions of the present disclosure will be explained. Regarding the second photosensitive resin composition, only the points different from the first photosensitive resin composition will be explained.
The second photosensitive resin composition of the present disclosure comprises an ethylenically unsaturated compound (A), a photoinitiator (B), an alkali-soluble resin (C), a fluororesin (D), and general formula (1). A photosensitive resin composition comprising a resin (E) having the structure represented by the above structure, wherein the resin (E) has a structural unit having the structure represented by the above general formula (1) and a crosslinking site. It is a resin having units.
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 fluororesin (D).
Used in the ethylenically unsaturated compound (A), photoinitiator (B), alkali-soluble resin (C), fluororesin (D), resin (E), and others contained in the second photosensitive resin composition The specific types and amounts of compounds that can be used 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 partition walls.

The resin film of the present disclosure is obtained from the first photosensitive resin composition or the second photosensitive resin composition described above. 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 applying the first photosensitive resin composition or the second photosensitive resin composition to a substrate and then heating it to obtain a resin film; The cured product can be obtained by a method for producing a cured product including an exposure step of exposing to high energy rays. The specific operations in the film forming process and the exposure process are the same as the method for forming partition walls, which will be described later. The method for producing the cured product described above is also part 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 resin (E). There is. The cured product of the present disclosure is preferably used as a partition, and particularly preferably used as a partition in an organic EL display, a quantum dot display, or the like.
A partition wall made of the cured product of the present disclosure is also an aspect of the present disclosure.
The present disclosure also includes an organic electroluminescent element including the partition wall of the present disclosure and a light-emitting layer or a wavelength conversion layer disposed in a region defined by the partition wall.
Moreover, a wavelength conversion layer provided with the partition wall of the present disclosure is also one of the present disclosure.
Furthermore, a display including the partition wall of the present disclosure is also one of the present disclosure.

Next, a method of forming partition walls using the first photosensitive resin composition or the second photosensitive resin composition of the present disclosure will be described.
The method for forming the partition wall may include (1) a film formation process, (2) an exposure process, and (3) a development process.
Each step will be explained below.

(1) Film forming step: 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 the first photosensitive resin composition. Alternatively, the second photosensitive resin composition is made into a fluororesin film.
Heating conditions are not particularly limited, but are preferably 80 to 100°C and 60 to 200 seconds.
Thereby, the solvent and the like contained in the first photosensitive resin composition or the second photosensitive resin composition can be removed.

As the substrate, a silicon wafer, metal, glass, ITO substrate, etc. can be used.
Further, an organic or inorganic film may be provided on the substrate in advance. For example, there may be an anti-reflection coating, an underlayer of multilayer resist, and a pattern may be formed thereon. Alternatively, the substrate may be cleaned in advance. For example, cleaning can be performed using ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol), or the like.

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 step Next, a desired photomask is set in an exposure device, and the fluorine-containing resin film is exposed to high-energy radiation through the photomask.
The high-energy rays are preferably at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and alpha rays.

The exposure amount of the high energy rays is preferably 1 mJ/cm ² or more and 200 mJ/cm ² or less, more preferably 10 mJ/cm ² or more and 100 mJ/cm ² or less.

(3) Development process Next, the fluororesin film after the exposure process is developed with an alkaline aqueous solution to form a fluororesin pattern film.
That is, a fluororesin pattern film is obtained by dissolving either the exposed portion of the fluororesin film or the unexposed portion of the film in an alkaline aqueous solution.

As the alkaline aqueous solution, a tetramethylammonium hydroxide (TMAH) aqueous solution, a tetrabutylammonium hydroxide (TBAH) aqueous solution, etc. can be used.
When the alkaline aqueous solution is a tetramethylammonium hydroxide (TMAH) aqueous solution, its concentration is preferably 0.1% by mass or more and 5% by mass or less, more preferably 2% by mass or more and 3% by mass or less. .

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

The development time (time during which the developer contacts the fluororesin film) is preferably 10 seconds or more and 3 minutes or less, more preferably 30 seconds or more and 2 minutes or less.

After development, a step of cleaning the fluororesin pattern film using deionized water or the like may be provided, if necessary. 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.

Partition walls produced in this way can be used as banks for displays.

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

The fluororesin of the present disclosure preferably includes a structural unit represented by the above general formula (5) as a structural unit having a crosslinking site.
The fluorine-containing resin of the present disclosure preferably has a fluorine atom content of 15 to 60% by mass.
The fluororesin of the present disclosure has a content of the structure represented by general formula (1) of 0.1 mol% or more and less than 50 mol%, based on the total amount of structural units constituting the resin as 100 mol%. It is preferable that there be.
The fluororesin of the present disclosure preferably has a weight average molecular weight of 5,000 or more and 40,000 or less.

The fluororesin of the present disclosure is a compatibilizer 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. It is thought that it acts as For example, by introducing the fluororesin of the present disclosure into a resin composition and using it, molded products such as resin films and partition walls (banks) in which uneven distribution of each component is improved can be produced. The fluororesin of the present disclosure can be particularly suitably used in a composition containing two or more resins in which the difference in fluorine atom content is 15 to 60% by mass.
The fluororesin of the present disclosure also functions as a surfactant, so it can also be used as a surfactant.

A polymer blend containing the fluororesin of the present disclosure is also part of the present disclosure. The types of resins included in the polymer blend together with the fluororesin of the present disclosure are not particularly limited, and for example, one type or a combination of two or more of olefin resins, epoxy resins, (meth)acrylic resins, urethane resins, fluororesins, etc. There are many things that can be mentioned.

The following inventions are disclosed in this specification.
[1] Ethylenically unsaturated compound (A), photopolymerization initiator (B), alkali-soluble resin (C), fluororesin (D), and resin having a structure represented by the following general formula (1) (E ), which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass.

(In general formula (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. , the above alkyl group has any number of hydrogen atoms substituted with fluorine atoms.)
[2] The photosensitive resin composition according to [1] above, wherein the resin (E) has a crosslinking site.
[3] Ethylenically unsaturated compound (A), photopolymerization initiator (B), alkali-soluble resin (C), fluororesin (D), and resin (E) having a structure represented by general formula (1) A photosensitive resin composition comprising 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. Resin composition.

(In general formula (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. , the above alkyl group has any number of hydrogen atoms substituted with fluorine atoms.)
[4] The photosensitive resin composition according to [3] above, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass.
[5] The photosensitive resin composition described in [3] above, which contains a structural unit represented by the following general formula (5) as the structural unit having the crosslinking site.

(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-, -O-C(=O)- , -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- , A ² represents a divalent linking group, and 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 the alkylene group Any number of hydrogen atoms in may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , A ³ represents a divalent to tetravalent linking group, and has 1 to 10 carbon atoms. It represents a straight chain, branched chain having 3 to 10 carbon atoms, or cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group can be replaced by a hydroxyl group or -OC(= O) may be substituted with -CH ₃ , Y ² and Y ³ represent a divalent linking group, each independently represents -O- or -NH-, and n represents an integer of 1 to 3. , r represents 0 or 1.)
[6] The photosensitive resin composition according to [5] above, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass.
[7] The resin (E) described in [3] above 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). photosensitive resin composition.

(In general formula (1-1), Ra is each independently 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 in the above alkyl group, any number of hydrogen atoms are substituted with fluorine atoms.Rc is a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorine-containing alkyl group (the hydrocarbon group and the fluorine-containing alkyl group). Rd represents a group selected from the group consisting of straight chain or branched chain and may include a cyclic structure. Rd is a divalent or trivalent organic group, and the organic group has a cyclic structure. A group selected from a straight-chain or branched aliphatic hydrocarbon group, an aromatic ring group, or a composite substituent thereof which may contain 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-, -OC(=O)-NH-, -C(=O)-OC(=O) -NH- or -C(=O)-NH-, ^A2 represents a divalent linking group, linear chain having 1 to 10 carbon atoms, branched chain having 3 to 10 carbon atoms, or 3 carbon atoms ~10 cyclic alkylene group, any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -O-C(=O) _-CH3 , and ^A3 is 2 to 4 represents a valent linking group, represents 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 in the hydrocarbon group The hydrogen atom of may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , Y ² and Y ³ represent a divalent linking group, and each independently represents -O- or -NH -, n represents an integer from 1 to 3, and r represents 0 or 1.)
[8] The photosensitive resin composition according to [7] above, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass.
[9] The 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 the above [3], which is a resin containing a structural unit.

(In general formula (1-1), Ra is each independently 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 in the above alkyl group, any number of hydrogen atoms are substituted with fluorine atoms.Rc is a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorine-containing alkyl group (the hydrocarbon group and the fluorine-containing alkyl group). Rd represents a group selected from the group consisting of straight chain or branched chain and may include a cyclic structure. Rd is a divalent or trivalent organic group, and the organic group has a cyclic structure. A group selected from a straight-chain or branched aliphatic hydrocarbon group, an aromatic ring group, or a composite substituent thereof which may contain 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-, -OC(=O)-NH-, -C(=O)-OC(=O) -NH- or -C(=O)-NH-, ^A2 represents a divalent linking group, linear chain having 1 to 10 carbon atoms, branched chain having 3 to 10 carbon atoms, or 3 carbon atoms ~10 cyclic alkylene group, any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -O-C(=O) _-CH3 , and ^A3 is 2 to 4 represents a valent linking group, represents 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 in the hydrocarbon group The hydrogen atom of may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , Y ² and Y ³ represent a divalent linking group, and each independently represents -O- or -NH -, n represents an integer of 1 to 3, and r represents 0 or 1. In the general formula (6), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a straight group having 1 to 15 carbon atoms. Represents a chain, branched chain having 3 to 15 carbon atoms, or cyclic alkyl group having 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms.)
[10] The photosensitive resin composition according to [9] above, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass.
[11] The photosensitive resin composition according to any one of [1] to [10] above, 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) based on the total solid content of the photosensitive resin composition is 10 to 70% by mass. thing.
[13] Photosensitivity according to any one of [1] to [12] above, wherein the content of the fluororesin (D) based on the total solid content of the photosensitive resin composition is 0.01 to 10% by mass. Resin composition.
[14] The photosensitive resin composition according to any one of [1] to [13] above, wherein the content of the resin (E) based on the total solid content of the photosensitive resin composition is 0.01 to 10% by mass. thing.
[15] The photosensitive resin according to any one of [1] to [14] above, wherein the difference in fluorine atom content between the alkali-soluble resin (C) and the fluororesin (D) is 15 to 60% by mass. Composition.
[16] The content of the structure represented by the general formula (1) contained in the resin (E) is 0.1 mol based on the total amount of structural units constituting the resin (E) as 100 mol%. % or more and less than 50 mol% of the photosensitive resin composition according to any one of [1] to [15] above.
[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] above, wherein the resin (E) has a weight average molecular weight of 5,000 or more and 40,000 or less.
[19] The photosensitivity according to any one of [1] to [18] above, further comprising at least one selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor. Resin composition.
[20] The photosensitive resin composition according to any one of [1] to [19] above, which is used for forming partition walls.
[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 comprising the cured product according to [22] above.
[24] An organic electroluminescent device comprising the partition wall according to [23] above, and a light-emitting layer or a wavelength conversion layer disposed in a region defined by the partition wall.
[25] A display comprising the partition wall according to [23] above.
[26] A method for producing a cured product, comprising a film forming step of applying the photosensitive resin composition according to any one of [1] to [20] above to a substrate and then heating it to obtain a resin film. and an exposure step of exposing the resin film to high-energy rays.
[27] A fluororesin 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 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. , the above alkyl group has any number of hydrogen atoms substituted with fluorine atoms.)
[28] The fluororesin described in [27] above, which contains a structural unit represented by the following general formula (5) as a structural unit having a crosslinking site.

(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-, -O-C(=O)- , -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- , A ² represents a divalent linking group, and 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 the alkylene group Any number of hydrogen atoms in may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , A ³ represents a divalent to tetravalent linking group, and has 1 to 10 carbon atoms. It represents a straight chain, branched chain having 3 to 10 carbon atoms, or cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group can be replaced by a hydroxyl group or -OC(= O) may be substituted with -CH ₃ , Y ² and Y ³ represent a divalent linking group, each independently represents -O- or -NH-, and n represents an integer of 1 to 3. , r represents 0 or 1.)
[29] The fluororesin according to [27] or [28] above, having a fluorine atom content of 15 to 60% by mass.
[30] The above [wherein the content of the structure represented by the general formula (1) above is 0.1 mol% or more and less than 50 mol%, based on the total amount of structural units constituting the resin as 100 mol%] The fluororesin according to any one of [27] to [29].
[31] The fluororesin according to any one of [27] to [30] above, which has a weight average molecular weight of 5,000 or more and 40,000 or less.
[32] A polymer blend comprising the fluororesin according to any one of [27] to [31] above.

Hereinafter, the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited to these Examples.

[Measurement of molar ratio of each structural 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 dispersity (ratio of number average molecular weight Mn to weight average molecular weight Mw; Mw/Mn) of the polymer are determined by high speed gel permeation chromatography (hereinafter sometimes referred to as GPC) manufactured by Tosoh Corporation, type HLC-8320GPC), one ALPHA-M column and one ALPHA-2500 column (both manufactured by Tosoh Corporation) were connected in series, and the measurement was performed using tetrahydrofuran (THF) as a developing solvent. A refractive index difference measurement detector was used as a detector.

1. Synthesis of fluororesin (D) (liquid repellent) [Synthesis of liquid repellent precursor 1]
2.7 g of 1,1-bis(trifluoromethyl)-1,3-butadiene (manufactured by Central Glass Co., Ltd., hereinafter referred to as BTFBE) at room temperature (approximately 20°C) in a 500 ml glass flask equipped with a stirrer. (0.014 mol), 2.3 g (0.014 mol) of 4-acetoxystyrene (produced by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as p-AcO-St), 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 (0.042 mol) of hydroxyethyl methacrylate (Tokyo Kasei Kogyo Co., Ltd., hereinafter referred to as HEMA). 03 mol), 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) (produced by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as AIBN) was collected. ), and after degassing with stirring, the inside of the flask was purged with nitrogen gas, the internal temperature was raised to 79°C, and the reaction was carried out overnight. When 200 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered 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 in a yield of 89%.

<NMR measurement results>
The composition ratio of each constituent unit of the liquid repellent precursor 1 is expressed as a molar ratio: constituent unit by BTFBE: constituent unit by p-AcO-St: constituent unit by MA-C6F: constituent 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 with a stirrer, 20 g of liquid repellent precursor 1 (hydroxyl equivalent: 0.03 mol), 0.21 g of triethylamine (hydroxyl equivalent: 0.0021 mol), and propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA). and 4.26 g (hydroxyl equivalent: 0.030 mol) of 2-isocyanatoethyl acrylate (manufactured by Showa Denko K.K., product name: Karenz AOI) were added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40°C to obtain 21.6 g of liquid repellent 1 as a white solid in a yield of 90%.

< ^13C -NMR measurement results>
In liquid repellent 1, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in molar ratio. In addition, the composition ratio of each structural unit that does not react with the crosslinking site (constituent unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C6F) is unchanged from the liquid repellent precursor 1 used ( The same as before the introduction of the crosslinking group) was confirmed. The fluorine atom content in the liquid repellent agent 1 was 38.6% by mass based on the structural units.

<GPC measurement results>
Mw=13,100, Mw/Mn=1.7

[Synthesis of liquid repellent precursor 2]
In a 300 ml glass flask equipped with a stirrer at room temperature (approximately 20°C), add 3.8 g (0.02 mol) of BTFBE, 3.2 g (0.02 mol) of p-AcO-St, and 2-(perfluorobutyl)ethyl. 16.6 g (0.05 mol) of methacrylate (product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as MA-C4F), 5.2 g (0.04 mol) of HEMA (product of Tokyo Chemical Industry Co., Ltd.), and 60 g of MEK. After adding 0.84 g (0.005 mol) of AIBN and degassing while stirring, the inside of the flask was purged with nitrogen gas, the internal temperature was raised to 79° C., and the reaction was carried out overnight. When 250 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered 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 in a yield of 90%.

<NMR measurement results>
The composition ratio of each constituent unit of the liquid repellent precursor 2 is expressed as a molar ratio: constituent unit by BTFBE: constituent unit by p-AcO-St: constituent unit by MA-C4F: constituent 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), 20 g of PGMEA were collected, and 5.4 g of Karenz AOI ( Hydroxyl group equivalent: 0.038 mol) was added, and the mixture was reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 100 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40°C to obtain 26.7 g of liquid repellent 2 as a white solid in a yield of 85%.

< ^13C -NMR measurement results>
In liquid repellent 2, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in terms of molar ratio. In addition, the composition ratio of each structural unit that does not react with the crosslinking site (the structural unit of BTFBE, the structural unit of p-AcO-St, the structural unit of MA-C4F) is unchanged from the liquid repellent precursor 2 used (crosslinking (same as before the introduction of the standard). The fluorine atom content in liquid repellent 2 was 31.6% by mass based on the structural units.

<GPC measurement results>
Mw=13,100, Mw/Mn=1.5

[Synthesis of liquid repellent precursor 3]
25.9 g (0.06 mol) of MA-C6F, 5.2 g (0.04 mol) of HEMA (product of Tokyo Kasei Kogyo Co., Ltd.), and MEK were placed in a 500 ml glass flask equipped with a stirrer at room temperature (approximately 20° C.). 62 g was collected, 0.84 g (0.005 mol) of AIBN was added, and after degassing with stirring, the inside of the flask was purged with nitrogen gas, the internal temperature was raised to 79° C., and the reaction was allowed to proceed overnight. When 250 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered and dried under reduced pressure at a temperature of 45° C. to obtain 28 g of liquid repellent precursor 3 as a white solid in a yield of 90%.

<NMR measurement results>
The composition ratio of each constituent unit of the liquid repellent precursor 3 was expressed as a molar ratio: MA-C6F constituent unit: HEMA constituent unit = 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), 60 g of PGMEA, and 7.1 g of Karenz AOI ( Hydroxyl group equivalent: 0.050 mol) was added, and the mixture was reacted at 45°C for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40° C. to obtain 30 g of liquid repellent 3 as a white solid in a yield of 85%.

< ^13C -NMR measurement results>
In liquid repellent 3, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in molar ratio. Furthermore, it was confirmed that the composition ratio of each structural unit (constituent unit based on 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). Based on the structural units, the fluorine atom content in the liquid repellent agent 3 was 40.6% by mass.

<GPC measurement results>
Mw=14,300, Mw/Mn=1.7

[Liquid repellent 4]
“RS-72A” manufactured by DIC (fluorine atom content 8% by mass)
[Liquid repellent 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 (approximately 20°C), add 2.9 g (0.015 mol) of BTFBE, 2.4 g (0.015 mol) of p-AcO-St, and 13.0 g of MA-C6F ( 0.03 mol), 3.9 g (0.03 mol) of HEMA, 5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl methacrylate (manufactured by Central Glass Co., Ltd.) .Hereinafter referred to as MA-BTHB-OH), 3.0 g (0.01 mol) and 50.0 g of MEK were collected, 0.84 g (0.005 mol) of AIBN was added, and the mixture was degassed while stirring. The inside of the flask was purged with nitrogen gas, the internal temperature was raised to 79°C, and the reaction was carried out overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered and dried under reduced pressure at a temperature of 45° C. to obtain 22.6 g of fluororesin precursor 1 as a white solid in a yield of 90%.

<NMR measurement results>
The composition ratio of each constituent unit of the fluororesin precursor 1 is expressed as a molar ratio: Constituent unit by BTFBE: Constituent unit by p-AcO-St: Constituent unit by MA-C6F: Constituent unit by HEMA: MA-BTHB- The constituent units of OH were 15:15:30:30:10. The fluorine atom content in the fluororesin precursor 1 was 40.9% by mass based on the structural units.

<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), 60 g of PGMEA, and 4.26 g of Karenz AOI ( Hydroxyl group equivalent: 0.03 mol) was added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40° C. to obtain 22.3 g of fluororesin 1 as a white solid in a yield of 85%.

< ^13C -NMR measurement results>
In fluororesin 1, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in molar ratio. In addition, the composition ratio of each constitutional unit that does not react with the crosslinking site (constituent unit by BTFBE, constitutional unit by p-AcO-St, constitutional unit by MA-C6F, constitutional unit by MA-BTHB-OH) is determined by the fluororesin used. It was confirmed that there was no change from Precursor 1 (same as before introduction of the crosslinking group). The fluorine atom content in the fluororesin 1 was 35.2% by mass based on the structural units.

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

<NMR measurement results>
The composition ratio of each constituent unit of the fluororesin precursor 2 is expressed as a molar ratio: Constituent unit by BTFBE: Constituent unit by p-AcO-St: Constituent unit by MA-C4F: Constituent unit by HEMA: MA-BTHB- The constituent units of OH were 15:15:30:30:10. The fluorine atom content in the fluororesin precursor 2 was 36.1% by mass based on the structural units.

<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), 60 g of PGMEA, and 4.26 g of Karenz AOI ( Hydroxyl group equivalent: 0.03 mol) was added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40° C. to obtain 21.3 g of fluororesin 2 as a white solid in a yield of 87%.

< ^13C -NMR measurement results>
In fluororesin 2, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 98:2 in molar ratio. In addition, the composition ratio of each structural unit that does not react with the crosslinking site (constituent unit by BTFBE, structural unit by p-AcO-St, structural unit by MA-C4F, structural unit by MA-BTHB-OH) is determined by the fluororesin used. It was confirmed that there was no change from Precursor 2 (same as before introduction of the crosslinking group). The fluorine atom content in the fluororesin 2 was 30.5% by mass based on the structural units.

<GPC measurement results>
Mw=9,100, Mw/Mn=1.4

[Synthesis of fluororesin precursor 3]
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 in a 500 ml glass flask equipped with a stirrer at room temperature (about 20 ° C.). After adding 0.84 g (0.005 mol) of AIBN and degassing while stirring, the inside of the flask was purged with nitrogen gas, the internal temperature was raised to 79° C., and the reaction was carried out overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered and dried under reduced pressure at a temperature of 45° C. to obtain 18.1 g of fluororesin precursor 3 as a white solid in a yield of 90%.

<NMR measurement results>
The composition ratio of each structural unit of the fluororesin precursor 3 was expressed as a molar ratio: HEMA structural unit: MA-BTHB-OH structural unit = 55:45. The fluorine atom content in the fluororesin precursor 3 was 25.1% by mass based on the structural units.

<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), 60 g of PGMEA, and 7.42 g of Karenz AOI ( Hydroxyl group equivalent: 0.055 mol) was added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40° C. to obtain 21 g of fluororesin 3 as a white solid in a yield of 84%.

< ^13C -NMR measurement results>
In fluororesin 3, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 98:2 in molar ratio. Furthermore, it was confirmed that the composition ratio of each structural unit (constituent unit composed 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). The fluorine atom content in the fluororesin 3 was 18.4% by mass based on the structural units.

<GPC measurement results>
Mw=8,100, Mw/Mn=1.4

[Fluororesin 4]
The above fluororesin precursor 1 was made into fluororesin 4. The fluorine atom content in the fluororesin 4 (fluororesin precursor 1) was 40.9% by mass based on the structural units.

[Fluororesin 5]
The above fluororesin precursor 2 was used as a fluororesin 5. Based on the structural units, the fluorine atom content in the 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 (approximately 20°C), add 1.0 g (0.005 mol) of BTFBE, 8.0 g (0.015 mol) of p-AcO-St, and 4.3 g of MA-C6F ( 0.01 mol), 3.9 g (0.03 mol) of HEMA, 1.5 g (0.005 mol) of MA-BTHB-OH, and 50.0 g of MEK were collected, and 0.84 g (0.005 mol) of AIBN was collected. After degassing with stirring, the inside of the flask was replaced with nitrogen gas, the internal temperature was raised to 79°C, and the reaction was allowed to proceed overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered and dried under reduced pressure at a temperature of 45° C. to obtain 16.06 g of fluororesin precursor 6 as a white solid in a yield of 90%.

<NMR measurement results>
The composition ratio of each constituent unit of the fluororesin precursor 6 is expressed as a molar ratio: Constituent unit by BTFBE: Constituent unit by p-AcO-St: Constituent unit by MA-C6F: Constituent unit by HEMA: MA-BTHB- The constituent units of OH were 5:50:10:30:5. The fluorine atom content in the fluororesin precursor 6 was 19.3% by mass based on the structural units.

<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), 60 g of PGMEA, and 2.13 g of Karenz AOI ( Hydroxyl group equivalent: 0.015 mol) was added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40° C. to obtain 11.2 g of fluororesin 6 as a white solid in a yield of 90%.

< ^13C -NMR measurement results>
In fluororesin 6, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in molar ratio. In addition, the composition ratio of each constitutional unit that does not react with the crosslinking site (constituent unit by BTFBE, constitutional unit by p-AcO-St, constitutional unit by MA-C6F, constitutional unit by MA-BTHB-OH) is determined by the fluororesin used. It was confirmed that there was no change from Precursor 6 (same as before introduction of the crosslinking group). The fluorine atom content in the fluororesin 6 was 14.4% by mass based on the structural units.

<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 (approximately 20°C), add 2.0 g (0.010 mol) of BTFBE, 0.5 g (0.003 mol) of p-AcO-St, and 34.5 g (34.5 g) of MA-C6F. 0.079 mol), 0.39 g (0.003 mol) of HEMA, 1.5 g (0.005 mol) of MA-BTHB-OH, and 100.0 g of MEK were collected, and 0.84 g (0.005 mol) of AIBN was collected. After degassing with stirring, the inside of the flask was replaced with nitrogen gas, the internal temperature was raised to 79°C, and the reaction was allowed to proceed overnight. When 500 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered and dried under reduced pressure at a temperature of 45° C. to obtain 35.2 g of fluororesin precursor 7 as a white solid in a yield of 90%.

<NMR measurement results>
The composition ratio of each constituent unit of the fluororesin precursor 7 is expressed as a molar ratio: Constituent unit by BTFBE: Constituent unit by p-AcO-St: Constituent unit by MA-C6F: Constituent unit by HEMA: MA-BTHB- The constituent units of OH were 10:3:79:3:5. The fluorine atom content in the fluororesin precursor 7 was 56.1% by mass based on the structural units.

<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), 100 g of PGMEA were collected, and 0.42 g of Karenz AOI ( Hydroxyl group equivalent: 0.03 mol) was added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 500 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40° C. to obtain 28.5 g of fluororesin 7 as a white solid in a yield of 95%.

< ^13C -NMR measurement results>
In fluororesin 7, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in molar ratio. In addition, the composition ratio of each constitutional unit that does not react with the crosslinking site (constituent unit by BTFBE, constitutional unit by p-AcO-St, constitutional unit by MA-C6F, constitutional unit by MA-BTHB-OH) is determined by the fluororesin used. It was confirmed that there was no change from Precursor 7 (same as before introduction of the crosslinking group). The fluorine atom content in the fluororesin 7 was 55.2% by mass based on the structural units.

<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 (approximately 20°C), add 2.9 g (0.015 mol) of BTFBE, 2.4 g (0.015 mol) of p-AcO-St, and 13.0 g of MA-C6F ( 0.03 mol), 3.9 g (0.03 mol) of HEMA, 3.0 g (0.01 mol) of MA-BTHB-OH, and 100.0 g of MEK were collected, and 3.41 g (0.020 mol) of AIBN was added. After degassing with stirring, the inside of the flask was purged with nitrogen gas, the internal temperature was raised to 81°C, and the reaction was carried out overnight. When 400 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered and dried under reduced pressure at a temperature of 45° C. to obtain 20.1 g of fluororesin precursor 8 as a white solid in a yield of 80%.

<NMR measurement results>
The composition ratio of each constituent unit of the fluororesin precursor 8 is expressed as a molar ratio: Constituent unit by BTFBE: Constituent unit by p-AcO-St: Constituent unit by MA-C6F: Constituent unit by HEMA: MA-BTHB- The constituent units of OH were 15:15:30:30:10. The fluorine atom content in the fluororesin precursor 8 was 40.9% by mass based on the structural units.

<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), 30 g of PGMEA, and 2.13 g of Karenz AOI ( Hydroxyl group equivalent: 0.03 mol) was added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40°C to obtain 11.2 g of fluororesin 8 as a white solid in a yield of 85%.

< ^13C -NMR measurement results>
In fluororesin 8, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in molar ratio. In addition, the composition ratio of each constitutional unit that does not react with the crosslinking site (constituent unit by BTFBE, constitutional unit by p-AcO-St, constitutional unit by MA-C6F, constitutional unit by MA-BTHB-OH) is determined by the fluororesin used. It was confirmed that there was no change from Precursor 8 (same as before introduction of the crosslinking group). The fluorine atom content in the fluororesin 8 was 35.2% by mass based on the structural units.

<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 (approximately 20°C), add 2.9 g (0.015 mol) of BTFBE, 2.4 g (0.015 mol) of p-AcO-St, and 13.0 g of MA-C6F ( 0.03 mol), 3.9 g (0.03 mol) of HEMA, 3.0 g (0.01 mol) of MA-BTHB-OH, and 40.0 g of MEK were collected, and 0.21 g (0.00125 mol) of AIBN was collected. After degassing with stirring, the inside of the flask was replaced with nitrogen gas, the internal temperature was raised to 70°C, and the reaction was allowed to proceed overnight. When 300 g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. This precipitate was filtered and dried under reduced pressure at a temperature of 45° C. to obtain 22.1 g of fluororesin precursor 9 as a white solid in a yield of 90%.

<NMR measurement results>
The composition ratio of each constituent unit of the fluororesin precursor 9 is expressed in molar ratio as follows: Constituent unit by BTFBE: Constituent unit by p-AcO-St: Constituent unit by MA-C6F: Constituent unit by HEMA: MA-BTHB- The constituent units of OH were 15:15:30:30:10. The fluorine atom content in the fluororesin precursor 9 was 40.9% by mass based on the structural units.

<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), 60 g of PGMEA, and 4.26 g of Karenz AOI ( Hydroxyl group equivalent: 0.03 mol) was added, and the mixture was reacted at 45° C. for 4 hours. After the reaction was completed, the reaction solution was concentrated, and 200 g of n-heptane was added to precipitate. This precipitate was filtered and dried under reduced pressure at 40° C. to obtain 21.1 g of fluororesin 9 as a white solid in a yield of 80%.

< ^13C -NMR measurement results>
In fluororesin 9, the amount of introduced acrylic acid derivative derived from Karenz AOI (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) were 99:1 in molar ratio. In addition, the composition ratio of each constitutional unit that does not react with the crosslinking site (constituent unit by BTFBE, constitutional unit by p-AcO-St, constitutional unit by MA-C6F, constitutional unit by MA-BTHB-OH) is determined by the fluororesin used. It was confirmed that there was no change from Precursor 9 (same as before introduction of the crosslinking group). The fluorine atom content in the fluororesin 9 was 35.2% by mass based on the structural units.

<GPC measurement results>
Mw=45,300, Mw/Mn=1.9

3. Preparation of photosensitive resin compositions Each component used in the preparation of photosensitive resin compositions of Examples and Comparative Examples is shown below.
<Ethylenically unsaturated compound (A)>
Ethylenically unsaturated compound: “DPHA” (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.
<Photopolymerization initiator (B)>
Photoinitiator 1: “Irgacure OXE-01” manufactured by BASF
Photoinitiator 2: “DETXs” (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co., Ltd.
Photoinitiator 3: “Irgacure OXE-04” manufactured by BASF
<Alkali-soluble resin (C)>
Alkali-soluble resin: "ZAR-2050H" manufactured by Nippon Kayaku Co., Ltd. (special BIS-A type epoxy acrylate, does not contain fluorine atoms)
<Additives>
Adhesive: “KAYAMER PM-21” manufactured by Nippon Kayaku Co., Ltd.
<Chain transfer agent>
Chain transfer agent: “Karens MT-PE1” manufactured by Showa Denko K.K.

[Preparation of photosensitive resin basic composition liquid]
2.0 parts by mass of Karenz 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), A photosensitive resin basic composition liquid was prepared by blending 1.0 parts by mass of PM-21 as an adhesive and 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]
Examples 1 to 26 And photosensitive resin compositions of Comparative Examples 1 to 16 were prepared. Using the obtained photosensitive resin composition, evaluation was performed by the method described below.

4. Amount of fluorine component on the surface Coating films were prepared 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]
After cleaning a 10 cm square alkali-free substrate with ultrapure water and then with acetone, the substrate was subjected to UV ozone treatment 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 coated on the resulting UV ozone-treated substrate using a spin coater at a rotation speed of 1,000 rpm, and coated on a hot plate. The mixture was heated at 100° C. for 150 seconds to form a coating film with a thickness of 1 μm.

[Evaluation and comparison of fluorine content]
The F1s spectrum of the surface of the coated film was measured using X-ray photoelectron spectroscopy (abbreviated as XPS), and the intensities were compared. XPS measurement was performed using JPS-9000MC manufactured by JEOL Ltd. In order to confirm the unevenness of the coating film, measurements were performed 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 stated conditions, the more covalent bonds containing fluorine are included on the film surface. From this, it can be said that a film with a large measured value of the spectrum contains more fluorine atoms on the film surface than a film with a small measured value of the spectrum.

A peak derived from fluorine was observed on the surface 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 value and the minimum value of the peak derived from fluorine observed on the surface of the coating film was 400 at most, and Comparative Examples 1 to 10 and 14 to It was confirmed that the difference between the maximum value and the minimum value was smaller than that of No. 16. From this, it was found that by including fluororesins 1 to 9, the amount of fluorine components on the surface of the coating film became more uniform.
Comparative Examples 11 to 13, which do not contain fluororesin (D), have a lower coating film surface than Examples 1 to 26, Comparative Examples 1 to 10, and Comparative Examples 14 to 16, which contain fluororesin (D). The observed peak intensity derived from fluorine was small. It was found that the amount of fluorine component on the surface of the coating film was influenced by the fluororesin (D).
Examples 1 to 20 and 23 to 26 using fluororesins 1 to 3 and 6 to 9 having crosslinking sites were compared with Examples 21 and 22 using fluororesin 4 or fluororesin 5 which did not contain crosslinking sites. Therefore, the difference between the maximum and minimum values of the fluorine-derived peaks observed on the surface of the coating film was smaller.

5. Bank evaluation [bank formation]
After cleaning a 10 cm square ITO substrate with ultrapure water and then with acetone, the substrate was subjected to UV ozone treatment for 5 minutes using the UV ozone treatment apparatus described above. Next, the resin compositions for consideration Examples 1 to 26 and Comparative Examples 1 to 16 were coated on the resulting UV ozone-treated substrate using a spin coater at a rotation speed of 1,000 rpm, and coated on a hot plate. It was heated at 80° C. for 150 seconds to form a fluorine-containing resin film and a comparative fluorine-containing resin film with a film thickness of 1 μm. Using a mask aligner (product of SUSS Microtech Co., Ltd.), the obtained resin film was irradiated with i-line (wavelength 365 nm) through a mask with a line and space of 5 μm for exposure.
The resulting cured film after exposure was evaluated for developer solubility, bank performance (sensitivity, resolution), and contact angle measurement.

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

[Bank performance (sensitivity, resolution)]
The optimal exposure amount Eop (mJ/cm ² ) for forming the bank, which is the line-and-space pattern, was determined and used as an index of sensitivity.
Further, the obtained bank pattern was observed with a laser microscope (manufactured by Keyence Corporation, VX-1100) (3000 times) to evaluate the resolution. If line edge roughness could not be observed, it was rated "excellent", if it was slightly observed, it was rated "good", and if it was noticeable, it was rated "unacceptable".

[Contact angle]
After heating the substrate with the cured film obtained in the above process at 230°C for 60 minutes, the contact angle of the cured film surface to water and propylene glycol monomethyl ether acetate (PGMEA) was measured using a contact angle meter (Kyowa Kaimen Kagaku). Measurements were made at 20 locations on the coating film using GMs-601 (manufactured by Co., Ltd.).

As a result of comparing the developer solubility, bank performance, and contact angle of banks (cured films) prepared from the photosensitive resin compositions of Examples 1 to 26 and Comparative Examples 1 to 16, it was found that all In Examples and Comparative Examples, the unexposed area was soluble and the exposed area was insoluble, so the photosensitive resin composition of the present disclosure had excellent curability. Among the bank performances, sensitivity was 150 to 200 mJ/cm ² in both Examples and Comparative Examples, and resolution was "Good" or "Excellent". Regarding bank resolution, it was found that Examples 1 to 26 were equal to 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 angle values 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, in which fluororesin 7 with a slightly higher fluorine atom content was used, line edge roughness was slightly confirmed ("good") compared to other examples, and the maximum and minimum values of the contact angle were The difference was somewhat large.
Example 25, which used fluororesin 8 with a slightly lower molecular weight, had a slightly smaller contact angle than the other examples.
In Example 26, in which fluororesin 9 having a slightly larger molecular weight was used, slight line edge roughness was observed.
Comparative Examples 11 to 13 that did not contain the fluororesin (D) had smaller contact angles than Examples 1 to 26, Comparative Examples 1 to 10, and Comparative Examples 14 to 16 that contained the fluororesin (D). .
Comparative Examples 14 and 15 with a high content of resin (E) and Comparative Example 16 with a low content of resin (E) had a larger difference between the maximum value and the minimum value of the contact angle compared to the example. .

Claims (32)

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

(In general formula (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. , in the alkyl group, any number of hydrogen atoms are substituted with fluorine atoms.) The photosensitive resin composition according to claim 1, wherein the resin (E) has a crosslinking site. A photosensitive material containing an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluororesin (D), and a resin (E) having a structure represented by general formula (1) A resin composition comprising:
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 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. , in the alkyl group, any number of hydrogen atoms are substituted with fluorine atoms.) The photosensitive resin composition according to claim 3, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass. The photosensitive resin composition according to claim 3, comprising a structural unit represented by the following general formula (5) as the structural unit having the crosslinking site.

(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-, -O-C(=O)- , -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- , A ² represents a divalent linking group, and 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 the alkylene group Any number of hydrogen atoms in may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , A ³ represents a divalent to tetravalent linking group, and has 1 to 10 carbon atoms. It represents a straight chain, branched chain having 3 to 10 carbon atoms, or cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group can be replaced by a hydroxyl group or -OC(= O) may be substituted with -CH ₃ , Y ² and Y ³ represent a divalent linking group, each independently represents -O- or -NH-, and n represents an integer of 1 to 3. , r represents 0 or 1.) The photosensitive resin composition according to claim 5, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass. The photosensitive resin according to claim 3, 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). Composition.

(In general formula (1-1), Ra is the same as Ra in general formula (1), and Rc represents a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorine-containing alkyl group (the hydrocarbon group and The fluorine-containing alkyl group represents a group selected from the group consisting of straight chain or branched chain and may include a cyclic structure.Rd is a divalent or trivalent organic group, and Rd is a divalent or trivalent organic group, and is a group selected from a linear or branched aliphatic hydrocarbon group that may contain a cyclic structure, an aromatic ring group, or a composite substituent thereof, in which some or all of the hydrogen atoms are fluorine atoms. or may be substituted with 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, and W ² represents a divalent linkage. Represents a 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, linear with 1 to 10 carbon atoms, branched with 3 to 10 carbon atoms or represents a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , and A ³ represents a divalent to tetravalent linking group, and represents 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; Any number of hydrogen atoms may be substituted with a hydroxyl group or -O-C(=O)-CH 3 , Y ² and ^{Y 3} _represent a divalent linking group, and each independently represents -O-C(=O)-CH 3 . - or -NH-, n represents an integer from 1 to 3, and r represents 0 or 1.) The photosensitive resin composition according to claim 7, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass. The 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 claim 3, which is a resin containing.

(In general formula (1-1), Ra is the same as Ra in general formula (1), and Rc represents a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorine-containing alkyl group (the hydrocarbon group and The fluorine-containing alkyl group represents a group selected from the group consisting of straight chain or branched chain and may include a cyclic structure.Rd is a divalent or trivalent organic group, and Rd is a divalent or trivalent organic group, and is a group selected from a linear or branched aliphatic hydrocarbon group that may contain a cyclic structure, an aromatic ring group, or a composite substituent thereof, in which some or all of the hydrogen atoms are fluorine atoms. or may be substituted with 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, and W ² represents a divalent linkage. Represents a 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, linear with 1 to 10 carbon atoms, branched with 3 to 10 carbon atoms or represents a cyclic alkylene group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the alkylene group may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , and A ³ represents a divalent to tetravalent linking group, and represents 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; Any number of hydrogen atoms may be substituted with a hydroxyl group or -O-C(=O)-CH 3 , Y ² and ^{Y 3} _represent a divalent linking group, and each independently represents -O-C(=O)-CH 3 . - or -NH-, n represents an integer of 1 to 3, and r represents 0 or 1. In the general formula (6), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ has a carbon number of 1 -15 straight chain, branched chain having 3 to 15 carbon atoms, or cyclic alkyl group having 3 to 15 carbon atoms, and any number of hydrogen atoms in the alkyl group are substituted with fluorine atoms. ) The photosensitive resin composition according to claim 9, which contains 30 to 550 parts by mass of the resin (E) when the fluororesin (D) is 100 parts by mass. The photosensitive resin composition according to claim 1 or 3, wherein the resin (E) has a fluorine atom content of 15 to 60% by mass. The photosensitive resin composition according to claim 1 or 3, wherein the content of the alkali-soluble resin (C) based on the total solid content of the photosensitive resin composition is 10 to 70% by mass. The photosensitive resin composition according to claim 1 or 3, wherein the content of the fluororesin (D) based on the total solid content of the photosensitive resin composition is 0.01 to 10% by mass. The photosensitive resin composition according to claim 1 or 3, wherein the content of the resin (E) is 0.01 to 10% by mass based on the total solid content of the photosensitive resin composition. The photosensitive resin composition according to claim 1 or 3, wherein the difference in fluorine atom content between the alkali-soluble resin (C) and the fluororesin (D) is 15 to 60% by mass. The content of the structure represented by the general formula (1) contained in the resin (E) is 0.1 mol% or more, with the total amount of structural units constituting the resin (E) being 100 mol%, The photosensitive resin composition according to claim 1 or 3, wherein the content is less than 50 mol%. The photosensitive resin composition according to claim 1 or 3, wherein the structure represented by the general formula (1) is a hexafluoroisopropanol group. The photosensitive resin composition according to claim 1 or 3, wherein the resin (E) has a weight average molecular weight of 5,000 or more and 40,000 or less. The photosensitive resin composition according to claim 1 or 3, further comprising at least one selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor. The photosensitive resin composition according to claim 1 or 3, which is used for forming partition walls. 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 wall comprising the cured product according to claim 22. An organic electroluminescent device comprising the partition wall according to claim 23 and a light emitting layer or a wavelength conversion layer disposed in a region defined by the partition wall. A display comprising the partition wall according to claim 23. 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 for producing a cured product, including an exposure step of exposing the resin film to high-energy rays. A fluororesin 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 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. , in the alkyl group, any number of hydrogen atoms are substituted with fluorine atoms.) The fluororesin according to claim 27, which contains a structural unit represented by the following general formula (5) as the structural unit having a crosslinking site.

(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-, -O-C(=O)- , -C(=O)-O-, -OC(=O)-NH-, -C(=O)-OC(=O)-NH- or -C(=O)-NH- , A ² represents a divalent linking group, and 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 the alkylene group Any number of hydrogen atoms in may be substituted with a hydroxyl group or -O-C(=O)-CH ₃ , A ³ represents a divalent to tetravalent linking group, and has 1 to 10 carbon atoms. It represents a straight chain, branched chain having 3 to 10 carbon atoms, or cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group can be replaced by a hydroxyl group or -OC(= O) may be substituted with -CH ₃ , Y ² and Y ³ represent a divalent linking group, each independently represents -O- or -NH-, and n represents an integer of 1 to 3. , r represents 0 or 1.) The fluororesin according to claim 27, having a fluorine atom content of 15 to 60% by mass. 28. The content of the structure represented by the general formula (1) is 0.1 mol% or more and less than 50 mol%, based on 100 mol% of the total amount of structural units constituting the resin. fluorine-containing resin. The fluororesin according to claim 27, which has a weight average molecular weight of 5,000 or more and 40,000 or less. A polymer blend comprising the fluororesin according to any one of claims 27 to 31.