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

Abstract

A photosensitive resin composition containing (a) an alkali-soluble resin containing a polyamide-imide (meth) acrylate resin (a-1) having a specific structure, (b) a liquid repellent agent, (c) a photopolymerization initiator, and (d) a photopolymerizable compound. According to the present invention, it is possible to provide a photosensitive resin composition which can exhibit liquid repellency at a lower light exposure and which can form a partition wall that exhibits excellent level difference formability and inkjet coating properties.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product formed by curing the photosensitive resin composition, a spacer, an organic electroluminescent element having a spacer, and an image display device comprising an organic electroluminescent element. Background Technology

[0002] 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.

[0003] 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.

[0004] 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.

[0005] Patent Document 1 describes how, by using a photosensitive resin composition containing a specific alkali-soluble resin, a spacer pattern with high liquid repellency on the upper surface of the spacer and excellent ink wetting properties at the opening can be obtained.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2022-47006 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] When forming an organic light-emitting layer using inkjet printing, it is necessary to form spacers with highly liquid-repellent properties on their upper surfaces. To achieve this high liquid-repellency, high exposure levels are typically required. However, increasing the exposure level leads to longer exposure times and higher manufacturing costs; therefore, an exposure level of 80 mJ / cm² is preferred. 2 The following is an exposé. Patent Document 1 describes how, by using a photosensitive resin composition containing a specific alkali-soluble resin, high liquid repellency can be achieved on the upper surface of the spacer wall, but specifically, 120 mJ / cm² is required. 2 The exposure.

[0011] Therefore, the object of the present invention is to provide a photosensitive resin composition that can exhibit liquid repellency with lower exposure and can form septum exhibiting excellent height difference formation and inkjet coating properties.

[0012] Furthermore, the present invention aims to provide a spacer wall formed by curing the photosensitive resin composition, an organic electroluminescent element having the spacer wall, and an image display device comprising the organic electroluminescent element.

[0013] Solution for solving the problem

[0014] The inventors conducted in-depth research and discovered that the above-mentioned problems can be solved by using a specific alkali-soluble resin in the photosensitive resin composition, thus completing the present invention.

[0015] That is, the main idea of ​​this invention is as follows.

[0016] [1] A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a liquid repellent, (c) a photopolymerization initiator and (d) a photopolymerizable compound, wherein the (a) alkali-soluble resin comprises a polyamide-imide (meth)acrylate resin (a-1) having a structure represented by the following general formula (1).

[0017] [Chemical Formula 1]

[0018]

[0019] (In equation (1), R) 1 ~R 3 This indicates a divalent aliphatic hydrocarbon group. X 1 ~X 3 (represent any structure in general formulas (2) to (4) respectively).

[0020] [Chemical Formula 2]

[0021]

[0022] (In equation (2), R) 4 ~R 6 This indicates a divalent aliphatic hydrocarbon group. X 4 and X 5 Each represents any structure in general formulas (2) to (4). 1 (Indicates aromatic hydrocarbons or alicyclic hydrocarbons).

[0023] [Chemical Formula 3]

[0024]

[0025] (In equation (3), R) 7This represents a monovalent aliphatic hydrocarbon group. Y 2 and Y 3 Each can be used independently to represent an aromatic hydrocarbon or an alicyclic hydrocarbon.

[0026] [Chemical Formula 4]

[0027]

[0028] (In equation (4), R) 8 This represents a monovalent aliphatic hydrocarbon group. Y 4 and Y 5 Each can be used independently to represent an aromatic hydrocarbon or an alicyclic hydrocarbon.

[0029] [2] According to the photosensitive resin composition of [1], wherein the liquid repellent (b) comprises a liquid repellent (b1) having an olefinic unsaturated bond group.

[0030] [3] The photosensitive resin composition according to [2] is characterized in that the liquid repellent (b1) comprises an acrylic resin (b2) containing repeating units represented by the following general formula (5) and fluorine atoms.

[0031] [Chemical Formula 5]

[0032]

[0033] (In equation (5), R) 11 Each can be used independently to represent a hydrogen atom or a methyl group, R 12 It represents an alkyl group having 2 to 6 carbon atoms, which is optionally interrupted by one or more of -O-, -CO-, -S-, and -NH-.

[0034] * indicates the bonding portion.

[0035] [4] The photosensitive resin composition according to [3], wherein the acrylic resin (b2) has fluoroalkyl and / or fluoroalkylene groups.

[0036] [5] According to the photosensitive resin composition of [1], wherein the content of (a) alkali-soluble resin is 200 parts by mass or less relative to 100 parts by mass of the (d) photopolymer compound.

[0037] [6] According to the photosensitive resin composition of [1], wherein the polyamide-imide (meth) acrylate resin (a-1) has a polystyrene equivalent weight-average molecular weight (Mw) of 1,000 or more and 10,000 or less, as determined by gel permeation chromatography (GPC).

[0038] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the photosensitive resin composition is used to form a spacer wall.

[0039] [8] The photosensitive resin composition according to [7], wherein the photosensitive resin composition is used to form a spacer wall with a height difference in one step by photolithography.

[0040] [9] A cured product formed by curing a photosensitive resin composition according to any one of [1] to [6].

[0041]

[10] A spacer wall formed by curing a photosensitive resin composition according to any one of [1] to [6].

[0042]

[11] An organic electroluminescent element having a spacer wall according to

[10] .

[0043]

[12] An image display device comprising an organic electroluminescent element according to

[11] .

[0044] Invention Effects

[0045] According to the present invention, a photosensitive resin composition can be provided that exhibits liquid repellency with lower exposure and can form septa exhibiting excellent height difference formation and inkjet coating properties.

[0046] Furthermore, the present invention can provide a spacer formed by curing a photosensitive resin composition, an organic electroluminescent element having the spacer, and an image display device including the organic electroluminescent element. Attached Figure Description

[0047] Figure 1 This is a top view showing an example of a substrate having spacer walls with height differences.

[0048] Figure 2 This is a cross-sectional view showing an example of a substrate having spacer walls with height differences. Detailed Implementation

[0049] 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.

[0050] In this invention, "(meth)acryl" means "acryl and / or methacryl".

[0051] In this invention, (ii) tricarboxylic anhydride refers to dicarboxylic anhydride and / or tricarboxylic anhydride.

[0052] In this invention, "all solid components" refers to all components in the photosensitive resin composition except for the solvent, even if the components other than the solvent are liquid at room temperature, they are included in the solid components.

[0053] 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.

[0054] In this invention, "A and / or B" refers to one or both of A and B, specifically A, B, or A and B.

[0055] In this invention, "(co)polymer" refers to both homopolymer and copolymer, and "polyacid (anhydride)" refers to "polyacid and / or polyacid anhydride".

[0056] In this invention, weight-average molecular weight refers to the weight-average molecular weight (Mw) obtained by GPC (gel permeation chromatography) converted to polystyrene.

[0057] In this invention, the acid value represents the acid value converted from the effective solid components, which is calculated by neutralization titration.

[0058] 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.

[0059] In this invention, the light-emitting part (pixel part) refers to the part that emits light when powered by electricity.

[0060] [1] Photosensitive resin composition

[0061] The photosensitive resin composition of the present invention is a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a liquid repellent, (c) a photopolymerization initiator, and (d) a photopolymerizable compound, wherein the (a) alkali-soluble resin contains a polyamide-imide (meth)acrylate resin (a-1) comprising the structure represented by the following general formula (1). The photosensitive resin composition of the present invention may further contain other components as needed, such as ultraviolet absorbers and polymerization inhibitors.

[0062] [Chemical Formula 6]

[0063]

[0064] (In equation (1), R) 1 ~R 3 This indicates a divalent aliphatic hydrocarbon group. X 1 ~X 3 (represent any structure in general formulas (2) to (4) respectively).

[0065] [Chemical Formula 7]

[0066]

[0067] (In equation (2), R) 4 ~R 6 This indicates a divalent aliphatic hydrocarbon group. X 4 and X 5 Each represents any structure in general formulas (2) to (4). 1 (Indicates aromatic hydrocarbons or alicyclic hydrocarbons).

[0068] [Chemical Formula 8]

[0069]

[0070] (In equation (3), R) 7 This represents a monovalent aliphatic hydrocarbon group. Y 2 and Y 3 Each can be used independently to represent an aromatic hydrocarbon or an alicyclic hydrocarbon.

[0071] [Chemical Formula 9]

[0072]

[0073] (In equation (4), R) 8 This represents a monovalent aliphatic hydrocarbon group. Y 4 and Y 5 Each can be used independently to represent an aromatic hydrocarbon or an alicyclic hydrocarbon.

[0074] In this invention, a spacer refers to, for example, a component used to divide the functional layer (organic layer, light-emitting part) in an active-drive organic electroluminescent element, or a component used to form a pixel containing a functional layer and a spacer by spraying ink, which is a material used to form the functional layer, into the divided area (pixel area) and drying it.

[0075] [1-1] Components and composition of the photosensitive resin composition

[0076] The components and their composition constituting the photosensitive resin composition of the present invention will be described.

[0077] The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, (b) a liquid repellent, (c) a photopolymerization initiator, and (d) a photopolymerizable compound.

[0078] [1-1-1] (a) Components; Alkali-soluble resin

[0079] The alkali-soluble resin of the present invention (a) contains a polyamide-imide (meth)acrylate resin (a-1) comprising the structure represented by the general formula (1).

[0080] <Polyamide-imide (meth)acrylate resin (a-1)>

[0081] Polyamide-imide (meth)acrylate resin (a-1) possesses an isocyanurate backbone, as well as amide and imide bonds, resulting in strong intermolecular forces and a tendency to resist thermal decomposition during heat treatment. It is believed that including polyamide-imide (meth)acrylate resin (a-1) in the photosensitive resin composition reduces smoke generation during the curing of the composition. Furthermore, because polyamide-imide (meth)acrylate resin (a-1) contains (meth)acryloyl groups, even with the presence of colorants, it can form a more robust cured film through photo- and thermo-curing processes, thereby improving the residual film yield after curing.

[0082] In the above formula (1), R 1 ~R 3 This indicates a divalent aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and can be saturated or unsaturated aliphatic, and can be linear, branched, or cyclic, and may also have substituents. Furthermore, R... 1 ~R 3 It can consist entirely of the same aliphatic hydrocarbon groups, or it can consist entirely of different aliphatic hydrocarbon groups.

[0083] In the above formula (1), X 1 ~X 3 Each represents any structure in general formulas (2) to (4). 1 ~X 3 They can all have the same structure, or they can all have different structures.

[0084] In the above formula (2), R 4 ~R 6 This indicates a divalent aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and can be saturated or unsaturated aliphatic, and can be linear, branched, or cyclic, and may also have substituents. Furthermore, R... 4 ~R 6 It can consist entirely of the same aliphatic hydrocarbon groups, or it can consist entirely of different aliphatic hydrocarbon groups.

[0085] X 4 and X 5 Each represents any structure in general formulas (2) to (4). 4 and X 5 They can all have the same structure, or they can all have different structures.

[0086] Y 1This indicates an aromatic hydrocarbon or an alicyclic hydrocarbon that optionally has substituents. The aromatic hydrocarbon and the alicyclic hydrocarbon preferably have 1 to 10 carbon atoms.

[0087] In the above formula (3), R 7 This indicates a monovalent aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and can be saturated or unsaturated aliphatic, and can be linear, branched, or cyclic, and may also have substituents.

[0088] Y 2 and Y 3 Each of these can be independently represented as an aromatic hydrocarbon or an alicyclic hydrocarbon, optionally having substituents. The aromatic hydrocarbon and the alicyclic hydrocarbon preferably have 1 to 10 carbon atoms.

[0089] In equation (4) above, R 8 This indicates a monovalent aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms, and can be saturated or unsaturated aliphatic, and can be linear, branched, or cyclic, and may also have substituents.

[0090] Y 4 and Y 5 Each can be used independently to represent an aromatic hydrocarbon or an alicyclic hydrocarbon that optionally has substituents.

[0091] Polyamide-imide (meth)acrylate resin (a-1) (hereinafter sometimes abbreviated as "resin (a-1)") is obtained, for example, by reacting a polyamide-imide resin having terminal acid groups or anhydride groups, obtained by reacting an isocyanurate-type polyisocyanate with a tricarboxylic acid anhydride, with a (meth)acrylate and a (di)tricarboxylic acid anhydride having an epoxy group in the molecule. However, it is not limited to this method as long as the raw materials and methods can achieve the same effect in the present invention.

[0092] Examples of isocyanurate-type polyisocyanates include: isocyanurate-type triisocyanates (HDI3N) synthesized from hexamethylene diisocyanate, isocyanurate-type triisocyanates (HTMDI3N) synthesized from trimethylhexamethylene diisocyanate, isocyanurate-type triisocyanates (IPDI3N) synthesized from isophorone diisocyanate, isocyanurate-type triisocyanates (HTDI3N) synthesized from hydrogenated toluene diisocyanate, isocyanurate-type triisocyanates (HXDI3N) synthesized from hydrogenated xylene diisocyanate, isocyanurate-type triisocyanates (NBDI3N) synthesized from norbornene diisocyanate, and isocyanurate-type triisocyanates (HMDI3N) synthesized from hydrogenated diphenylmethane diisocyanate. From the viewpoint of suppressing curing shrinkage, for example, isocyanurate-type triisocyanates synthesized from isophorone diisocyanate (IPDI3N), isocyanurate-type triisocyanates synthesized from hydrogenated toluene diisocyanate (HTDI3N), isocyanurate-type triisocyanates synthesized from hydrogenated xylene diisocyanate (HXDI3N), isocyanurate-type triisocyanates synthesized from norbornene diisocyanate (NBDI3N), isocyanurate-type triisocyanates synthesized from hydrogenated diphenylmethane diisocyanate (HMDI3N), etc., are preferred, and isocyanurate-type triisocyanates synthesized from isophorone diisocyanate (IPDI3N) are even more preferred.

[0093] Examples of tricarboxylic anhydrides that react with isocyanurate-type polyisocyanates include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic anhydride, propane tricarboxylic anhydride, cyclohexane tricarboxylic anhydride, methylcyclohexane tricarboxylic anhydride, cyclohexene tricarboxylic anhydride, and methylcyclohexene tricarboxylic anhydride. From the viewpoint of suppressing curing shrinkage, alicyclic tricarboxylic anhydrides such as cyclohexane tricarboxylic anhydride, methylcyclohexane tricarboxylic anhydride, cyclohexene tricarboxylic anhydride, and methylcyclohexene tricarboxylic anhydride are preferred, with cyclohexane tricarboxylic anhydride being more preferred.

[0094] Examples of cyclohexane tricarboxylic acid anhydrides include: cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, and cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride.

[0095] The (meth)acrylates with epoxy groups in the molecules used in this invention are not particularly limited in other specific structures as long as their molecular structure contains epoxy and (meth)acryloyl groups, and a wide variety of compounds can be used.

[0096] Examples of (meth)acrylates containing epoxy groups in their molecules include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, cyclohexyl monoepoxy acrylate, and their derivatives (e.g., analogs obtained by reacting acrylic acid or methacrylic acid with an epoxycyclohexane compound, such as 3,4-epoxycyclohexyl methacrylate). These can be used individually or in combination of two or more. Among these, substances with a molecular weight of 1000 or less are preferred from the viewpoint of becoming polyamide-imide resins containing olefinic unsaturated groups, acid groups, and secondary hydroxyl groups that exhibit excellent heat resistance in the cured product.

[0097] Regarding (di)carboxylic acid anhydrides that react with polyamide-imide resins having terminal acid or anhydride groups and (meth)acrylates having epoxy groups in their molecules, examples of dicarboxylic acid anhydrides include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylenetetrahydrophthalic acid, chlorogenic acid, and methyltetrahydrophthalic acid anhydrides. From the viewpoint of electrical properties, aliphatic dicarboxylic acid anhydrides such as succinic acid, 1,2-cyclopropanedicarboxylic acid, 2,2-dimethylsuccinic acid, caronic acid, 1,2-cyclohexanedicarboxylic acid, butylsuccinic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, n-octylsuccinic acid, decylsuccinic acid, and dodecylsuccinic acid anhydrides are preferred.

[0098] As tricarboxylic anhydrides, substances identical to the tricarboxylic anhydrides that react with isocyanurate-type polyisocyanates mentioned above can be listed. From the viewpoint of developability, aliphatic tricarboxylic anhydrides are preferred, and alicyclic tricarboxylic anhydrides are more preferred.

[0099] The weight-average molecular weight (Mw) of the resin (a-1) converted from polystyrene, as determined by gel permeation chromatography (GPC), is typically 1000 or more, preferably 1500 or more, more preferably 2000 or more, further preferably 2500 or more, and even more preferably 3000 or more. Furthermore, it is typically 10000 or less, preferably 9000 or less, more preferably 8000 or less, and even more preferably 7000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1000 to 10000 is preferred, 1500 to 9000 is more preferred, 2000 to 8000 is even more preferred, and 3000 to 7000 is even more preferred. By setting it above the lower limit, there is a tendency to reduce smoke generation. By setting it below the upper limit, there is a tendency for improved development and solubility.

[0100] Regarding the reaction between the alicyclic isocyanurate-type polyisocyanate and the alicyclic tricarboxylic anhydride, the total amount of anhydride groups to carboxylic acid is preferably 1.0 mol to 3.0 mol, more preferably 1.2 mol to 2.8 mol, and even more preferably 1.4 mol to 2.6 mol, relative to 1 mol of isocyanate groups in the alicyclic isocyanurate-type polyisocyanate. When the total amount of anhydride groups to carboxylic acid exceeds 1.0 mol, isocyanate group residue can be prevented, high molecular weight can be suppressed, and good developability can be achieved. When the total amount of anhydride groups to carboxylic acid is less than 3.0 mol, alicyclic tricarboxylic anhydride residue can be prevented, and its formation as developing residue can be suppressed.

[0101] The acid value of resin (a-1) is not particularly limited, but is preferably 20 mg KOH / g or higher, more preferably 40 mg KOH / g or higher, and even more preferably 60 mg KOH / g or higher. Furthermore, it is preferably 200 mg KOH / g or lower, and even more preferably 150 mg KOH / g or lower. The above upper and lower limits can be combined arbitrarily. For example, 20–200 mg KOH / g is preferred, 40–200 mg KOH / g is more preferred, and 60–150 mg KOH / g is even more preferred.

[0102] Setting the value above the lower limit tends to improve the developing solubility and resolution. Setting the value below the upper limit tends to improve the residual film yield.

[0103] The specific structure of the alkali-soluble resin having olefinic double bonds is not particularly limited. From the viewpoint of developing solubility, acrylic copolymer resin (a-2) and / or epoxy (meth)acrylate resin (a-3) are preferred. From the viewpoint of reducing degassing, epoxy (meth)acrylate resin (a-3) is more preferred.

[0104] The acrylic copolymer resin (a-2) is described in detail below.

[0105] [Acrylic copolymer resin (a-2)]

[0106] From the viewpoint of curability, acrylic copolymer resin (a-2) preferably has olefinic double bonds in its side chains.

[0107] From the viewpoint of developing solubility, acrylic copolymer resin (a-2-1) containing a partial structure represented by the following general formula (I) is preferred among acrylic copolymer resins (a-2-1).

[0108] [Chemical Formula 10]

[0109]

[0110] In equation (I), R A and RB Each atom represents a hydrogen atom or a methyl group independently. * indicates a bonded bond.

[0111] From the viewpoint of reproducibility, the partial structure represented by the formula (I) is preferably the partial structure represented by the following general formula (I-1).

[0112] [Chemical Formula 11]

[0113]

[0114] In equation (I-1), R A and R B The meaning is the same as in equation (I). R 1 It indicates a divalent hydrocarbon group having 1 to 4 carbon atoms that optionally have a substituent.

[0115] From the viewpoint of sensitivity, the partial structure represented by the above formula (I) is preferably the partial structure represented by the following formula (I-2).

[0116] [Chemical Formula 12]

[0117]

[0118] In equation (I-2), R A and R B It has the same meaning as in equation (I).

[0119] When the acrylic copolymer resin (a-2-1) contains a portion of the structure represented by the general formula (I), the content of the portion of the structure represented by the general formula (I) in the acrylic copolymer resin (a-2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, even more preferably 50 mol% or more, particularly preferably 70 mol% or more, most preferably 80 mol% or more, and preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less. The upper and lower limits can be combined arbitrarily; for example, 5 to 99 mol%, more preferably 20 to 99 mol%, further preferably 30 to 97 mol%, even more preferably 50 to 97 mol%, particularly preferably 70 to 95 mol%, and most preferably 80 to 95 mol%. By setting the lower limit or above, there is a tendency to reduce residue. Furthermore, by setting the upper limit or below, there is a tendency to improve development adhesion.

[0120] When the acrylic copolymer resin (a-2-1) contains a portion of the structure represented by the general formula (I-1), the content of the portion of the structure represented by the general formula (I-1) in the acrylic copolymer resin (a-2-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 8 mol% or more, even more preferably 10 mol% or more, and preferably 99 mol% or less, more preferably 60 mol% or less, further preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 99 mol%, more preferably 1 to 60 mol%, more preferably 5 to 40 mol%, even more preferably 8 to 30 mol%, and particularly preferably 10 to 20 mol%. By setting the value above the lower limit, there is a tendency for increased sensitivity and reduced residue. Furthermore, by setting the value below the upper limit, there is a tendency for improved development adhesion.

[0121] When the acrylic copolymer resin (a-2-1) contains a portion of the structure represented by the general formula (I-2), the content of the portion of the structure represented by the general formula (I-2) in the acrylic copolymer resin (a-2-1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 70 mol% or more, and preferably 99 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, and most preferably 85 mol% or less. The upper and lower limits can be combined arbitrarily; for example, 10–99 mol%, more preferably 20–99 mol%, more preferably 30–95 mol%, even more preferably 40–95 mol%, particularly preferably 50–90 mol%, and most preferably 70–85 mol%. Setting the value above the lower limit tends to increase sensitivity. Furthermore, setting the value below the upper limit tends to increase developability.

[0122] When the acrylic copolymer resin (a-2-1) contains a partial structure represented by the general formula (I), other optional partial structures are not particularly limited. From the viewpoint of developing adhesion, for example, it is preferable to contain a partial structure represented by the following general formula (I').

[0123] [Chemical Formula 13]

[0124]

[0125] In the above formula (I'), R D R represents a hydrogen atom or a methyl group. EThe term indicates an alkyl group optionally having a substituent, an aryl group optionally having a substituent (aromatic cycloyl group), or an alkenyl group optionally having a substituent.

[0126] (R) E )

[0127] In the formula (I'), R E The term indicates an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkenyl group optionally having a substituent.

[0128] As R E The alkyl group in the film can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 3 or more, even more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 20 are preferred, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, and particularly preferably 5 to 12. Setting the value above the lower limit tends to increase film strength and improve development adhesion. Furthermore, setting the value below the upper limit tends to reduce residue.

[0129] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. Among these, dicyclopentyl and dodecyl are preferred from the viewpoint of film strength, and dicyclopentyl is more preferred.

[0130] Substituents optionally present as alkyl groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl, with hydroxyl and polyethylene glycol groups being preferred from the viewpoint of reproducibility.

[0131] As R E The aryl group (aromatic cyclic group) in the formula can be categorized as: monovalent aromatic hydrocarbon cyclic group and monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 6 or more, and further preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. The upper and lower limits can be combined arbitrarily; for example, 4 to 24 is preferred, more preferably 4 to 22, even more preferably 6 to 20, and particularly preferably 6 to 18. 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.

[0132] Aromatic hydrocarbon rings, which are the cyclic groups of aromatic hydrocarbons, can be monocyclic or fused rings. Examples 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.

[0133] Aromatic heterocyclic groups can be monocyclic or fused rings, and examples include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol 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, quinazoline ketone rings, and azurite rings. From a curing point of view, benzene ring groups and naphthyl ring groups are preferred, with benzene ring groups being more preferred.

[0134] Examples of substituents that may be optionally present in the aryl group include: methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, polyethylene glycol, phenyl, and carboxyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol are preferred.

[0135] As R E The alkenyl group in the compound can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, more preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 is preferred, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14. 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.

[0136] Examples of alkenyl groups include vinyl, propenyl, butenyl, and cyclohexenyl. Among these, from the viewpoint of curability, vinyl and propenyl are preferred, and vinyl is more preferred.

[0137] Substituents optionally present in the alkenyl group include, for example, methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0138] Of these, from the perspective of imaging, as R E Preferably alkyl or alkenyl, more preferably alkyl, and even more preferably dicyclopentyl.

[0139] When the acrylic copolymer resin (a-2-1) contains a portion of the structure represented by the general formula (I'), the content of the portion of the structure represented by the general formula (I') in the acrylic copolymer resin (a-2-1) is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, even more preferably 30 mol% or less, and particularly preferably 10 mol% or less. The upper and lower limits can be combined arbitrarily; for example, 0.5 to 90 mol%, more preferably 0.5 to 70 mol%, further preferably 1 to 50 mol%, even more preferably 1.5 to 30 mol%, and particularly preferably 2 to 10 mol%. By setting it above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting it below the upper limit, there is a tendency for reduced residue.

[0140] In the case where the acrylic copolymer resin (a-2-1) contains a partial structure represented by the general formula (I), from the viewpoint of heat resistance and film strength, it is preferable to further contain a partial structure represented by the following general formula (I'').

[0141] [Chemical Formula 14]

[0142]

[0143] In the above formula (I''), R F R represents a hydrogen atom or a methyl group. G The denotes an alkyl group, an alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a mercapto group, or an alkyl thioether group, which may optionally have a substituent. t represents an integer from 0 to 5.

[0144] (R) G )

[0145] In the formula (I''), R G The term indicates an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, a hydroxyl group, a carboxyl group optionally having a substituent, a halogen atom, an alkoxy group optionally having a substituent, a mercapto group, or an alkyl thioether group optionally having a substituent.

[0146] As R GThe alkyl group in the formula can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 3 or more, even more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 20 is preferred, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, and particularly preferably 5 to 12. 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.

[0147] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. Among these, dicyclopentyl and dodecyl are preferred from the viewpoint of good adhesion, and dicyclopentyl is more preferred.

[0148] Substituents optionally present as alkyl groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl, with hydroxyl and polyethylene glycol groups being preferred from the viewpoint of reproducibility.

[0149] As R G The alkenyl group in the compound can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, more preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. For example, 2 to 22 is preferred, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14. 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.

[0150] Examples of alkenyl groups include vinyl, propenyl, butenyl, and cyclohexenyl. Among these, from the viewpoint of curability, vinyl and propenyl are preferred, and vinyl is more preferred.

[0151] Substituents optionally present in the alkenyl group include, for example, methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0152] As R G Halogen atoms in ink can be listed as fluorine, chlorine, bromine, and iodine atoms. Among these, fluorine atoms are preferred from the perspective of ink repellency.

[0153] As R GThe alkoxy group in the sample can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. For example, 1 to 20 is preferred, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12. 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.

[0154] Substituents optionally present as alkoxy groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0155] As R G The alkyl sulfide group in the formula can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. For example, 1 to 20 carbon atoms are preferred, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12. 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.

[0156] Examples of alkyl thioether groups include methyl thioether, ethyl thioether, propyl thioether, and butyl thioether. Among these, methyl thioether and ethyl thioether are preferred from the viewpoint of reproducibility.

[0157] Substituents optionally present in the alkyl group of the alkyl sulfide group include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol are preferred.

[0158] Of these, from the perspective of imaging, as R G Preferably, hydroxyl and carboxyl groups are used, with carboxyl groups being more preferred.

[0159] (t)

[0160] In the formula (I''), t represents an integer from 0 to 5. From the viewpoint of reproducibility, 0 to 2 is preferred, 0 to 1 is more preferred, and 0 is even more preferred.

[0161] When the acrylic copolymer resin (a-2-1) contains a portion of the structure represented by the general formula (I''), the content of the portion of the structure represented by the general formula (I'') in the acrylic copolymer resin (a-2-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more, particularly preferably 5 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, even more preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 90 mol%, more preferably 1 to 70 mol%, further preferably 2 to 50 mol%, even more preferably 2 to 30 mol%, particularly preferably 3 to 20 mol%, and most preferably 5 to 10 mol%. By setting the lower limit or above, there is a tendency for improved developing adhesion. Furthermore, by setting the upper limit or below, there is a tendency for reduced residue.

[0162] In the case where the acrylic copolymer resin (a-2-1) contains a partial structure represented by the general formula (I), from the viewpoint of reproducibility, it is preferable to further contain a partial structure represented by the following general formula (I''').

[0163] [Chemical Formula 15]

[0164]

[0165] In the above formula (I'''), R H It represents a hydrogen atom or a methyl group.

[0166] When the acrylic copolymer resin (a-2-1) contains a portion of the structure represented by the general formula (I'''), the content of the portion of the structure represented by the general formula (I''') in the acrylic copolymer resin (a-2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 30 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 50 mol% or less. The upper and lower limits can be combined arbitrarily; for example, 5 to 90 mol%, more preferably 5 to 80 mol%, even more preferably 10 to 70 mol%, and particularly preferably 30 to 50 mol%. By setting it above the lower limit, there is a tendency to reduce residue.

[0167] Furthermore, by setting it below the aforementioned upper limit value, there is a tendency for improved imaging adhesion.

[0168] The acid value of the acrylic copolymer resin (a-2) is not particularly limited, but is preferably 5 mg KOH / g or higher, more preferably 10 mg KOH / g or higher, even more preferably 20 mg KOH / g or higher, and even more preferably 25 mg KOH / g or higher. Furthermore, it is preferably 100 mg KOH / g or lower, more preferably 80 mg KOH / g or lower, even more preferably 60 mg KOH / g or lower, and even more preferably 40 mg KOH / g or lower. The upper and lower limits can be combined arbitrarily; for example, 5–100 mg KOH / g is preferred, 10–80 mg KOH / g is more preferred, 20–60 mg KOH / g is even more preferred, and 25–40 mg KOH / g is even more preferred. Setting the value above the lower limit tends to reduce residue. Furthermore, setting the value below the upper limit tends to improve developing adhesion.

[0169] The weight-average molecular weight (Mw) of the acrylic copolymer resin (a-2) 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. Furthermore, it is preferably 30000 or less, more preferably 20000 or less, further preferably 15000 or less, even more preferably 10000 or less, and particularly preferably 8000 or less. The upper and lower limits can be combined arbitrarily; for example, 1000 to 30000 is preferred, more preferably 2000 to 20000, further preferably 3000 to 15000, even more preferably 4000 to 10000, and particularly preferably 5000 to 8000. Setting the value above the lower limit tends to improve the adhesion during development. Furthermore, setting the value below the upper limit tends to reduce residue.

[0170] When (a) the alkali-soluble resin includes acrylic copolymer resin (a-2), the content of acrylic copolymer resin (a-2) in (a) the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more. Furthermore, it is generally preferred to be 100% by mass or less, more preferably 80% by mass or less, even more preferably 50% by mass or less. The upper and lower limits can be combined arbitrarily; for example, 5 to 100% by mass is preferred, more preferably 10 to 100% by mass, even more preferably 15 to 80% by mass, and particularly preferably 20 to 50% by mass.

[0171] Setting the value above the lower limit tends to improve the developing solubility. Setting the value below the upper limit tends to increase the cone angle.

[0172] The following is a detailed description of epoxy (meth)acrylate resin (a-3).

[0173] [Epoxy (meth)acrylate resin (a-3)]

[0174] Epoxy (meth)acrylate resin (a-3) 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-), and simultaneously adding a carboxyl group of a polybasic acid anhydride to the hydroxyl group generated in the process. Furthermore, a resin obtained by simultaneously adding a polyol during the addition of a polybasic acid anhydride can also be included. Furthermore, resins obtained by reacting the carboxyl group of the resin obtained in the above reaction with a compound having a functional group that can be further reacted are also included in epoxy (meth)acrylate resin (a-3).

[0175] 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.

[0176] 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.

[0177] Specifically, examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic varnish epoxy resin, cresol varnish epoxy resin, biphenyl phenolic varnish 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. Epoxy resins having an aromatic ring on the main chain are preferred.

[0178] From the perspective of the strength of the cured film, bisphenol A type epoxy resin, phenolic varnish epoxy resin, cresol varnish 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 even more preferred.

[0179] 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.

[0180] 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.

[0181] By using polyols, there is a tendency to increase the molecular weight of epoxy (meth)acrylate resin (a-3), introduce branched chains into the molecule, and thus 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.

[0182] 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.

[0183] The acid value of the epoxy (meth)acrylate resin (a-3) 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. Furthermore, it is 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.

[0184] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (a-3) 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.

[0185] When (a) the alkali-soluble resin contains epoxy (meth)acrylate resin (a-3), the content of epoxy (meth)acrylate resin (a-3) in (a) the alkali-soluble resin 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 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 even more preferred, 80-100% by mass is even more preferred, and particularly preferably 90-100% by mass. By setting it to the lower limit or above, there is a tendency for degassing to decrease.

[0186] Epoxy (meth)acrylate resin (a-3) can be synthesized by 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.

[0187] 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.

[0188] They can be used individually or in combination with two or more.

[0189] 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.

[0190] Regarding the epoxy (meth)acrylate resin (a-3), from the viewpoint of degassing during element light emission, it is preferable to contain at least one selected from the group consisting of epoxy (meth)acrylate resin (a-3-1) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (a-3-1)") containing a partial structure represented by the following general formula (I), epoxy (meth)acrylate resin (a-3-2) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (a-3-2)") containing a partial structure represented by the following general formula (ii), and epoxy (meth)acrylate resin (a-3-3) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (a-3-3)") containing a partial structure represented by the following general formula (iii).

[0191] Regarding epoxy (meth)acrylate resins (a-3), among these, from the viewpoint of reducing degassing during element light emission, epoxy (meth)acrylate resins (a-3-1) containing a partial structure represented by the following general formula (i) are preferred, and epoxy (meth)acrylate resins (a-3-1) containing a partial structure represented by the following general formula (i) are more preferred.

[0192] One possible reason is that it has a rigid main frame, making it less prone to thermal decomposition.

[0193] [Chemical Formula 16]

[0194]

[0195] In equation (i), R a R represents a hydrogen atom or a methyl group. b The symbol represents a divalent hydrocarbon group that may optionally have substituents. The benzene ring in formula (i) may also be further substituted with any substituents. * indicates a bonded bond.

[0196] (R) b )

[0197] In equation (i), R b This indicates a divalent hydrocarbon group that may optionally have substituents.

[0198] 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.

[0199] As divalent aliphatic groups, linear, branched, and cyclic groups can be listed. Among these, linear groups are preferred from the viewpoint of development solubility, while cyclic groups are preferred from the viewpoint of reducing developer penetration into the exposed area. 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 to improve development adhesion. Furthermore, by setting the value below the upper limit, there is a tendency to reduce residue.

[0200] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene. Among these, methylene is preferred from the viewpoint of reducing residue.

[0201] 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.

[0202] 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, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 5 is even more preferred. 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. Among these, from the viewpoint of developing adhesion, groups obtained by removing two hydrogen atoms from the adamantane ring are preferred.

[0203] 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.

[0204] 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, 5 to 15 is more preferred, and 6 to 10 is even more preferred. 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.

[0205] 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.

[0206] 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. Among these, 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.

[0207] 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.

[0208] 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.

[0209] 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, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 3 is 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 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, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 3 is 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.

[0211] 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). Among these, from the viewpoint of skeletal rigidity and membrane hydrophobicity, groups represented by the following formula (iA) are preferred. * in the chemical formula indicates a bond.

[0212] [Chemical Formula 17]

[0213]

[0214] As mentioned above, 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.

[0215] From the perspective of solidification, unsubstituted is preferred.

[0216] From the viewpoint of developing solubility, the partial structure represented by the above formula (i) is preferably the partial structure represented by the following formula (i-1).

[0217] [Chemical Formula 18]

[0218]

[0219] In equation (i-1), R a and R b This has the same meaning as in equation (i). 1 This indicates a divalent hydrocarbon group with 1 to 4 carbon atoms that may optionally have substituents. * indicates a bond. The benzene ring in formula (i-1) may also be further substituted with any substituents.

[0220] (R) 1 )

[0221] In the general formula (i-1), R 1 This refers to a divalent hydrocarbon group having 1 to 4 carbon atoms, optionally with a substituent. Examples of divalent hydrocarbon groups include alkylene groups and alkenylene groups.

[0222] The alkylene group can be straight-chain or branched, but from the viewpoint of development and solubility, a straight-chain 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 4 or less, more preferably 3 or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 4 is preferred, 1 to 3 is more preferred, and 2 to 3 is even more preferred. 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 the amount of degassing generated during element light emission.

[0223] Specific examples of alkylene compounds include methylene, ethylene, propylene, and butylene. From the viewpoint of reducing degassing, methylene or ethylene is preferred, and ethylene is more preferred.

[0224] The alkenyl group can be either straight-chain or branched, but from the viewpoint of development and solubility, a straight-chain group is preferred. The number of carbon atoms is not particularly limited, but is generally 2 or more, and preferably 4 or less, more preferably 3 or less. For example, 2 to 4 is preferred, and 2 to 3 is more preferred. By setting it to the lower limit or above, there is a tendency for the residual film rate to increase. Furthermore, by setting it to the upper limit or below, there is a tendency for the amount of degassing generated during element light emission to decrease.

[0225] Specific examples of alkenyl groups include vinylidene, propenylidene, and butenylidene. From the viewpoint of degassing, vinylidene is preferred.

[0226] The substituents optionally present in the divalent hydrocarbon group having 1 to 4 carbon atoms are not particularly limited. Examples include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0227] Of these, R is preferred from the perspective of reducing degassing. 1 It is a divalent alkylene group having 1 to 4 carbon atoms, more preferably methylene or ethylene, and even more preferably ethylene.

[0228] The epoxy (meth)acrylate resin (a-3-1) contains one or more partial structures represented by the formula (i-1) in one molecule.

[0229] The number of partial structures represented by formula (i) contained in one molecule of epoxy (meth)acrylate resin (a-3-1) 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, 1 to 10 is preferred, 2 to 10 is more preferred, and 3 to 8 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.

[0230] The number of partial structures represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (a-3-1) 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, 1 to 10 is preferred, 2 to 10 is more preferred, and 3 to 8 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.

[0231] The following are specific examples of epoxy (meth)acrylate resins (a-3-1).

[0232] [Chemical Formula 19]

[0233]

[0234] [Chemical Formula 20]

[0235]

[0236] [Chemical Formula 21]

[0237]

[0238] [Chemical Formula 22]

[0239]

[0240] [Chemical Formula 23]

[0241]

[0242] [Chemical Formula 24]

[0243]

[0244] [Chemical Formula 25]

[0245]

[0246] As another option, from the viewpoint of developing adhesion, the epoxy (meth)acrylate resin (a-3) is preferably an epoxy (meth)acrylate resin (a-3-2) containing a partial structure represented by the following formula (ii).

[0247] [Chemical Formula 26]

[0248]

[0249] In equation (ii), R c Each can be used independently to represent a hydrogen atom or a methyl group. R d This indicates a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain. * indicates a bond.

[0250] (R) d )

[0251] In equation (ii), R d It represents a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain.

[0252] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0253] 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, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 3 is 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.

[0254] 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.

[0255] Examples of aliphatic rings among 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.

[0256] 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, 1 to 10 is preferred, 2 to 5 is more preferred, and 3 to 4 is even more preferred. 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.

[0257] 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.

[0258] 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. Among these, fluorene rings are preferred from the viewpoint of patterning properties.

[0259] 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.

[0260] As divalent aliphatic groups, linear, branched, and cyclic groups can be listed. Among these, linear groups are preferred from the viewpoint of development solubility, while cyclic groups are preferred from the viewpoint of reducing developer penetration into the exposed area. 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 combined arbitrarily; for example, 1 to 25 is preferred, 3 to 20 is more preferred, and 6 to 15 is even more preferred. 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.

[0261] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene. Among these, from the viewpoint of residues, methylene is preferred.

[0262] 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.

[0263] The number of rings in the divalent cyclic aliphatic 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, and even more preferably 3 or less.

[0264] 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 them above the lower limit, there is a tendency for improved development adhesion. Furthermore, by setting them below the upper limit, there is a tendency for reduced residue.

[0265] Examples of divalent cyclic aliphatic groups include those obtained by removing two hydrogen atoms from cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isoborane, and adamantane rings. Among these, groups obtained by removing two hydrogen atoms from an adamantane ring are preferred from the viewpoint of good adhesion.

[0266] 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.

[0267] 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, 5 to 20 is more preferred, and 6 to 15 is even more preferred. 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.

[0268] 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.

[0269] 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. Among these, 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.

[0270] Substituents that may be optionally present in a divalent aromatic cyclic group include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. From the viewpoint of curability, unsubstituted substituents are preferred.

[0271] 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.

[0272] 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, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 3 is 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.

[0273] 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, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 3 is 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.

[0274] As a group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic cyclic groups, examples include groups represented by the formulas (iA) to (iF). Among these, from the viewpoint of reducing residue, groups represented by the formula (iC) are preferred.

[0275] 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.

[0276] From the viewpoint of imaging adhesion, the partial structure represented by formula (ii) is preferably the partial structure represented by formula (ii-1) below.

[0277] [Chemical Formula 27]

[0278]

[0279] In equation (ii-1), R c The same meaning as in equation (ii). R α This indicates a monovalent cyclic hydrocarbon group that may optionally have substituents. n is an integer greater than or equal to 1. The benzene ring in formula (ii-1) may also be further substituted with any substituents. * indicates a bond.

[0280] (R) α )

[0281] In equation (ii-1), R α This indicates a monovalent cyclic hydrocarbon group that may optionally have substituents.

[0282] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0283] 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.

[0284] Furthermore, the aliphatic cyclic group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 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 4 to 30, even more preferably 6 to 20, and particularly preferably 8 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.

[0285] 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.

[0286] 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, 1 to 10 is preferred, 2 to 10 is more preferred, and 3 to 5 is even more preferred. 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.

[0287] 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, 5 to 20 is more preferred, and 6 to 15 is even more preferred. 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.

[0288] Examples of aromatic rings in aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Among these, fluorene rings are preferred from the viewpoint of good adhesion to radiometric imaging.

[0289] 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.

[0290] n 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, 1 to 3 is preferred, and 1 to 2 is more preferred. 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.

[0291] Of these, R is preferred from the viewpoint of robust film curing strength and electrical properties. α It is a monovalent aliphatic cyclic group, more preferably adamantyl alkyl.

[0292] As described above, 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.

[0293] The following are specific examples of some structures represented by the above equation (ii-1).

[0294] [Chemical Formula 28]

[0295]

[0296] [Chemical Formula 29]

[0297]

[0298] [Chemical Formula 30]

[0299]

[0300] [Chemical Formula 31]

[0301]

[0302] [Chemical Formula 32]

[0303]

[0304] From the viewpoint of imaging adhesion, the partial structure represented by the above formula (ii) is preferably the partial structure represented by the following formula (ii-2).

[0305] [Chemical Formula 33]

[0306]

[0307] In equation (ii-2), R c The same meaning as in equation (ii). R 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.

[0308] (R) β )

[0309] In equation (ii-2), R β This indicates a divalent cyclic hydrocarbon group that may optionally have substituents.

[0310] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0311] 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, 1 to 10 is preferred, and 2 to 5 is 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.

[0312] 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.

[0313] Aliphatic rings among aliphatic cyclic groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. Among these, from the viewpoint of imaging adhesion, the adamantane ring is preferred.

[0314] 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, 1 to 10 is preferred, 2 to 10 is more preferred, and 3 to 5 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.

[0315] 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.

[0316] Examples of aromatic rings in aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Among these, fluorene rings are preferred from the viewpoint of good adhesion to radiometric imaging.

[0317] 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. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0318] Of these, from the perspective of solidification, R is preferred. β It is a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group.

[0319] 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.

[0320] As described above, 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.

[0321] The following are specific examples of some structures represented by the above equation (ii-2).

[0322] [Chemical Formula 34]

[0323]

[0324] [Chemical Formula 35]

[0325]

[0326] [Chemical Formula 36]

[0327]

[0328] [Chemical Formula 37]

[0329]

[0330] From the viewpoint of solidification, the partial structure represented by the above formula (ii) is preferably the partial structure represented by the following formula (ii-3).

[0331] [Chemical Formula 38]

[0332]

[0333] In equation (ii-3), R c and R dThe same meaning as in equation (ii). R 1 The meaning is the same as in equation (i-1). * indicates a bond.

[0334] The epoxy (meth)acrylate resin (a-3-2) may contain one or more of the partial structures represented by the formula (ii-3) in one molecule.

[0335] The number of partial structures represented by formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (a-3-2) 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, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 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.

[0336] As another option, from the viewpoint of reducing degassing during element light emission, it is preferred that the epoxy (meth)acrylate resin (a-3) is an epoxy (meth)acrylate resin (a-3-3) containing a partial structure represented by the following general formula (iii).

[0337] [Chemical Formula 39]

[0338]

[0339] In equation (iii), R e 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.

[0340] (γ)

[0341] 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.

[0342] 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.

[0343] Examples of alkylene compounds include methylene, ethylene, propylene, butylene, hexylene, and heptylene. From the viewpoint of balancing development adhesion and development solubility, methylene, ethylene, and propylene are preferred, and dimethylmethylene (2,2-propylene) is more preferred.

[0344] 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.

[0345] As divalent cyclic hydrocarbon groups, examples include divalent aliphatic cyclic groups or divalent aromatic cyclic groups.

[0346] The number of rings in the aliphatic cyclic 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, 1 to 10 is preferred, and 2 to 5 is 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.

[0347] 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.

[0348] Examples of aliphatic rings among 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.

[0349] 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, 1 to 10 is preferred, 2 to 10 is more preferred, and 3 to 5 is even more preferred. 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.

[0350] 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.

[0351] Examples of aromatic rings in aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Among these, fluorene rings are preferred from the viewpoint of good adhesion to radiometric imaging.

[0352] 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.

[0353] Of these, from the viewpoint of reducing residue, γ is preferably an alkylene group optionally having a substituent, and more preferably a dimethylmethylene group.

[0354] As described above, 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 substituents are preferred.

[0355] From the viewpoint of developing solubility, the partial structure represented by formula (iii) is preferably the partial structure represented by formula (iii-1) below.

[0356] [Chemical Formula 40]

[0357]

[0358] In equation (iii-1), R e And γ have the same meaning as in equation (iii). 1 The meaning is the same as in formula (i-1). * indicates a bond. The benzene ring in formula (iii-1) can also be further substituted with any substituents.

[0359] The number of partial structures represented by formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (a-3-3) 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, 1 to 18 is preferred, 5 to 18 is more preferred, and 10 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.

[0360] The number of partial structures represented by formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (a-3-3) 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.

[0361] The following are specific examples of epoxy (meth)acrylate resins (a-3-3).

[0362] [Chemical Formula 41]

[0363]

[0364] [Chemical Formula 42]

[0365]

[0366] [Chemical Formula 43]

[0367]

[0368] In (a) the alkali-soluble resin, either epoxy (meth)acrylate resin (a-3) or acrylic copolymer resin (a-2) may be included alone, or both may be included. Furthermore, (a) the alkali-soluble resin may also include alkali-soluble resins other than alkali-soluble resin (b).

[0369] Regarding the content of (a) alkali-soluble resin in the photosensitive resin composition of the present invention, 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 further 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, 5 to 90% by mass is preferred, 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.

[0370] When the photosensitive resin composition of the present invention contains epoxy (meth)acrylate resin (a-3), the content of epoxy (meth)acrylate resin (a-3) is not particularly limited, but 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, 5 to 90% by mass is preferred, 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 value or above, there is a tendency to improve developability. Furthermore, by setting the upper limit value or below, there is a tendency to reduce degassing during element light emission.

[0371] Furthermore, when the photosensitive resin composition of the present invention includes acrylic copolymer resin (a-2), the content of acrylic copolymer resin (a-2) is not particularly limited, but 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, 5 to 90% by mass is preferred, 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 value or above, there is a tendency to improve developability. Furthermore, by setting the upper limit value or below, there is a tendency to reduce degassing during element light emission.

[0372] Furthermore, in the total solid components of the photosensitive resin composition, the combined content of (a) alkali-soluble resin and (d) photopolymerizable compound 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, more preferably 10 to 99% by mass, further preferably 30 to 99% by mass, even more preferably 50 to 97% by mass, particularly preferably 70 to 97% by mass, especially preferably 80 to 95% by mass, and most preferably 90 to 95% by mass. 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.

[0373] As for the proportion of (a) alkali-soluble resin to (d) photopolymerizable compound in the photosensitive resin composition, relative to 100 parts by mass of (d) photopolymerizable compound, (a) alkali-soluble resin 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, 50 to 400 parts by mass is preferred, 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 the lower limit value or above, there is a tendency for improved development adhesion. Furthermore, by setting the upper limit value or below, there is a tendency for improved curability.

[0374] [1-1-2] (b) Components; liquid repellent

[0375] The liquid repellent in the photosensitive resin composition of the present invention (b) preferably comprises a liquid repellent (b1) having an olefinic unsaturated bond group.

[0376] Furthermore, the liquid repellent (b1) preferably comprises an acrylic resin (b2) containing repeating units represented by the following general formula (5) and fluorine atoms.

[0377] [Chemical Formula 44]

[0378]

[0379] (In equation (5), R) 11 Each can be used independently to represent a hydrogen atom or a methyl group, R 12 This indicates an alkyl group having 2 to 6 carbon atoms, optionally having substituents, which is optionally interrupted by one or more of -O-, -C(=O)-, -S-, and -NH-. ** indicates a bonding portion.

[0380] R 12 The alkyl group preferably has 2 or more carbon atoms, more preferably 4 or more carbon atoms, and further preferably 6 or less, more preferably 5 or less. The upper and lower limits can be combined arbitrarily; for example, 2 to 6 are preferred, more preferably 4 to 5. By setting the value above the lower limit, synthesis becomes easier. Furthermore, by setting the value below the upper limit, the degree of freedom of the olefinic unsaturated bonds increases, tending to improve curability and liquid repellency.

[0381] In addition, R 12The alkyl group is optionally interrupted by one or more of -O-, -C(=O)-, -S-, and -NH-. Alternatively, it is optionally interrupted by -O-, -C(=O)-, or -NH-, and yet another option is optionally interrupted by -OC(=O)-NH-.

[0382] In R 12 When a substituent is present, examples of substituents include hydroxyl groups and alkoxy groups having 1 to 3 carbon atoms. Preferably, the substituent is unsubstituted or substituted with a hydroxyl group, and more preferably unsubstituted.

[0383] As R 12 From the perspective of liquid repellency, the groups shown in -(C2H4)2-NHCOO-(C2H4)2- and -(CH)2-CHOH-(CH2)- are preferred, and the groups shown in -(C2H4)2-NHCOO-(C2H4)2- are even more preferred.

[0384] By containing acrylic resin (b2), ink repellency (liquid repellency) can be imparted to the surface of the resulting spacer wall. Therefore, it is believed that when manufacturing organic electroluminescent elements by inkjet printing, ink can be prevented from adhering to the spacer wall, and ink injected between adjacent areas can be prevented from mixing with each other.

[0385] By using a liquid repellent having an olefinic unsaturated group such as general formula (5), 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, it is believed that the resulting spacer wall can exhibit high ink repellency.

[0386] By using a resin containing fluorine atoms, the resin tends to align along the surface of the spacer wall, thus preventing ink bleeding and color mixing. More specifically, the presence of fluorine-containing groups repels the ink, preventing ink bleeding and color mixing caused by ink crossing the spacer wall and entering adjacent areas.

[0387] The acrylic resin (b2) preferably has fluoroalkyl and / or fluoroalkylene groups, more preferably has any one or both of perfluoroalkyl and perfluoroalkylene ether chains. By having any one or both of fluoroalkyl and fluoroalkylene groups, or any one or both of perfluoroalkyl and perfluoroalkylene ether chains, the fluorine-containing resin is more likely to be further oriented along the surface of the spacer wall, exhibiting higher ink repellency and a tendency to further prevent ink bleeding and color mixing.

[0388] Examples of perfluoroalkyl groups include perfluorobutyl, perfluorohexyl, and perfluorooctyl.

[0389] Examples of perfluoroalkylene ether chains include, for example, -CF2-O-, -(CF2)2-O-, -(CF2)3-O-, -CF2-C(CF3)O-, -C(CF3)-CF2-O-, and divalent groups having these repeating units.

[0390] Acrylic resin (b2) may also have constituent units other than repeating units represented by general formula (5) and constituent units containing fluorine atoms. For example, constituent units containing epoxy groups, constituent units containing carboxyl groups, and constituent units having alkene chains can be listed.

[0391] As commercially available acrylic resins (b2), fluorinated organic compounds can be used under trade names such as "Megafac RS-72-K" and "Megafac RS-90" manufactured by DIC Corporation.

[0392] The fluorine atom content in the acrylic resin (b2) is not particularly limited, but it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more. Furthermore, it is preferably 50% by mass or less, more preferably 35% by mass or less. The upper and lower limits can be combined arbitrarily; for example, 1 to 50% by mass is preferred, more preferably 10 to 50% by mass, even more preferably 20 to 35% by mass, and even more preferably 25 to 35% by mass. By setting it above the lower limit, a high contact angle is easily ensured; furthermore, by setting it below the upper limit, the tendency to flow out to the pixel portion can be suppressed.

[0393] The molecular weight of the acrylic resin (b2) is not particularly limited; it can be a low molecular weight compound or a high molecular weight compound. A high molecular weight compound is preferred because it can suppress flowability caused by post-baking, thereby suppressing outflow from the spacer wall. From this viewpoint, the weight-average molecular weight of the acrylic resin (b2) is preferably 100 or more, more preferably 500 or more; preferably 100,000 or less, more preferably 10,000 or less. The upper and lower limits can be combined arbitrarily; for example, 100 to 100,000 is preferred, more preferably 500 to 10,000.

[0394] Acrylic resin (b2) can be used alone or in combination with two or more.

[0395] In this invention, as (b) the liquid repellent, liquid repellents other than acrylic resin (b2) can be used in combination.

[0396] The content of the liquid repellent (b) 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, further preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. The upper and lower limits can be combined arbitrarily; for example, 0.01 to 5% by mass is preferred, more preferably 0.05 to 5% by mass, further preferably 0.1 to 3% by mass, and particularly preferably 0.2 to 1% by mass. By setting the lower limit or above, there is a tendency to improve ink repellency. Furthermore, by setting the upper limit or below, there is a tendency to easily obtain a uniform coating when applying ink to the pixel portion after the spacer wall is formed.

[0397] The content of acrylic resin (b2) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more in all solid components 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 1% by mass or less. The upper and lower limits can be combined arbitrarily; for example, 0.01 to 5% by mass is preferred, more preferably 0.1 to 3% by mass, and even more preferably 0.2 to 1% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. Furthermore, by setting it to the upper limit or below, there is a tendency to easily obtain a uniform coating film when applying ink to the pixel area after the spacer wall is formed.

[0398] [1-1-3] (c) Component; Photopolymerization initiator

[0399] (c) Photopolymerization initiators are components that directly absorb light, initiate decomposition or hydrogen abstraction reactions, and generate polymerization-active free radicals. Depending on the requirements, polymerization accelerators (chain transfer agents), sensitizing pigments, and other additives can be added.

[0400] Examples of photopolymerization initiators include: metallocene compounds containing titanocene compounds as described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197; hexaaryl diimidazole derivatives as described in Japanese Patent Application Publication No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives as described in Japanese Patent Application Publication No. 10-39503; α-aminoalkylphenyl ketone derivatives; and oxime ester compounds as described in Japanese Patent Application Publication Nos. 2000-80068 and 2006-36750.

[0401] Specifically, examples of titanium cyclopentadienyl derivatives include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorobenzene-1-yl) titanium, dicyclopentadienyl bis(2,4,6-trifluorobenzene-1-yl) titanium, and dicyclopentadienyl dichloride. (2,6-difluorophenyl-1-yl)titanium, dicyclopentadienyl di(2,4-difluorophenyl-1-yl)titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, di(methylcyclopentadienyl)bis(2,6-difluorophenyl-1-yl)titanium, dicyclopentadienyl[2,6-difluoro-3-(pyrrolo-1-yl)-phenyl-1-yl]titanium, etc.

[0402] In addition, examples of hexaaryl diimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0403] In addition, examples of halomethylated oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole, etc.

[0404] In addition, examples of halomethyl-s-triazine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0405] In addition, examples of α-aminoalkyl phenyl ketone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisopentyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

[0406] As photopolymerization initiators, oxime ester compounds are particularly effective in terms of sensitivity and printability. They are especially useful in applications using alkali-soluble resins containing phenolic hydroxyl groups, where their excellent sensitivity is a primary concern. Because their structures simultaneously contain structures that absorb ultraviolet light, transfer light energy, and generate free radicals, oxime ester compounds achieve high sensitivity even in small quantities and are thermally stable, allowing for the production of highly sensitive photosensitive resin compositions in small amounts.

[0407] Examples of oxime ester compounds include those represented by the following general formula (IV).

[0408] [Chemical Formula 45]

[0409]

[0410] In equation (IV) above, R 21a The group represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic cycloal group optionally having a substituent.

[0411] R 21b This indicates any substituent containing an aromatic ring.

[0412] R 22a This indicates an alkyl acyl group that optionally has a substituent, or an aromatic acyl group that optionally has a substituent.

[0413] n represents an integer that is either 0 or 1.

[0414] R 21a The number of alkyl carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility and sensitivity in the solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, and more preferably 10 or less. Specific examples of alkyl groups include methyl, ethyl, propyl, cyclopentylethyl, propyl, etc.

[0415] Examples of substituents that may be optionally present in the alkyl group include: aromatic cycloalgides, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl or N-acetyl-N-acetoxyamino groups, etc., and unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0416] As R 21a 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.

[0417] Specific examples of aromatic cyclic groups include phenyl, naphthyl, pyridyl, furanyl, etc. Among these, from the viewpoint of reproducibility, phenyl or naphthyl is preferred, and phenyl is more preferred.

[0418] Examples of substituents that may be optionally present in an aromatic cyclic group include: hydroxyl, carboxyl, halogen atom, amino, amide, alkyl, alkoxy, and groups formed by the linkage of these substituents. From the viewpoint of reproducibility, alkyl, alkoxy, and groups formed by the linkage of these groups are preferred, and alkoxy groups formed by the linkage are more preferred.

[0419] Of these, R is preferred from the perspective of ease of synthesis. 21a The alkyl group is optionally substituted, more preferably unsubstituted, and even more preferably methyl. On the other hand, from the viewpoint of developability, R is preferred. 21a An aromatic cyclic group optionally having substituents is preferred, and more preferably an aromatic cyclic group having alkoxy groups formed by linkage as substituents.

[0420] In addition, as R 21b Preferably, the following groups are included: optionally substituted carbazole group, optionally substituted thioxanone group, or optionally substituted diphenyl sulfide group. Among these, the optionally substituted diphenyl sulfide group is preferred from the viewpoint of NMP tolerance.

[0421] In addition, R 22a The number of carbon atoms in the alkyl acyl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is generally 2 or more, preferably 3 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. Specific examples of alkyl acyl groups include acetyl, propionyl, butyryl, etc.

[0422] Substituents that may be optionally present in the alkyl acyl group include: aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, etc. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0423] In addition, R 22a The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is generally 7 or more, preferably 8 or more, and generally 20 or less, preferably 15 or less, and more preferably 10 or less. Specific examples of aryl groups include benzoyl and naphthyl groups.

[0424] Examples of substituents that may be optionally present in the aryl group include hydroxyl, carboxyl, halogen, amino, amide, and alkyl groups. From the viewpoint of ease of synthesis, unsubstituted substituents are preferred.

[0425] Of these, R is preferred from the perspective of NMP tolerance. 22a The alkanoyl group is optionally substituted, more preferably unsubstituted, and even more preferably acetyl.

[0426] Furthermore, from the perspective of reducing liquid crystal layer contamination caused by colorants, the initiator described in Japanese Patent Application Publication No. 2016-133574 may be preferred.

[0427] Photopolymerization initiators can be used alone or in combination of two or more.

[0428] To improve sensing sensitivity, sensitizing pigments and polymerization accelerators corresponding to the wavelength of the image exposure light source can be incorporated into the photopolymerization initiator as needed. Examples of sensitizing pigments include: coumarin pigments described in Japanese Patent Application Publication Nos. 4-221958 and 4-219756; heterocyclic coumarin pigments described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; 3-ketocoumarin compounds described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; pyrrolemethylammonium pigments described in Japanese Patent Application Publication No. 6-19240; and others, such as Japanese Patent Application Publication Nos. 47-2528 and 54-1552. Pigments having a dialkylaminobenzene skeleton as described in Japanese Published Publication No. 92, 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.

[0429] Among these sensitizing pigments, amino-containing sensitizing pigments are preferred, and compounds having both an amino and a phenyl group within the same molecule are more preferred. Particularly preferred are, 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; 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)benzoxazole. Compounds containing p-dialkylaminophenyl, such as 1,3,4-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, and (p-diethylaminophenyl)pyrimidine, are preferred. Among these, 4,4'-dialkylaminobenzophenone is the most preferred.

[0430] Sensitizing pigments can be used alone or in combination with two or more.

[0431] As polymerization accelerators, examples include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and n-methyldiethanolamine, and thiol compounds described later. A polymerization accelerator can be used alone or in combination with two or more.

[0432] [1-1-4] (d) Component; photopolymerizable compound

[0433] The photosensitive resin composition of the present invention contains a (d) photopolymerizable compound. It is believed that by including the (d) photopolymerizable compound, high sensitivity can be achieved.

[0434] The photopolymerizable compound used herein refers to a compound having one or more olefinic unsaturated bonds (olefinic double bonds) within its molecule. Considering the potential for increased polymerizability, crosslinking ability, and the resulting difference in developer solubility between exposed and unexposed areas, compounds having two or more olefinic unsaturated bonds within their molecule are preferred. Furthermore, this unsaturated bond is preferably derived from (meth)acryloyloxy, that is, more preferably a (meth)acrylate compound.

[0435] 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.

[0436] Examples of photopolymerizable compounds include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polyvalent carboxylic acids.

[0437] Examples of esters of 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, glyceryl acrylate, etc.; methacrylates formed by replacing the acrylates of these compounds with methacrylates; itaconic acid esters formed by replacing the acrylates of these compounds with itaconic acid esters; crotonic acid esters formed by replacing the acrylates of these compounds with crotonic acid esters; and maleic acid esters formed by replacing the acrylates of these compounds with maleic acid esters.

[0438] 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.

[0439] 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.

[0440] 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.

[0441] 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 Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Co., Ltd.).

[0442] Among these, from the viewpoint of appropriate cone angle and sensitivity, as (d) photopolymerizable compounds, ester (meth)acrylates or carbamate (meth)acrylates are preferred, and dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-tris(meth)acryloyloxymethyl ethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dicarboxylic anhydride adducts of dipentaerythritol penta(meth)acrylate, and dicarboxylic anhydride adducts of pentaerythritol tri(meth)acrylate are more preferred.

[0443] They can be used individually or in combination with two or more.

[0444] In the photosensitive resin composition of the present invention, (d) the molecular weight of the photopolymerizable compound is not particularly limited, but from the viewpoints of sensitivity, ink repellency, and cone angle, 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, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. The upper and lower limits can be combined arbitrarily; for example, 100 to 1000 is preferred, more preferably 150 to 1000, further preferably 200 to 1000, even more preferably 300 to 700, particularly preferably 400 to 700, and most preferably 500 to 700.

[0445] (d) The number of carbon atoms in the photopolymerizable compound is not particularly limited, but from the viewpoint of sensitivity, ink repellency and cone angle, it is preferably 7 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, even more preferably 35 or less, and particularly preferably 30 or less.

[0446] 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.

[0447] From the perspectives of sensitivity, ink repellency, and cone angle, ester (meth)acrylates, epoxy (meth)acrylates, and carbamate (meth)acrylates are preferred. Among them, the following are further preferred: trifunctional or higher ester (meth)acrylates such as pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate; and anhydride adducts of trifunctional or higher ester (meth)acrylates such as 2,2,2-tri(meth)acryloyloxymethyl ethyl phthalate and dipentaerythritol penta(meth)acrylate.

[0448] Regarding the content of the photopolymerizable compound (d) in the photosensitive resin composition of the present invention, 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 further preferably 80% by mass or less, more preferably 70% by mass or less, even more 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, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, more preferably 20 to 60% by mass, even more preferably 30 to 55% by mass or less, and particularly preferably 40 to 50% by mass. By setting it to the lower limit or above, there is a tendency to obtain suitable internal curing properties. By setting it to the upper limit or below, there is a tendency for good developability.

[0449] [1-1-5] Ultraviolet absorbers

[0450] 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.

[0451] Examples of ultraviolet absorbers include: benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthrene compounds, and dyes.

[0452] These ultraviolet absorbers can be used alone or in combination with two or more.

[0453] Among these, from the viewpoint of increasing the cone angle, benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferred, with benzotriazole compounds being particularly preferred.

[0454] Among benzotriazole compounds, from the perspective of cone shape, the benzotriazole compound described in the following general formula (Z1) is preferred.

[0455] [Chemical Formula 46]

[0456]

[0457] In the above formula (Z1), R 1e and R 2e Each of the following 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.

[0458] [Chemical Formula 47]

[0459]

[0460] In the above formula (Z2), R 4e R represents an alkylene group that may optionally have substituents. 5e This indicates an alkyl group that may optionally have substituents.

[0461] [Chemical Formula 48]

[0462]

[0463] In the above formula (Z3), R 6e R7e indicates an alkylene group that may optionally have substituents, and R7e indicates a hydrogen atom or a methyl group.

[0464] (R) 1e and R 2e )

[0465] In the formula (Z1), R 1e and R 2e Each of the following can be independently represented: a hydrogen atom, an alkyl group optionally having a substituent, a group represented by general formula (Z2), or a group represented by general formula (Z3).

[0466] As alkyl groups, examples include straight-chain, branched, or cyclic alkyl groups. In terms of the number of carbon atoms, it 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, 1 to 10 is preferred, 2 to 6 is more preferred, and 4 to 6 is even more preferred.

[0467] Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl. Among these, tert-butyl is preferred.

[0468] Substituents optionally present as alkyl groups include, for example, methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl.

[0469] (R) 3e )

[0470] In the formula (Z1), R 3e It represents a hydrogen atom or a halogen atom.

[0471] Halogen atoms include: fluorine, chlorine, bromine, and iodine.

[0472] Of these, from a synthetic point of view, R is preferred. 3e It is a hydrogen atom.

[0473] (R) 4e )

[0474] In the formula (Z2), R 4e This indicates an alkylene group that may optionally have substituents.

[0475] 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.

[0476] Examples of alkylene compounds include methylene, ethylene, propylene, propylene, and butylene. Among these, ethylene is preferred.

[0477] Substituents optionally present as alkylene groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl.

[0478] Among these, R is preferred. 4e It is ethylene.

[0479] (R) 5e )

[0480] In the formula (Z2), R 5e This indicates an alkyl group that may optionally have substituents.

[0481] 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.

[0482] Examples of alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl.

[0483] Substituents optionally present as alkyl groups include, for example, methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl.

[0484] Of these, from the perspective of cone shape, R is preferred. 5e It can be based on Geng, Xin, or Ren.

[0485] (R) 6e )

[0486] In the aforementioned formula (Z3), R 6e This indicates an alkylene group that may optionally have substituents.

[0487] 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.

[0488] Examples of alkylene compounds include methylene, ethylene, propylene, propylene, and butylene. Among these, ethylene is preferred.

[0489] Substituents optionally present as alkylene groups include, for example: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl.

[0490] Of these, from the viewpoint of cone shape, the preferred option is: R 1e For tert-butyl, R 2e For the group represented by the 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 the formula (Z3) (where R6e 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 the formula (Z2) (where R 4e Ethylene and R 5e (alkyl group with 7 to 9 carbon atoms), R 3e Compounds containing hydrogen atoms.

[0491] Examples of benzotriazole compounds include, for instance: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, a mixture of octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate, 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-ditert-pentyl- 2-Hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, heptyl 3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, nonyl 3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol. 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.

[0492] 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. EVERSORA-234, EVERSORA 77, EVERSORA 78, EVERSORA 80, EVERSORA 81 (manufactured by Taiwan Yung-Kuang Chemical Industry Co., Ltd.); Tominabe (registered trademark, same below) 100, Tominabe 600 (manufactured by APIC Corporation); SEESORA (registered trademark, same below) 701, SEESORA 702, SEESORA 703, SEESORA 704, SEESORA 706, SEESORA 707, SEESORA 709 (manufactured by Shipro Chemical Co., Ltd.); RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0493] Examples of triazine compounds include, for instance, 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 ester, 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.

[0494] Commercially available triazine compounds include, for example: TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479 (manufactured by BASF), etc.

[0495] Other ultraviolet absorbers include, for example, benzophenone compounds such as Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORA-30, EVERSORA-31, EVERSORA-32 (manufactured by Taiwan Yung-Kuang Chemical Co., Ltd.), Tominabe 800 (manufactured by APIC Corporation), SEESORA-300, SEESORA-301, SEESORA-301S, SEESORA-302, SEESORA-303, SEESORA-305, SEESORA-306, SEESORA-307, and SEESORA-351 (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. Among these, from the perspective of exposure sensitivity, cinnamic acid derivatives and naphthalene derivatives are preferred, with cinnamic acid derivatives being particularly preferred.

[0496] 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.

[0497] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the proportion relative to the photopolymerization initiator (c) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, further preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less. The upper and lower limits can be combined arbitrarily; for example, preferably 10 to 500 parts by mass, more preferably 30 to 300 parts by mass, further preferably 50 to 200 parts by mass, and particularly preferably 80 to 150 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.

[0498] [1-1-6] Polymerization inhibitors

[0499] 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.

[0500] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, methyl hydroquinone and methoxyphenol are preferred from the viewpoint of polymerization inhibition ability, and methyl hydroquinone is more preferred.

[0501] Polymerization inhibitors can be used alone or in combination with two or more. Typically, when manufacturing (a) alkali-soluble resins, polymerization inhibitors are sometimes included in the resin. These can be used as polymerization inhibitors contained in the photosensitive resin composition of the present invention, or the same or different polymerization inhibitors can be added during the manufacture of the photosensitive resin composition based on the polymerization inhibitors contained in the resin.

[0502] 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 0.0005% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more, and further preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less. The upper and lower limits can be combined arbitrarily; for example, it is preferably 0.0005 to 0.3% by mass, more preferably 0.001 to 0.2% by mass, and even more preferably 0.01 to 0.1% by mass. By setting it to the lower limit or above, there is a tendency to increase the cone angle. Furthermore, by setting it to the upper limit or below, there is a tendency to maintain high sensitivity.

[0503] [1-1-7] Amino compounds

[0504] The photosensitive resin composition of the present invention may also contain amino compounds to promote thermosetting.

[0505] When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound in the photosensitive resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, in the total solid components of the photosensitive resin composition. Furthermore, it is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper and lower limits can be combined arbitrarily; for example, it is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass. By setting it below the upper limit, there is a tendency to maintain storage stability. By setting it above the lower limit, there is a tendency to ensure sufficient thermosetting properties.

[0506] As an amino compound, examples include amino compounds having at least two hydroxymethyl groups, or alkoxymethyl groups obtained by condensing hydroxymethyl groups with an alcohol having 1 to 8 carbon atoms as functional groups. Specifically, examples include: melamine resin obtained by condensing melamine with formaldehyde; benzomelamine resin obtained by condensing benzomelamine with formaldehyde; glycourea resin obtained by condensing glycourea with formaldehyde; urea-formaldehyde resin obtained by condensing urea with formaldehyde; resin obtained by co-condensing melamine, benzomelamine, glycourea, or urea with formaldehyde; and modified resin obtained by modifying the hydroxymethyl groups of the above resins by condensing with an alcohol.

[0507] They can be used individually or in combination with two or more.

[0508] As an amino compound, melamine resin and its modified resin are preferred, modified resins with a hydroxymethyl modification ratio of 70% or more are further preferred, and modified resins with a modification ratio of 80% or more are particularly preferred.

[0509] Examples of melamine resins and their modified resins that are amino compounds include, for example, Cymel (registered trademark, hereinafter the same) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158 manufactured by Cytec Corporation, and Nikalac (registered trademark, hereinafter the same) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302 manufactured by Sanwa Chemical Corporation.

[0510] Examples of benzo-modified melamine resins and their modified resins include Cymel 1123, 1125, and 1128 manufactured by Cytec.

[0511] Examples of glycourea resins and their modified resins include Cymel 1170, 1171, 1174, and 1172 manufactured by Cytec, and Nikalc MX-270 manufactured by Sanwa Chemical.

[0512] Examples of urea resins and their modified resins include, for example, UFR 65 and 300 manufactured by Cytec Corporation (registered trademark, hereinafter the same) and Nikalc MX-290 manufactured by Sanwa Chemical Corporation.

[0513] [1-1-8] Coloring agents

[0514] The photosensitive resin composition of the present invention may also contain a colorant for the purpose of coloring the spacer walls. Known colorants such as pigments and dyes can be used as colorants.

[0515] When using pigments, known dispersants and dispersing aids can be used to ensure that the pigment exists stably in the photosensitive resin composition without agglomeration. In particular, by coloring the ink-repellent spacers black, a clear pixel display effect can be obtained. As a black colorant, in addition to black dyes, black pigments, carbon black, titanium black, etc., mixing organic pigments to color them black is also effective in imparting low conductivity.

[0516] From the viewpoint of plate-making and color characteristics, the content of the colorant is preferably 60% by mass or less, more preferably 40% by mass or less, in the total solid components of the photosensitive resin composition.

[0517] As another approach, when a colorant is included in the photosensitive resin composition, there is a tendency for reduced curability of the spacer walls, reduced liquid repellency of the spacer walls, and easy degassing. Therefore, it is ideal that the content of the colorant in the photosensitive resin composition is low, for example, preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 0% by mass, relative to the total solids content of the photosensitive resin composition.

[0518] [1-1-9] Coating properties improver, developing agent improver

[0519] The photosensitive resin composition of the present invention may also contain a coating improver and a development modifier to improve coating properties and developing solubility.

[0520] As a coating improver or development modifier, a known surfactant can be used, for example.

[0521] Surfactants can be used to improve the coatability of the coating liquid in a photosensitive resin composition and the developability of the coating film, and are preferably fluorinated surfactants or organosilicon surfactants.

[0522] 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.

[0523] As fluorinated surfactants, compounds having a fluoroalkyl or fluoroalkylene group at at least one site in the terminal, main chain, or side chain are preferred. Specifically, examples include: 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, and 1,1,2,2,3,3-hexafluorodecane, etc. Examples of their commercially available products include: BM Chemie's "BM-1000" and "BM-1100", DIC's "Megafac F470", "Megafac F475", "Megafac F554" and "Megafac F559", 3M Japan's "FC430" and Neos' "DFX-18".

[0524] Examples of silicone-based surfactants include: "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", and "SH8400" manufactured by Dow Corning Toray, and "BYK323" and "BYK330" manufactured by BYKChemie.

[0525] As a surfactant, it can also include surfactants other than fluorinated surfactants and organosilicon surfactants. Other surfactants include, for example, nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0526] 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. Commercially available examples include Kao Corporation's "EMULGEN 104P" and "EMULGEN A60," among other polyoxyethylene surfactants.

[0527] 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. Among these, special polymeric surfactants are preferred, and special polycarboxylic acid type polymeric surfactants are even more preferred. Examples of anionic surfactants include, for example, Kao Corporation's "Emal (registered trademark) 10" among alkyl sulfate esters, Kao Corporation's "Perex (registered trademark) NB-L" among alkylnaphthalene sulfonates, and Kao Corporation's "Homogenol (registered trademark, hereinafter the same) L-18" and "Homogenol L-100" among special polymeric surfactants.

[0528] Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Examples of amphoteric surfactants include betaine-type compounds, imidazoline salts, imidazoline compounds, and amino acid compounds. Quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of cationic or benign surfactants include, for example, Kao Corporation's "Acetamin 24" (registered trademark) as an alkylamine salt, and Kao Corporation's "KOTAMIN 24P" and "KOTAMIN 86W" as quaternary ammonium salts.

[0529] Surfactants can be used alone or in combination with 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. Among these, combinations of silicone surfactants and fluorinated surfactants are preferred. Examples of silicone-based / fluorinated surfactant combinations include: BYK-300 or BYK-330 manufactured by BYK Chemie / DFX-18 manufactured by Neos; BYK-300 or BYK-330 manufactured by BYK Chemie / S-393 manufactured by AGC SEIMI CHEMICAL; BYK-300 or BYK-330 manufactured by BYK Chemie / F-554 or F-559 manufactured by DIC; KP340 manufactured by Shin-Etsu Silicone / F-478 or F-475 manufactured by DIC; SH7PA manufactured by Dow Corning Toray / DS-401 manufactured by Daikin; L-77 manufactured by NUC / FC4430 manufactured by 3M Japan.

[0530] As a developer modifier, for example, a known developer modifier containing an organic carboxylic acid or its anhydride may also be used.

[0531] When the photosensitive resin composition of the present invention contains a coating enhancer and a developer modifier, from the viewpoint of sensitivity, the content of the coating enhancer and the developer modifier is generally preferably 20% by mass or less, and more preferably 10% by mass or less, respectively, in the total solid components of the photosensitive resin composition.

[0532] [1-1-10] Silane coupling agent

[0533] 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.

[0534] When the photosensitive resin composition of the present invention contains a silane coupling agent, from the viewpoint of adhesion, the content of the silane coupling agent is preferably 20% by mass or less, more preferably 15% by mass or less, in the total solid components of the photosensitive resin composition.

[0535] [1-1-11] Phosphoric acid-based binding enhancer

[0536] To improve adhesion to the substrate, the photosensitive resin composition of the present invention may also contain a phosphate-based adhesion enhancer. As a phosphate-based adhesion enhancer, phosphate esters containing (meth)acryloyloxy groups are preferred, with substances represented by the following general formulas (Va), (Vb), and (Vc) being particularly preferred.

[0537] [Chemical Formula 49]

[0538]

[0539] 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.

[0540] When the photosensitive resin composition of the present invention contains a phosphoric acid-based adhesion enhancer, its content is not particularly limited, but 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 in the total solid components 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 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.

[0541] [1-1-12] Inorganic fillers

[0542] To improve both the strength of the cured product and the excellent flatness and cone angle of the coating film based on moderate interaction with the alkali-soluble resin (formation of the matrix structure), the photosensitive resin composition of the present invention may also contain inorganic fillers. Examples of inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, and substances obtained by surface treatment of them with various silane coupling agents.

[0543] The average particle size of the inorganic filler is preferably 0.005 to 20 μm, more preferably 0.01 to 10 μm. Here, the average particle size refers to the value measured using a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter, etc. Among inorganic fillers, silica sol and silica sol modifiers are preferred because they tend to have excellent effects on improving dispersion stability and cone angle.

[0544] When the photosensitive resin composition of the present invention contains an inorganic filler, its content, from the viewpoint of sensitivity, is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 80% by mass or less, more preferably 70% by mass or less, in the total solid components of the photosensitive resin composition. The upper and lower limits can be combined arbitrarily; for example, preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

[0545] [1-1-13] Solvent

[0546] The photosensitive resin composition of the present invention preferably contains a solvent, which can be used to dissolve or disperse the components as described above in the solvent. There are no particular limitations on the solvent; for example, the organic solvents described below can be listed.

[0547] 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... Diol alkyl ether acetates, including methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl 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 mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate, etc.; and diols such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate. Diacetates; alkyl acetates such as cyclohexanol acetate; ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl pentyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentyl ketone; mono- or polyols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentyl alcohol, glycerol, and benzyl alcohol; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecyl... Aliphatic hydrocarbons such as alkanes; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane; 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; and halogenated hydrocarbons such as butyl chloride and pentyl chloride.Ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran, etc.

[0548] 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).

[0549] 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.

[0550] Solvents can be used alone or in combination with two or more.

[0551] The solvent is preferably used in such a manner that the total solid content of 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.

[0552] [1-2] Method for preparing photosensitive resin composition

[0553] 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.

[0554] [2] Spare walls and their formation methods

[0555] 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. That is, the cured product of the present invention is formed by curing the photosensitive resin composition of the present invention, for example, for forming spacers.

[0556] 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.

[0557] 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.

[0558] 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.

[0559] 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.

[0560] 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, as well as 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.

[0561] 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.

[0562] 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.

[0563] 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)methacrylic acid resin; polysulfone; and polyimide.

[0564] 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.

[0565] The photosensitive resin composition of the present invention exhibits excellent control over surface curing and internal curing properties, and is therefore preferably used to form spacer walls with a height difference. Here, a spacer wall with a height difference refers to a spacer wall having a first spacer wall and a second spacer wall with different heights, for example, a spacer wall in which the height of the first spacer wall is greater than that of the second spacer wall.

[0566] By using spacers with varying heights, there is a tendency to achieve a uniform film thickness in the organic layer (light-emitting portion). Furthermore, by providing a second spacer between pixels, insulation between pixels can be ensured, suppressing light emission from areas other than the pixels.

[0567] The height difference, i.e., the height difference between the upper surface of the first partition wall and the upper surface of the second partition wall, is preferably 0.7 μm or more, more preferably 0.8 μm or more, and even more preferably 0.9 μm or more. Furthermore, it is preferably 1.3 μm or less, more preferably 1.2 μm or less, and even more preferably 1.1 μm or less. The upper and lower limits can be arbitrarily combined; for example, it is preferably 0.7–1.3 μm, more preferably 0.8–1.2 μm, and even more preferably 0.9–1.1 μm.

[0568] By setting the value above the lower limit, there is a tendency to ensure linear inkjet coating. Furthermore, by setting the value below the upper limit, there is a tendency to ensure inter-pixel insulation.

[0569] Figure 1 and Figure 2 An example of a substrate having spacer walls with height differences is shown. Figure 1 It is a top view. Figure 2 It is along Figure 1 A cross-sectional view of line XX. The substrate 1 has a partition wall 2 with a height difference, and the area with an opening in the partition wall 2, that is, the area divided by the partition wall 2, is called a pixel part 3. The partition wall 2 has an upper surface 11 of a first partition wall and an upper surface 12 of a second partition wall, and the height difference between the upper surface 11 of the first partition wall and the upper surface 12 of the second partition wall forms a height difference 13.

[0570] One method for forming spacers with height differences is, for example, using a negative halftone mask in the exposure step of the photolithography process described above. As a negative halftone mask, for example, the portion corresponding to the pixel portion 3 is a light-blocking portion (0% transmittance), the portion corresponding to the upper surface 11 of the first spacer is an opening with the highest average transmittance (fully transparent opening), and the portion corresponding to the upper surface 12 of the second spacer is an opening with an average transmittance lower than the fully transparent opening (intermediately transparent opening). According to this method, by utilizing the difference in average transmittance between the fully transparent opening and the intermediately transparent opening, i.e., the difference in exposure, a difference in residual film rate can be generated, thereby forming a height difference.

[0571] By using a halftone mask in this way, spacer walls with height differences can be formed in one step using photolithography. In this one-step formation, continuous spacer walls without a clear boundary between the first and second spacer walls can be produced.

[0572] [3] Organic electroluminescent elements

[0573] The organic electroluminescent element of the present invention has the spacer wall of the present invention.

[0574] Various organic electroluminescent elements can be manufactured using a substrate with a spacer pattern produced by the method described above. The method for forming the organic electroluminescent element 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 element.

[0575] As types of organic electroluminescent elements, bottom-emitting type and top-emitting type can be listed.

[0576] 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.

[0577] Examples of luminescent layers include organic electroluminescent layers described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent Publication No. 5734681. Quantum dots, as described in Japanese Patent Publication No. 5653387 and Japanese Patent Publication No. 5653101, can also be used.

[0578] As a solvent used in forming the organic layer with ink, water, organic solvents, and mixtures thereof can be used. There are no particular limitations on the organic solvent, as long as it can be removed from the formed film after ink injection. 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.

[0579] 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 to form the organic layer is appropriately selected according to the type of organic electroluminescent element being manufactured. When using inkjet printing to inject ink, 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 in the ink, changing the solvent, or adding viscosity modifiers.

[0580] [4] Image display device

[0581] 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 Shizuo 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.

[0582] Example

[0583] 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.

[0584] The components of the photosensitive resin compositions used in the following examples and comparative examples are described below.

[0585] Alkali-soluble resins

[0586] a-1: An alkali-soluble resin produced according to the method described in Japanese Patent Application Publication No. 2023-55623. Equivalent to polyamide-imide (meth)acrylate resin.

[0587] According to the above method, polyamide-imide (meth)acrylate resin (a-1) was obtained from 242.8 g of isocyanurate-type polyisocyanate: isophorone diisocyanate modified isocyanurate (EVONIK company "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), 188.1 g of tricarboxylic anhydride: cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 170.4 g of (meth)acrylate with epoxy groups in the molecule: glycidyl methacrylate, and 118.8 g of tricarboxylic anhydride: cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride.

[0588] The polyamide-imide (meth)acrylate resin (a-1) used in the experimental example has a weight-average molecular weight of 5100 and an acid value of 80 mg KOH / g.

[0589] a-2: An alkali-soluble resin with the following structure. Weight-average molecular weight (Mw) 7000, acid value 62 mgKOH / g, equivalent to epoxy (meth)acrylate resin.

[0590] [Chemical Formula 50]

[0591]

[0592] a-3: An alkali-soluble resin (a mixture of substances with m and n ranging from 1 to 20) having the following structure. Weight-average molecular weight (Mw) 8000, acid value 80 mg KOH / g, equivalent to epoxy (meth)acrylate resin.

[0593] [Chemical Formula 51]

[0594]

[0595] Liquid repellent

[0596] b-1: An acrylic copolymer resin containing perfluoroalkyl constituent units, olefinic unsaturated double bonds, and carboxyl constituent units. Mw90000, fluorine atoms comprising 20% ​​by mass.

[0597] Photopolymerization initiators

[0598] c-1: An oxime ester photopolymerization initiator with the following chemical structure.

[0599] [Chemical Formula 52]

[0600]

[0601] <Photopolymerizable compounds>

[0602] d-1: A multifunctional monomer manufactured by Kyoeisha Chemical Co., Ltd. (Light Acrylate PE-4A).

[0603] <Chain transfer agent>

[0604] e-1: KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd.

[0605] <UV absorber>

[0606] e-2: Methylhydroquinone manufactured by Seiko Chemicals.

[0607] <UV absorber>

[0608] e-3: BASF TINUVIN 384-2.

[0609] <Preparation of Photosensitive Resin Composition>

[0610] The components were used according to the proportions listed in Table 1, and a solvent containing propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) in a ratio of 80:20 was used to prepare the photosensitive resin compositions of Examples 1 and Comparative Examples 1-2, with the total solid content of the photosensitive resin composition being 14.5% by mass. It should be noted that the proportions (by mass) of each component in Table 1 refer to the solid content of each component in the total solid content of the photosensitive resin composition.

[0611] <Contact Angle Performance and Exposure Evaluation>

[0612] A photosensitive resin composition was spin-coated onto a glass substrate to achieve a film thickness of 1.0 μm after heat curing. After vacuum drying for 1 minute, the film was dried for 120 seconds on a hot plate at 127°C with a 0.3 mm approach. The resulting coating was measured to have an intensity of 500 mW / cm² at a wavelength of 365 nm. 2Ultraviolet radiation, from an exposure dose of 20 mJ / cm 2 (The device is set to a lower limit of 100 mJ / cm²) 2 10mJ / cm 2 Each substrate is fully exposed at intervals.

[0613] Next, a developer solution consisting of 2.38% by mass of TMAH (tetramethylammonium hydroxide) aqueous solution was used for rinsing and development at 24°C and 0.05 MPa for 60 seconds. After that, development was stopped with pure water and the mixture was cleaned by water rinse spray.

[0614] Then, the substrate is heated and cured (baked) in an oven at 230°C for 30 minutes to obtain a substrate for contact angle evaluation.

[0615] The contact angle was measured when PGMEA was dropped onto the obtained contact angle evaluation substrate, and the exposure amount exhibiting a contact angle of more than 46° was verified.

[0616] Contact angles were measured using a Kyowa Interface Science DMo-601 contact angle measuring device at 23°C and 50% RH. 1.0 μL of PGMEA was dropped onto a substrate used for contact angle evaluation, and the contact angle was measured after 10 seconds. The results are shown in Table 1. Table 1 also shows the exposure levels exhibiting contact angles greater than 46°.

[0617] <Blockers with height differences and evaluation>

[0618] (Formation of septum)

[0619] On an electrode substrate with an 8 nm thick ITO film, a 120 nm thick silver film, and a 10 nm thick ITO film sequentially deposited on its entire surface, a photosensitive resin composition was applied using a spin coater. This resulted in a 1.0 μm thick film after heat curing. After vacuum drying for 1 minute, the film was dried for 120 seconds at a 0.3 mm approach on a heated plate at 127°C. The resulting coating was exposed using a photomask (a photomask with a 14 μm wide linear fully transparent opening and a 14 μm wide intermediate transparent opening (in the form of a Cr oxide film with 9% transmittance at 365 nm)) using a Canon MPA-600FA exposure machine. The intensity at 365 nm during exposure was 500 mW / cm². 2 Exposure is expressed as +10 mJ / cm at the contact angle. 2The process was carried out under air. Next, a developing solution consisting of 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution was used, and the substrate was rinsed and developed for 60 seconds at 24°C and 0.05 MPa water pressure. Afterward, development was stopped with pure water, and the substrate was cleaned by water spray. Through these operations, unwanted parts of the patterned substrate were removed. The substrate was then cured in an oven at 230°C for 30 minutes to obtain a spacer wall substrate with height differences.

[0620] (Measurement of membrane thickness of the spacer wall)

[0621] For the aforementioned spacer wall substrate with height differences, the film thicknesses of the cured film corresponding to the fully permeable opening (first spacer wall) and the cured film corresponding to the intermediate permeable opening (second spacer wall) were measured. Tencor's Alpha-Step D-600 was used for the measurements.

[0622] (Evaluation of height difference)

[0623] The film thickness difference (height difference, ΔH) between the first and second spacers was calculated and evaluated according to the following criteria. The results are shown in Table 1. A larger film thickness difference indicates better height difference formation performance. In cases of insufficient height difference formation, the height of the second spacer becomes too high, preventing the filled ink from passing over it and resulting in poor coating. From a coating performance perspective, a lower height for the second spacer is better; therefore, the following evaluation criteria were used.

[0624] A: The height of the second spacer is less than 0.4 μm.

[0625] B: The height of the second spacer is 0.4 μm.

[0626] C: The height of the second spacer is greater than 0.4 μm.

[0627] <Inkjet Coating Adaptability Evaluation>

[0628] (Formation of septum)

[0629] On an electrode substrate with an 8 nm thick ITO layer, a 120 nm thick silver layer, and a 10 nm thick ITO layer sequentially deposited on its entire surface, a photosensitive resin composition was applied using a spin coater. After heat curing, the film thickness was 1.0 μm. After vacuum drying for 1 minute, it was dried for 120 seconds on a hot plate at 127°C with a 0.3 mm approach. The resulting coating was exposed using a photomask (an elliptical pixel area with a long side of 200 μm and a short side of 75 μm) with a Canon MPA-600FA exposure machine. The intensity at a wavelength of 365 nm during exposure was the contact angle exposure dose + 10 mJ / cm. 2The process is carried out under air-conditioning conditions. Next, a developing solution consisting of 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution is used, and the substrate is rinsed and developed for 60 seconds at 24°C and 0.05 MPa water pressure. Afterward, development is stopped with pure water, and the substrate is cleaned by water rinsing spray. Through these operations, unwanted parts of the patterned substrate are removed. The substrate is then cured in an oven at 230°C for 30 minutes to obtain the spacer wall substrate.

[0630] (Evaluation of coating performance)

[0631] For the pixel area of ​​the spacer substrate, inkjet coating was performed using a Fujifilm DMP-2850 inkjet printer. Isoamyl benzoate was used as the solvent alone, and 40 pL was applied to each of the 15 pixels. The results were evaluated based on whether shrinkage occurred within the pixel area, according to the following criteria: Shrinkage was considered to have occurred if circular depressions formed on the coating surface or holes to the extent that the glass substrate was visible during inkjet coating of the pixel area.

[0632] (Evaluation Criteria)

[0633] A: No shrinkage occurred in any of the pixels.

[0634] B: The number of pixels that have shrunk is less than 50%.

[0635] C: More than 50% of the pixels have shrunk.

[0636] [Table 1]

[0637]

[0638] As shown in Table 1, Example 1 can achieve a lower limit value of 20 mJ / cm² for the device. 2 This very low exposure level exhibits liquid repellency.

[0639] In contrast, to exhibit liquid repellency, Comparative Example 1 required 80 mJ / cm². 2 The exposure level required for Comparative Example 2 is 100 mJ / cm². 2 Exposure.

[0640] This is believed to be because, in the photosensitive resin composition of Example 1, in addition to the photopolymerization reaction during exposure, the polyamide-imide (meth)acrylate resin (a-1) contained therein has a high thermosetting property due to its amide-imide structure, which also causes a thermosetting reaction caused by the heat of the heating plate. Therefore, even a low exposure curing reaction will occur, and the dissolution of the liquid repellent during development is suppressed.

[0641] Furthermore, as shown in Table 1, Example 1 can create a greater height difference compared to Comparative Examples 1-2.

[0642] Polyamide-imide (meth)acrylate resin (a-1) has improved thermal reactivity due to its amide-imide structure. Its shrinkage rate increases when heated in an oven, especially in the middle permeable opening where the photopolymerization reaction is weak. This can be considered to help form a large height difference.

[0643] Furthermore, as shown in Table 1, Example 1 exhibited no shrinkage across all 15 pixels, demonstrating good coating properties. On the other hand, Comparative Examples 1 and 2 showed shrinkage across all pixels.

[0644] This is believed to be because, in the photosensitive resin composition of Example 1, in addition to the photopolymerization reaction during exposure, the polyamide-imide (meth)acrylate resin (a-1) contained therein has a high thermosetting property due to its amide-imide structure, which also causes a thermosetting reaction caused by the heat of the heating plate. Therefore, even a low exposure curing reaction will occur, the dissolution of the liquid repellent into the pixel during development is suppressed, and pixel contamination caused by the liquid repellent is suppressed.

[0645] Explanation of reference numerals in the attached figures

[0646] 1: Substrate;

[0647] 2: Partition walls with height differences;

[0648] 3: Pixel section;

[0649] 11: The upper surface of the first partition wall;

[0650] 12: The upper surface of the second partition wall;

[0651] 13: Height difference.

Claims

1. A photosensitive resin composition comprising (a) an alkali-soluble resin, (b) a liquid repellent, (c) a photopolymerization initiator, and (d) a photopolymerizable compound. The (a) alkali-soluble resin contains a polyamide-imide (meth)acrylate resin (a-1) comprising a structure represented by the following general formula (1). [Chemical Formula 1] In equation (1), R 1 ~R 3 X represents a divalent aliphatic hydrocarbon group. 1 ~X 3 Each represents any structure in general formulas (2) to (4). [Chemical Formula 2] In equation (2), R 4 ~R 6 X represents a divalent aliphatic hydrocarbon group. 4 and X 5 Y represents any structure in general formulas (2) to (4). 1 Indicates aromatic hydrocarbons or alicyclic hydrocarbons. [Chemical Formula 3] In equation (3), R 7 Y represents a monovalent aliphatic hydrocarbon group. 2 and Y 3 Each can be used independently to represent an aromatic hydrocarbon or an alicyclic hydrocarbon. [Chemical Formula 4] In equation (4), R 8 Y represents a monovalent aliphatic hydrocarbon group. 4 and Y 5 Each can be used independently to represent an aromatic hydrocarbon or an alicyclic hydrocarbon.

2. The photosensitive resin composition according to claim 1, wherein, The liquid repellent (b) comprises a liquid repellent (b1) having an olefinic unsaturated bond group.

3. The photosensitive resin composition according to claim 2, characterized in that, The liquid repellent (b1) comprises an acrylic resin (b2) containing repeating units represented by the following general formula (5) and fluorine atoms. [Chemical Formula 5] In equation (5), R 11 Each can be used independently to represent a hydrogen atom or a methyl group, R 12 Describing an alkyl group having 2 to 6 carbon atoms, which is optionally interrupted by one or more of -O-, -CO-, -S-, and -NH-. * indicates the bonding portion.

4. The photosensitive resin composition according to claim 3, wherein, The acrylic resin (b2) has fluoroalkyl and / or fluoroalkylene groups.

5. The photosensitive resin composition according to claim 1, wherein, The content of (a) alkali-soluble resin is less than 200 parts by mass relative to 100 parts by mass of the photopolymer compound (d).

6. The photosensitive resin composition according to claim 1, wherein, The polyamide-imide (meth)acrylate resin (a-1) has a polystyrene-converted weight-average molecular weight (Mw) of more than 1,000 and less than 10,000, as determined by gel permeation chromatography (GPC).

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein, The photosensitive resin composition is used to form spacer walls.

8. The photosensitive resin composition according to claim 7, wherein, The photosensitive resin composition is used to form spacer walls with height differences in a single step by photolithography.

9. A cured product, said cured product being formed by curing a photosensitive resin composition according to any one of claims 1 to 6.

10. A spacer wall, said spacer wall being cured from a photosensitive resin composition according to any one of claims 1 to 6.

11. An organic electroluminescent element, the organic electroluminescent element comprising the spacer wall according to claim 10.

12. An image display device comprising an organic electroluminescent element according to claim 11.

Images