Photosensitive resin composition, cured product, spacer wall, organic electroluminescent element, and image display device

Abstract

The present application provides a photosensitive resin composition that can balance high ink repellency and inkjet coatability. The photosensitive resin composition of the present application is characterized by being a photosensitive resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a compound having a cyclic ether group having 2 to 3 carbon atoms and having an aromatic ring and / or a heterocycle, and (E) a compound having a crosslinking group and having a fluorine atom and / or a siloxane chain, the content ratio of the (E) compound being 2 mass parts or more and 8 mass parts or less with respect to 100 mass parts of the (D) compound.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, cured products, spacers, organic electroluminescent elements, and image display devices.

[0002] This application claims priority based on Japanese Patent Application No. 2024-031833, filed in Japan on March 4, 2024, the contents of which are incorporated herein by reference. Background Technology

[0003] Conventionally, organic light-emitting elements included in organic electroluminescent displays and the like are manufactured by stacking various functional layers within the area surrounded by spacers after forming spacers (dams) on a substrate. As a method for easily forming such spacers, a photolithography method using a photosensitive resin composition is known.

[0004] Furthermore, as a method for stacking various functional layers within a region surrounded by partition walls, a known method is to first prepare an ink containing materials constituting the functional layers, and then inject the prepared ink into the region surrounded by partition walls. In this method, inkjet printing is often used because it is easy to accurately inject a specified amount of ink into a specified location.

[0005] Furthermore, when using ink to form a functional layer, it is sometimes necessary to give the spacer ink-repellent (liquid-repellent) properties for purposes such as preventing ink from adhering to the spacer wall and preventing ink injected into adjacent areas from mixing with each other.

[0006] In addition, in recent years, various properties have been required for the spacers beyond ink repellency, leading to the development of various photosensitive resin compositions.

[0007] Patent document 1 describes how, by applying an initiator with a specific structure and a fluorinated atom resin with crosslinking groups, it is possible to control both the height difference between the spacers (the height difference between the first spacer and the second spacer) and the inkjet coating properties.

[0008] Patent document 2 describes that by applying a photoacid generator and an acid curing agent, and using a photosensitive composition containing an ink repellent having olefinic double bonds, a resin-cured film with good ink repellency can be formed and a fine, high-precision pattern can be formed.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: International Publication No. 2021 / 125160

[0012] Patent Document 2: Japanese Patent No. 6536578 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] In recent years, the practical application of inkjet-based components and devices has been advancing, with the aim of maintaining high ink repellency and improving the precision of inkjet coating. In particular, when performing inkjet coating over large areas, a large number of pixels where the ink does not spread may lead to a decrease in yield.

[0015] The inventors conducted research and found that the photosensitive composition described in Patent Document 1 did not adequately balance high ink repellency and inkjet coating properties. On the other hand, while the photosensitive resin composition described in Patent Document 2 describes an effect of reducing residue in the central portion of the pixel opening, it does not describe adaptability to inkjet coating spread across the entire pixel when inkjet coating a large pixel area.

[0016] Solution for solving the problem

[0017] Through in-depth research, the inventors discovered that by further combining compounds with specific structures in a specific proportion in a photosensitive resin composition containing a photopolymerization initiator, an alkali-soluble resin, and a photopolymerizable compound, the aforementioned problems can be solved, thus completing this invention. Specifically, this invention is a photosensitive resin composition characterized in that the photosensitive resin composition contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, a specific (D) compound, and a specific (E) compound, wherein the content of compound (E) is 2 parts by mass or more and 8 parts by mass or less relative to 100 parts by mass of compound (D).

[0018] That is, the main idea of ​​this invention is as follows.

[0019] [1] A photosensitive resin composition, characterized in that the photosensitive resin composition contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a compound, and (E) a compound, wherein the (D) compound is a compound having a cyclic ether group having 2 to 3 carbon atoms and having an aromatic ring and / or a heterocyclic ring, and the (E) compound is a compound having a crosslinking group and having a fluorine atom and / or a siloxane chain, wherein the content of the (E) compound is 2 parts by mass or more and 8 parts by mass or less relative to 100 parts by mass of the (D) compound.

[0020] [2] According to the photosensitive resin composition of [1], wherein the content of the compound (D) is 10 parts by mass or more relative to 100 parts by mass of the alkali-soluble resin (B).

[0021] [3] The photosensitive resin composition according to [1] or [2] is characterized in that the (D) compound has a structural unit represented by the following formula (1).

[0022] [Chemical Formula 1]

[0023]

[0024] (In equation (1), R) d11 Each represents a divalent aliphatic hydrocarbon group. n represents an integer of 1 or 2. The benzene ring in formula (1) may be further optionally substituted with any substituents. *Each represents a bond.

[0025] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the acid value of the (D) compound is less than 1 mg KOH / g.

[0026] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (B) alkali-soluble resin comprises an epoxy (meth)acrylate having an aromatic ring in the main chain.

[0027] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the (C) photopolymerizable compound comprises a reaction product of pentaerythritol with (poly) glycol and (meth)acrylic acid, or a reaction product of dipentaerythritol with (poly) glycol and (meth)acrylic acid.

[0028] [7] The photosensitive resin composition according to any one of [1] to [6] further comprises an aliphatic thiol compound.

[0029] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the colorant is not present, or the proportion of the colorant is 5% by mass or less relative to the total solid content of the photosensitive resin composition.

[0030] [9] A cured product formed by curing a photosensitive resin composition as described in any one of [1] to [8].

[0031]

[10] A spacer wall comprising a solidified material as described in [9].

[0032]

[11] An organic electroluminescent element having a spacer wall as described in

[10] .

[0033]

[12] An image display device comprising an organic electroluminescent element as described in

[11] .

[0034] Invention Effects

[0035] According to the present invention, a photosensitive resin composition that can achieve both high ink repellency and inkjet coating properties can be provided. Detailed Implementation

[0036] The present invention will now be described in detail. The following description is an example of an embodiment of the present invention, and the present invention is not limited thereto without departing from its spirit.

[0037] In this invention, "(meth)acryl" means "acryl and / or methacryl".

[0038] In this invention, "total solids content" refers to all components in the photosensitive resin composition except for the solvent. Even if a component other than the solvent is liquid at room temperature, it is not included in the solvent but is included in the total solids content.

[0039] In this invention, the numerical range represented by “~” refers to the range that includes the values ​​recorded before and after “~” as the lower limit and upper limit.

[0040] In this invention, "A and / or B" refers to one or both of A and B, specifically A, B, or A and B.

[0041] In this invention, "(co)polymer" refers to both homopolymer and copolymer, and "polyacid (anhydride)" refers to "polyacid and / or polyacid anhydride".

[0042] In this invention, weight-average molecular weight refers to the weight-average molecular weight (Mw) obtained by GPC (gel permeation chromatography) converted to polystyrene.

[0043] In this invention, the acid value represents the acid value converted from the effective solid components, which is calculated by neutralization titration.

[0044] In this invention, the term "partition wall material" refers to dam material, wall material, or wall material. Similarly, "partition wall" refers to dam, wall, or wall.

[0045] Spacers are used, for example, to divide the functional layer (organic layer, light-emitting part) in an active-drive organic electroluminescent element, for example, to form a pixel containing a functional layer and spacers by spraying ink, which is a material used to form the functional layer, into the divided area (pixel area) and drying it.

[0046] [1] Photosensitive resin composition

[0047] [1-1] Components and composition of the photosensitive resin composition

[0048] The components and their composition constituting the photosensitive resin composition of the present invention will be described.

[0049] The photosensitive resin composition of the present invention contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a compound, and (E) a compound. The photosensitive resin composition of the present invention may further contain other components as needed, such as chain transfer agents, ultraviolet absorbers, polymerization inhibitors, etc.

[0050] [1-1-1] (A) Component: Photopolymerization initiator

[0051] The photosensitive resin composition of the present invention contains (A) a photopolymerization initiator. The photopolymerization initiator is a compound that polymerizes the olefinic unsaturated bonds of (C) a photopolymerizable compound by means of active light.

[0052] In the photosensitive resin composition of the present invention, as the photopolymerization initiator (A), a photopolymerization initiator commonly used in the art can be used. Examples of such photopolymerization initiators include: metallocene compounds containing dititanium compounds as described in Japanese Patent Application Publication No. 59-152396 and Japanese Patent Application Publication No. 61-151197; hexaaryl biimidazole derivatives as described in Japanese Patent Application Publication No. 2000-56118; halomethylated oxadiazole derivatives, halomethyltriazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, and other free radical activators and α-aminoalkylphenyl ketone derivatives as described in Japanese Patent Application Publication No. 10-39503; and oxime ester compounds described later.

[0053] Examples of metallocene compounds include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl) titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl) titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl) titanium, dicyclopentadienyl bis(2,6-difluorophenyl) titanium, dicyclopentadienyl bis(2,4-difluorophenyl) titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl) titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl) titanium, and dicyclopentadienyl [2,6-di-fluoro-3-(pyrrolo-1-yl)phenyl] titanium.

[0054] Examples of biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0055] Examples of halomethylated oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)ethylidene]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)ethylidene)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0056] Examples of halomethyltriazine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)triazine.

[0057] Examples of α-aminoalkylphenyl ketone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butane-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

[0058] As a photopolymerization initiator (A), oxime ester compounds are preferred from the viewpoints of sensitivity and printability. In particular, oxime ester compounds are more effective when using alkali-soluble resins containing phenolic hydroxyl groups in the photosensitive resin composition. Oxime ester compounds have high photoreaction quantum yields and highly reactive free radicals, thus high sensitivity can be obtained with small amounts, and they are stable to thermal reactions, enabling the production of photosensitive resin compositions with high sensitivity even with small quantities.

[0059] Examples of oxime ester compounds include those represented by the general formula (A1) below.

[0060] [Chemical Formula 2]

[0061]

[0062] In formula (A1), R e21a The group represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic cycloal group optionally having a substituent.

[0063] R e21b It represents any functional group containing an aromatic ring.

[0064] R e22a This indicates an alkyl acyl group that may optionally have a substituent, or an aromatic acyl group that may optionally have a substituent.

[0065] n represents an integer that is either 0 or 1.

[0066] R e21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility and sensitivity to solvents, it is preferably 1 or more, more preferably 2 or more, and further preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, and cyclohexylmethyl.

[0067] Substituents optionally present as alkyl groups include, for example, aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl, N-acetyl-N-acetoxyamino, methoxycarbonyl, and ethoxycarbonyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred; from the viewpoint of sensitivity and ink repellency, methoxycarbonyl and ethoxycarbonyl groups are preferred.

[0068] As R e21a The aromatic cyclic group in the aromatic cyclic group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic group is not particularly limited, but from the viewpoint of solubility in the photosensitive resin composition, 5 or more is preferred. Furthermore, from the viewpoint of developability, 30 or less is preferred, more preferably 20 or less, and even more preferably 12 or less. For example, 5 to 30 is preferred, more preferably 5 to 20, and even more preferably 5 to 12.

[0069] Examples of aromatic cyclic groups include phenyl, naphthyl, pyridyl, and furanyl. From the viewpoint of reproducibility, phenyl and naphthyl are preferred, and phenyl is more preferred.

[0070] Substituents that may be optionally present in an aromatic cyclic group include, for example, hydroxyl, carboxyl, halogen, amino, amide, alkyl, alkoxy, and groups formed by linking these substituents. From the viewpoint of reproducibility, alkyl, alkoxy, and groups formed by linking them are preferred, and linked alkoxy groups are more preferred.

[0071] From a sensitivity perspective, R e21a Preferably, it is an alkyl group that optionally has a substituent, or an aromatic cycloal group that optionally has a substituent.

[0072] As R e21bPreferably, it is a carbazole group, a thioxanone group, a diphenyl sulfide group, a fluorenyl group, or an indole group that are optionally substituted. From the viewpoint of sensitivity, a carbazole group that is optionally substituted is more preferred, and from the viewpoint of developing solubility and inkjet coating properties, a diphenyl sulfide group is more preferred.

[0073] R e22a The number of carbon atoms in the alkanoyl group is not particularly limited, but from the viewpoint of solubility and sensitivity to solvents, it is preferably 2 or more, further preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and even more preferably 5 or less. For example, it is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, and even more preferably 2 to 5.

[0074] Examples of alkyl acyl groups include acetyl, propionyl, and butyryl.

[0075] Substituents that may be optionally present on the alkyl acyl group include, for example, aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0076] R e22a The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of solubility and sensitivity to solvents, it is preferably 7 or more, more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. For example, it is preferably 7 to 20, more preferably 7 to 15, and even more preferably 7 to 10. Examples of aryl groups include benzoyl and naphthyl.

[0077] Substituents that may be optionally present in the aryl group include, for example, hydroxyl, carboxyl, halogen, amino, amide, and alkyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0078] From a sensitivity perspective, R e22a Preferably, it is an alkyl acyl group that optionally has a substituent, more preferably an unsubstituted alkyl acyl group, and even more preferably an acetyl group.

[0079] For example, photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, International Publication No. 2012 / 68879, International Publication No. 2021 / 175855, and Japanese Patent Application Publication No. 2016-133574 can be used.

[0080] The oxime ester compounds are more preferably the following (A1-1) to (A1-6) oxime ester compounds, further preferably (A1-3) and (A1-6), and particularly preferably (A1-6).

[0081] [Chemical Formula 3]

[0082]

[0083] (A) A single photopolymerization initiator can be used alone, or two or more can be used in combination.

[0084] (A) In photopolymerization initiators, sensitizing pigments and polymerization accelerators corresponding to the wavelength of the image exposure light source can be combined as needed to improve sensitivity. Examples of sensitizing pigments include: xanthones as described in Japanese Patent Application Publication Nos. 4-221958 and 4-219756; heterocyclic coumarin pigments as described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; 3-coumarinone compounds as described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; methylene pyrrole pigments as described in Japanese Patent Application Publication Nos. 6-19240; and Japanese Patent Application Publication Nos. 47-2528 and 54-15529. Pigments having a dialkylaminobenzene skeleton as described in Japanese Published Publication No. 2, Japanese Published Publication No. 45-37377, Japanese Published Publication No. 48-84183, Japanese Published Publication No. 52-112681, Japanese Published Publication No. 58-15503, Japanese Published Publication No. 60-88005, Japanese Published Publication No. 59-56403, Japanese Published Publication No. 2-69, Japanese Published Publication No. 57-168088, Japanese Published Publication No. 5-107761, Japanese Published Publication No. 5-210240, and Japanese Published Publication No. 4-288818.

[0085] As sensitizing pigments, amino-containing sensitizing pigments are preferred, and compounds having both an amino group and a phenyl group within the same molecule are more preferred. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone are further preferred; benzophenone-based compounds such as 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, and 2,5-bis(p-diethylaminophenyl)-1,3,4- Compounds containing p-dialkylaminophenyl, such as oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc., are particularly preferred to be 4,4'-dialkylaminobenzophenone.

[0086] Sensitizing pigments can be used alone or in combination with two or more.

[0087] As polymerization accelerators, aromatic amines such as ethyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminoacetophenone, as well as aliphatic amines such as n-butylamine and N-methyldiethanolamine can be used.

[0088] Polymerization accelerators can be used alone or in combination with two or more.

[0089] The proportion of photopolymerization initiator (A) in the photosensitive resin composition of the present invention is not particularly limited. Relative to the total solid content of the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, even more preferably 12% by mass or less, particularly preferably 10% by mass or less, and most preferably 8% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, further preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, particularly preferably 2 to 8% by mass, and particularly preferably 3 to 8% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to reduce residue.

[0090] The proportion of photopolymerization initiator (A) to photopolymerizable compound (C) in the photosensitive resin composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 4 parts by mass or more, even more preferably 6 parts by mass or more, particularly preferably 10 parts by mass or more, and preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 200 parts by mass is preferred, more preferably 2 to 200 parts by mass, further preferably 4 to 100 parts by mass, even more preferably 6 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass. By setting the value above the lower limit, there is a tendency to improve ink repellency. By setting the value below the upper limit, there is a tendency to reduce residue.

[0091] [1-1-2] (B) Component: Alkali-soluble resin

[0092] The photosensitive resin composition of the present invention contains (B) an alkali-soluble resin. As an alkali-soluble resin, there is no particular limitation as long as it can be developed with an alkali developer. Various resins containing carboxyl groups and / or hydroxyl groups can be listed as alkali-soluble resins. Among these, resins containing carboxyl groups are preferred from the viewpoint of obtaining a spacer wall with a suitable cone angle, suppressing the leakage of liquid repellent from the spacer wall surface due to thermal melting during post-baking, and thus maintaining ink repellency.

[0093] [Base-soluble resins with olefinic double bonds (b)]

[0094] In the photosensitive resin composition of the present invention, (B) the alkali-soluble resin preferably comprises an alkali-soluble resin (b) having olefinic double bonds (hereinafter sometimes abbreviated as "alkali-soluble resin (b)"). There is a tendency that the sensitivity is increased by including an alkali-soluble resin (b) having olefinic double bonds, and the ink repellency of the spacer wall is increased by suppressing the outflow of the liquid repellent during development.

[0095] The specific structure of the alkali-soluble resin (b) having olefinic double bonds is not particularly limited. From the viewpoint of development solubility, epoxy (meth)acrylate resin (B1) and / or acrylic copolymer resin (B2) are preferred. From the viewpoint of reducing degassing, epoxy (meth)acrylate resin (B1) is more preferred.

[0096] The following is a detailed description of epoxy (meth)acrylate resin (B1).

[0097] [Epoxy (meth)acrylate resin (B1)]

[0098] Epoxy (meth)acrylate resin (B1) is a resin obtained by adding an acid or ester compound having an olefinic unsaturated bond (olefinic double bond) to an epoxy resin, and further adding a polybasic acid or its anhydride. For example, a resin obtained by ring-opening addition of the epoxy group of the epoxy resin to the carboxyl group of an acid having an olefinic unsaturated bond, thereby adding an olefinic unsaturated bond to the epoxy resin via an ester bond (-COO-), while simultaneously adding a carboxyl group of a polybasic acid anhydride to the hydroxyl group generated in the process. Another example is a resin obtained by simultaneously adding a polyol during the addition of a polybasic acid anhydride. Furthermore, resins obtained by reacting the carboxyl group of the resin obtained in the above reaction with a compound having a functional group capable of further reaction are also included in epoxy (meth)acrylate resin (B1).

[0099] It should be noted that resins containing an isocyanuric acid backbone (B3) as described below are not included in epoxy (meth)acrylate resins (B1).

[0100] As mentioned above, epoxy (meth)acrylate resins do not actually have epoxy groups in their chemical structure, and are not limited to "(meth)acrylate". However, since epoxy compounds (epoxy resins) are the raw materials and "(meth)acrylate" is a representative example, it is named as such according to common usage.

[0101] Furthermore, from the viewpoint of degassing, epoxy (meth)acrylate resins with aromatic rings in the main chain can be used more preferably as epoxy (meth)acrylate resins (B1).

[0102] Here, epoxy resin refers to the raw material compound included before the resin is formed by thermosetting. As this epoxy resin, it can be appropriately selected from known epoxy resins. Furthermore, the epoxy resin can be a compound obtained by reacting a phenolic compound with an epoxy halide. As the phenolic compound, compounds having divalent or higher phenolic hydroxyl groups are preferred; these can be monomers or polymers.

[0103] Specifically, examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic varnish type epoxy resin, cresol varnish type epoxy resin, biphenyl phenolic varnish type epoxy resin, triphenol epoxy resin, epoxides of polymers of phenol and dicyclopentadiene, dihydroxyfluorene type epoxy resin, dihydroxyalkyleneoxyfluorene type epoxy resin, diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene, and diglycidyl ether of 1,1-bis(4'-hydroxyphenyl)adamantane. Resins with an aromatic ring in the main chain are preferred.

[0104] From the viewpoint of cured film strength, bisphenol A type epoxy resin, phenolic varnish type epoxy resin, cresol varnish type epoxy resin, epoxide of polymer of phenol and dicyclopentadiene, and epoxide of 9,9-bis(4'-hydroxyphenyl)fluorene are preferred, and bisphenol A type epoxy resin is more preferred.

[0105] Examples of acids containing olefinic unsaturated bonds include: (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citralic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and the reaction product of (meth)acrylic acid and ε-caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.

[0106] Examples of polybasic acids (anhydrides) include, for example, succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and their anhydrides. They can be used alone or in combination with two or more. Among these, from the viewpoint of reducing residue in the pixel area after development, succinic anhydride, maleic anhydride, and itaconic anhydride are preferred, with succinic anhydride being more preferred.

[0107] By using polyols, the molecular weight of epoxy (meth)acrylate resin (B1) can be increased, and branching can be introduced into the molecule, tending to achieve a balance between molecular weight and viscosity. Furthermore, there is a tendency to increase the incorporation rate of acid groups into the molecule, making it easier to achieve a balance between sensitivity, adhesion, etc.

[0108] Examples of polyols include: trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. They can be used alone or in combination with two or more.

[0109] The acid value of the epoxy (meth)acrylate resin (B1) is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, further preferably 40 mg KOH / g or more, even more preferably 60 mg KOH / g or more. It is also preferably 200 mg KOH / g or less, more preferably 180 mg KOH / g or less, further preferably 150 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less. The upper and lower limits can be combined arbitrarily; for example, 10–200 mg KOH / g is preferred, more preferably 10–180 mg KOH / g, further preferably 20–150 mg KOH / g, even more preferably 40–120 mg KOH / g, and particularly preferably 60–100 mg KOH / g. By setting it above the lower limit, residue is easily reduced. Furthermore, by setting it below the upper limit, there is a tendency for degassing during element light emission to decrease.

[0110] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (B1) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, even more preferably 4000 or more, particularly preferably 5000 or more, especially preferably 6000 or more, most preferably 7000 or more. Furthermore, it is preferably 30000 or less, more preferably 20000 or less, further preferably 15000 or less, and especially preferably 10000 or less. The upper and lower limits can be combined arbitrarily, preferably 1000–30000, more preferably 2000–30000, further preferably 3000–20000, even more preferably 4000–20000, especially preferably 5000–15000, particularly preferably 6000–15000, and most preferably 7000–10000. By setting the value above the lower limit, there is a tendency for degassing to decrease during element light emission. Furthermore, by setting it below the aforementioned upper limit value, there is a tendency for residue to decrease.

[0111] Epoxy (meth)acrylate resin (B1) can be synthesized by conventionally known methods. Specifically, it can be synthesized by dissolving the epoxy resin in an organic solvent, adding the acid or ester compound having an olefinic unsaturated bond in the presence of a catalyst and a thermal polymerization inhibitor to carry out an addition reaction, and then further adding a polybasic acid or its anhydride to continue the reaction.

[0112] Examples of organic solvents include: methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of catalysts include: tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride; phosphorus compounds such as triphenylphosphine; and antimony compounds such as triphenylantimony. Examples of inhibitors of thermal polymerization include: hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.

[0113] They can be used individually or in combination with two or more.

[0114] For acid or ester compounds having olefinic unsaturated bonds, an amount of 0.7 to 1.3 stoichiometric equivalents, more preferably 0.9 to 1.1 stoichiometric equivalents, relative to the stoichiometric equivalents of the epoxy group 1 in the epoxy resin can be used. The temperature for the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C. For polybasic acids (anhydrides), an amount of 0.1 to 1.2 stoichiometric equivalents, more preferably 0.2 to 1.1 stoichiometric equivalents, relative to the stoichiometric equivalents of the hydroxyl group 1 generated in the addition reaction can be used.

[0115] From the viewpoint of degassing during element light emission, epoxy (meth)acrylate resin (B1) preferably contains at least one selected from the group consisting of epoxy (meth)acrylate resin (B1-1) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (B1-1)") containing a partial structure represented by the following general formula (i), epoxy (meth)acrylate resin (B1-2) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (B1-2)") containing a partial structure represented by the following general formula (ii), and epoxy (meth)acrylate resin (B1-3) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (B1-3)") containing a partial structure represented by the following general formula (iii).

[0116] Regarding epoxy (meth)acrylate resins (B1), among these, from the viewpoint of reducing degassing during element light emission, epoxy (meth)acrylate resins (B1-1) containing a partial structure represented by the following general formula (i) are preferred, and epoxy (meth)acrylate resins (B1-1) containing a partial structure represented by the following general formula (i) are more preferred. One reason for this is that it has a rigid main framework, making it less susceptible to thermal decomposition, etc.

[0117] [Chemical Formula 4]

[0118]

[0119] In equation (i), R b11 R represents a hydrogen atom or a methyl group. b12 The symbol represents a divalent hydrocarbon group that may optionally have substituents. The benzene ring in formula (i) may be further substituted with any substituents. k represents an integer from 1 to 2, and * represents a bond.

[0120] (R) b12 )

[0121] In equation (i), R b12 This indicates a divalent hydrocarbon group that may optionally have substituents.

[0122] As divalent hydrocarbon groups, examples include divalent aliphatic groups, divalent aromatic cyclic groups, and groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic cyclic groups.

[0123] Divalent aliphatic groups can be categorized as linear, branched, or cyclic aliphatic groups. From the viewpoint of developer solubility, linear aliphatic groups are preferred; conversely, from the viewpoint of reducing developer penetration into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is typically 1 or more, preferably 3 or more, more preferably 6 or more, and further preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 20 is preferred, more preferably 3 to 15, and even more preferably 6 to 10. By setting the value above the lower limit, there is a tendency for improved developer adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0124] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene. From the viewpoint of reducing residue, methylene is preferred.

[0125] As a divalent branched aliphatic group, examples can be listed that have the following structure: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl as side chains on the above-mentioned divalent straight-chain aliphatic group.

[0126] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and further preferably 10 or less, more preferably 5 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. Setting the value above the lower limit tends to increase the residual film rate. Furthermore, setting the value below the upper limit tends to reduce residue. Examples of divalent cyclic aliphatic groups include those obtained by removing two hydrogen atoms from the rings of cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isoboronane, and adamantane. From the viewpoint of developing adhesion, groups obtained by removing two hydrogen atoms from the adamantane ring are preferred.

[0127] Substituents that may be optionally present as divalent aliphatic groups include, for example, alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0128] Examples of divalent aromatic cyclic groups include divalent aromatic hydrocarbon cyclic groups and divalent aromatic heterocyclic groups. The number of carbon atoms is typically 4 or more, preferably 5 or more, more preferably 6 or more, and further preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 20 is preferred, more preferably 5 to 15, and even more preferably 6 to 10. Setting the value above the lower limit tends to improve the adhesion of the developing solution. Furthermore, setting the value below the upper limit tends to reduce residue.

[0129] The aromatic hydrocarbon ring in a divalent aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of divalent aromatic hydrocarbon cyclic groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, benzo[a]pyrene rings, cyclopentadiene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0130] Aromatic heterocycles, as divalent aromatic heterocyclic groups, can be monocyclic or fused rings. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazolium rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazolium rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazine rings, quinoxaline rings, phenanthridine rings, primidine rings, quinazoline rings, quinazolineone rings, and azurite rings. From the viewpoint of photocurability, benzene rings and naphthalene rings with two free valences are preferred, and benzene rings with two free valences are more preferred.

[0131] Substituents optionally present in the divalent aromatic cyclic group include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and glycidyl ether groups. From the viewpoint of curability, unsubstituted groups are preferred.

[0132] Examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups include groups formed by linking one or more of the aforementioned divalent aliphatic groups to one or more of the aforementioned divalent aromatic cyclic groups.

[0133] The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0134] The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0135] As a group formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups, examples include groups represented by the following formulas (iA) to (iF). From the viewpoint of good degassing due to the rigidity of the skeleton, groups represented by the following formula (iA) are preferred. * in the chemical formula indicates a bond.

[0136] [Chemical Formula 5]

[0137]

[0138] The benzene ring in formula (i) can be further substituted with any substituents. Examples of substituents for the benzene ring in formula (i) include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; within the chemically permissible range, there can be one or more substituents.

[0139] From the perspective of solidification, unsubstituted is preferred.

[0140] (k)

[0141] When k=2, there is a tendency for improved curability, which is preferred. Furthermore, within the same molecule, the k=1 and k=2 partial structures can coexist.

[0142] From the viewpoint of developing solubility, the partial structure represented by formula (i) is preferably the partial structure represented by the following formula (i-1).

[0143] [Chemical Formula 6]

[0144]

[0145] In equation (i-1), R b11 R b12 And k has the same meaning as equation (i).

[0146] R X * Represents a hydrogen atom or a polybasic acid residue. * Represents a bond. The benzene ring in formula (i-1) can also be further substituted with any substituents.

[0147] R X The term "polyacid residue" refers to a monovalent or divalent group obtained by removing one or two OH groups from a polyacid. Examples of polyacids include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, inner methylene tetrahydrophthalic acid, chloramphenic acid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.

[0148] From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0149] The benzene ring in formula (i-1) can also be further replaced by any substituents. As substituents, the substituents listed in relation to the benzene ring in formula (i) are preferred.

[0150] An epoxy (meth)acrylate resin (B1) molecule may contain one or more of the partial structures represented by formula (B1-1), for example, R X Partial structure of hydrogen atom and R X The partial structures of polyacid residues can coexist.

[0151] The number of partial structures represented by formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (B1) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Furthermore, it is preferably 20 or less, and even more preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. Preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 15. By setting it to the lower limit or above, there is a tendency to reduce degassing. By setting it to the upper limit or below, there is a tendency to improve developability.

[0152] One molecule of epoxy (meth)acrylate resin (B1-1) may contain one or more of the partial structures represented by formula (i-1).

[0153] The number of partial structures represented by formula (i) contained in one molecule of epoxy (meth)acrylate resin (B1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and preferably 10 or less, even more preferably 8 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 10, and even more preferably 3 to 8. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0154] The following are specific examples of epoxy (meth)acrylate resins (B1-1).

[0155] [Chemical Formula 7]

[0156]

[0157] [Chemical Formula 8]

[0158]

[0159] [Chemical Formula 9]

[0160]

[0161] [Chemical Formula 10]

[0162]

[0163] [Chemical Formula 11]

[0164]

[0165] [Chemical Formula 12]

[0166]

[0167] [Chemical Formula 13]

[0168]

[0169] [Chemical Formula 14]

[0170]

[0171] [Chemical Formula 15]

[0172]

[0173] As another option, from the viewpoint of developing adhesion, epoxy (meth)acrylate resin (B1) is preferably an epoxy (meth)acrylate resin (B1-2) containing a partial structure represented by the following formula (ii).

[0174] [Chemical Formula 16]

[0175]

[0176] In equation (ii), R b13 Each can independently represent a hydrogen atom or a methyl group. R b14 This indicates a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain. * indicates a bonded bond.

[0177] (R) b14 )

[0178] In equation (ii), R b14 This indicates a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain.

[0179] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0180] The number of rings in the aliphatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0181] The aliphatic cyclic group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 40 is preferred, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. Setting the value above the lower limit tends to improve the adhesion of the developing sample. Furthermore, setting the value below the upper limit tends to reduce residue.

[0182] Examples of aliphatic rings that can be classified as aliphatic ring groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. Among these, the adamantane ring is preferred from the viewpoint of good adhesion to radiometric imaging.

[0183] The number of rings in the aromatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 5, and even more preferably 3 to 4. By setting the value above the lower limit, there is a tendency to reduce residue. Furthermore, by setting the value below the upper limit, there is a tendency to improve the adhesion of the developing solution.

[0184] Aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic group is typically 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 40 is preferred, more preferably 6 to 40, even more preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15. Setting the value above the lower limit tends to reduce residue. Furthermore, setting the value below the upper limit tends to improve development adhesion.

[0185] Examples of aromatic rings in aromatic cyclic groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, benzo[a]pyrene rings, cyclopentadiene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings. From the viewpoint of patterning properties, fluorene rings are preferred.

[0186] The divalent hydrocarbon group in a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. Examples include divalent aliphatic groups, divalent aromatic cyclic groups, and groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic cyclic groups.

[0187] Divalent aliphatic groups can be categorized as linear, branched, or cyclic aliphatic groups. From the viewpoint of developer solubility, linear aliphatic groups are preferred; conversely, from the viewpoint of reducing developer penetration into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is typically 1 or more, preferably 3 or more, more preferably 6 or more, and further preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined; for example, 1 to 25 is preferred, more preferably 3 to 20, and even more preferably 6 to 15. By setting the value above the lower limit, there is a tendency for improved developer adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0188] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene. From the viewpoint of residues, methylene is preferred.

[0189] As a divalent branched aliphatic group, examples can be listed that have the following structure: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl as side chains on the above-mentioned divalent straight-chain aliphatic group.

[0190] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0191] Examples of divalent cyclic aliphatic groups include those obtained by removing two hydrogen atoms from cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isoborane, and adamantane rings. From the viewpoint of good adhesion, groups obtained by removing two hydrogen atoms from an adamantane ring are preferred.

[0192] Substituents that may be optionally present as divalent aliphatic groups include, for example, alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0193] Examples of divalent aromatic cyclic groups include divalent aromatic hydrocarbon cyclic groups and divalent aromatic heterocyclic groups. The number of carbon atoms is typically 4 or more, preferably 5 or more, more preferably 6 or more, and further preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. Setting the value above the lower limit tends to improve the adhesion of the developing solution. Furthermore, setting the value below the upper limit tends to reduce residue.

[0194] The aromatic hydrocarbon ring in a divalent aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of divalent aromatic hydrocarbon cyclic groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, benzo[a]pyrene rings, cyclopentadiene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0195] Aromatic heterocycles, as divalent aromatic heterocyclic groups, can be monocyclic or fused rings. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazolium rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazolium rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazine rings, quinoxaline rings, phenanthridine rings, primidine rings, quinazoline rings, quinazolineone rings, and azurite rings. From the viewpoint of photocurability, benzene rings and naphthalene rings with two free valences are preferred, and benzene rings with two free valences are more preferred.

[0196] Substituents optionally present in the divalent aromatic cyclic group include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. From the viewpoint of curability, unsubstituted substituents are preferred.

[0197] Examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups include groups formed by linking one or more of the aforementioned divalent aliphatic groups to one or more of the aforementioned divalent aromatic cyclic groups.

[0198] The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0199] The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0200] A group consisting of one or more divalent aliphatic groups linked to one or more divalent aromatic cyclic groups, such as those represented by formulas (iA) to (iF). From the viewpoint of reducing residue, groups represented by formula (iC) are preferred.

[0201] The bonding form of the cyclic hydrocarbon group as a side chain is not particularly limited compared to these divalent hydrocarbon groups. For example, the form in which a hydrogen atom of an aliphatic group or an aromatic cyclic group is replaced by a side chain can be listed; the form in which a carbon atom of an aliphatic group is incorporated to form a cyclic hydrocarbon group as a side chain can also be listed.

[0202] From the viewpoint of imaging adhesion, the partial structure represented by formula (ii) is preferably the partial structure represented by the following formula (ii-1).

[0203] [Chemical Formula 17]

[0204]

[0205] In equation (ii-1), R b13 It has the same meaning as equation (ii). α This indicates a monovalent cyclic hydrocarbon group that may optionally have substituents. p is an integer greater than or equal to 1. The benzene ring in formula (ii-1) may be further substituted with any substituents. * indicates a bond.

[0206] (R) α )

[0207] In equation (ii-1), R α This indicates a monovalent cyclic hydrocarbon group that may optionally have substituents.

[0208] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0209] The number of rings in the aliphatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, and more preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 6 are preferred, 1 to 4 are more preferred, and 2 to 3 are even more preferred. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0210] The aliphatic cyclic group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 40 is preferred, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. Setting the value above the lower limit tends to improve the adhesion of the developing sample. Furthermore, setting the value below the upper limit tends to reduce residue.

[0211] Examples of aliphatic rings that can be classified as aliphatic ring groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoint of imaging adhesion, the adamantane ring is preferred.

[0212] The number of rings in the aromatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 10, and even more preferably 3 to 5. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0213] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. Furthermore, the number of carbon atoms in the aromatic cyclic group is typically 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. Setting the value above the lower limit tends to improve the adhesion of the developing solution. Furthermore, setting the value below the upper limit tends to reduce residue.

[0214] Examples of aromatic rings in aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the viewpoint of imaging adhesion, fluorene rings are preferred.

[0215] Substituents optionally present in the cyclic hydrocarbon group include, for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0216] p represents an integer greater than or equal to 1, preferably greater than or equal to 2, and further preferably less than or equal to 3. For example, it is preferably 1 to 3, and more preferably 1 to 2. By setting it to the lower limit or above, there is a tendency for improved development adhesion. Furthermore, by setting it to the upper limit or below, there is a tendency for reduced residue.

[0217] From the perspective of robust film curing and electrical properties, R α Preferably, it is a monovalent aliphatic cyclic group, and more preferably, it is an adamantyl group.

[0218] The benzene ring in formula (ii-1) can be further substituted with any substituents. Examples of substituents include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; there can be one or more. From the viewpoint of curability, unsubstituted is preferred.

[0219] The following are specific examples of some structures represented by equation (ii-1).

[0220] [Chemical Formula 18]

[0221]

[0222] [Chemical Formula 19]

[0223]

[0224] [Chemical Formula 20]

[0225]

[0226] [Chemical Formula 21]

[0227]

[0228] [Chemical Formula 22]

[0229]

[0230] From the viewpoint of imaging adhesion, the partial structure represented by formula (ii) is preferably the partial structure represented by the following formula (ii-2).

[0231] [Chemical Formula 23]

[0232]

[0233] In equation (ii-2), R b13 It has the same meaning as equation (ii). β This indicates a divalent cyclic hydrocarbon group that may optionally have substituents. The benzene ring in formula (ii-2) may also be further substituted with any substituents. * indicates a bond.

[0234] (R) β )

[0235] In equation (ii-2), R β This indicates a divalent cyclic hydrocarbon group that may optionally have substituents.

[0236] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0237] The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 5. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0238] The aliphatic cyclic group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 40 is preferred, 6 to 35 is more preferred, and 8 to 30 is even more preferred. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0239] Aliphatic rings among aliphatic cyclic groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoint of imaging adhesion, the adamantane ring is preferred.

[0240] The number of rings in the aromatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, and further preferably 10 or less, more preferably 5 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 10, and even more preferably 3 to 5. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0241] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. Furthermore, the number of carbon atoms in the aromatic cyclic group is typically 4 or more, preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. It is also preferred to have 40 or fewer carbon atoms, more preferably 30 or fewer, even more preferably 20 or fewer, and particularly preferably 15 or fewer. The upper and lower limits can be combined arbitrarily; for example, 4 to 40 is preferred, 6 to 30 is more preferred, 8 to 20 is even more preferred, and particularly preferably 10 to 15. Setting the value above the lower limit tends to improve the adhesion of the developing solution. Furthermore, setting the value below the upper limit tends to reduce residue.

[0242] Examples of aromatic rings in aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the viewpoint of imaging adhesion, fluorene rings are preferred.

[0243] Substituents optionally present in the cyclic hydrocarbon group include, for example, alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0244] From the perspective of solidification, R β Preferably, it is a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.

[0245] As another option, from the viewpoint of imaging adhesion, R is preferred. β It is a divalent aromatic cyclic group, more preferably a divalent fluorene cyclic group.

[0246] The benzene ring in formula (ii-2) can be further substituted with any substituents. Examples of substituents for the benzene ring in formula (ii-2) include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; there can be one or more. From the viewpoint of curability, unsubstituted substituents are preferred.

[0247] The following are specific examples of some structures represented by equation (ii-2).

[0248] [Chemical Formula 24]

[0249]

[0250] [Chemical Formula 25]

[0251]

[0252] [Chemical Formula 26]

[0253]

[0254] [Chemical Formula 27]

[0255]

[0256] From the viewpoint of solidification, the partial structure represented by formula (ii) is preferably the partial structure represented by the following formula (ii-3).

[0257] [Chemical Formula 28]

[0258]

[0259] In equation (ii-3), R b13 and R b14 It has the same meaning as equation (ii). Y1 R Y2 Each is independent, and R in equation (i-1) X They have the same meaning. * indicates a bonding bond.

[0260] One molecule of epoxy (meth)acrylate resin (B1-2) may contain one or more of the partial structures represented by formula (ii-3).

[0261] The number of partial structures represented by formula (ii) contained in one molecule of epoxy (meth)acrylate resin (B1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0262] As a further alternative, from the viewpoint of reducing degassing during element light emission, epoxy (meth)acrylate resin (B1) is preferably an epoxy (meth)acrylate resin (B1-3) containing a partial structure represented by the following formula (iii).

[0263] [Chemical Formula 29]

[0264]

[0265] In equation (iii), R b15 γ represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group optionally with substituents, or a divalent cyclic hydrocarbon group optionally with substituents. The benzene ring in formula (iii) may also be further substituted with any substituents. * represents a bonded bond.

[0266] (γ)

[0267] In formula (iii), γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent.

[0268] The alkylene group can be linear or branched. From the viewpoint of development solubility, a linear group is preferred, while from the viewpoint of development adhesion, a branched group is preferred. The number of carbon atoms is not particularly limited, but is generally 1 or more, preferably 2 or more, and further preferably 6 or less, more preferably 4 or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 6 is preferred, more preferably 2 to 4. By setting the value above the lower limit, there is a tendency to improve development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency to reduce residue.

[0269] Examples of alkylene compounds include methylene, ethylene, propylene, butylene, hexylene, and heptylene. From the viewpoint of balancing adhesion and solubility in development, methylene, ethylene, and propylene are preferred, and dimethylmethylene (2,2-propylene) is more preferred.

[0270] Substituents optionally present in the alkylene group include, for example, alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of balancing development adhesion and development solubility, unsubstituted groups are preferred.

[0271] As divalent cyclic hydrocarbon groups, examples include divalent aliphatic cyclic groups or divalent aromatic cyclic groups.

[0272] The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 5. By setting the value above the lower limit, there is a tendency for improved imaging adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0273] Furthermore, the aliphatic cyclic group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and more preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 40 is preferred, 6 to 35 is more preferred, and 8 to 30 is even more preferred. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0274] Examples of aliphatic rings that can be classified as aliphatic ring groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. From the viewpoint of imaging adhesion, the adamantane ring is preferred.

[0275] The number of rings in the aromatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 10, and even more preferably 3 to 5. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0276] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic group is typically 4 or more, preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. Furthermore, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 40 is preferred, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15. Setting the value above the lower limit tends to improve the adhesion of the developing solution. Furthermore, setting the value below the upper limit tends to reduce residue.

[0277] Examples of aromatic rings in aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the viewpoint of imaging adhesion, fluorene rings are preferred.

[0278] Substituents optionally present in the cyclic hydrocarbon group include, for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxyl. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0279] From the viewpoint of reducing residue, γ is preferably an alkylene group that optionally has a substituent, more preferably a dimethylmethylene group.

[0280] The benzene ring in formula (iii) can be further substituted with any substituents. Examples of substituents for the benzene ring in formula (iii) include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; there can be one or more. From the viewpoint of curability, unsubstituted is preferred.

[0281] From the viewpoint of developing solubility, the partial structure represented by formula (iii) is preferably the partial structure represented by the following formula (iii-1).

[0282] [Chemical Formula 30]

[0283]

[0284] In equation (iii-1), R b15 γ has the same meaning as in equation (iii). Z R in equation (i-1) X The meanings are the same. * indicates a bond. The benzene ring in formula (iii-1) can also be further substituted with any substituents.

[0285] The number of partial structures represented by formula (iii) contained in one molecule of epoxy (meth)acrylate resin (B1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 18 or less, even more preferably 15 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 18, more preferably 5 to 18, and even more preferably 10 to 15. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0286] The number of partial structures represented by formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin (B1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and preferably 18 or less, even more preferably 15 or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 18 is preferred, 3 to 18 is more preferred, and 5 to 15 is even more preferred. By setting the value above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for reduced residue.

[0287] The following are specific examples of epoxy (meth)acrylate resins (B1-3).

[0288] [Chemical Formula 31]

[0289]

[0290] [Chemical Formula 32]

[0291]

[0292] [Chemical Formula 33]

[0293]

[0294] <Acrylic Copolymer Resin (B2)>

[0295] As for (B) alkali-soluble resin, from the viewpoint of compatibility with pigments, dispersants, etc., acrylic copolymer resin (B2) is preferred, and the acrylic copolymer resin described in Japanese Patent Application Publication No. 2014-137466 is preferred.

[0296] Examples of acrylic copolymer resins (B2) include copolymers of an olefinic unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (B2-1)") with other olefinic unsaturated monomers that can be copolymerized (hereinafter referred to as "unsaturated monomer (B2-2)").

[0297] Examples of unsaturated monomers (B2-1) include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesocarboxylic acid; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl]; mono(meth)acrylates of polymers with carboxyl and hydroxyl groups at both ends, such as ω-carboxylated polycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

[0298] These unsaturated monomers (B2-1) can be used alone or in combination of two or more.

[0299] Examples of unsaturated monomers (B2-2) include: N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthene; methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, allyl methacrylate, benzyl methacrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (methyl) acrylate, polyethylene glycol (degree of polymerization 2-10) mono(methyl) acrylate, polypropylene glycol (degree of polymerization 2-10) mono(methyl) acrylate, cyclohexyl methacrylate, isobornyl methacrylate, tricyclohexyl methacrylate [5.2.1.0] 2 ,6Decane-8-yl ester, dicyclopentenyl (meth)acrylate, glyceryl mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane, etc. (meth)acrylates; cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0] 2,6 Vinyl ethers such as decane-8-yl vinyl ether, pentacyclic pentadecyl vinyl ether, and 3-(ethoxymethyl)-3-ethyloxetane; macromonomers with mono(meth)acryloyl groups at the ends of polymer chains such as polystyrene, poly(meth)acrylate, poly(meth)acrylate n-butyl acrylate, and polysiloxane.

[0300] These unsaturated monomers (B2-2) can be used alone or in combination of two or more.

[0301] In copolymers of unsaturated monomer (B2-1) and unsaturated monomer (B2-2), when the total amount of unsaturated monomer (B2-1) and unsaturated monomer (B2-2) is set to 100% by mass, the copolymerization ratio of unsaturated monomer (B2-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing unsaturated monomer (B2-1) within such a range, there is a tendency to obtain photosensitive compositions with excellent alkali developability and storage stability.

[0302] As copolymers of unsaturated monomer (B2-1) and unsaturated monomer (B2-2), examples include those disclosed in Japanese Patent Application Publication Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728.

[0303] The copolymer of unsaturated monomer (B2-1) and unsaturated monomer (B2-2) can be manufactured by known methods, for example, by controlling its structure, Mw, and Mw / Mn (Mn is the number average molecular weight) by the methods disclosed in Japanese Patent Application Publication No. 2003-222717, Japanese Patent Application Publication No. 2006-259680, and International Patent Publication No. 2007 / 029871.

[0304] In addition, the resin described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 can also be used as the acrylic copolymer resin (B2).

[0305] <Resin containing isocyanuric acid backbone (B3)>

[0306] From the viewpoint of gas barrier properties, resin (B3) containing an isocyanuric acid backbone may also be used as (B) alkali-soluble resin. Here, as resin (B3), resins containing an isocyanuric acid backbone as described in International Publication No. 2022 / 215712, Japanese Patent Application Publication No. 2020-75994, and Japanese Patent Application Publication No. 2023-55623 are preferred.

[0307] In (B) the alkali-soluble resin, it may contain any one of epoxy (meth)acrylate resin (B1), acrylic copolymer resin (B2), and resin containing an isocyanuric acid backbone (B3), or it may contain multiple types. Furthermore, it may also contain other alkali-soluble resins.

[0308] In the photosensitive resin composition of the present invention, the content of (B) alkali-soluble resin in the total solids of the photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less. The upper and lower limits can be combined arbitrarily; for example, preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass. By setting the lower limit or above, there is a tendency to improve developability. Furthermore, by setting the upper limit or below, there is a tendency to reduce degassing during element light emission.

[0309] When the photosensitive resin composition of the present invention contains epoxy (meth)acrylate resin (B1), the content of epoxy (meth)acrylate resin (B1) is not particularly limited. In the total solids content of the photosensitive resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less. The upper and lower limits can be combined arbitrarily; for example, it is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass. By setting it to the lower limit or above, there is a tendency to improve developability. Furthermore, by setting it to the upper limit or below, there is a tendency to reduce degassing during element light emission.

[0310] When the alkali-soluble resin (B) contains epoxy (meth)acrylate resin (B1), the content of epoxy (meth)acrylate resin (B1) in the alkali-soluble resin (B) is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. Furthermore, it is generally 100% by mass or less. The upper and lower limits can be combined arbitrarily; for example, 30-100% by mass is preferred, 50-100% by mass is more preferred, 70-100% by mass is more preferred, 80-100% by mass is even more preferred, and 90-100% by mass is particularly preferred. By setting it above the lower limit, there is a tendency for degassing to decrease.

[0311] The total content of (B) alkali-soluble resin and (C) photopolymerizable compound in the total solids composition of the photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, even more preferably 80% by mass or more, most preferably 90% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. The upper and lower limits can be combined arbitrarily; for example, 5 to 99% by mass is preferred, 10 to 99% by mass is more preferred, 30 to 99% by mass is more preferred, 50 to 97% by mass is even more preferred, 70 to 97% by mass is particularly preferred, 80 to 95% by mass is especially preferred, and 90 to 95% by mass is most preferred. By setting the lower limit value or above, there is a tendency to improve curability. Furthermore, by setting the upper limit value or below, there is a tendency to reduce degassing during element light emission.

[0312] As for the proportion of (B) alkali-soluble resin to (C) photopolymerizable compound in the photosensitive resin composition, it is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, and preferably 400 parts by mass or less, more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 120 parts by mass or less. The upper and lower limits can be combined arbitrarily; for example, it is preferably 50 to 400 parts by mass, more preferably 60 to 300 parts by mass, further preferably 70 to 200 parts by mass, and particularly preferably 80 to 120 parts by mass. By setting it to the lower limit or above, there is a tendency for improved development adhesion. Furthermore, by setting it to the upper limit or below, there is a tendency for improved curability.

[0313] [1-1-3] (C) Component; Photopolymerizable compound

[0314] The photosensitive resin composition of the present invention contains a (C) photopolymerizable compound. It is believed that high sensitivity can be achieved by including the (C) photopolymerizable compound.

[0315] Photopolymerizable compounds are those having one or more olefinic unsaturated bonds (olefinic double bonds) within their molecules. From the viewpoints of polymerizability, crosslinking ability, and the ability to amplify the difference in developer solubility between exposed and unexposed areas, compounds having two or more olefinic unsaturated bonds within their molecules are preferred. These unsaturated bonds are more preferably derived from (meth)acryloyloxy groups, that is, (meth)acrylate compounds are even more preferred.

[0316] In the photosensitive resin composition of the present invention, it is particularly desirable to use a polyfunctional olefin monomer having two or more olefin unsaturated bonds in one molecule. The number of olefin unsaturated groups in the polyfunctional olefin monomer is not particularly limited, but preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and preferably 15 or less, more preferably 10 or less, further preferably 8 or less, particularly preferably 7 or less. The upper and lower limits can be combined arbitrarily; for example, 2 to 15 is preferred, more preferably 3 to 10, further preferably 4 to 8, and particularly preferably 5 to 7. By setting the value above the lower limit, there is a tendency for increased polymerizability and higher sensitivity. By setting the value below the upper limit, there is a tendency for better developability.

[0317] Examples of photopolymerizable compounds include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; esters obtained by esterification reactions of aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and other polyhydroxy compounds with unsaturated and polycarboxylic acids; compounds obtained by reacting aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and other polyhydroxy compounds with lactone compounds and unsaturated carboxylic acids; and compounds obtained by reacting aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and other polyhydroxy compounds with (poly)ethylene glycol compounds and unsaturated carboxylic acids.

[0318] Examples of acrylates formed from aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glyceryl acrylate; acrylates of these compounds can be replaced with methyl methacrylate. Methacrylates of these compounds; itaconic acid esters in which the acrylates of these compounds are replaced with itaconic acid esters; crotonic acid esters in which the acrylates of these compounds are replaced with crotonic acid esters; maleic acid esters in which the acrylates of these compounds are replaced with maleic acid esters; reactants of pentaerythritol and caprolactone with (meth)acrylic acid; reactants of dipentaerythritol and caprolactone with (meth)acrylic acid; reactants of pentaerythritol and (poly)ethylene glycol with (meth)acrylic acid; reactants of dipentaerythritol and (poly)ethylene glycol with (meth)acrylic acid.

[0319] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, and other acrylates and methacrylates of aromatic polyhydroxy compounds.

[0320] Esters, obtained through the esterification reaction of polyvalent hydroxyl compounds such as aliphatic and aromatic polyhydroxyl compounds with unsaturated and polyvalent carboxylic acids, do not necessarily have to be a single substance. Examples include: condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0321] Examples of photopolymerizable compounds used in the photosensitive resin compositions of the present invention, other than those described above, include, for example, urethane (meth)acrylates such as reaction products of polyisocyanate compounds with hydroxyl-containing (meth)acrylates or reaction products of polyisocyanate compounds with polyols and hydroxyl-containing (meth)acrylates; epoxy acrylates such as addition reactions of polyvalent epoxy compounds with hydroxyl-containing (meth)acrylates or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate.

[0322] Examples of urethane (meth)acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoesha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

[0323] From the viewpoint of appropriate cone angle, sensitivity, and inkjet coating properties, the following compounds are preferred as photopolymerizable compounds: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and compounds obtained by reacting aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, or other polyhydroxy compounds with (poly) glycol compounds and unsaturated carboxylic acids; more preferably: dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-[tris(meth)acryloyloxymethyl]ethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, a reaction product of pentaerythritol with (poly) glycol and (meth)acrylic acid, and a reaction product of dipentaerythritol with (poly) glycol and (meth)acrylic acid; even more preferably: a reaction product of pentaerythritol with (poly) glycol and (meth)acrylic acid, and a reaction product of dipentaerythritol with (poly) glycol and (meth)acrylic acid.

[0324] The following are further preferred as reactants of pentaerythritol with polyethylene glycol and methacrylic acid, and as reactants of dipentaerythritol with polyethylene glycol and methacrylic acid.

[0325] [Chemical Formula 34]

[0326]

[0327] In formula (C-1), m represents 1 to 3. In formula (C-2), n represents 1 to 3. Further preferred are (C) photopolymerizable compounds containing formula (C-1).

[0328] They can be used individually or in combination with two or more.

[0329] In the photosensitive resin composition of the present invention, the molecular weight of (C) the photopolymerizable compound is not particularly limited, but from the viewpoint of sensitivity, cone angle, and inkjet coating properties, it is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, even more preferably 300 or more, particularly preferably 400 or more, especially preferably 500 or more, preferably 1000 or less, and more preferably 700 or less. The upper and lower limits can be combined arbitrarily; for example, it is preferably 100 to 1000, more preferably 150 to 1000, further preferably 200 to 1000, even more preferably 300 to 700, especially preferably 400 to 700, and particularly preferably 500 to 700.

[0330] (C) The number of carbon atoms in the photopolymerizable compound is not particularly limited. From the viewpoint of sensitivity, cone angle, and inkjet coating properties, it is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, even more preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, further preferably 35 or less, and particularly preferably 30 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 7 to 50, more preferably 10 to 50, further preferably 15 to 40, even more preferably 20 to 35, and particularly preferably 25 to 30.

[0331] In the photosensitive resin composition of the present invention, the content of the photopolymerizable compound (C) in the total solids of the photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less. The upper and lower limits can be combined arbitrarily, for example, preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, even more preferably 30 to 55% by mass, and particularly preferably 40 to 50% by mass. By setting it above the lower limit, there is a tendency to obtain suitable internal curing properties. By setting it below the upper limit, there is a tendency for good developability.

[0332] [1-1-4] (D) compound

[0333] (D) The compound is a compound having a cyclic ether group with 2 to 3 carbon atoms and having an aromatic ring and / or a heterocycle. Examples of cyclic ether groups with 2 to 3 carbon atoms include oxobutyl and epoxy groups.

[0334] Compounds containing oxocyclic butyl and aromatic rings include those containing phenylene, biphenylene, and fluorene groups. Specifically, examples include compounds described in UBE Corporation's "ETERNACOLL OXBP" and "ETERNACOLL OXIPA", Toa Synthetic Co., Ltd.'s "OXT-121", Japanese Patent Application Publication No. 2000-336082, and Japanese Patent Application Publication No. 2014-131969.

[0335] Examples of compounds having epoxy groups and aromatic rings and / or heterocycles include: bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenolic varnish type epoxy resins, cresol phenolic varnish type epoxy resins, epoxy resins containing biphenyl phenolic varnish, polymeric epoxy resins of phenol and dicyclopentadiene, naphthalene type epoxy resins, triphenol methane type epoxy resins, fluorene bisphenol type epoxy resins, diglycidyl ethers of 9,9-bis(4'-hydroxyphenyl)fluorene, diglycidyl tetrahydrophthalate, diglycidyl phthalate and other glycidyl esters; tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol and other glycidyl amines; triglycidyl isocyanurate and other heterocyclic epoxy resins.

[0336] (D) The compound may preferably be a compound with an aromatic ring in its main chain.

[0337] From the viewpoint of reducing degassing, bisphenol A type epoxy resin, phenolic varnish epoxy resin, cresol varnish epoxy resin, polymeric epoxy resin of phenol and dicyclopentadiene, epoxy resin containing biphenyl phenolic varnish, and diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene are preferred, bisphenol A type epoxy resin and epoxy resin containing biphenyl phenolic varnish are more preferred, and epoxy resin containing biphenyl phenolic varnish is even more preferred.

[0338] As epoxy resins, the following are preferred: bisphenol A type epoxy resins (e.g., Mitsubishi Chemical's "jER828", "jER1001", "jER1002", "jER1004", and Nippon Kayaku Co., Ltd.'s "NER-1302" (epoxy equivalent 323, softening point 76℃) etc.), Nippon Kayaku Co., Ltd.'s RE-310S (epoxy equivalent 183), bisphenol F type resins (e.g., Mitsubishi Chemical's "jER807", "jER4004P", "jER4005P", "jER4007P", and Nippon Kayaku Co., Ltd.'s "NER-7406" (epoxy equivalent 350, softening point 66℃) etc.), bisphenol S type epoxy resins, biphenyl glycidyl ether (e.g., Mitsubishi Chemical's "jERYX-4000"), phenolic varnish type epoxy resins (e.g. Examples of epoxy resins include: Nippon Kayaku Co., Ltd.'s "EPPN-201", Mitsubishi Chemical Co., Ltd.'s "jER152" and "jER154", and Dow Chemical Co., Ltd.'s "DEN-438"); (ortho, meta, and para-)cresol phenolic varnish-type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EOCN-102S", "EOCN-1020", and "EOCN-104S"); triglycidyl isocyanurate esters (e.g., Nissan Chemical Co., Ltd.'s "TEPIC"); triphenol methane-type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EPPN-501", "EPPN-502", and "EPPN-503"); and alicyclic epoxy resins (e.g., CELLOXIDE 2021P and "CELLOXIDE"). EHPE), epoxy resins obtained by reacting dicyclopentadiene with phenol and then glycidizing the phenolic resin (e.g., DIC's "EXA-7200", Nippon Kayaku Co., Ltd.'s "NC-7300", "XD-1000"), biphenyl-type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "NC-7000"), and Osaka Organic Chemical Industry Co., Ltd.'s "E-201".

[0339] More preferably, a compound containing biphenylphenolic varnish epoxy resin, and even more preferably a compound having the structural unit shown in the following formula (1) (D1).

[0340] [Chemical Formula 35]

[0341]

[0342] In equation (1), R d11 Each represents a divalent aliphatic hydrocarbon group. n represents an integer of 1 or 2. The benzene ring in formula (1) can be further substituted by any substituents. * Each represents a bond.

[0343] By including compound (D1) in the photosensitive resin composition, there is a tendency for improved inkjet coating properties. This is presumably because compound (D1) contains many aromatic rings in its main chain, thus exhibiting a tendency to resist thermal decomposition during heat treatment. Furthermore, since the main chain also contains aliphatic hydrocarbon groups, it possesses flexibility that enhances reactivity with alkali-soluble resins, enabling the formation of a strong cross-linked structure.

[0344] (R) d11 )

[0345] In equation (1), R d11 It represents a divalent aliphatic hydrocarbon group.

[0346] Divalent aliphatic hydrocarbon groups can be categorized as straight-chain or branched aliphatic hydrocarbon groups. The number of carbon atoms is preferably 1 or more, further preferably 6 or less, more preferably 3 or less, and even more preferably 2 or less. For example, 1 to 6 is preferred, more preferably 1 to 3, and even more preferably 1 to 2. By setting the value above the aforementioned lower limit, there is a tendency for high reactivity. By setting the value below the aforementioned upper limit, there is a tendency for reduced degassing.

[0347] Examples of divalent aliphatic hydrocarbon groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, and n-hexylene. From the viewpoint of inkjet coating properties, methylene is preferred.

[0348] The benzene ring in formula (1) can be further substituted with any substituents. Examples of substituents include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited; there can be one or more.

[0349] From the perspectives of ink repellency, inkjet coating properties, and ease of synthesis, the benzene ring in formula (1) is preferably unsubstituted.

[0350] (n)

[0351] In equation (1), n ​​represents an integer of 1 or 2. From the perspective of ink repellency and inkjet coating properties, n is preferably 2.

[0352] Furthermore, the compound (D1) more preferably contains a structural unit represented by the following general formula (2).

[0353] [Chemical Formula 36]

[0354]

[0355] In equation (2), R d11 The meaning is the same as in formula (1). m1∶m2 is 2∶8~5∶5. The benzene ring in formula (2) can be further replaced by any substituents. *Each represents a bond.

[0356] The following are specific examples of compound (D1).

[0357] [Chemical Formula 37]

[0358]

[0359] From the viewpoint of ink repellency and inkjet coating properties, the weight-average molecular weight of compound (D) is typically 1000 or more, preferably 1500 or more, preferably 20000 or less, more preferably 10000 or less, further preferably 7000 or less, even more preferably 5000 or less, particularly preferably 4000 or less, and especially preferably 3000 or less. The upper and lower limits can be combined arbitrarily; for example, preferably 1000 to 20000, more preferably 1000 to 10000, further preferably 1000 to 7000, even more preferably 1000 to 5000, especially preferably 1000 to 4000, and particularly preferably 1500 to 3000. Setting the value above the lower limit tends to improve inkjet coating properties. Setting the value below the upper limit tends to improve developability.

[0360] (D) The acid value of the compound is preferably 1 mg KOH / g or less, more preferably 0.1 mg KOH / g or less, and even more preferably 0.01 mg KOH / g or less. By setting it to the upper limit or below, there is a tendency for the storage stability of the photosensitive resin composition to become good.

[0361] (D) The epoxy equivalent of the compound is not particularly limited, but is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less. The upper and lower limits can be combined arbitrarily; for example, 100 to 1000 is preferred, more preferably 150 to 500, even more preferably 200 to 300, and even more preferably 200 to 250. Setting the value above the lower limit tends to improve storage stability. Setting the value below the upper limit tends to improve inkjet coating properties.

[0362] In the photosensitive resin composition of the present invention, the content of compound (D) in the total solids of the photosensitive resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 6% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 50% by mass, more preferably 2 to 30% by mass, further preferably 3 to 20% by mass, even more preferably 5 to 15% by mass, and particularly preferably 6 to 10% by mass. By setting the lower limit value or above, there is a tendency for improved inkjet coating properties. By setting the upper limit value or below, there is a tendency for improved developability.

[0363] As for the proportion of compound (D) to alkali-soluble resin (B) in the photosensitive resin composition, it is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 17 parts by mass or more, and preferably less than 100 parts by mass, more preferably less than 80 parts by mass, further preferably less than 50 parts by mass, and particularly preferably less than 25 parts by mass. The upper and lower limits can be combined arbitrarily; for example, it is preferably 10 to 100 parts by mass, more preferably 12 to 80 parts by mass, further preferably 15 to 50 parts by mass, and particularly preferably 17 to 25 parts by mass. Setting it to the lower limit or above tends to improve inkjet coating properties. Furthermore, setting it to the upper limit or below tends to improve storage stability.

[0364] In this invention, the ratio of compound (D) to compound (E) described later is preferably appropriate. This is presumably because compound (D) has a cyclic ether group, and therefore reacts with compound (E) and the acidic site of the alkali-soluble resin to form a strong cross-linked structure. When fabricating the spacer, this structure can suppress the outflow of the liquid repellent from the cross-linked structure to the pixel during heating, thereby improving inkjet coating properties.

[0365] In the photosensitive resin composition of the present invention, the content of compound (E) is 2 parts by mass or more, preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and further preferably 8 parts by mass or less, preferably 6 parts by mass or less, relative to 100 parts by mass of compound (D). The above-mentioned upper and lower limits can be combined arbitrarily. For example, it can be 2 to 6 parts by mass, 3 to 6 parts by mass, 3 to 8 parts by mass, 4 to 8 parts by mass, or 4 to 6 parts by mass. By setting it to the lower limit or above, there is a tendency for improved liquid repellency. Furthermore, by setting it to the upper limit or below, there is a tendency for improved inkjet coating properties.

[0366] Furthermore, as another aspect, in the photosensitive resin composition of the present invention, the content of compound (E) relative to 100 parts by mass of compound (D) is 2.0 parts by mass or more, more preferably 2.1 parts by mass or more, even more preferably 2.3 parts by mass or more, particularly more preferably 3.0 parts by mass or more, especially preferably 4.0 parts by mass or more, and further preferably 8.0 parts by mass or less, preferably 6.0 parts by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it can be 2.0 to 6.0 parts by mass, 3.0 to 6.0 parts by mass, 3.0 to 8.0 parts by mass, 4.0 to 8.0 parts by mass, or 4.0 to 6.0 parts by mass. By setting it to the lower limit or above, there is a tendency for improved liquid repellency. Furthermore, by setting it to the upper limit or below, there is a tendency for improved inkjet coating properties.

[0367] [1-1-5] (E) compound

[0368] In regard to the photosensitive resin composition of the present invention, as compound (E), there is a compound having a crosslinking group and having fluorine atoms and / or siloxane chains.

[0369] By using a photosensitive resin composition containing an (E) compound, ink-repellent properties can be imparted to the upper surface of the resulting spacer wall, thus preventing color mixing in each pixel.

[0370] It should be noted that compounds (E) are not included in alkali-soluble resins (B). That is, in this invention, if a compound can be classified as a compound (E), it will be treated as a compound (E) even if it can also be classified as an alkali-soluble resin (B).

[0371] In this invention, compound (E) is sometimes referred to as "liquid repellent".

[0372] Examples of compounds (E) include compound (E1) and compound (E2).

[0373] Compound (E1): Fluorine-containing atomized resin with crosslinking groups.

[0374] Compound (E2): A resin containing crosslinking groups and siloxane chains.

[0375] <Compound (E1)>

[0376] Examples of crosslinking groups include epoxy groups, olefinic unsaturated groups, or active groups that generate free radicals through irradiation with active energy rays.

[0377] Examples of active groups that generate free radicals through irradiation with active energy rays include benzophenone, acetophenone, α-hydroxyketone, α-aminoketone, α-diketone, and α-diketone-dialkylacetal. From the viewpoint of the overlap between the wavelength distribution of the light source used for exposure and the absorbance spectrum of the active group, α-hydroxyketone is preferred.

[0378] From the viewpoint of inhibiting the outflow of compound (E1) into the developer, olefinic unsaturated groups are preferred as crosslinking groups.

[0379] It is believed that by using compound (E1), the cross-linking reaction on the surface of the formed coating can be accelerated during exposure, making it difficult for the liquid repellent to flow out during the development process. As a result, the resulting spacer wall can exhibit high ink repellency.

[0380] The compound (E1) is oriented on the surface of the spacer wall, and tends to prevent ink bleeding and color mixing. More specifically, it has groups with fluorine atoms that repel ink, thus preventing ink bleeding and color mixing caused by ink crossing the spacer wall into adjacent areas.

[0381] Furthermore, from the viewpoint of residue and inkjet coating properties, compound (E1) is preferably found to have acidic groups, and more preferably contains carboxyl groups.

[0382] Compound (E1) preferably has one or more of fluoroalkyl, fluoroalkylene, fluoroalkylene ether chains, and fluoroaromatic groups. Among these, from the perspective of ink repellency, it is more preferable to have perfluoroalkyl, perfluoroalkylene, perfluoroalkylene ether chains, and perfluoroaromatic groups. By having one or more of fluoroalkyl, fluoroalkylene, fluoroalkylene ether chains, and fluoroaromatic groups, the fluorinated atom resin is more likely to be oriented on the surface of the spacer wall, exhibiting higher ink repellency and a tendency to further prevent ink bleeding and color mixing.

[0383] Examples of fluoroalkyl groups include: fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, and fluorohexyl. Examples of perfluoroalkyl groups include: perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, and perfluorohexyl.

[0384] Examples of fluoroalkylene chains include: fluoromethyl chain, fluoroethyl chain, fluoropropylene chain, fluorobutylene chain, and fluorohexylene chain. Examples of perfluoroalkylene chains include: perfluoromethyl chain, perfluoroethyl chain, perfluoropropylene chain, perfluorobutylene chain, and perfluorohexylene chain.

[0385] Examples of perfluoroalkylene ether chains include: -CF2-O-, -(CF2)2-O-, -(CF2)3-O-, -CF2-C(CF3)2-O-, -C(CF3)2-CF2-O-, and divalent groups having these repeating units. Examples of fluoroalkylene ether chains include those where a portion, but not all, of the F in the perfluoroalkylene ether chain is replaced by H.

[0386] Examples of perfluoroaromatic groups include perfluorophenyl, perfluoronaphthyl, and perfluoroanthrayl. Examples of fluoroaromatic groups include fluoroaromatic groups formed by replacing part, but not all, of the F in a perfluoroaromatic group with H.

[0387] Examples of compounds (E1) include: acrylic copolymer resins having epoxy groups and perfluoroalkyl groups; acrylic copolymer resins having epoxy groups and perfluoroalkylene ether chains; acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkyl groups; acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkylene ether chains; epoxy (meth)acrylate resins having epoxy groups and perfluoroalkyl groups; epoxy (meth)acrylate resins having epoxy groups and perfluoroalkylene ether chains; epoxy (meth)acrylate resins having olefinic unsaturated groups and perfluoroalkyl groups; and epoxy (meth)acrylate resins having olefinic unsaturated groups and perfluoroalkylene ether chains. From the viewpoint of ink repellency, acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkyl groups, and acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkylene ether chains are preferred, and acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkylene ether chains are even more preferred.

[0388] As a compound (E1), for example, the following can be used under the trade name DIC: “Megafac (registered trademark, hereinafter the same) F116”, “Megafac F120”, “Megafac F142D”, “Megafac F144D”, “Megafac F150”, “Megafac F160”, “Megafac F171”, “Megafac F172”, “Megafac F173”, “Megafac F177”, “Megafac F178A”, “Megafac F178K”, “Megafac F179”, “Megafac F183”, “Megafac F184”, “Megafac F191”, “Megafac F812”, “Megafac F815”, “Megafac F824”, “Megafac F833”, “Megafac RS101”, “Megafac RS102”, “Megafac RS105”, etc. Commercially available fluorinated organic compounds including “RS201”, “MegafacRS202”, “Megafac RS301”, “Megafac RS303”, “Megafac RS304”, “Megafac RS401”, “Megafac RS402”, “Megafac RS501”, “Megafac RS502”, “Megafac RS-72-K”, “Megafac RS-78”, “Megafac RS-90”, “DEFENSA (registered trademark, hereinafter the same) MCF300”, “DEFENSA MCF310”, “DEFENSA MCF312”, and “DEFENSA MCF323”.

[0389] As acrylic copolymer resins with olefinic unsaturated groups and perfluoroalkyl groups, “MEGAFACE RS-72-K”, “MEGAFACE RS-78”, and “MEGAFACE RS-90” are preferred.

[0390] The proportion of fluorine atoms in compound (E1) is not particularly limited, but in fluorine-containing resins with crosslinking groups, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and even more preferably 18% by mass or more. Furthermore, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less; these upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 40% by mass, and particularly preferably 18 to 30% by mass. By setting it to the lower limit or above, there is a tendency to exhibit a high contact angle. By setting it to the upper limit or below, it is possible to suppress the flow of (E) compound to the pixel portion, and there is a tendency for inkjet coating properties to become better.

[0391] There are no particular restrictions on the molecular weight of compound (E1); it can be a low molecular weight compound or a high molecular weight compound. High molecular weight compounds are preferred because they can suppress exudation during development, flowability caused by post-baking, and flow out from the spacer walls.

[0392] When compound (E1) is a high molecular weight compound, the number average molecular weight of the fluorinated atomic resin having crosslinking groups is preferably 100 or more, more preferably 500 or more, and even more preferably 1000 or more. Furthermore, it is preferably 150,000 or less, more preferably 130,000 or less, and even more preferably 100,000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 150,000, more preferably 500 to 130,000, and even more preferably 1,000 to 100,000.

[0393] The weight-average molecular weight of compound (E1) is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. Furthermore, it is preferably 150,000 or less, and even more preferably 130,000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1,000 to 150,000, more preferably 5,000 to 130,000, and even more preferably 10,000 to 130,000.

[0394] <Compound (E2)>

[0395] Compound (E2) is a resin containing crosslinking groups and siloxane chains. Examples of compounds (E2) include compounds (E2-1) and (E2-2).

[0396] <Compound (E2-1)>

[0397] The compound (E2-1) has the following general formula (e2-1) structure.

[0398] R 61 R62 R 63 Si-O-(SiR) 64 R 65 -O) n -SiR 66 R 67 R 68

[0399] ... (e2-1)

[0400] In equation (e2-1), R 61 R 62 R 63 R 64 R 65 R 66 R 67 R 68 Each can independently represent a monovalent organic group or a hydrogen atom. n represents an integer greater than or equal to 0.

[0401] As a monovalent organic group, a hydrocarbon group having 1 to 10 carbon atoms is preferred, and examples include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; and substituted alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and nonafluorobutylethyl. These organic groups optionally have ester bonds. Furthermore, R 61 R 62 R 63 R 64 R 65 R 66 R 67 R 68 One or more of the components have crosslinking groups. As crosslinking groups, the crosslinking groups described in compound (E1) are preferred.

[0402] In formula (e2-1), n ​​is an integer greater than or equal to 0, preferably greater than or equal to 5, more preferably greater than or equal to 10, and further preferably less than or equal to 2000, more preferably less than or equal to 1500, even more preferably less than or equal to 1000, even more preferably less than or equal to 500, and particularly preferably less than or equal to 300. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 5 to 2000 is preferred, more preferably 5 to 1500, even more preferably 5 to 1000, even more preferably 10 to 500, and particularly preferably 10 to 300. By setting the value above the lower limit, there is a tendency for increased ink repellency. By setting the value below the upper limit, there is a tendency for increased coating uniformity.

[0403] From the viewpoint of residue and inkjet coating properties, compound (E2-1) preferably has acidic groups, and more preferably contains carboxyl groups.

[0404] Commercially available resins containing crosslinking groups and siloxane chains can be, for example, compounds sold under trade names such as "BYK-UV3500 series" manufactured by BYK-Chemie and "8SS" series manufactured by Taisei Fine Chemical.

[0405] As compounds that have crosslinking groups and contain fluorine atoms and siloxane chains, examples include those commercially available under trade names such as the "8FS" series manufactured by Taisei Fine Chemical Co., Ltd., and the "KP" series manufactured by Shin-Etsu Chemical Co., Ltd.

[0406] (E) compounds can be compounds that contain both fluorine atoms and siloxane chains in a single molecule, or a mixture of multiple (E) compounds.

[0407] <Compound (E2-2)>

[0408] Compound (E2-2) is a copolymer resin having at least (E2-2-1) and (E2-2-2), where (E2-2-1) is a repeating unit represented by the following general formula (e2-2-1), and (E2-2-2) is a repeating unit containing an olefinic unsaturated group.

[0409] [Chemical Formula 38]

[0410]

[0411] R 71 R 72 R 73 Each is an alkyl group having 1 to 3 carbon atoms. R 74 It can be a hydrogen atom or a methyl group. L 71 * indicates a divalent organic group. * indicates a bond.

[0412] <(E2-2-1) Repeating Unit>

[0413] R in equation (e2-2-1) 71 ~R 73 The alkyl group having 1 to 3 carbon atoms can be exemplified by methyl, ethyl, propyl, and isopropyl. From the viewpoint of liquid repellency and inkjet wetting and spreading properties, methyl and ethyl are preferred, and methyl is more preferred.

[0414] L 71 The divalent organic group is preferably a single bond, an alkylene group with 1 to 50 carbon atoms, or an alkene group with 1 to 50 carbon atoms.

[0415] As L 71Alkylenes having 1 to 50 carbon atoms, for example: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, isopropylene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene.

[0416] L 71 The alkylene group having 1 to 50 carbon atoms is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably methylene, ethylene, n-propylene, or isopropylene.

[0417] L 71 The alkeneoxy group having 1 to 50 carbon atoms is, for example, a group formed by substituting one -CH2- group of the alkylene group with -O-. L 71 The alkene oxide with 1 to 50 carbon atoms is preferably an alkene oxide with 1 to 15 carbon atoms, more preferably an alkene oxide with 1 to 8 carbon atoms, and even more preferably a methylene oxide, ethoxide oxide, propoxy oxide, oxatrimethylene, butoxy oxide, oxatetramethylene, pentylene oxide, heptyloxy, or octyloxy.

[0418] In L 71 When the divalent organic group is an alkylene group with 1 to 50 carbon atoms or an alkene group with 1 to 50 carbon atoms, a portion of the -CH2- group can be replaced by a carbonyl group (-C(=O)-), a phenylene group, an amide bond, or an urethane bond, and a hydroxyl group can be substituted on the carbon atom.

[0419] L 71 More preferably, it is an alkylene group having 1 to 5 carbon atoms.

[0420] A specific example of the repeating unit (E2-2-1) is shown below. * in the formula represents the bonding portion.

[0421] [Chemical Formula 39]

[0422]

[0423] From the perspective of liquid repellency and inkjet wetting and spreading properties, (e2-2-12) is preferred.

[0424] The repeating unit (e2-2-1) can be present in one or more of the compounds (E2-2).

[0425] <Repeating Unit (E2-2-2)>

[0426] The repeating unit (E2-2-2) is not particularly limited in structure as long as it contains an olefinic unsaturated group in its side chain. For example, vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy are preferred, with (meth)acryloyl and (meth)acryloyloxy being the most preferred.

[0427] As a repeating unit (E2-2-2), the following structures can be listed for example.

[0428] [Chemical Formula 40]

[0429]

[0430] From the viewpoint of inkjet wetting and spreading properties, (e2-2-23) and (e2-2-24) are preferred, and (e2-2-23) is even more preferred.

[0431] The repeating unit (e2-2-2) can be present in one or more of the compounds (E2-2).

[0432] In compound (E2-2), the molar ratio of repeating unit (E2-2-1) to repeating unit (E2-2-2) is not particularly limited. For example, relative to the total molar percentage of repeating unit (E2-2-1) and repeating unit (E2-2-2) of 100 mol%, the repeating unit (E2-2-1) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. Furthermore, it is preferably 95 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, even more preferably 30 mol% or less, and particularly preferably 24 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it can be 5–95 mol%, 5–70 mol%, 10–50 mol%, 10–30 mol%, or 15–24 mol%. By setting it above the lower limit, there is a tendency for increased liquid repellency. Furthermore, by setting it below the upper limit, there is a tendency for improved inkjet wetting and spreading properties.

[0433] In compound (E2-2), the content of silicon atoms is not particularly limited, but relative to the mass of compound (E2-2), it is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more. Furthermore, it is preferably 50% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 5 to 20% by mass, and even more preferably 7 to 10% by mass. By setting it above the lower limit, there is a tendency for increased liquid repellency. Furthermore, by setting it below the upper limit, there is a tendency for improved inkjet wetting and spreading properties.

[0434] Compound (E2-2) optionally has repeating units other than repeating unit (E2-2-1) and repeating unit (E2-2-2).

[0435] Other repeating units include, for example: repeating units having a carboxyl group; repeating units having an ester bond other than repeating unit (E2-2-1) and repeating unit (E2-2-2).

[0436] The compound (E2-2) is preferably free of fluorine atoms. By being free of fluorine atoms, its environmental accumulation is reduced, thereby lowering the environmental impact.

[0437] The number-average molecular weight (Mn) of compound (E2-2) is preferably 1000 or more, more preferably 2000 or more, and even more preferably 2500 or more. Furthermore, it is preferably 20000 or less, more preferably 10000 or less, and even more preferably 5000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 20000, more preferably 2000 to 10000, and even more preferably 2500 to 5000. By setting it to the lower limit or above, there is a tendency for improved inkjet wetting and spreading properties. Furthermore, by setting it to the upper limit or below, gelation and other defects are less likely to occur, synthesis becomes easier, and inkjet wetting and spreading properties also tend to improve.

[0438] The weight-average molecular weight (Mw) of compound (E2-2) is preferably 3,000 or more, more preferably 5,000 or more, further preferably 8,000 or more, even more preferably 10,000 or more, and particularly preferably 13,000 or more. Furthermore, it is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 20,000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 3,000 to 100,000, more preferably 5,000 to 100,000, further preferably 8,000 to 50,000, even more preferably 10,000 to 50,000, and particularly preferably 13,000 to 20,000. By setting it to the lower limit or above, there is a tendency for improved inkjet wetting and spreading properties. Furthermore, by setting it to the upper limit or below, gelation and other defects are less likely to occur, synthesis becomes easier, and inkjet wetting and spreading properties also tend to improve.

[0439] There are no particular limitations on the synthesis method of compound (E2-2), and well-known synthetic methods can be used. For example, the method described in Japanese Patent Application Publication No. 2023-169574 can be used for synthesis.

[0440] The content of compound (E) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total solids content of the photosensitive resin composition. Furthermore, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 2% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to easily obtain a uniform coating film when the ink is applied to the pixel area after forming the spacer.

[0441] When the photosensitive resin composition of the present invention contains compound (E1), the content of compound (E1) is not particularly limited. Relative to the total solids content of the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. Furthermore, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 2% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to easily obtain a uniform coating film when the ink is applied to the pixel portion after forming the spacer.

[0442] When the photosensitive resin composition of the present invention contains compound (E2), the content of compound (E2) is not particularly limited. Relative to the total solids content of the photosensitive resin composition, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. Furthermore, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and even more preferably 0.3 to 2% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to easily obtain a uniform coating film when the ink is applied to the pixel portion after forming the spacer.

[0443] In the photosensitive resin composition of the present invention, a surfactant may be used together with compound (E). The surfactant may be used, for example, to improve the coatability of the coating liquid as a photosensitive resin composition and the developability of the coating film, and examples include fluorinated surfactants without crosslinking groups and organosilicon surfactants without crosslinking groups.

[0444] In particular, since it has the function of removing residues of the photosensitive resin composition from the unexposed area during development, and also has the function of exhibiting wetting properties, it is preferably an organosilicon surfactant, and more preferably a polyether-modified organosilicon surfactant.

[0445] As a fluorinated surfactant without crosslinking groups, it is preferable to have a fluoroalkyl or fluoroalkylene group at at least one of the terminals, main chain, and side chain.

[0446] Commercially available fluorinated surfactants without crosslinking groups include, for example: BM Chemie's "BM-1000" and "BM-1100"; DIC's "MEGAFACE F142D", "MEGAFACE F172", "MEGAFACE F173", "MEGAFACE F183", "MEGAFACE F470", "MEGAFACE F475", "MEGAFACE F554", and "MEGAFACE F559"; NEOS's "DFX-18"; 3M Japan's "Fluorad FC430", "Fluorad FC431", "FC-4430", and "FC4432"; and AGC's "Asahi Guard (registered trademark) AG710", "Surflon (registered trademark, hereinafter the same) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", and "Surflon...". SC-104", "Surflon SC-105", "Surflon SC-106".

[0447] Commercially available silicone surfactants include, for example: "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032 Additive", and "SH8400" manufactured by Dow Corning Toray; and "BYK 323" and "BYK 330" manufactured by BYK-Chemie.

[0448] As surfactants, they can also contain surfactants other than fluorinated surfactants and organosilicon surfactants. Examples of surfactants include nonionic, anionic, cationic, and amphoteric surfactants.

[0449] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, and polyoxyethylene sorbitol fatty acid esters.

[0450] As examples of their commercially available products, polyoxyethylene surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation can be cited.

[0451] Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic alcohol sulfate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and special polymeric surfactants. Special polymeric surfactants are preferred, and special polycarboxylic acid type polymeric surfactants are even more preferred.

[0452] As commercially available products, examples of these include alkyl sulfate salts such as "Emal (registered trademark, hereinafter the same) 10" manufactured by Kao Corporation; alkyl naphthalene sulfonates such as "Pelex (registered trademark) NB-L" manufactured by Kao Corporation; and special polymeric surfactants such as "Homogenol (registered trademark, hereinafter the same) L-18" and "Homogenol L-100" manufactured by Kao Corporation.

[0453] Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.

[0454] As commercially available products, among alkylamine salts, for example, Kao Corporation's "Acetamin (registered trademark) 24" can be listed, and among quaternary ammonium salts, for example, Kao Corporation's "Quartamin (registered trademark, hereinafter the same) 24P" and "Quartamin 86W" can be listed.

[0455] Examples of amphoteric surfactants include: betaine-type compounds, imidazoline salts, imidazoline compounds, and amino acids.

[0456] Surfactants can be used alone or in combination of two or more. Examples include combinations of silicone surfactants and fluorinated surfactants, combinations of silicone surfactants and special polymeric surfactants, and combinations of fluorinated surfactants and special polymeric surfactants. Combinations of silicone surfactants and fluorinated surfactants are preferred.

[0457] Examples of combinations of silicone-based and fluorinated surfactants include: NEOS's "DFX-18", BYK-Chemie's "BYK-300" or "BYK-330" and AGC SeimiChemical's "S-393"; Shin-Etsu Silicone's "KP340" and DIC's "F-554" or "F-559"; Dow Corning Toray's "SH7PA" and DAIKIN's "DS-401"; and NUC's "L-77" and 3M Japan's "FC4430".

[0458] [1-1-6] Solvent

[0459] The photosensitive resin composition of the present invention typically contains a solvent and is used with the above-mentioned components dissolved or dispersed in the solvent. There are no particular limitations on the solvent; for example, the organic solvents described below can be listed.

[0460] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, etc., dialkyl ethers of glycols; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, etc., dialkyl ethers of glycols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate, and other diol alkyl ether acetates; ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and other diol diacetates; cyclohexanol acetate and other alkyl acetates; pentyl ether, diethyl ether Ethers such as dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl pentylene ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentylene ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentylene ketone; monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; and cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclic hydrocarbons. Alicyclic hydrocarbons such as hexyl; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as pentyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and pentyl chloride; ether ketones such as methoxymethylpentanone; and nitrile compounds such as acetonitrile and benzyl nitrile.Tetrahydrofurans, dimethyltetrahydrofurans, dimethoxytetrahydrofurans, and other tetrahydrofuran derivatives, etc.

[0461] Commercially available solvents corresponding to the above can be listed as follows: Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No.1 and No.2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellulose Solvent, Ethyl Cellulose Solvent, Ethyl Cellulose Solvent Acetate, Methyl Cellulose Solvent Acetate, Diethylene Glycol Dimethyl Ether (Diglyme) (all are trade names).

[0462] The solvent is capable of dissolving or dispersing the components in the photosensitive resin composition and can be selected according to the method of using the photosensitive resin composition according to the present invention. From the viewpoint of coatability, a solvent with a boiling point of 60 to 280°C at atmospheric pressure (1013.25 hPa) is preferred, and a solvent with a boiling point of 70 to 260°C is more preferred. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.

[0463] Solvents can be used alone or in combination with two or more.

[0464] The solvent is preferably used in such a manner that the total solids content in the photosensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 18% by mass or more, and also preferably 90% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. The upper and lower limits can be combined arbitrarily; for example, preferably 10–90% by mass, more preferably 10–50% by mass, further preferably 15–40% by mass, and particularly preferably 18–30% by mass. By setting the value above the lower limit, there is a tendency to obtain a coating even with high film thickness. Furthermore, by setting the value below the upper limit, there is a tendency to obtain moderate coating uniformity.

[0465] [1-1-7] Ultraviolet absorbers

[0466] The photosensitive resin composition of the present invention may also contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used for exposure. By including an ultraviolet absorber, there is a tendency to obtain effects such as improved cone shape after development or reduced residue remaining in the unexposed area after development. From the viewpoint of not hindering the light absorption of the photopolymerization initiator, compounds with extremely high absorption in the wavelength range of 250 nm to 400 nm can be used as ultraviolet absorbers.

[0467] Examples of ultraviolet absorbers include: benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.

[0468] Ultraviolet absorbers can be used alone or in combination with two or more.

[0469] From the viewpoint of increasing the cone angle, benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferred, with benzotriazole compounds being particularly preferred.

[0470] From the viewpoint of cone shape, the benzotriazole compound described by the following general formula (Z1) is preferred.

[0471] [Chemical Formula 41]

[0472]

[0473] In equation (Z1), R 1e and R 2e Each of these can independently represent a hydrogen atom, an alkyl group optionally having substituents, a group represented by the following general formula (Z2), or a group represented by the following general formula (Z3). R 3e It represents a hydrogen atom or a halogen atom.

[0474] [Chemical Formula 42]

[0475]

[0476] In equation (Z2), R 4e R represents an alkylene group that may optionally have substituents. 5e This indicates an alkyl group that may optionally have substituents.

[0477] [Chemical Formula 43]

[0478]

[0479] In equation (Z3), R 6e R represents an alkylene group that may optionally have substituents. 7eIt represents a hydrogen atom or a methyl group.

[0480] (R) 1e and R 2e )

[0481] In equation (Z1), R 1e and R 2e Each of these can independently represent a hydrogen atom, an alkyl group optionally having a substituent, a group represented by formula (Z2), or a group represented by formula (Z3).

[0482] As an alkyl group, examples include straight-chain, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more; furthermore, it is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The upper and lower limits can be combined arbitrarily, for example, preferably 1 to 10, more preferably 2 to 6, and even more preferably 4 to 6.

[0483] Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, with tert-butyl being preferred.

[0484] Substituents optionally present as alkyl groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl.

[0485] (R) 3e )

[0486] In equation (Z1), R 3e It represents a hydrogen atom or a halogen atom.

[0487] Halogen atoms include: fluorine, chlorine, bromine, and iodine.

[0488] From a synthetic point of view, R is preferred. 3e It is a hydrogen atom.

[0489] (R) 4e )

[0490] In equation (Z2), R 4e This indicates an alkylene group that may optionally have substituents.

[0491] Examples of alkylene compounds include linear, branched, or cyclic alkylene compounds. They typically have 1 or more carbon atoms, preferably 2 or more, and more preferably 6 or fewer, more preferably 4 or fewer, and even more preferably 3 or fewer. The upper and lower limits can be combined arbitrarily; for example, 1 to 6 are preferred, 1 to 4 are more preferred, and 2 to 3 are even more preferred.

[0492] Examples of alkylene compounds include methylene, ethylene, propylene, and butylene, with ethylene being preferred.

[0493] Substituents optionally present as alkylene groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl.

[0494] R 4e Ethylene is preferred.

[0495] (R) 5e )

[0496] In equation (Z2), R 5e This indicates an alkyl group that may optionally have substituents.

[0497] As an alkyl group, examples include straight-chain, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, even more preferably 7 or more, and further preferably 15 or less, more preferably 10 or less, even more preferably 9 or less. The upper and lower limits can be combined arbitrarily; for example, 5 to 15 is preferred, more preferably 5 to 10, and even more preferably 7 to 9.

[0498] Examples of alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl.

[0499] Substituents optionally present as alkyl groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl.

[0500] From the perspective of cone shape, R 5e The preferred bases are heptyl, quinyl, and nonyl.

[0501] (R) 6e )

[0502] In equation (Z3), R 6e This indicates an alkylene group that may optionally have substituents.

[0503] Examples of alkylene compounds include linear, branched, or cyclic alkylene compounds. They typically have 1 or more carbon atoms, preferably 2 or more, and more preferably 6 or fewer, more preferably 4 or fewer, and even more preferably 3 or fewer. The upper and lower limits can be combined arbitrarily; for example, 1 to 6 are preferred, 1 to 4 are more preferred, and 2 to 3 are even more preferred.

[0504] Examples of alkylene compounds include methylene, ethylene, propylene, and butylene. Among these, ethylene is preferred.

[0505] Substituents optionally present as alkylene groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl.

[0506] From the perspective of cone shape, the preferred option is: R 1e For tert-butyl, R 2e For the group represented by formula (Z2) (where R 4e Ethylene and R 5e (alkyl group with 7 to 9 carbon atoms), R 3e Compounds containing hydrogen atoms; or R 1e For hydrogen atoms, R 2e For the group represented by formula (Z3) (where R 6e Ethylene and R 7e (methyl), R 3e Compounds containing hydrogen atoms, more preferably: R 1e For tert-butyl, R 2e For the group represented by formula (Z2) (where R 4e Ethylene and R 5e (alkyl group with 7 to 9 carbon atoms), R 3e Compounds containing hydrogen atoms.

[0507] Examples of benzotriazole compounds include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, octyl 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, and 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate. Ethylhexyl ester, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)- [4-Hydroxyphenyl]heptyl propionate, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]nonyl propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1 (-Methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, heptyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, nonyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate. Among these, from the viewpoint of cone angle and exposure sensitivity, the preferred options are heptyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, nonyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, and mixtures thereof.

[0508] Commercially available benzotriazole compounds include, for example: Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.); JF77, JF78, JF79, JF80, JF83 (manufactured by Jōhoku Chemical Industry Co., Ltd.); TINUVIN (registered trademark, hereinafter the same) PS, TINUVIN99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 326, TINUVIN 900, TINUVIN 928, TINUVIN1130 (manufactured by BASF); EVERSORB 70, EVERSORB 71, EVERSORB 72, EVERSORB 73, EVERSORB 74, EVERSORB 75, EVERSORB 76, EVERSORB 234, EVESROB 77, EVESROB 78, EVESROB 80, EVESROB 81 (manufactured by Taiwan Yung-Kuang Chemical Industrial Co., Ltd.); Tominabe (registered trademark, same below) 100, Tominabe 600 (manufactured by APIC Corporation); SEESORB (registered trademark, same below) 701, SEESORB 702, SEESORB 703, SEESORB 704, SEESORB 706, SEESORB 707, SEESORB 709 (manufactured by Shipro Chemical Co., Ltd.); RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0509] Examples of triazine compounds include: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-octoxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 2-ethylhexyl glycidyl ether, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. Among these, hydroxyphenyl triazine compounds are preferred from the viewpoint of cone angle and exposure sensitivity.

[0510] Commercially available triazine compounds include, for example: TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (manufactured by BASF).

[0511] Other ultraviolet absorbers include, for example, benzophenone compounds such as Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVESROB10, EVESROB11, EVESROB12 (manufactured by Taiwan Yung-Kuang Chemical Co., Ltd.), Tominabe 800 (manufactured by APIC Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, and SEESORB151 (manufactured by Shipro Chemical Co., Ltd.); Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.), benzoic acid esters such as phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; naphthalene derivatives such as α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; anthracene and its derivatives such as anthracene and 9,10-dihydroxyanthracene; dyes such as azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenyl cyanoacrylate dyes, triazine dyes, and p-aminobenzoic acid dyes. From the perspective of exposure sensitivity, cinnamic acid derivatives and naphthalene derivatives are preferred, with cinnamic acid derivatives being particularly preferred.

[0512] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and further preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less. The upper and lower limits can be combined arbitrarily; for example, preferably 0.01 to 15% by mass, more preferably 0.05 to 15% by mass, further preferably 0.1 to 10% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 1 to 3% by mass. By setting it above the lower limit, there is a tendency for the cone angle to increase. Furthermore, by setting it below the upper limit, there is a tendency for higher sensitivity.

[0513] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the proportion relative to the photopolymerization initiator (A) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. The upper and lower limits can be combined arbitrarily, for example, preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, further preferably 20 to 100 parts by mass, and particularly preferably 30 to 50 parts by mass. By setting the lower limit value or above, there is a tendency for the cone angle to increase. Furthermore, by setting the upper limit value or below, there is a tendency for higher sensitivity.

[0514] [1-1-8] Polymerization inhibitors

[0515] The photosensitive resin composition of the present invention may also contain polymerization inhibitors. It is believed that by containing polymerization inhibitors, free radical polymerization is hindered, thereby increasing the cone angle of the resulting spacer walls.

[0516] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of cone shape, methyl hydroquinone and methoxyphenol are preferred, and methyl hydroquinone is more preferred.

[0517] The polymerization inhibitor can be used alone or in combination with two or more. Typically, when manufacturing (B) alkali-soluble resins, the resin sometimes contains a polymerization inhibitor, which can be used as the polymerization inhibitor contained in the photosensitive resin composition of the present invention. Alternatively, in addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor can be added during the manufacture of the photosensitive resin composition.

[0518] When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, and further preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. The upper and lower limits can be combined arbitrarily, for example, preferably 0.01 to 5% by mass, more preferably 0.1 to 0.3% by mass, and even more preferably 0.3 to 1% by mass. By setting it above the lower limit, there is a tendency to increase the cone angle. Furthermore, by setting it below the upper limit, there is a tendency to maintain high sensitivity.

[0519] [1-1-9] Silane coupling agent

[0520] To improve adhesion to the substrate, the photosensitive resin composition of the present invention may contain a silane coupling agent. Examples of silane coupling agents include epoxy, methacrylic, amino, and imidazole-based silane coupling agents. From the viewpoint of improving adhesion, epoxy and imidazole-based silane coupling agents are particularly preferred.

[0521] [1-1-10] Phosphoric acid compounds

[0522] In order to improve adhesion to the substrate, the photosensitive resin composition of the present invention may also contain a phosphoric acid compound. As a phosphoric acid compound, phosphate esters containing (meth)acryloyloxy groups are preferred, and compounds represented by the following general formulas (Va), (Vb), and (Vc) are preferred.

[0523] [Chemical Formula 44]

[0524]

[0525] In the above general formulas (Va), (Vb), and (Vc), R 8 Represents a hydrogen atom or a methyl group, where r and r' are integers from 1 to 10, and s is 1, 2, or 3.

[0526] When the photosensitive resin composition of the present invention contains a phosphoric acid compound, its content is not particularly limited. In the total solids content of the photosensitive resin composition, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. Furthermore, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. The upper and lower limits can be combined arbitrarily; for example, it is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and even more preferably 0.3 to 1% by mass. By setting it to the lower limit or above, there is a tendency to improve adhesion to the substrate. Furthermore, by setting it to the upper limit or below, there is a tendency to improve surface curability.

[0527] [1-1-11] Chain transfer agent

[0528] The photosensitive resin composition of the present invention may also contain a chain transfer agent. Examples of chain transfer agents include thiol-containing compounds and carbon tetrachloride. Since they tend to have high chain transfer effects, thiol-containing compounds are more preferred. Because thiol-containing compounds have low SH bond energies, they are prone to bond breaking and chain transfer reactions, thus tending to improve surface curability.

[0529] In chain transfer agents, from the viewpoint of cone angle and surface curability, thiol-containing compounds with aromatic rings are preferred, as are aliphatic thiol-containing compounds, and aliphatic thiol-containing compounds are more preferred.

[0530] Examples of thiol-containing compounds with aromatic rings include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene. From the viewpoint of cone angle, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred.

[0531] As aliphatic thiol-containing compounds, multifunctional aliphatic thiol-containing compounds are preferred. Examples include: butanediol bis(3-mercaptopropionate), butanediol dithioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dithioglycolate, trimethylolpropane tri(3-mercaptopropionate), trimethylolpropane trithioglycolate, trihydroxyethyl trithiopropionate, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tri(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tri(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0532] Among them, the preferred ingredients are trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetras(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetras(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and more preferably pentaerythritol tetras(3-mercaptopropionate) and pentaerythritol tetras(3-mercaptobutyrate).

[0533] They can be used individually or in combination with two or more.

[0534] [1-1-12] Coloring agents

[0535] The photosensitive resin composition of the present invention may also contain a colorant for the purpose of coloring the spacer walls. As a colorant, known colorants such as pigments and dyes can be used, but from the viewpoint of heat resistance, pigments are preferred.

[0536] When a photosensitive resin composition contains a colorant, it may contain one colorant or two or more colorants. From the viewpoint of uniformly blocking light in the visible light region, two or more colorants are preferred.

[0537] Examples of pigments include organic pigments and inorganic pigments. When used as a spacer, organic pigments are preferred from the viewpoint of electrical insulation.

[0538] Organic pigments can be categorized into organic coloring pigments and organic black pigments. Here, organic coloring pigments refer to organic pigments that exhibit colors other than black, such as red pigments, orange pigments, blue pigments, purple pigments, green pigments, yellow pigments, and white pigments.

[0539] In the photosensitive resin composition of the present invention, the content of the colorant in the photosensitive resin composition is not particularly limited. For example, relative to the total solids content of the photosensitive resin composition, it is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, especially more preferably 5% by mass or less, particularly preferably 1% by mass or less, and most preferably 0% by mass. By setting the content within the above range, the curability and ink repellency of the spacer wall can be improved.

[0540] [1-1-13] Dispersant

[0541] In the case where the photosensitive resin composition of the present invention contains a colorant, a dispersant is preferably contained in order to finely disperse the colorant and stabilize the dispersion.

[0542] As a dispersant, a polymeric dispersant having functional groups is preferred. Furthermore, from the perspective of dispersion stability, polymeric dispersants having the following functional groups are preferred: carboxyl groups; phosphate groups; sulfonic acid groups; or their salts; primary, secondary, or tertiary amino groups; quaternary ammonium salt groups; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. In particular, from the viewpoint that a small amount of dispersant can be used to disperse colorants, polymeric dispersants having tertiary amino or quaternary ammonium salt groups are especially preferred.

[0543] Examples of polymeric dispersants include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants containing monomers with amino groups and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0544] As polymeric dispersants, examples by trade name include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0545] The weight-average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more. Furthermore, it is preferably 100,000 or less, more preferably 50,000 or less. The above upper and lower limits can be combined arbitrarily. For example, the weight-average molecular weight (Mw) of the polymeric dispersant is preferably 700 to 100,000, more preferably 1,000 to 50,000. From the viewpoint of the dispersion stability of the colorant, the dispersant preferably contains an acrylic polymeric dispersant with functional groups. From the viewpoint of dispersibility and storage properties, a polymeric dispersant having basic functional groups and having either or both of polyester bonds and polyether bonds is preferred.

[0546] Polymer dispersants can be used alone or in combination with two or more.

[0547] From the viewpoint of dispersibility, the amount of dispersant relative to the total solids content of the photosensitive resin composition is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. Furthermore, it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0548] [1-1-14] Photoacid-producing agent

[0549] The photosensitive resin composition of the present invention may also contain a photoacid-generating agent. From the viewpoint of storage stability, the amount of solids in the photosensitive resin composition is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and particularly preferably completely free of solids.

[0550] [1-2] Method for preparing photosensitive resin composition

[0551] The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components using a mixer. It should be noted that, in order to make the prepared photosensitive resin composition homogeneous, filtration can also be performed using a membrane filter or the like.

[0552] [2] Spare walls and their formation methods

[0553] The photosensitive resin composition of the present invention is preferably used to form spacers, particularly spacers for dividing the organic layer (light-emitting portion) of an organic electroluminescent element. The spacers of the present invention are formed by curing the photosensitive resin composition of the present invention.

[0554] The method for forming spacers using the photosensitive resin composition of the present invention is not particularly limited, and existing known methods can be employed. Examples of methods for forming spacers include a coating step that involves coating the photosensitive resin composition onto a substrate to form a photosensitive resin composition layer, and an exposure step that exposes the photosensitive resin composition layer. A specific example of such a method for forming spacers is photolithography.

[0555] In photolithography, a photosensitive resin composition is coated onto the entire surface of the area on the substrate where spacers are to be formed to form a photosensitive resin composition layer. After the formed photosensitive resin composition layer is exposed to a predetermined spacer pattern, it is developed to form spacers on the substrate.

[0556] In the photolithography process, the photosensitive resin composition is coated onto a substrate. On the substrate where spacers are to be formed, the photosensitive resin composition is coated using contact transfer coating devices such as roller coaters, reverse coaters, and bar coaters, as well as non-contact coating devices such as spin coaters (rotary coating devices) and curtain coating flow coating devices. The solvent is removed by drying as needed to form a photosensitive resin composition layer.

[0557] Next, in the exposure process, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet light or excimer laser using a negative mask, causing the photosensitive resin composition layer to be partially exposed in accordance with the pattern of the spacer walls. Exposure can be performed using a light source that emits ultraviolet light, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp. The exposure amount varies depending on the composition of the photosensitive resin composition, and is preferably 10–400 mJ / cm². 2 about.

[0558] Next, in the developing process, the photosensitive resin composition layer corresponding to the pattern of the spacer walls is developed using a developing solution, thereby forming the spacer wall pattern. The developing method is not particularly limited; immersion or spray methods can be used. Specific examples of developing solutions include: organic developing solutions such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine; and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Furthermore, defoamers and surfactants may be added to the developing solution.

[0559] Then, the developed spacer pattern is post-baked to heat-cur it, thereby obtaining the spacer. The post-baking is preferably carried out at 150-250°C for 15-60 minutes.

[0560] After the spacer walls are formed, a cleaning process can be performed to clean the unexposed areas. There are no particular limitations on the cleaning method; examples include plasma irradiation, excimer laser irradiation, and UV irradiation. In excimer laser irradiation and UV irradiation, organic matter adhering to the pixel area can be decomposed and removed by light irradiation.

[0561] The substrate used to form the spacers is not particularly limited, and is appropriately selected according to the type of organic electroluminescent element manufactured using the substrate with the spacers formed thereon. Preferred substrate materials include glass and various resin materials. Specific examples of resin materials include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resin; polysulfone; and polyimide.

[0562] Among the materials used for these substrates, glass and polyimide are preferred due to their excellent heat resistance. Furthermore, depending on the type of organic electroluminescent element being manufactured, transparent electrode layers such as ITO and ZnO can be pre-formed on the surface of the substrate where the spacers are to be formed.

[0563] The membrane thickness (height) of the spacer is typically 0.5–10 μm.

[0564] [3] Organic electroluminescent elements

[0565] The organic electroluminescent element of the present invention has the spacer wall of the present invention.

[0566] Various organic electroluminescent devices can be manufactured using a substrate having a spacer pattern created by the method described above. The method for forming the organic electroluminescent device is not particularly limited, but it is preferable to form an organic layer such as a pixel by injecting ink into the area surrounded by the spacers on the substrate after forming the spacer pattern using the method described above, thereby manufacturing the organic electroluminescent device.

[0567] As types of organic electroluminescent elements, bottom-emitting type and top-emitting type can be listed.

[0568] In a bottom-emitting type, for example, a spacer wall is formed on a glass substrate on which transparent electrodes are stacked, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are stacked in the opening surrounded by the spacer wall. In a top-emitting type, for example, a spacer wall is formed on a glass substrate on which metal electrode layers are stacked, and an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the opening surrounded by the spacer wall.

[0569] Organic electroluminescent layers, as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent Publication No. 5734681, can also be used. Quantum dots, as described in Japanese Patent Publication No. 5653387 and Japanese Patent Publication No. 5653101, can also be used.

[0570] As a solvent used in the ink for forming the organic layer, water, organic solvents, and mixtures thereof can be used. There are no particular limitations as long as the organic solvent can be removed from the film formed after the ink is injected. Examples of organic solvents include: toluene, xylene, anisole, mesitylene, tetrahydronaphthalene, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, and 3-phenoxytoluene. Furthermore, surfactants, antioxidants, viscosity modifiers, and ultraviolet absorbers can be added to the ink, for example.

[0571] As a method for injecting ink into a region surrounded by a partition wall, inkjet printing is preferred from the perspective of easily injecting a small amount of ink into a predetermined location. The ink used in forming the organic layer is appropriately selected depending on the type of organic electroluminescent element being manufactured. When injecting ink by inkjet printing, the viscosity of the ink is not particularly limited as long as it can be well ejected from the inkjet head, but is preferably 4 to 20 mPa·s, more preferably 5 to 10 mPa·s. The viscosity of the ink can be adjusted by adjusting the solid content of the ink, changing the solvent, or adding a viscosity modifier.

[0572] [4] Image display device

[0573] The image display device of the present invention includes the organic electroluminescent element of the present invention. As long as it includes the organic electroluminescent element of the present invention, the model and structure of the image display device are not particularly limited; for example, an active-drive type organic electroluminescent element can be assembled using conventional methods. For example, the image display device of the present invention can be formed using the methods described in "Organic EL Display" (OHM Corporation, published August 20, 2004, authored by Shizushi Tokito, Chinatsuya Adachi, and Hideyuki Murata). For example, an organic electroluminescent element emitting white light can be combined with a color filter for image display, or organic electroluminescent elements emitting different colors such as RGB can be combined for image display.

[0574] Example

[0575] The present invention will be described below with specific examples, but it is not limited to the following examples as long as it does not depart from the spirit of the present invention.

[0576] The components of the photosensitive resin compositions used in the following examples and comparative examples are described below.

[0577] Alkali-soluble resins

[0578] b-1: Alkali-soluble resins having the following structural units (epoxy (meth)acrylate resins (a mixture of compounds having a solid component acid value of 80 mg KOH / g, a weight-average molecular weight (Mw) of 8000 converted from polystyrene by GPC, and having m and n of 1 to 20)).

[0579] [Chemical Formula 45]

[0580]

[0581] In the above formula, * represents a bond with a monovalent group or hydrogen atom represented by the following formula.

[0582] [Chemical Formula 46]

[0583]

[0584] b-2: Alkali-soluble resin having the following structural units (epoxy (meth)acrylate resin (Nippon Kayaku Co., Ltd. "ZCR-8055H" (weight-average molecular weight Mw=7000, acid value=64mgKOH / g). It has a partial structure represented by the following formula)).

[0585] [Chemical Formula 47]

[0586]

[0587] (Where, m∶n = 4∶6~3∶7. The * in the above formula represents the connecting bond between structural units. The ** in the above formula represents the bond with a hydrogen atom or a monovalent group represented by the following formula).

[0588] [Chemical Formula 48]

[0589]

[0590] b-3: Alkali-soluble resin-VIII as described in International Publication No. 2024 / 034637, paragraph 0449.

[0591] <Photopolymerizable compounds>

[0592] c-1: KAYARAD DPEA-12 (a reaction product of dipentaerythritol, polyethylene glycol, and methacrylic acid) manufactured by Nippon Kayaku Co., Ltd.

[0593] c-2: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Nippon Kayaku Co., Ltd.

[0594] Photopolymerization initiators

[0595] a-1: A compound having the following structure. This compound can be prepared by the method described in International Publication No. 2009 / 131189.

[0596] [Chemical Formula 49]

[0597]

[0598] (D) compound

[0599] d-1: NC-3500 manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 207, weight average molecular weight 1900); d-1 has structural units with n=1 and 2 in formula (1).

[0600] d-2: NC-3000 manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 277, weight average molecular weight 1400); d-2 has a structural unit with n=1 in the above formula (1).

[0601] d-3: RE-310S manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 183, weight average molecular weight 410); d-3 is equivalent to bisphenol A type epoxy resin.

[0602] d-4: XD-1000 manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 245-260, weight average molecular weight 920-930); d-4 is an epoxy resin with a dicyclopentane backbone.

[0603] (E) compound

[0604] e-1: An acrylic copolymer resin containing perfluoroalkyl structural units, olefinic double bond structural units, and carboxyl structural units. Weight-average molecular weight 90,000, fluorine content 20% by mass.

[0605] e-2: Si-based liquid repellent (a copolymer resin having structural units of the following formula. Weight average molecular weight 14000, (moles of e2-2-1X): (moles of e2-2-2X) = 22:78. * indicates bonding part): e-2 is equivalent to compound (E2-2). It can be manufactured by the method described in Japanese Patent Application Publication No. 2023-169574.

[0606] [Chemical Formula 50]

[0607]

[0608] Surfactant: Megafac F554 manufactured by DIC.

[0609] <Additives>

[0610] f-1: KAYAMER PM-21 (phosphate compound) manufactured by Nippon Kayaku Co., Ltd.

[0611] f-2: Methylhydroquinone (polymerization inhibitor).

[0612] [Chemical Formula 51]

[0613]

[0614] f-3: BASF's TINUVIN384-2 (ultraviolet absorber); a compound containing the following structural formula.

[0615] [Chemical Formula 52]

[0616]

[0617] Dispersant-1: A high-molecular-weight acrylic AB block copolymer composed of A blocks with quaternary ammonium salt groups and tertiary amino groups on the side chains, and B blocks without quaternary ammonium salt groups and tertiary amino groups. Amine value: 70 mg KOH / g. Acid value: less than 1 mg KOH / g.

[0618] Solvent 1: Propylene glycol monomethyl ether acetate.

[0619] Solvent 2: 3-Methoxy-1-butanol.

[0620] [Preparation of Pigment Dispersion]

[0621] <Pigment Dispersion 1>

[0622] The pigments, dispersants, alkali-soluble resins, and solvents listed in Table 1 were mixed in the mass ratios specified in Table 1 to obtain a mixture. The mixture was dispersed for 3 hours using a paint shaker within a temperature range of 25–45°C. Zirconia beads with a diameter of 0.5 mm were added in an amount 2.5 times the mass of the dispersion. After dispersion, the beads and dispersion were separated using a filter to prepare pigment dispersion 1.

[0623] It should be noted that the solvent amounts in Table 1 also include amounts derived from dispersants and alkali-soluble resins. Furthermore, blank columns in Table 1 indicate that the component was not incorporated (0 parts by mass).

[0624] [Table 1]

[0625]

[0626] <Preparation of Photosensitive Resin Composition>

[0627] Using the proportions listed in Tables 2 and 3, and with propylene glycol monomethyl ether acetate, the components were stirred until homogeneous to prepare the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-5, in a manner that ensured the total solids content of the photosensitive resin composition was 15% by mass. It should be noted that the proportions (by mass) of each component in Tables 2 and 3 refer to the solids content of each component in the total solids content of the photosensitive resin composition.

[0628] The performance of the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-5 was evaluated by the methods described below.

[0629] <Fabrication and Evaluation of Substrates for Contact Angle Measurement>

[0630] On a glass substrate, various photosensitive resin compositions were coated using a spin coater to achieve a film thickness of 1.0 μm after heat curing. The substrate was then dried on a hot plate at 114°C for 2 minutes to obtain the coated substrate. Next, without a photomask, a Canon MPA-600FA reflective projection exposure machine was used at an illuminance of 500 mW / cm². 2 Exposure of 100mJ / cm 2 The obtained coating was exposed to the entire surface under the specified conditions. Next, it was spray-developed for 60 seconds with a 2.38% (w / w) TMAH (tetramethylammonium hydroxide) aqueous solution at 24°C, followed by rinsing with pure water for 20 seconds. The substrate was then cured in an oven at 230°C for 60 minutes to obtain a contact angle measurement substrate with the cured material applied to its entire surface.

[0631] Contact angle was measured using a Drop Master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd., at 23°C and 50% humidity. 1.0 μL of propylene glycol methyl ether acetate was dropped onto the substrate used for contact angle measurement, and the contact angle was measured after 1 second. The results are shown in Tables 2 and 3. A larger contact angle indicates higher ink repellency.

[0632] A: The contact angle is 40 degrees or more.

[0633] B: Contact angle less than 40 degrees.

[0634] Using various photosensitive resin compositions, the formation and performance evaluation of spacers were carried out by the methods described below.

[0635] (Formation of septum)

[0636] On an ITO film formed on the surface of a glass substrate, various photosensitive resin compositions were coated using a spin coater to achieve a film thickness of 1.0 μm after heat curing. The substrate was then dried on a hot plate at 114°C for 2 minutes to obtain a coated substrate. The resulting coating was then subjected to exposure using a Canon MPA-600FA reflective projection exposure machine (with multiple 60 μm × 240 μm light-blocking portions spaced 20 μm apart) with a lattice-shaped opening at an illuminance of 500 mW / cm². 2 Exposure of 100mJ / cm 2 Exposure was performed under the following conditions. Next, the substrate was spray-developed for 60 seconds with a 2.38% (w / w) TMAH (tetramethylammonium hydroxide) aqueous solution at 24°C, followed by rinsing with pure water for 1 minute. Through these operations, the unexposed areas were removed, and the resulting patterned substrate was cured in an oven at 230°C for 60 minutes to obtain the spacer wall substrate.

[0637] (Evaluation of inkjet coating performance)

[0638] In a substrate having the aforementioned lattice-shaped spacers, inkjet coating was performed on the pixel opening areas using Fujifilm DMP-2831. Isoamyl benzoate was used as the solvent alone, with 40 pL coated per pixel for 24 pixels, and wetting and spreading properties were evaluated. The more pixels that were sufficiently wetted and spread out of the 24 pixels, the better the inkjet coating performance.

[0639] A: The number of pixels wetted and spread by the ink within 24 pixels exceeds 20.

[0640] B: The number of pixels in a 24-pixel grid that are wetted and spread by the ink exceeds 12 but is less than 20.

[0641] C: The number of pixels where the ink wets and spreads within 24 pixels is less than 12.

[0642] [Table 2]

[0643]

[0644] [Table 3]

[0645]

[0646] Examples 1-8 exhibited good inkjet coating properties and achieved sufficient contact angles. This is presumably because the (D) compound, containing cyclic ether groups, in the photosensitive resin compositions of Examples 1-8 reacts with the acidic sites of the ink repellent and the alkali-soluble resin to form a strong cross-linked structure. Furthermore, by adjusting the ratio of (D) compound to (E) compound, there is a tendency to suppress the outflow of the ink repellent.

[0647] Comparative Example 1 does not contain (D) compound, so during the fabrication of the spacer, the liquid repellent decomposes during heating and flows out into the pixel, resulting in deterioration of inkjet coating properties.

[0648] In Comparative Example 2, since the proportion of compound (E) is too high compared to compound (D), the outflow suppression of the liquid repellent is insufficient, and it is speculated that the inkjet coating performance is deteriorated.

[0649] Compared with Comparative Examples 3 and 4, Examples 1 and 2 showed a tendency for better inkjet coating properties. This is presumably because the (D) compound contained in Examples 1 and 2 has many aromatic rings in its main chain, making it less prone to thermal decomposition during heat treatment, thus improving the overall heat resistance of the coating film and suppressing the outflow of liquid repellent.

[0650] In Example 8, even when a colorant is present, the content of compound (E) is 2 parts by mass or more and 8 parts by mass or less relative to 100 parts by mass of compound (D), thus ensuring both liquid repellency and inkjet coating properties.

[0651] To ensure ink repellency on the spacer wall surface, it is also important to use (E) compounds, which have crosslinking groups and contain fluorine atoms and / or siloxane chains, as liquid repellents. The liquid repellent used in Comparative Example 5 (a compound equivalent to (E) compound) does not have crosslinking groups. Therefore, after UV exposure, the liquid repellent is not easily fixed to the coating surface and is washed away in the developing solution during the developing process, resulting in deterioration of the ink repellency on the spacer wall surface and presumably also deterioration of inkjet coating properties.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a compound, and (E) a compound. The compound (D) is a compound having a cyclic ether group with 2 to 3 carbon atoms and having an aromatic ring and / or a heterocycle. The compound (E) is a compound having crosslinking groups and having fluorine atoms and / or siloxane chains. The content of compound (E) is 2 or more but less than 8 parts by mass relative to 100 parts by mass of compound (D).

2. The photosensitive resin composition according to claim 1, wherein, The content of compound (D) is 10 parts by mass or more relative to 100 parts by mass of alkali-soluble resin (B).

3. The photosensitive resin composition according to claim 1 or 2, characterized in that, The compound (D) has a structural unit represented by the following formula (1), [Chemical Formula 1] In equation (1), R d11 Each represents a divalent aliphatic hydrocarbon group, n represents an integer of 1 or 2, the benzene ring in formula (1) is further optionally substituted by any substituent, and * represents a bond.

4. The photosensitive resin composition according to claim 1 or 2, wherein, The acid value of compound (D) is less than 1 mg KOH / g.

5. The photosensitive resin composition according to claim 1 or 2, wherein, The (B) alkali-soluble resin contains epoxy (meth)acrylates with an aromatic ring in the main chain.

6. The photosensitive resin composition according to claim 1 or 2, wherein, The (C) photopolymerizable compound comprises a reaction product of pentaerythritol with (poly) glycol and (meth)acrylic acid, or a reaction product of dipentaerythritol with (poly) glycol and (meth)acrylic acid.

7. The photosensitive resin composition according to claim 1 or 2, wherein, The photosensitive resin composition also contains an aliphatic thiol compound.

8. The photosensitive resin composition according to claim 1 or 2, wherein, The photosensitive resin composition contains no colorant, or the proportion of colorant is less than 5% by mass relative to the total solid content of the photosensitive resin composition.

9. A cured product formed by curing the photosensitive resin composition as described in claim 1 or 2.

10. A spacer wall comprising the solidified material as described in claim 9.

11. An organic electroluminescent element having the spacer wall as described in claim 10.

12. An image display device comprising an organic electroluminescent element as described in claim 11.

Images