Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, image display device, and method for forming the cured product.

Abstract

Provided is a photosensitive resin composition that has high liquid repellency even with a low curing temperature and that does not cause flaws such as infiltration of ink. A photosensitive resin composition according to the present invention contains a photopolymerizable compound (A), a photoinitiator (B), an alkali-soluble resin (C), and a liquid repelling agent (D). The photosensitive resin composition is characterized in that: the alkali-soluble resin (C) contains a copolymer resin (C1) having, in the main chain, a repeating unit including an aliphatic multi-ring structure; and the liquid repelling agent (D) contains a compound (D1) having a crosslinking group and having a fluorine atom and / or a siloxane chain.

Description

[Technical Field]

[0001] This invention relates to a photosensitive resin composition. Furthermore, it relates to a cured product obtained by curing a photosensitive resin composition; a partition wall composed of the cured product; and an organic electroluminescent device, a color filter, and an image display device equipped with the partition wall. The invention also relates to a method for forming the cured product. This application claims priority based on Japanese Patent Application No. 2021-102054, filed in Japan on June 18, 2021, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] In recent years, color filters using luminescent nanocrystalline particles such as quantum dots to form pixels have been investigated in order to reduce power consumption and widen the color gamut of displays. There are two methods for manufacturing color filters: photolithography and inkjet, and it is known that the latter can reduce the loss of ink material (see, for example, Patent Document 1). When manufacturing a color filter containing luminescent nanocrystalline particles using an inkjet method, ink containing luminescent nanocrystalline particles is ejected into a region (pixel area) surrounded by pre-fabricated partitions to form pixels. Organic electroluminescent elements, used in organic electroluminescent displays and the like, are manufactured by forming partitions (banks) on a substrate and stacking various functional layers within the region enclosed by these partitions. The inkjet method is a known method for stacking functional layers within these partitions. Both the partitions for color filters containing luminescent nanocrystalline particles and the partitions for organic electroluminescent elements require high ink-repellent (liquid-repellent) properties to prevent mixing of inks between adjacent pixel areas when ink is ejected by inkjet. Patent Document 2 describes that a colored photosensitive resin composition with high liquid repellency and good linearity can be obtained by using two specific alkali-soluble resins in combination as a material for forming liquid-repellent partitions by photolithography. Typically, when forming partitions like the ones described above using photolithography, the final pattern is formed through a heat curing process at a temperature of 200°C or higher for 30 minutes or more, which is performed after development. The example described in Patent Document 2 also describes heating and curing in an oven at 230°C for 30 minutes. On the other hand, in recent years, from the perspective of reducing manufacturing costs and addressing substrates with limited heat resistance, such as plastic substrates, there has been a demand for lower temperatures and shorter firing times for photosensitive resin compositions that maintain the same performance even with lower temperatures or shorter firing times than before. To meet these performance requirements, methods using blocked isocyanates (e.g., Patent Document 3) and methods combining epoxy-containing materials with thermally activated delayed-response fluorescent compounds (e.g., Patent Document 4) are known. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-086745 [Patent Document 2] International Publication No. 2019 / 146685 [Patent Document 3] Patent No. 5708313 [Patent Document 4] Japanese Patent Publication No. 2020-30290 [Overview of the project] [Problems that the invention aims to solve]

[0004] Patent documents 3 and 4 describe examples showing that the required performance was obtained even when the heat firing process was performed at 150°C, but they do not specifically mention liquid repellency. Thus, the prior art for photosensitive resin compositions that have high liquid repellency and can be cured at lower temperatures than conventional methods is insufficient. The inventors investigated and found that, in the colored photosensitive resin composition described in Patent Document 2, when a partition was formed under conditions where the firing temperature and time were reduced to 90°C and 30 minutes, and ink was inkjet coated inside this partition, a problem occurred in which the ink seeped into the partition. The seeping (penetration) of ink into the partition means that at the same time, some component may move from inside the partition into the ink, potentially contaminating the inkjet coated material, which is problematic. On the other hand, Patent Documents 3 and 4 do not describe liquid repellents, and the liquid repellency when using liquid repellents remains unknown.

[0005] Therefore, the present invention aims to provide a photosensitive resin composition that has high liquid repellency even at low curing temperatures and does not experience problems such as ink seepage (hereinafter, such properties may be referred to as "seepage resistance"). Furthermore, the present invention aims to provide a cured product obtained by curing a photosensitive resin composition that has high liquid repellency even at a low curing temperature and does not experience problems such as ink seepage, a partition made from the cured product, an organic electroluminescent element equipped with a partition, a color filter equipped with a partition, and an image display device equipped with a partition. Furthermore, the present invention aims to provide a method for producing a cured product using a photosensitive resin composition that has high liquid repellency even at low curing temperatures and does not experience problems such as ink seepage. [Means for solving the problem]

[0006] As a result of diligent research by the present inventors, we have found that the above problems can be solved by using an alkali-soluble resin containing a specific resin in a photosensitive resin composition containing a liquid-repellent agent, and have completed the present invention. In other words, the gist of this invention is as follows.

[0007] [1] A photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent, The (C) alkali-soluble resin contains a copolymer resin (C1) having repeating units containing an aliphatic polycyclic structure in its main chain. A photosensitive resin composition characterized in that the (D) liquid repellent contains a compound (D1) having a crosslinking group and having a fluorine atom and / or a siloxane chain. [2] The photosensitive resin composition of [1], wherein the copolymer resin (C1) has repeating units (I) represented by the following general formula (I).

[0008] [ka]

[0009] (In formula (I), R 1 ~R 4 Each of these independently represents a hydrogen atom or a hydrocarbon group. n represents an integer between 0 and 2. * represents a bonding group. [3] The photosensitive resin composition of [1] or [2], wherein the copolymer resin (C1) has repeating units (II) having carboxyl groups. [4] The photosensitive resin composition of [3] wherein the repeating unit (II) having a carboxyl group contains a repeating unit represented by the following general formula (II-1).

[0010] [ka]

[0011] (In formula (II-1), R 5 (* represents a hydrogen atom or organic group. * represents a bond.) [5] A photosensitive resin composition according to any of [1] to [4], wherein the copolymer resin (C1) is contained in an amount of 20% by mass or more relative to the total solid content of the photosensitive resin composition. [6] A photosensitive resin composition according to any of [1] to [5], wherein the (C) alkali-soluble resin further contains an alkali-soluble resin in addition to the copolymer resin (C1). [7] A photosensitive resin composition containing (E) a coloring agent, any of [1] to [6]. [8] A photosensitive resin composition further containing a solvent, any of [1] to [7]. [9] A photosensitive resin composition of any of [1] to [8] for heat firing at 140°C or below. A cured product obtained by curing any of the photosensitive resin compositions

[10] , [1], to [9]. A partition wall composed of hardened material from

[11] and

[10] . Organic electroluminescent element with partitions

[12]

[11] . A color filter equipped with partitions

[13]

[11] and further containing luminescent nanocrystalline particles. An image display device equipped with partitions

[14]

[11] . A method for forming a cured product using any of the photosensitive resin compositions

[15] [1] to [8], comprising at least the following steps (1) to (4). Step (1): A step of applying the photosensitive resin composition onto a substrate to form a coating film. Step (2): A step of exposing at least a portion of the coating film formed in step (1). Step (3): A step of developing the coating film exposed in step (2). Step (4): A step of firing the coating film developed in step (3).

[16] A method for forming the cured product of

[15] , wherein the firing temperature in step (4) is 140°C or lower.

[17] A method for forming a cured product according to

[15] or

[16] , comprising a post-exposure step of exposing the coating film developed in step (3) after step (3). [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive resin composition that has high liquid repellency even at low curing temperatures and does not experience problems such as ink seepage. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 is a schematic cross-sectional view of an example of a color filter equipped with the partition wall of the present invention. [Figure 2A] Figure 2A is a schematic diagram of the ink penetration evaluation results in the present invention. [Figure 2B] Figure 2B is a schematic diagram of the ink penetration evaluation results in the present invention. [Modes for carrying out the invention]

[0014] The present invention will be described in detail below. The following description is merely an example of an embodiment of the present invention, and the present invention is not limited to these embodiments unless it exceeds the essence of the invention. In this invention, the following terms have the meanings set forth below. "(Meth)acrylic" means "either acrylic or methacrylic, or both." "Total solids content" refers to the total amount of components other than the solvent in the photosensitive resin composition. Even if components other than the solvent are liquid at room temperature, they are not included in the solvent and are included in the total solids content. A numerical range represented using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. The term "(co)polymer" means that it includes both monopolymers (homopolymers) and copolymers. The terms "(acid)anhydride" and "(anhydride)...acid" mean that the term includes both the acid and its anhydride. "Partitioning material" refers to bank material, wall material, or wall material. "Partitioning" refers to bank, wall, or wall. "Weight-average molecular weight" refers to the weight-average molecular weight (Mw) calculated on a polystyrene basis using GPC (gel permeation chromatography). Unless otherwise specified, "acid value" refers to the acid value on an effective solids basis and is calculated by neutralization titration.

[0015] In the present invention, the partition wall can be used, for example, to partition the functional layer (organic layer, light-emitting part) in an actively driven organic electroluminescent element, and by dispensing and drying ink, which is the material for constituting the functional layer, into the partitioned region (pixel region), it can be used to form a pixel including the functional layer and the partition wall. It can also be used to partition the pixel region in a color filter containing luminescent nanocrystalline particles, and by dispensing and drying ink into the partitioned region, it can be used to form a pixel.

[0016] [1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent as essential components. It may also contain other components as needed, for example, (E) a colorant and (F) a dispersant.

[0017] [1-1] Components and composition of photosensitive resin composition The components and composition of the photosensitive resin composition of the present invention will be described below.

[0018] [1-1-1](A) Photopolymerizable compound The photosensitive resin composition of the present invention contains (A) a photopolymerizable compound. It is believed that the inclusion of (A) the photopolymerizable compound improves the curability of the coating film and enhances the ink-repellent properties. A photopolymerizable compound refers to a compound having one or more ethylenically unsaturated bonds in its molecule. For example, it is preferable that the compound has two or more ethylenically unsaturated bonds in its molecule, as this can enhance polymerizability, crosslinkability, and the resulting difference in developer solubility between the exposed and unexposed areas. The ethylenically unsaturated bonds are preferably derived from a (meth)acryloyloxy group, and it is even more preferable that the photopolymerizable compound is a (meth)acrylate compound.

[0019] In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule. The number of ethylenic unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably two or more, more preferably three or more, even more preferably five or more, and also preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, and particularly preferably 7 or less. The above upper and lower limits can be combined arbitrarily. For example, 2 to 15 is preferred, 2 to 10 is more preferred, 3 to 8 is even more preferred, and 5 to 7 is particularly preferred. Setting the value above the lower limit tends to improve polymerizability and increase ink repellency. Setting the value below the upper limit tends to improve developability.

[0020] Specific examples of photopolymerizable compounds include, for example, 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 polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

[0021] Examples of esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids include acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters obtained by replacing the acrylate of these exemplary compounds with methacrylate; itaconic acid esters obtained by replacing the acrylate of these exemplary compounds with itaconate; crotonic acid esters obtained by replacing the acrylate of these exemplary compounds with crotonate; and maleic acid esters obtained by replacing the acrylate of these exemplary compounds with maleate.

[0022] Examples of esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0023] Esters obtained by the esterification reaction of polyhydroxy compounds, such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily monovalent. However, some typical 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 glycerin.

[0024] Other useful examples of polyfunctional ethylenic monomers include urethane (meth)acrylates obtained by reacting polyisocyanate compounds with hydroxyl group-containing (meth)acrylic acid esters or polyisocyanate compounds with polyols and hydroxyl group-containing (meth)acrylic acid esters; epoxy acrylates such as addition products of polyvalent epoxy compounds with hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

[0025] Examples of the above-mentioned urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoei Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).

[0026] From the viewpoint of adhesion of the partition wall to the substrate and ink repellency, it is preferable to use (A) esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates as the photopolymerizable compound, and it is more preferable to use dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, 2-tris(meth)acryloyloxymethylethyl phthalic acid, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dibasic acid anhydride adducts of dipentaerythritol penta(meth)acrylate, and dibasic acid anhydride adducts of pentaerythritol tri(meth)acrylate. (A) A single photopolymerizable compound may be used, or two or more may be used in combination.

[0027] (A) The molecular weight of the photopolymerizable compound is not particularly limited, but from the viewpoint of ink repellency and the formation of fine, thin septa, it is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, and more preferably 700 or less. The above upper and lower limits can be combined arbitrarily. For example, 100 to 1000 is preferred, 150 to 1000 is more preferred, 200 to 1000 is even more preferred, 300 to 700 is even more preferred, 400 to 700 is particularly preferred, and 500 to 700 is particularly preferred.

[0028] (A) The number of carbon atoms in the photopolymerizable compound is not particularly limited, but from the viewpoint of ink repellency and residue suppression, 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, particularly preferably 30 or less. The above upper and lower limits can be combined arbitrarily. For example, 7 to 50 is preferred, 10 to 50 is more preferred, 15 to 40 is even more preferred, 20 to 35 is even more preferred, and 25 to 30 is particularly preferred.

[0029] From the viewpoint of ink repellency and the formation of fine, high-definition partitions with thin lines, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred, and more preferably are triplicate or more triplicate ester (meth)acrylates such as pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate, and adducts of acid anhydrides to triplicate or more triplicate ester (meth)acrylates such as 2,2,2-tris(meth)acryloyloxymethylethylphthalic acid and dipentaerythritol penta(meth)acrylate.

[0030] From the viewpoint of improving the permeability of the septum, it is preferable to use ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates having one or more hydroxyl groups in the molecule, such as pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, and di Pentaerythritol di(meth)acrylate, glycidyl(meth)acrylate adducts to glycerol (number of adducts 1-3), glycidyl(meth)acrylate adducts to pentaerythritol (number of adducts 1-4), glycidyl(meth)acrylate adducts to dipentaerythritol (number of adducts 1-6), glycidyl(meth)acrylate adducts to sorbitol (number of adducts 1-6), glycidyl acrylate adducts to 3-butene-1,2-diol (number of adducts 2), reaction products of diglycidyl compounds of bisphenols with (meth)acrylic acid, and alkylene oxide modified products thereof are more preferred. Two or more of these may be used in combination.

[0031] (A) The hydroxyl group equivalent of the photopolymerizable compound is preferably 1200 g / mol or less, more preferably 800 g / mol or less, even more preferably 400 g / mol or less, even more preferably 350 g / mol or less, particularly preferably 300 g / mol or less, and also preferably 100 g / mol or more, more preferably 150 g / mol or more, even more preferably 200 g / mol or more, and particularly preferably 225 g / mol or more. The above upper and lower limits can be combined arbitrarily. For example, 100 to 1200 g / mol is preferred, 150 to 600 g / mol is more preferred, 200 to 400 g / mol is even more preferred, 225 to 350 g / mol is even more preferred, and particularly preferably 225 to 300 g / mol. Setting it below the upper limit tends to improve developability and resistance to ink penetration at the septum, and setting it above the lower limit tends to improve ink repellency.

[0032] The content of (A) the photopolymerizable compound in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more, relative to the total solid content of the photosensitive resin composition, and also preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 80% by mass is preferred, 5 to 80% by mass is more preferred, 10 to 70% by mass is even more preferred, 15 to 60% by mass is even more preferred, and 25 to 50% by mass is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to form fine, high-definition partitions with narrow line widths.

[0033] The content ratio of (A) photopolymerizable compound to 100 parts by mass of (C) alkali-soluble resin is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, most preferably 30 parts by mass or more, and also preferably 200 parts by mass or less, more preferably 180 parts by mass or less, even more preferably 160 parts by mass or less, even more preferably 140 parts by mass or less, and particularly preferably 120 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 200 parts by mass is preferred, 5 to 180 parts by mass is more preferred, 10 to 160 parts by mass is even more preferred, 15 to 140 parts by mass is even more preferred, 20 to 125 parts by mass is particularly preferred, 30 to 125 parts by mass is particularly preferred, and 50 to 105 parts by mass is most preferred. Setting the value above the lower limit tends to improve ink repellency. By setting the value below the aforementioned upper limit, it tends to be possible to form a highly detailed partition with a narrow line width.

[0034] [1-1-2](B) Photopolymerization initiator The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. The (B) photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes (A) a photopolymerizable compound by active light, for example, a compound that polymerizes the ethylenically unsaturated bonds of (A) a photopolymerizable compound.

[0035] The photosensitive resin composition of the present invention may use (B) a photopolymerization initiator that is commonly used in this field. Examples of such photopolymerization initiators include metallocene compounds containing titanocene compounds as described in Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197; hexaarylbiimidazole derivatives as described in Japanese Patent Publication No. 2000-56118; radical activators such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives as described in Japanese Patent Publication No. 10-39503; and oxime ester compounds as described in Japanese Patent Publication No. 2000-80068 and Japanese Patent Publication No. 2006-36750.

[0036] Examples of metallocene compounds include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl), dicyclopentadienyltitanium di(2,6-difluorophenyl), dicyclopentadienyltitanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), and dicyclopentadienyltitanium [2,6-di-fluoro-3-(pyro-1-yl)-phenyl].

[0037] Examples of biimidazole 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.

[0038] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0039] 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.

[0040] Examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

[0041] Oxime ester compounds are particularly effective as photopolymerization initiators in terms of sensitivity and printmaking properties. For example, when using alkali-soluble resins containing phenolic hydroxyl groups, sensitivity is unfavorable, making oxime ester compounds with excellent sensitivity particularly useful. Oxime ester compounds have a high quantum yield in photoreactions and the radicals they generate are highly active, so they are highly sensitive even in small amounts and are stable against thermal reactions, making it possible to obtain highly sensitive photosensitive resin compositions in small quantities.

[0042] Examples of oxime ester compounds include those represented by the following general formula (IV).

[0043] [ka]

[0044] In formula (IV), R 21a This represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group. R 21b represents any substituent containing an aromatic ring. R 22a This represents an optionally substituted alkanoyl group or an optionally substituted alloyl group. n represents an integer, either 0 or 1.

[0045] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in the solvent and sensitivity, it is preferably 1 or more, more preferably 2 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopentylmethyl group, cyclopentylethyl group, and cyclohexylmethyl group. Examples of the substituent that the alkyl group may have include, for example, an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0046] R 21a Examples of the aromatic ring group in include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but from the viewpoint of solubility in the photosensitive resin composition, it is preferably 5 or more. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, 5 to 30 is preferable, 5 to 20 is more preferable, and 5 to 12 is even more preferable.

[0047] Examples of the aromatic ring group include, for example, a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. Examples of the substituent that the aromatic ring group may have include, for example, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group formed by linking these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group formed by linking these are preferable, and a linked alkoxy group is more preferable. From the viewpoint of sensitivity, R 21a is preferably an alkyl group that may have a substituent or an aromatic ring group that may have a substituent.

[0048] R 21b is preferably a carbazolyl group that may be substituted, a thioxanthonyl group that may be substituted, a diphenyl sulfide group that may be substituted, a fluorenyl group that may be substituted, or an indolyl group that may be substituted. From the viewpoint of sensitivity, a carbazolyl group that may be substituted is more preferable.

[0049] R 22aThe number of carbon atoms in the alkanoyl group is not particularly limited, but from the viewpoint of solubility in the solvent and sensitivity, it is preferably 2 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and even more preferably 5 or less. For example, 2 to 20 is preferred, 2 to 15 is more preferred, 2 to 10 is even more preferred, and 2 to 5 is even more preferred. Examples of alkanoyl groups include acetyl, ethiloyl, propanoyl, and butanoyl groups. Examples of substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0050] R 22a The number of carbon atoms in the aroyl group is not particularly limited, but from the viewpoint of solubility in the solvent and sensitivity, it is preferably 7 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. For example, 7 to 20 is preferred, 7 to 15 is more preferred, and 7 to 10 is even more preferred. Examples of aroyl groups include benzoyl groups and naphthoyl groups. Examples of substituents that the aroyl group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and alkyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0051] From the perspective of sensitivity, R 22a It is preferably an alkanoyl group which may have substituents, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

[0052] For example, photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, and International Publication No. 2012 / 68879 can be used.

[0053] The photopolymerization initiator may be used alone or in combination of two or more types.

[0054] The photopolymerization initiator may, if necessary, be formulated with a sensitizing dye and polymerization accelerator corresponding to the wavelength of the image exposure light source to increase sensitivity. Examples of sensitizing dyes include xanthene dyes described in Japanese Patent Publication No. 4-221958 and Japanese Patent Publication No. 4-219756; heterocyclic coumarin dyes described in Japanese Patent Publication No. 3-239703 and Japanese Patent Publication No. 5-289335; 3-ketocoumarin compounds described in Japanese Patent Publication No. 3-239703 and Japanese Patent Publication No. 5-289335; pyrometene dyes described in Japanese Patent Publication No. 6-19240; Japanese Patent Publication No. 47-2528 and Japanese Patent Publication No. 54-155292. Examples include dyes having a dialkylaminobenzene skeleton as described in Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. 60-88005, Japanese Patent Publication No. 59-56403, Japanese Patent Publication No. 2-69, Japanese Patent Publication No. 57-168088, Japanese Patent Publication No. 5-107761, Japanese Patent Publication No. 5-210240, and Japanese Patent Publication No. 4-288818.

[0055] As sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl Compounds containing a p-dialkylaminophenyl group, such as benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)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 more preferred, and 4,4'-dialkylaminobenzophenone is particularly preferred. Sensitizing dyes may be used individually or in combination of two or more.

[0056] As polymerization accelerators, for example, aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used. Polymerization accelerators may be used individually or in combination of two or more types.

[0057] The content of (B) the photopolymerization initiator 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, even more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and also preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 12% by mass or less, particularly preferably 10% by mass or less, and most preferably 8% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 25% by mass is preferred, 0.01 to 20% by mass is more preferred, 0.1 to 15% by mass is even more preferred, 1 to 10% by mass is even more preferred, 2 to 8% by mass is particularly preferred, and 3 to 7% by mass is particularly preferred. Setting it above the lower limit tends to improve ink repellency. Setting it below the upper limit tends to reduce residue.

[0058] The blending ratio of (B) photopolymerization initiator to (A) photopolymerizable compound in the photosensitive resin composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 6 parts by mass or more, particularly preferably 10 parts by mass or more, and also preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 200 parts by mass is preferred, more preferably 3 to 200 parts by mass, even more preferably 5 to 100 parts by mass, even more preferably 8 to 50 parts by mass, and particularly preferably 10 to 20 parts by mass. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to reduce residue.

[0059] A chain transfer agent may be used in combination with the photopolymerization initiator. Examples of chain transfer agents include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a mercapto group-containing compound because it tends to have a high chain transfer effect. This is thought to be because the low SH bond energy makes bond cleavage more likely, leading to hydrogen abstraction reactions and chain transfer reactions. The use of a chain transfer agent is effective in improving sensitivity and surface hardening properties.

[0060] A mercapto group-containing compound may have multiple mercapto groups within its molecule. Examples of mercapto group-containing compounds include aromatic ring-containing mercapto group-containing compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene; Hexanedithiol, Decandithiol, Butanediol bis(3-mercaptopropionate), Butanediol bisthioglycolate, Ethylene glycol bis(3-mercaptopropionate), Ethylene glycol bisthioglycolate, Trimethylolpropane tris(3-mercaptopropionate), Trimethylolpropane tristhioglycolate, Trishydroxyethyl tristhiopropionate, Pentaerythritol tetrakis(3-mercaptopropionate), Pentaerythritol tris(3 Examples include aliphatic mercapto group-containing compounds such as 1,3,5-mercaptopropionate, butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0061] Preferred mercapto group-containing compounds having an aromatic ring include 2-mercaptobenzothiazole and 2-mercaptobenzimidazole. Preferred aliphatic mercapto group-containing compounds include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0062] From the standpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, with trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione being more preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) being even more preferred. Aliphatic mercapto group-containing compounds may be used individually or in combination of two or more.

[0063] From the viewpoint of increasing the taper angle, it is preferable to use a photopolymerization initiator system that combines one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole with a photopolymerization initiator. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.

[0064] From the viewpoint of sensitivity, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). Furthermore, from the viewpoint of sensitivity, it is preferable to use a combination of one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate), and a photopolymerization initiator.

[0065] When the photosensitive resin composition of the present invention contains a chain transfer agent, the content ratio of the chain transfer agent is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 0.8% by mass or more, relative to the total solid content of the photosensitive resin composition, and also preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, and even more preferably 2% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 0.01 to 5% by mass is preferred, 0.1 to 4% by mass is more preferred, 0.5 to 3% by mass is even more preferred, and 0.8 to 2% by mass is particularly preferred. Setting it above the lower limit tends to improve ink repellency. Setting it below the upper limit tends to form fine-lined, high-definition partitions.

[0066] The content ratio of the chain transfer agent to the photopolymerization initiator (B) in the photosensitive resin composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and also preferably 500 parts by mass or less, more preferably 300 parts by mass or less, even more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 500 parts by mass is preferred, 10 to 300 parts by mass is more preferred, 15 to 100 parts by mass is even more preferred, and particularly preferably 20 to 50 parts by mass. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to form fine, high-definition partitions with narrow line widths.

[0067] [1-1-3](C) Alkali-soluble resin The photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. The (C) alkali-soluble resin contains a copolymer resin (C1) (hereinafter sometimes abbreviated as "copolymer resin (C1)") having repeating units containing an aliphatic polycyclic structure in its main chain. Because the main chain contains repeating units with aliphatic polycyclic structures, it is not as rigid as aromatic hydrocarbon ring structures, but it has repeating units with a sterically bulky structure. Due to a certain degree of flexibility, the reaction sites come closer together during photo- and / or thermal curing reactions, so as not to excessively hinder the curing reaction, and furthermore, after curing, its bulky structure is thought to exhibit a function that efficiently suppresses the penetration of inks and the like (hereinafter sometimes referred to as penetration resistance).

[0068] The copolymer resin (C1) preferably has repeating units represented by the following general formula (I) (hereinafter sometimes referred to as "repeating unit (I)").

[0069] [ka]

[0070] In formula (I), R 1 ~R 4Each of these independently represents a hydrogen atom or a hydrocarbon group. n represents an integer from 0 to 2. * represents a bonding group.

[0071] <Repeating Unit (I)> In formula (I), R 1 ~R 4 Each of these is independently a hydrogen atom or a hydrocarbon group. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aromatic ring groups, and aralkyl groups.

[0072] The alkyl group can be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, and preferably 15 or less, and even more preferably 8 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 15 is preferred, 3 to 15 is more preferred, and 6 to 8 is even more preferred. Setting the value above the lower limit tends to result in good ink penetration resistance. Setting the value below the upper limit tends to result in good developability. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0073] The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 or more, more preferably 3 or more, preferably 10 or less, and more preferably 8 or less. The above upper and lower limits can be combined arbitrarily. For example, 2 to 10 is preferred, and 3 to 8 is more preferred. Setting the value above the lower limit tends to result in good stain resistance. Setting the value below the upper limit tends to result in good developability. Examples of alkenyl groups include vinyl, allyl, butenyl, and pentenyl groups.

[0074] The number of carbon atoms in the alkynyl group is not particularly limited, but is preferably 2 or more, more preferably 3 or more, preferably 10 or less, and more preferably 8 or less. The above upper and lower limits can be combined arbitrarily. For example, 2 to 10 is preferred, and 3 to 8 is more preferred. Setting the value above the lower limit tends to result in good stain resistance. Setting the value below the upper limit tends to result in good developability. Examples of alkynyl groups include the ethynyl group and the propargyl group.

[0075] Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above 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 result in good stain resistance. Setting the value below the upper limit tends to result in good developability. Examples of aromatic ring groups include phenyl, naphthyl, tolyl, and xylyl groups.

[0076] The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, and also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 20 is preferred, 6 to 15 is more preferred, and 7 to 10 is even more preferred. Setting it above the lower limit tends to result in good stain resistance. Setting it below the upper limit tends to result in good developability. Examples of aralkyl groups include those in which one hydrogen atom of the alkyl group is substituted with the aromatic ring group. Examples include the benzyl group and the phenethyl group.

[0077] R 1 ~R 4Each of these independently represents a hydrogen atom or a hydrocarbon group, but R 1 and R 4 They may be linked together to form a ring structure, and similarly, R 2 and R 3 They may be connected to form a ring structure. From the viewpoint of ease of synthesis, R 1 ~R 4 Preferably, one of them is a hydrogen atom, R 1 ~R 4 It is more preferable that all of them are hydrogen atoms.

[0078] n represents an integer between 0 and 2, but from a developmental standpoint, it is preferable that n is 0.

[0079] Examples of repeating units (I) include those represented by the following general formulas (I-1) to (I-3), with the repeating unit represented by the following general formula (I-1) being more preferable from the viewpoint of stain resistance.

[0080] [ka]

[0081] <Repeating Unit (II)> The copolymer resin (C1) preferably has repeating units (II) having carboxyl groups (hereinafter sometimes referred to as "repeating units (II)"). The structure of the repeating unit (II) having a carboxyl group is not particularly limited, but examples include repeating units derived from unsaturated group-containing carboxylic acids and unsaturated group-containing carboxylic acid anhydrides. From the viewpoint of achieving both developability and stain resistance, and being able to adjust the strength of these properties as needed, it is preferable to include a repeating unit represented by the following general formula (II-1) (hereinafter sometimes referred to as "repeating unit (II-1)").

[0082] [ka]

[0083] In formula (II-1), R 5 * represents a hydrogen atom or organic group. * represents a bond.

[0084] Examples of organic groups include alkyl groups which may have substituents and aryl groups which may have substituents. Preferably, the alkyl and aryl groups have 1 to 18 carbon atoms.

[0085] R 5 When the group is an alkyl group, the number of carbon atoms is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, even more preferably 4 or more, and preferably 9 or less, and even more preferably 7 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 9 is preferred, 2 to 9 is more preferred, and 4 to 7 is even more preferred. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0086] R 5 When the group is an aryl group, the number of carbon atoms is not particularly limited, but it is preferably 6 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 6 to 20 is preferred, 6 to 15 is more preferred, and 6 to 10 is even more preferred. Examples of aryl groups include phenyl, naphthyl, tolyl, and xylyl groups.

[0087] Examples of substituents that alkyl groups and aryl groups may have include hydroxyl groups and (meth)acryloyl groups.

[0088] From the standpoint of stain resistance, R 5 A unit having the structure represented by the following general formula (II-2) is even more preferable.

[0089] [ka]

[0090] In formula (II-2), R 6 * represents a hydrogen atom or a methyl group. e represents an integer from 1 to 5. * represents a bond.

[0091] In formula (II-2), e is preferably 1 to 3, and more preferably 1 to 2, from the viewpoint of stain resistance.

[0092] As the repeating unit (II-1), any of the repeating units represented by the following general formulas (II-3) to (II-6) is more preferred, and the repeating unit represented by the following general formula (II-3) or the following general formula (II-4) is particularly preferred.

[0093] [ka]

[0094] In equations (II-3) to (II-6), * represents a combination.

[0095] <Other repeating units> The copolymer resin (C1) may have repeating units other than repeating unit (I) and repeating unit (II). Other repeating units, though not limited to them, include, for example, the repeating units represented by the following general formulas (III-1) to (III-5) (hereinafter sometimes referred to as "repeating units (III-1) to (III-5)").

[0096] [ka]

[0097] In formulas (III-1) to (III-4), R 5 This is equivalent to equation (II-1), and R 7* represents a hydrogen atom or a methyl group. * represents a bonding bond.

[0098] [ka]

[0099] In formula (III-5), R 8 * represents an alkyl group which may have substituents. * represents a bond.

[0100] The presence of repeating units represented by formula (III-5) tends to improve the heat resistance of the copolymer resin (C1).

[0101] R 8 Examples of alkyl groups that may have substituents in the compound include methyl, ethyl, propyl, and benzyl groups.

[0102] The copolymer resin (C1) preferably has repeating units (I), repeating units (II-1), and repeating units (III-1) from the viewpoint of surface smoothness and stain resistance, and more preferably has repeating units (I), repeating units (II-1), repeating units (III-1), and repeating units (III-4).

[0103] [Method for producing copolymer resin (C1)] The method for producing the copolymer resin (C1) is not particularly limited, and conventionally known methods can be used. For example, it can be produced by the following steps (i) to (iii). The ring-opening precursor polymer obtained in step (ii) can also be used as the copolymer resin (C1).

[0104] (Step i) A step of preparing a precursor polymer containing repeating units represented by formula (I) and repeating units represented by formula (III-4).

[0105] (Step ii) A step in which the precursor polymer is reacted with alcohols or water to open the ring of the acid anhydride skeleton in formula (III-4), thereby generating a carboxyl group or its ester in the precursor polymer to obtain a ring-opening precursor polymer.

[0106] In step (ii), it is more preferable to use a compound represented by the following general formula (II-2-1) as the alcohol used, from the viewpoint of stain resistance.

[0107] [ka]

[0108] In formula (II-2-1), R 6 e is equivalent to equation (II-2).

[0109] (Step iii) Optionally, a step in which the ring-opening precursor polymer obtained in (Step ii) is reacted with a compound having an epoxy group and an ethylenic double bond.

[0110] Examples of compounds having epoxy groups and ethylenic double bonds include glycidyl methacrylate.

[0111] The copolymer resin (C1) may be manufactured, for example, according to the methods described in International Publication No. 2016 / 194619 or International Publication No. 2017 / 154439.

[0112] The content of repeating units (I) in the copolymer resin (C1) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 10 to 50% by mass is preferred, 20 to 40% by mass is more preferred, and 25 to 30% by mass is even more preferred. Setting the value above the lower limit tends to result in good stain resistance. Setting the value below the upper limit tends to result in good developability.

[0113] The content of repeating units (I) in the copolymer resin (C1) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 20 to 80 mol% is preferred, 30 to 70 mol% is more preferred, and 40 to 60 mol% is even more preferred. Setting the value above the lower limit tends to result in good stain resistance. Setting the value below the upper limit tends to result in good developability.

[0114] When the copolymer resin (C1) has repeating units (II-1), the percentage of repeating units is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 40 mol% is preferred, 10 to 30 mol% is more preferred, and 15 to 20 mol% is even more preferred. Setting the value above the lower limit tends to result in good developability. Setting the value below the upper limit tends to result in good stain resistance.

[0115] When the copolymer resin (C1) has repeating units (III-1), the content is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less in the total repeating units. The above upper and lower limits can be combined arbitrarily. For example, 5 to 40 mol% is preferred, 10 to 30 mol% is more preferred, and 15 to 20 mol% is even more preferred. Setting it above the lower limit tends to result in good stain resistance. Setting it below the upper limit tends to result in good developability.

[0116] When the copolymer resin (C1) has repeating units (III-4), the content is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less of the total repeating units. The above upper and lower limits can be combined arbitrarily. For example, 5 to 40 mol% is preferred, 10 to 30 mol% is more preferred, and 15 to 20 mol% is even more preferred. Setting the value above the lower limit tends to facilitate synthesis. Setting the value below the upper limit tends to result in good stain resistance and developability.

[0117] When the copolymer resin (C1) has repeating units (II-1), repeating units (III-1), and repeating units (III-4), the content of repeating unit (II-1) to the total content of repeating units (II-1), repeating units (III-1), and repeating units (III-4) in the copolymer resin (C1) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and also preferably 90 mol% or less, more preferably 70 mol% or less, and even more preferably 50 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 10 to 90 mol% is preferred, 20 to 70 mol% is more preferred, and 30 to 50 mol% is even more preferred. Setting the value above the lower limit tends to result in good developability. Setting the value below the upper limit tends to result in good stain resistance.

[0118] The acid value of the copolymer resin (C1) is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 50 mg KOH / g or more, and also preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 100 mg KOH / g or less, and particularly preferably 80 mg KOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 10 to 200 mg KOH / g is preferred, 10 to 150 mg KOH / g is more preferred, 30 to 100 mg KOH / g is even more preferred, and 50 to 80 mg KOH / g is particularly preferred. Setting it above the lower limit tends to improve developability. Setting it below the upper limit tends to improve developability adhesion.

[0119] The weight-average molecular weight (Mw) of the copolymer resin (C1) is not particularly limited, but is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, even more preferably 5000 or more, particularly preferably 6000 or more, and also preferably 35000 or less, more preferably 20000 or less, even more preferably 15000 or less, and particularly preferably 10000 or less. The above upper and lower limits can be arbitrarily combined. For example, 2000 to 35000 is preferred, 3000 to 35000 is more preferred, 4000 to 20000 is even more preferred, 5000 to 15000 is even more preferred, and 6000 to 10000 is particularly preferred. Setting it above the lower limit tends to improve developability. Setting it below the upper limit tends to improve developability.

[0120] The double bond equivalent of the copolymer resin (C1) is not particularly limited, but is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and especially preferably 500 or more. It is also preferably 800 or less, more preferably 700 or less, and even more preferably 600 or less. The above upper and lower limits can be combined arbitrarily. For example, 200 to 800 is preferred, 300 to 800 is more preferred, 400 to 700 is even more preferred, and 500 to 600 is especially preferred. Setting it above the lower limit tends to result in good developability. Setting it below the upper limit tends to result in good stain resistance.

[0121] The content of copolymer resin (C1) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total solid content of the photosensitive resin composition. Also, is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 80% by mass is preferred, 10 to 80% by mass is more preferred, 20 to 60% by mass is even more preferred, 30 to 60% by mass is even more preferred, and particularly preferably 40 to 50% by mass. Setting it above the lower limit tends to result in good stain resistance. Setting it below the upper limit tends to result in a development method that is more likely to be dissolution development.

[0122] (C) The content of copolymer resin (C1) in the alkali-soluble resin is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and preferably 100% by mass or less. For example, 20 to 100% by mass is preferred, 30 to 100% by mass is more preferred, 40 to 100% by mass is even more preferred, and 45 to 100% by mass is particularly preferred. Setting it above the lower limit tends to result in good stain resistance. Setting it below the upper limit tends to result in a development method that is more likely to be dissolution development.

[0123] The (C) alkali-soluble resin in the photosensitive resin composition of the present invention may further contain an alkali-soluble resin other than the copolymer resin (C1) (hereinafter sometimes referred to as "other alkali-soluble resin"). Including other alkali-soluble resins is preferable because it is possible to impart further properties, including improved developability, while maintaining the aforementioned stain resistance.

[0124] As for other alkali-soluble resins, from the viewpoint of developability, it is preferable to include epoxy (meth)acrylate resins (C2) other than copolymer resin (C1) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C2)"), and more preferably epoxy (meth)acrylate resins (C2) having aromatic rings in the main chain. From the viewpoint of ink repellency, it is preferable to include acrylic copolymer resins (C3) having ethylenically unsaturated groups in the side chains (hereinafter sometimes referred to as "acrylic copolymer resin (C3)").

[0125] [Epoxy (meth)acrylate resin (C2)] Epoxy (meth)acrylate resin (C2) is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin, optionally reacting it with an isocyanate group-containing compound, and then further reacting it with a polybasic acid or its anhydride. For example, one example is a resin in which an ethylenically unsaturated group is added to the epoxy resin via an ester bond (-COO-) by ring-opening addition of the carboxyl group of an unsaturated monocarboxylic acid to the epoxy group of the epoxy resin, and one of the carboxyl groups of a polybasic acid anhydride is added to the resulting hydroxyl group. Another example is a resin in which a polyhydric alcohol is added simultaneously when adding the polybasic acid anhydride.

[0126] A resin obtained by reacting the carboxyl group of the resin obtained in the above reaction with a compound having a further reactive functional group is also included in the epoxy (meth)acrylate resin (C2) described above.

[0127] Examples of epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, dihydrooxylfluorene type epoxy resin, dihydrooxylalkylene oxylfluorene 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 aromatic rings in the main chain can be suitably used.

[0128] From the viewpoint of heat resistance, preferred epoxy resins include bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene, with bisphenol A epoxy resin being even more preferred.

[0129] Examples of epoxy resins include bisphenol A type epoxy resins (e.g., "jER(registered trademark, same hereinafter) 828", "jER1001", "jER1002", "jER1004" from Mitsubishi Chemical Corporation, and "NER-1302" from Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76℃)), bisphenol F type resins (e.g., "jER807", "jER4004P", "jER4005P", "jER4007P" from Mitsubishi Chemical Corporation, and "NER-7406" from Nippon Kayaku Co., Ltd. (epoxy (Equivalent weight 350, softening point 66℃), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., "jERYX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (e.g., "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "jER152" and "jER154" manufactured by Mitsubishi Chemical Corporation, and "DEN-438" manufactured by Dow Chemical Corporation), (o,m,p-) cresol novolac type epoxy resin (e.g., "EOCN(registered trademark, hereinafter the same)-102S" manufactured by Nippon Kayaku Co., Ltd.) "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC®" manufactured by Nissan Chemical Corporation), trisphenolmethane type epoxy resin (for example, "EPPN®-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resin ("Celoxide® 2021P", "Celoxide EHPE" manufactured by Daicel Corporation), and the reaction of dicyclopentadiene with phenol. Epoxy resins obtained by glycidylating phenolic resins (for example, "EXA-7200" from DIC Corporation, "NC-7300" and "XD-1000" from Nippon Kayaku Co., Ltd.), biphenyl-type epoxy resins (for example, "NC-7000" from Nippon Kayaku Co., Ltd.), and "E-201" from Osaka Organic Chemical Industry Co., Ltd. can be preferably used, with "XD-1000" from Nippon Kayaku Co., Ltd., "NC-3000" from Nippon Kayaku Co., Ltd., "ESF-300" from Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "E-201" from Osaka Organic Chemical Industry Co., Ltd. being more preferable. Epoxy resins may be used individually or in combination of two or more types.

[0130] Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and 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 phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and reaction products of (meth)acrylic acid and ε-caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred. Ethylene-unsaturated monocarboxylic acids may be used individually or in combination of two or more.

[0131] Examples of polybasic acids (anhydrides) include 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, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides. From the viewpoint of suppressing outgassing from the cured product and ensuring long-term reliability, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred. As for the polybasic acid (anhydride), one type may be used alone, or two or more types may be used in combination.

[0132] By using polyhydric alcohols, the molecular weight of epoxy (meth)acrylate resin (C2) can be increased, allowing for the introduction of branching within the molecule, which tends to balance molecular weight and viscosity. Furthermore, the rate of acid group introduction into the molecule can be increased, making it easier to balance sensitivity and adhesion. Preferred polyhydric alcohols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Polyhydric alcohols may be used individually or in combination of two or more types.

[0133] In addition to the aforementioned resins, other examples of epoxy (meth)acrylate resins (C2) include the resin described in Korean Published Patent No. 10-2013-0022955.

[0134] From the viewpoint of developability and solubility, the epoxy (meth)acrylate resin (C2) preferably contains at least one selected from the group consisting of epoxy (meth)acrylate resins having a substructure represented by the following general formula (i) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C2-1)") and epoxy (meth)acrylate resins having a substructure represented by the following general formula (ii) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C2-2)").

[0135] [ka]

[0136] In formula (i), R a R represents a hydrogen atom or a methyl group. b represents a divalent hydrocarbon group which may have substituents. k represents 1 or 2. The benzene ring in formula (i) may be further substituted with any substituent. * represents each bond.

[0137] [ka]

[0138] In formula (ii), R c Each of these independently represents either a hydrogen atom or a methyl group. d R represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.e and R f each independently represents a divalent aliphatic group which may have a substituent. l and m each independently represent an integer of 0 to 2. * each represents a bond.

[0139] <Epoxy (meth) acrylate resin (C2-1)>

[0140]

Chemical formula

[0141] In formula (i), R a represents a hydrogen atom or a methyl group. R b represents a divalent hydrocarbon group which may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may be further substituted by an arbitrary substituent. * each represents a bond.

[0142] (R b ) In formula (i), R b represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

[0143] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. Among these, from the viewpoint of development solubility, a linear aliphatic group is preferable, while from the viewpoint of reducing the penetration of the developer into the exposed area, a cyclic aliphatic group is preferable. The number of carbon atoms of the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferable, 3 to 15 is more preferable, and 6 to 10 is still more preferable. By setting the value to be not less than the lower limit value, the film strength tends to be improved. By setting the value to be not more than the upper limit value, the ink repellency tends to be improved.

[0144] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene groups. From the viewpoint of ink repellency and manufacturing cost, the methylene group is preferred. Examples of divalent branched aliphatic groups include structures having a divalent linear aliphatic group with one or more methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl groups as side chains.

[0145] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, and more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, and 2 to 5 is more preferred. Setting the value above the lower limit tends to improve film strength. Setting the value below the upper limit tends to improve developability. Examples of divalent cyclic aliphatic groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, dicyclopentane rings, norbornane rings, isobornane rings, and adamantane rings, all of which have two free valencies. From the viewpoint of film strength and developability, adamantane rings and dicyclopentane rings, which have two free valencies, are preferred.

[0146] Examples of substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0147] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic ring groups. The number of carbon atoms in the divalent aromatic ring group is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above 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 film strength. Setting the value below the upper limit tends to improve developability.

[0148] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring. Examples of divalent aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings, all of which have two free valencies.

[0149] The aromatic heterocyclic group may consist of a monocyclic ring or a fused ring. 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, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, all of which have two free valencies. From the viewpoint of manufacturing cost, benzene rings and naphthalene rings, which have two free valencies, are preferred, and benzene rings, which have two free valencies, are more preferred.

[0150] Examples of substituents that the divalent aromatic ring group may have include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. From the viewpoint of curability, unsubstituted groups are preferred.

[0151] Examples of groups formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups formed by linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and still preferably 3 or less. The above 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 still preferred. Setting the value above the lower limit tends to improve developability. Setting the value below the upper limit tends to improve film strength. The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and still preferably 3 or less. The above 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 still preferred. Setting the value above the lower limit tends to improve film strength. Setting the value below the upper limit tends to improve developability.

[0152] Specific examples of groups formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following general formulas (iA) to (iF). From the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane, the group represented by the following general formula (iA) is preferred.

[0153] [ka]

[0154] The benzene ring in formula (i) may be further optionally substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

[0155] From the viewpoint of development solubility, the partial structure represented by formula (i) is preferably a partial structure represented by the following general formula (i-1).

[0156] [Chemical formula]

[0157] In formula (i-1), R a , R b and k are synonymous with R a , R b and k in formula (i). R Y represents a hydrogen atom or a polybasic acid residue. The benzene ring in formula (i-1) may be further optionally substituted with any substituent. * each represents a bond.

[0158] In R Y in formula (i-1), the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.

[0159] The benzene ring in formula (i-1) may be further substituted with any substituent. Examples of substituents include hydroxyl groups, methyl groups, methoxy groups, ethyl groups, ethoxy groups, propyl groups, and propoxy groups. The number of substituents is not particularly limited; there may be one or two or more.

[0160] The repeating unit structure represented by formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (C2-1) may be one type or two or more types.

[0161] The number of substructures represented by formula (i) contained in one molecule of epoxy (meth)acrylate resin (C2-1) 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, and even more preferably 8 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferred, 2 to 10 is more preferred, and 3 to 8 is even more preferred. Developability tends to improve when the value is above the lower limit. Ink repellency tends to improve when the value is below the upper limit.

[0162] The number of substructures represented by formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (C2-1) 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, and even more preferably 8 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferred, 2 to 10 is more preferred, and 3 to 8 is even more preferred. Developability tends to improve when the value is above the lower limit. Ink repellency tends to improve when the value is below the upper limit.

[0163] The following are specific examples of epoxy (meth)acrylate resin (C2-1).

[0164] [ka]

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] <Epoxy (meth)acrylate resin (C2-2)>

[0171] [ka]

[0172] In formula (ii), R c Each of these independently represents either a hydrogen atom or a methyl group. d R represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. e and R f Each of the following independently represents a divalent aliphatic group which may have substituents. l and m each independently represent an integer between 0 and 2. * represents a bond.

[0173] (R d ) In equation (ii), R d This represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

[0174] The number of rings in the aliphatic ring group is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and still preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is still preferred, and 2 to 3 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability. The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0175] Examples of aliphatic rings in the aliphatic ring group include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, and adamantane rings. From the viewpoint of heat resistance, the adamantane ring is preferred.

[0176] The number of rings in the aromatic ring group is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and also preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. The above 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. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0177] Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, 6 to 40 is more preferred, 8 to 30 is even more preferred, 10 to 20 is even more preferred, and 12 to 15 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0178] Examples of aromatic rings in the aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings. From the viewpoint of heat resistance, fluorene rings are preferred.

[0179] In a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited, but examples include a divalent aliphatic group, a divalent aromatic ring group, and a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

[0180] Divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. Linear aliphatic groups are preferred from the viewpoint of improving developability. Cyclic aliphatic groups are preferred from the viewpoint of heat resistance. The number of carbon atoms in the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, and also preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The above 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. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0181] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene groups. From the viewpoint of heat resistance, the methylene group is preferred. Examples of divalent branched aliphatic groups include structures having the aforementioned divalent linear aliphatic group with, as a side chain, one or more methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, or tert-butyl groups.

[0182] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and still preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is still preferred, and 2 to 3 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0183] Examples of divalent cyclic aliphatic groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, dicyclopentane rings, norbornane rings, isobornane rings, and adamantane rings, all of which have two free valencies. From the viewpoint of heat resistance, adamantane rings, which have two free valencies, are preferred.

[0184] Examples of substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0185] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic ring groups. The number of carbon atoms in the divalent aromatic ring group is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and also preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above 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 ink repellency. Setting the value below the upper limit tends to improve developability.

[0186] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring. Examples of divalent aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings, all of which have two free valencies.

[0187] The aromatic heterocyclic group may consist of a monocyclic ring or a fused ring. 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, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, all of which have two free valencies. From the viewpoint of manufacturing cost, benzene rings and naphthalene rings, which have two free valencies, are preferred, and benzene rings, which have two free valencies, are more preferred.

[0188] Examples of substituents that the divalent aromatic ring group may have include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. From the viewpoint of curability, unsubstituted groups are preferred.

[0189] Examples of groups formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups formed by linking one or more of the aforementioned divalent aliphatic groups and one or more of the aforementioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and still preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is still preferred, and 2 to 3 is particularly preferred. Setting the value above the lower limit tends to improve developability. Setting the value below the upper limit tends to improve heat resistance. The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and still preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is still preferred, and 2 to 3 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0190] Examples of groups formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by formulas (iA) to (iF). From the viewpoint of film strength, the group represented by formula (iC) is preferred.

[0191] The manner in which a cyclic hydrocarbon group, which is a side chain, is bonded to a divalent hydrocarbon group is not particularly limited, but examples include a configuration in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group, or a configuration in which one of the carbon atoms of the aliphatic group is included in the cyclic hydrocarbon group that forms the side chain.

[0192] (Re , R f ) In equation (ii), R e and R f Each of these independently represents a divalent aliphatic group which may have substituents.

[0193] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. From the viewpoint of heat resistance, cyclic aliphatic groups are preferred.

[0194] The number of carbon atoms in the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, and also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, 3 to 15 is more preferred, and 6 to 10 is even more preferred. Setting the value above the lower limit tends to improve adhesion to the substrate and ink repellency. Setting the value below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0195] Examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene groups. From the viewpoint of rigidity of the skeleton, the methylene group is preferred.

[0196] Examples of divalent branched aliphatic groups include structures in which the aforementioned divalent linear aliphatic group has one or more methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl groups as side chains.

[0197] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 12 or less, and more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferred, 1 to 10 is more preferred, and 2 to 10 is even more preferred. Setting the value above the lower limit tends to improve adhesion to the substrate and ink repellency. Setting the value below the upper limit tends to suppress deterioration of sensitivity and film loss during development, and tends to improve resolution.

[0198] Examples of divalent cyclic aliphatic groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, adamantane rings, and dicyclopentadiene rings, all of which have two free valencies. From the viewpoint of heat resistance, dicyclopentadiene rings and adamantane rings, which have two free valencies, are preferred.

[0199] Examples of substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0200] (l, m) In formula (ii), l and m each represent an integer between 0 and 2 independently. Setting them to be above the lower limit tends to improve adhesion to the substrate. Setting them to be below the upper limit tends to improve developability. From the viewpoint of developability, it is preferable that l and m are 0. From the viewpoint of adhesion to the substrate, it is preferable that l and m are 1 or greater.

[0201] From the viewpoint of film strength and ink repellency, the substructure represented by formula (ii) is preferably the substructure represented by the following general formula (ii-1).

[0202] [ka]

[0203] In formula (ii-1), R c , R e , R f , l and m are equivalent to those in formula (ii) above. α represents a monovalent cyclic hydrocarbon group which may have substituents. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with any substituent. * represents each bond.

[0204] (R α ) In equation (ii-1), R α This represents a monovalent cyclic hydrocarbon group which may have substituents. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

[0205] The number of rings in the aliphatic ring group is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and still preferably 3 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 6 is preferred, 1 to 4 is more preferred, 1 to 3 is still preferred, and 2 to 3 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability. The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, 4 to 30 is more preferred, 6 to 20 is even more preferred, and 8 to 15 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0206] Examples of aliphatic rings in the aliphatic ring group include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, and adamantane rings. From the viewpoint of achieving both ink repellency and developability, the adamantane ring is preferred.

[0207] The number of rings in the aromatic ring group is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and preferably 10 or less, and even more preferably 5 or less. The above 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 ink repellency. Setting the value below the upper limit tends to improve developability. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and also preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above 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 ink repellency. Setting the value below the upper limit tends to improve developability.

[0208] Examples of aromatic rings in the aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the viewpoint of achieving both ink repellency and developability, fluorene rings are preferred.

[0209] Substituents that the cyclic hydrocarbon group may have include C1-C5 alkyl groups such as hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl groups; C1-C5 alkoxy groups such as methoxy and ethoxy groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0210] n represents an integer greater than or equal to 1, preferably 2 or greater, and preferably 3 or less. For example, 1 to 3 is preferred, and 2 to 3 is more preferred. Setting it above the lower limit tends to improve ink repellency. Setting it below the upper limit tends to improve developability.

[0211] From the perspective of achieving both ink repellency and developability, R α It is preferable that the group is a monovalent aliphatic ring group, and more preferably an adamantyl group.

[0212] The benzene ring in formula (ii-1) may be further substituted with any substituent. Examples of substituents include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. The number of substituents is not particularly limited; there may be one or two or more. From the viewpoint of curability, it is preferable that the molecule be unsubstituted.

[0213] The following are specific examples of substructures represented by equation (ii-1).

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] From the viewpoint of development adhesion, the substructure represented by formula (ii) is preferably the substructure represented by the following general formula (ii-2).

[0220] [ka]

[0221] In formula (ii-2), R c , R e , R f , l and m are equivalent to those in formula (ii) above. β represents a divalent cyclic hydrocarbon group which may have substituents. The benzene ring in formula (ii-2) may be further substituted with any substituent. * represents each bond.

[0222] (R β ) In equation (ii-2), R β This represents a divalent cyclic hydrocarbon group which may have substituents. Examples of cyclic hydrocarbon groups include aliphatic ring groups and aromatic ring groups.

[0223] The number of rings in the aliphatic ring group is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, preferably 10 or less, and more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, and 2 to 5 is more preferred. Setting the value above the lower limit tends to improve developability. Setting the value below the upper limit tends to improve ink repellency. The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and also preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The above 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. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability. Examples of aliphatic rings in the aliphatic ring group include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, and adamantane rings. From the viewpoint of achieving both ink repellency and developability, the adamantane ring is preferred.

[0224] The number of rings in the aromatic ring group is not particularly limited, but it is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and preferably 10 or less, and even more preferably 5 or less. The above 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 ink repellency. Setting the value below the upper limit tends to improve developability. Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, particularly preferably 10 or more, and also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above 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 10 to 15 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0225] Examples of aromatic rings in the aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the viewpoint of ink repellency and developability, fluorene rings are preferred.

[0226] Examples of substituents that the cyclic hydrocarbon group may have include C1-C5 alkyl groups such as hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl groups; C1-C5 alkoxy groups such as methoxy and ethoxy groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0227] From the perspective of achieving both ink repellency and developability, and heat resistance, R β It is preferable that it is a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. From the viewpoint of achieving both ink repellency and developability, and heat resistance, R β It is preferable that the ring is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

[0228] The benzene ring in formula (ii-2) may be further substituted with any substituent. Examples of substituents include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. The number of substituents is not particularly limited and may be one or two or more. From the viewpoint of curability, the benzene ring in formula (ii-2) is preferably unsubstituted.

[0229] The following are specific examples of the substructure represented by equation (ii-2).

[0230] [ka]

[0231] [ka]

[0232] [ka]

[0233] [ka]

[0234] From the viewpoint of developability, the substructure represented by formula (ii) is preferably the substructure represented by the following general formula (ii-3).

[0235] [ka]

[0236] In formula (ii-3), R c , R d , R e , R f , l and m are equivalent to those in formula (ii) above. Z Each of these independently represents either a hydrogen atom or a polybasic acid residue.

[0237] R Z The polybasic acid residue in formula (i-1) is R Y The items listed as such can be preferably adopted.

[0238] The substructure represented by formula (ii-3) contained in one molecule of epoxy (meth)acrylate resin (C2-2) may be one type or two or more types.

[0239] The number of substructures represented by formula (ii) contained in one molecule of epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 is still preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0240] The number of substructures represented by formula (ii-1) contained in one molecule of epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 is still preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0241] The number of substructures represented by formula (ii-2) contained in one molecule of epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 15 is more preferred, 1 to 10 is still preferred, and 3 to 10 is particularly preferred. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to improve developability.

[0242] The number of substructures represented by formula (ii-3) contained in one molecule of epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 15 or less, and still preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 15 is more preferred, 1 to 10 is still preferred, and 3 to 10 is particularly preferred. Setting the value above the lower limit tends to improve developability. Setting the value below the upper limit tends to improve ink repellency.

[0243] The acid value of the epoxy (meth)acrylate resin (C2) is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 50 mg KOH / g or more, even more preferably 70 mg KOH / g or more, particularly preferably 80 mg KOH / g or more, and also preferably 200 mg KOH / g or less, more preferably 180 mg KOH / g or less, even more preferably 150 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and particularly preferably 110 mg KOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 10 to 200 mg KOH / g is preferred, 30 to 180 mg KOH / g is more preferred, 50 to 150 mg KOH / g is even more preferred, 70 to 120 mg KOH / g is even more preferred, and particularly preferably 80 to 110 mg KOH / g. Developability tends to improve when the value is above the lower limit. Setting the value below the aforementioned upper limit tends to improve ink repellency and film strength.

[0244] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (C2) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, even more preferably 3000 or more, particularly preferably 3500 or more, and also preferably 30000 or less, more preferably 15000 or less, even more preferably 10000 or less, even more preferably 8000 or less, and particularly preferably 5000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 30000 is preferred, 1000 to 15000 is more preferred, 2000 to 10000 is even more preferred, 3000 to 8000 is even more preferred, and 3500 to 5000 is particularly preferred. Setting it above the lower limit tends to improve ink repellency and film strength. Setting it below the upper limit tends to reduce residue.

[0245] [Acrylic copolymer resin (C3)] The acrylic copolymer resin (C3) has an ethylenically unsaturated group in its side chain. By having an ethylenically unsaturated group, film loss due to an alkaline developer during development is less likely to occur due to photocuring by exposure, and the surface smoothness becomes good. Also, having a flexible main skeleton tends to improve the adhesion to the substrate.

[0246] (Repeating unit represented by general formula (1)) The partial structure including the side chain having an ethylenically unsaturated group that the acrylic copolymer resin (C3) has is not particularly limited, but from the viewpoints of the ease of radical divergence due to the flexibility of the film and the adhesion to the substrate, it preferably has a repeating unit represented by the following general formula (1).

[0247] [Chemical formula]

[0248] In formula (1), R a1 and R a2 each independently represent a hydrogen atom or a methyl group. * represents a bond.

[0249] Among the repeating units represented by formula (1), from the viewpoints of sensitivity and alkali developability, a repeating unit represented by the following general formula (1’) is preferable.

[0250] [[ID=二十九]] [Chemical formula]

[0251] In formula (1’), R a1 and R a2 each independently represent a hydrogen atom or a methyl group. R x represents a hydrogen atom or a polybasic acid residue.

[0252] The polybasic acid residue can preferably adopt those listed as R Y in formula (i - 1).

[0253] When the acrylic copolymer resin (C3) contains repeating units represented by formula (1), the content is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, and also preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, even more preferably 75 mol% or less, and particularly preferably 70 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 10 to 90 mol% is preferred, 20 to 85 mol% is preferred, 30 to 80 mol% is even preferred, even more preferably 40 to 75 mol%, and particularly preferably 50 to 70 mol%. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to reduce residue.

[0254] When the acrylic copolymer resin (C3) contains repeating units represented by general formula (1'), the content is not particularly limited, but preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, particularly preferably 35 mol% or more, and also preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 70 mol% or less, and particularly preferably 65 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 10 to 80 mol% is preferred, 20 to 80 mol% is more preferred, 25 to 75 mol% is even more preferred, 30 to 70 mol% is even more preferred, and particularly preferably 35 to 65 mol%. Setting the value above the lower limit tends to improve ink repellency. Setting the value below the upper limit tends to make it easier to ensure developable adhesion.

[0255] (The repeating unit represented by general formula (2)) When the acrylic copolymer resin (C3) contains repeating units represented by general formula (1), the other repeating units included are not particularly limited, but from the viewpoint of development adhesion, it is preferable to have repeating units represented by the following general formula (2).

[0256] [ka]

[0257] In formula (2), R a3 R represents a hydrogen atom or a methyl group. a4 This represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.

[0258] (R a4 ) In equation (2), R a4 This represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. R a4 Examples of alkyl groups include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 8 or more, and also 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 above upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 18 is preferred, 3 to 16 is even preferred, 5 to 14 is even more preferred, and 8 to 12 is particularly preferred. Setting the value above the lower limit tends to increase film strength and improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0259] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability, dicyclopentanyl or dodecanyl groups are preferred, and dicyclopentanyl groups are more preferred. Examples of the substituent that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxy group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

[0260] R a4 Examples of the aromatic ring group in include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less. The above upper and lower limits can be arbitrarily combined. For example, 6 to 24 is preferred, 6 to 22 is more preferred, 6 to 20 is still more preferred, and 6 to 18 is particularly preferred. By setting it to be not less than the lower limit value, the development adhesion tends to be improved. By setting it to be not more than the upper limit value, the residue tends to be reduced. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. The aromatic heterocyclic group can be a monocyclic or fused ring, and examples include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings. From the viewpoint of developability, benzene rings or naphthalene rings are preferred, and benzene rings are more preferred.

[0261] Examples of substituents that the aromatic ring group may have include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0262] R a4 Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, 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. Setting the value above the lower limit tends to improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0263] Examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0264] R a4 Of these, alkyl groups and alkenyl groups are preferred from the viewpoint of developability and film strength, and alkyl groups are more preferred.

[0265] When the acrylic copolymer resin (C3) contains repeating units represented by formula (2), the content is not particularly limited, but preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 70 mol% is preferred, 5 to 60 mol% is more preferred, 10 to 50 mol% is even more preferred, and particularly preferably 20 to 40 mol%. Setting the value above the lower limit tends to improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0266] (The repeating unit represented by general formula (3)) When the acrylic copolymer resin (C3) contains repeating units represented by formula (1), it is preferable that the other repeating units included also contain repeating units represented by the following general formula (3) from the viewpoint of heat resistance and film strength.

[0267] [ka]

[0268] In the above equation (3), R a5 R represents a hydrogen atom or a methyl group. a6represents an optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted alkynyl group, hydroxyl group, carboxyl group, halogen atom, optionally substituted alkoxy group, thiol group, or optionally substituted alkyl sulfide group. t represents an integer from 0 to 5.

[0269] (R a6 ) In equation (3), R a6 This represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group. R a6 Examples of alkyl groups include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or 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. The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 18 is more preferred, 3 to 16 is even more preferred, 3 to 14 is even more preferred, and 5 to 12 is particularly preferred. Setting the value above the lower limit tends to improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0270] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability and film strength, dicyclopentanyl and dodecanyl groups are preferred, and dicyclopentanyl groups are more preferred. Examples of substituents that the alkyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0271] R a6 Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, 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. Setting the value above the lower limit tends to improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0272] Examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0273] R a6 Examples of alkynyl groups include linear, branched, or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, 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. Setting the value above the lower limit tends to improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0274] Examples of substituents that the alkynyl group may have include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0275] R a6 Examples of halogen atoms in this product include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred from the viewpoint of developability.

[0276] R a6 Examples of alkoxy groups include linear, branched, or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or 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, 1 to 18 is more preferred, 1 to 16 is even more preferred, 1 to 14 is even more preferred, and 1 to 12 is particularly preferred. Setting the value above the lower limit tends to improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0277] Examples of substituents that the alkoxy group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, and methacryloyl groups, with hydroxy and oligoethylene glycol groups being preferred from the viewpoint of developability.

[0278] R a6 Examples of alkyl sulfide groups include linear, branched, or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or 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, 1 to 18 is more preferred, 1 to 16 is even more preferred, 1 to 14 is even more preferred, and 1 to 12 is particularly preferred. Setting the value above the lower limit tends to improve development adhesion. Setting the value below the upper limit tends to reduce residue.

[0279] Examples of substituents that the alkyl group in the alkyl sulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, and methacryloyl groups, with hydroxy and oligoethylene glycol groups being preferred from the viewpoint of developability.

[0280] R a6 Of these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0281] In equation (3), t represents an integer from 0 to 5, and from the viewpoint of ease of manufacturing, it is preferable that t is 0.

[0282] When the acrylic copolymer resin (C3) contains repeating units represented by formula (3), the content is not particularly limited, but it is preferably 0.5 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, and particularly preferably 5 mol% or more in the total repeating units. Also, it is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 0.5 to 50 mol% is preferred, more preferably 0.5 to 40 mol%, even more preferably 1 to 30 mol%, even more preferably 2 to 20 mol%, and particularly preferably 5 to 15 mol%. Setting it above the lower limit tends to improve development adhesion. Setting it below the upper limit tends to reduce residue.

[0283] (The repeating unit represented by general formula (4)) When the acrylic copolymer resin (C3) has repeating units represented by formula (1), it is preferable that the other repeating units included are those represented by the following general formula (4) from the viewpoint of developability.

[0284] [ka]

[0285] In the above equation (4), R a7 represents a hydrogen atom or a methyl group.

[0286] When the acrylic copolymer resin (C3) contains repeating units represented by formula (4), the content is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and also preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less in the total repeating units. The above upper and lower limits can be combined arbitrarily. For example, 5 to 80 mol% is preferred, 10 to 70 mol% is more preferred, and 20 to 60 mol% is even more preferred. There is a tendency for developability to improve when the value is above the lower limit. There is a tendency for developability to improve when the value is below the upper limit.

[0287] The acid value of the acrylic copolymer resin (C3) is not particularly limited, but is preferably 30 mg KOH / g or higher, more preferably 40 mg KOH / g or higher, even more preferably 50 mg KOH / g or higher, and even more preferably 60 mg KOH / g or higher. It is also preferably 150 mg KOH / g or lower, more preferably 140 mg KOH / g or lower, even more preferably 130 mg KOH / g or lower, and even more preferably 120 mg KOH / g or lower. The above upper and lower limits can be combined arbitrarily. For example, 30 to 150 mg KOH / g is preferred, 40 to 140 mg KOH / g is more preferred, 50 to 130 mg KOH / g is even more preferred, and 60 to 120 mg KOH / g is particularly preferred. Developability tends to improve when the value is above the lower limit. Developability tends to improve when the value is below the upper limit.

[0288] The weight-average molecular weight (Mw) of the acrylic copolymer resin (C3) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, even more preferably 4000 or more, even more preferably 6000 or more, particularly preferably 7000 or more, most preferably 8000 or more, and also preferably 30000 or less, more preferably 20000 or less, even more preferably 15000 or less, and particularly preferably 10000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 30000 is preferred, 2000 to 30000 is more preferred, 4000 to 20000 is even more preferred, 6000 to 20000 is even more preferred, 7000 to 15000 is especially preferred, and 8000 to 10000 is particularly preferred. Setting it above the lower limit tends to improve developability. Setting it below the upper limit tends to improve developability.

[0289] Examples of acrylic copolymer resins (C3) include the resins described in Japanese Patent Publication No. Hei 8-297366 and Japanese Patent Publication No. 2001-89533.

[0290] In the present invention, (C) the alkali-soluble resin may further include other alkali-soluble resins other than epoxy (meth)acrylate resin (C2) and acrylic copolymer resin (C3).

[0291] (C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and more preferably 60 mg KOH / g or more. It is also preferably 300 mg KOH / g or less, more preferably 200 mg KOH / g or less, even more preferably 100 mg KOH / g or less, and particularly preferably 80 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, 30 to 300 mg KOH / g is preferred, 30 to 200 mg KOH / g is preferred, 50 to 100 mg KOH / g is even more preferred, and 60 to 80 mg KOH / g is particularly preferred. Setting it above the lower limit tends to improve developability. Setting it below the upper limit tends to improve developability adhesion. (C) When the alkali-soluble resin is a mixture of two or more types, the acid value refers to the weighted average value according to the proportion of each type.

[0292] The content of (C) alkali-soluble resin in the photosensitive resin composition of the present invention 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, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, even more preferably 30% by mass or more, and especially preferably 40% by mass or more, relative to the total solid content of the photosensitive resin composition, and also preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 to 90% by mass is preferred, 10 to 90% by mass is more preferred, 15 to 90% by mass is even more preferred, 20 to 80% by mass is even more preferred, 30 to 80% by mass is particularly preferred, 35 to 70% by mass is even more preferred, and 40 to 60% by mass is particularly preferred. Setting it above the lower limit tends to reduce residue. Setting it below the upper limit tends to improve ink repellency.

[0293] The sum of the content of (A) the photopolymerizable compound and (C) the alkali-soluble resin in the total solid content of the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 60% by mass or more, particularly preferably 80% by mass or more, and also preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 10 to 95% by mass is preferred, 30 to 95% by mass is more preferred, 60 to 92% by mass is even more preferred, and 80 to 90% by mass is particularly preferred. Setting it above the lower limit tends to improve the adhesion of the partition wall to the substrate. Setting it below the upper limit tends to improve light shielding and ink repellency.

[0294] [1-1-4](D) Liquid repellent The photosensitive resin composition of the present invention contains (D) a liquid repellent, and a compound (D1) having a crosslinking group and a fluorine atom and / or a siloxane chain. By including the liquid repellent, ink-repellent properties can be imparted to the upper surface of the resulting partition, thereby preventing color mixing between pixels. Hereafter, compound (D1) will be referred to as follows: Compound (D1-1): Fluorine atom-containing resin having a crosslinking group, and / or Compound (D1-2): Resin containing a crosslinking group and a siloxane chain It is preferable that it includes.

[0295] <Compound (D1-1)> Examples of crosslinking groups include epoxy groups, ethylenically unsaturated groups, or active groups that generate radicals upon irradiation with active energy rays. Examples of active groups that generate radicals upon irradiation with active energy rays include benzophenone groups, acetophenone groups, α-hydroxyketone groups, α-aminoketone groups, α-diketone groups, and α-diketone dialkylacetal groups. Of these, α-hydroxyketone groups are preferred from the viewpoint of the overlap between the wavelength distribution of the light source used for exposure and the absorbance spectrum of the active group. As the crosslinking group, an ethylenically unsaturated group is preferred from the viewpoint of suppressing the leaching of the liquid repellent into the developer. By using a liquid repellent having crosslinking groups, the crosslinking reaction on the surface of the formed coating can be accelerated when the coating is exposed to light. This makes it less likely for the liquid repellent to wash out during the developing process, and as a result, the resulting partition wall can exhibit high ink repellency.

[0296] Compound (D1-1), which is a fluorine atom-containing resin, tends to orient itself on the surface of the partition wall, preventing ink bleeding and color mixing. More specifically, the groups containing fluorine atoms tend to repel ink, preventing ink bleeding and color mixing caused by ink penetrating beyond the partition wall into adjacent areas.

[0297] The fluorine atom-containing resin having a crosslinking group preferably has one or more of the following: a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group. A perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkylene ether chain, or a perfluoroaromatic group is preferred, and having a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkylene ether chain, or a perfluoroaromatic group is more preferable in terms of liquid repellency. Having one or more of the fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group makes it easier for the fluorine atom-containing resin to orient itself on the surface of the partition, resulting in higher ink repellency and a tendency to further prevent ink bleeding and color mixing.

[0298] Examples of per- or fluoroalkyl groups include per- or fluoromethyl groups, per- or fluoroethyl groups, per- or fluoropropyl groups, per- or fluorobutyl groups, and per- or fluorohexyl groups. Examples of per or fluoroalkylene chains include per or fluoromethylene chains, per or fluoroethylene chains, per or fluoropropylene chains, per or fluorobutylene groups, and per or fluorohexylene chains. Examples of perfluoroalkylene ether chains include -CF2-O-, -(CF2)2-O-, -(CF2)3-O-, -CF2-C(CF3)O-, -C(CF3)-CF2-O-, and divalent groups having repeating units of these. Examples of fluoroalkylene ether chains include fluoroalkylene ether chains in which some but not all of the F atoms in a perfluoroalkylene ether chain are replaced with H atoms. Examples of per- or fluoroaromatic groups include per- or fluorophenyl groups, per- or fluoronaphthyl groups, and per- or fluoroanthracyl groups.

[0299] Examples of fluorine atom-containing resins having crosslinking groups include acrylic copolymer resins having epoxy groups and perfluoroalkyl groups, acrylic copolymer resins having epoxy groups and perfluoroalkylene ether chains, acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkyl groups, acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene ether chains, epoxy (meth)acrylate resins having epoxy groups and perfluoroalkyl groups, epoxy (meth)acrylate resins having epoxy groups and perfluoroalkyl groups, epoxy (meth)acrylate resins having ethylenically unsaturated groups and perfluoroalkyl groups, and epoxy (meth)acrylate resins having ethylenically unsaturated groups and perfluoroalkylene ether chains. From the viewpoint of ink repellency, acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkyl groups, and acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene ether chains are preferred, and acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene ether chains are even more preferred.

[0300] Examples of commercially available fluorine atom-containing resins with crosslinking groups include, for example, DIC's "Megafac (registered trademark, hereinafter the same) F116", "Megafac F120", "Megafac F142D", "Megafac F144D", "Megafac F150", "Megafac F160", "Megafac F171", "Megafac F172", "Megafac F173", "Megafac F177", "Megafac F178A", "Megafac F178K", ​​"Megafac F179", "Megafac F183", "Megafac F184", "Megafac F191", and "Megafac F812". "Megafuck F815", "Megafuck F824", "Megafuck F833", "Megafuck RS101", "Megafuck RS102", "Megafuck RS105", "Megafuck RS201", "Megafuck RS202", "Megafuck RS301", "Megafuck RS303", "Megafuck RS304", "Megafuck RS401", "Megafuck RS402", "Megafuck RS501", "Megafuck RS502", "Megafuck RS-72-K", "Megafuck RS-78", "Megafuck RS-90", "DEFENSA (registered trademark, same applies hereinafter)" You can use fluorine-containing organic compounds that are commercially available under the product names "MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", "Florard FC430", "Florard FC431", "FC-4430", and "FC4432" from 3M Japan, and "Asahi Guard (registered trademark) AG710", "Surflon (registered trademark, same applies hereinafter) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", and "Surflon SC-106" from AGC Inc. "Megafac RS-72-K", "Megafac RS-78", and "Megafac RS-90" can be suitably used as acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene groups.

[0301] The fluorine atom content in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more. Also, 50% by mass or less is preferred, and 35% by mass or less is more preferred. The above upper and lower limits can be combined arbitrarily. For example, 5 to 50% by mass is preferred, 10 to 50% by mass is more preferred, 15 to 35% by mass is even more preferred, and 20 to 35% by mass is particularly preferred. Setting it above the lower limit tends to suppress outflow to the pixel area. Setting it below the upper limit tends to show a high contact angle.

[0302] The molecular weight of the fluorine atom-containing resin having a crosslinking group is not particularly limited, and it may be a low molecular weight compound or a high molecular weight compound. A high molecular weight compound is preferable because it suppresses bleed-out during development and fluidity during post-bake, and can suppress outflow from the septum. When the fluorine atom-containing resin having a crosslinking group is a high molecular weight compound, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 or more, more preferably 500 or more, and even more preferably 1000 or more. It is also preferably 150,000 or less, more preferably 130,000 or less, and even more preferably 100,000 or less. The above upper and lower limits can be arbitrarily combined. For example, 100 to 150,000 is preferred, 500 to 130,000 is more preferred, and 1,000 to 100,000 is even more preferred.

[0303] Furthermore, the weight-average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 1000 or more, more preferably 5000 or more, and even more preferably 10000 or more. It is also preferably 150000 or less, and even more preferably 130000 or less. The above upper and lower limits can be combined arbitrarily. For example, 1000 to 150000 is preferred, 5000 to 130000 is more preferred, and 10000 to 130000 is even more preferred.

[0304] <Compound (D1-2)> As the crosslinking group, the crosslinking group described in compound (D1-1) is preferably used.

[0305] The siloxane chain of compound (D1-2) is preferably a polysiloxane represented by the following general formula (d1-2). R 61 R 62 R 63 Si-O-(SiR 64 R 65 -O)n―SiR 66 R 67 R 68 (d1-2) In formula (d1-2), R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 Each of these independently represents a monovalent organic group or a hydrogen atom.

[0306] Preferably, the monovalent organic group is a hydrocarbon group having 1 to 10 carbon atoms, such as alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl groups; aryl groups such as phenyl, tolyl, and xylyl groups; aralkyl groups such as benzyl and phenethyl groups; and substituted alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and nonafluorobutylethyl groups. These organic groups may also have ester bonds.

[0307] n is an integer greater than or equal to 0, preferably 5 or more, more preferably 10 or more, preferably 2000 or less, more preferably 1500 or less, even more preferably 1000 or less, even more preferably 500 or less, and particularly preferably 300 or less. The above upper and lower limits can be combined arbitrarily. For example, preferably 5 to 2000, more preferably 5 to 1500, even more preferably 5 to 1000, even more preferably 10 to 500, and particularly preferably 10 to 300. Setting it above the lower limit tends to increase ink repellency. Setting it below the upper limit tends to increase the uniformity of the coating film.

[0308] Commercially available resins containing crosslinking groups and siloxane chains include, for example, compounds sold under the product names "BYK-UV3500 series" by BYK Chemie Inc. and "8SS" series by Taisei Fine Chemical Co., Ltd.

[0309] Examples of compounds that have a crosslinking group and also contain fluorine atoms and siloxane chains include the "8FS" series manufactured by Taisei Fine Chemical Co., Ltd. and the "KP series" manufactured by Shin-Etsu Chemical Co., Ltd., which are commercially available.

[0310] Compound (D1) may be a compound containing both a fluorine atom and a siloxane chain in a single molecule, and multiple compounds (D1) may be used in mixture form.

[0311] The content ratio of (D) liquid repellent 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, even more preferably 0.1% by mass or more, and also preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 0.01 to 5% by mass is preferred, 0.05 to 3% by mass is more preferred, and 0.1 to 2% by mass is even more preferred. Setting it above the lower limit tends to improve ink repellency. Setting it below the upper limit tends to make it easier to obtain a uniform coating film when applying ink to the pixel area after partition formation.

[0312] The content of compound (D1) 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, even more preferably 0.1% by mass or more, and also preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 0.01 to 5% by mass is preferred, 0.05 to 3% by mass is more preferred, and 0.1 to 2% by mass is even more preferred. Setting it above the lower limit tends to improve ink repellency. Setting it below the upper limit tends to make it easier to obtain a uniform coating film when applying ink to the pixel portion after partition formation.

[0313] When the photosensitive resin composition of the present invention contains compound (D1-1), the content ratio of compound (D1-1) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 0.01 to 5% by mass is preferred, 0.05 to 3% by mass is more preferred, and 0.1 to 2% by mass is even more preferred. Setting it above the lower limit tends to improve ink repellency. Setting it below the upper limit tends to make it easier to obtain a uniform coating film when applying ink to the pixel portion after partition formation.

[0314] When the photosensitive resin composition of the present invention contains compound (D1-2), the content ratio of compound (D1-2) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and also preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 0.1 to 5% by mass is preferred, 0.2 to 3% by mass is more preferred, and 0.5 to 2% by mass is even more preferred. Setting it above the lower limit tends to improve ink repellency. Setting it below the upper limit tends to make it easier to obtain a uniform coating film when applying ink to the pixel portion after partition formation.

[0315] In the photosensitive resin composition of the present invention, a surfactant may be used together with (D) the liquid repellent. The surfactant can be used, for example, to improve the applicability of the photosensitive resin composition as a coating liquid and the developability of the coating film, and examples include fluorine-based surfactants and silicone-based surfactants that do not have crosslinking groups. In particular, silicone-based surfactants are preferred, and polyether-modified silicone-based surfactants are even more preferred, because they have the effect of removing residue of the photosensitive resin composition from unexposed areas during development and also have the function of exhibiting wettability.

[0316] As fluorine-based surfactants that do not have crosslinking groups, compounds having a fluoroalkyl or fluoroalkylene group at least one of the terminal, main chain, or side chains are preferred. Examples of commercially available fluorine-based surfactants that do not have crosslinking groups include BM Chemie's "BM-1000" and "BM-1100," DIC's "Megafac F142D," "Megafac F172," "Megafac F173," "Megafac F183," "Megafac F470," "Megafac F475," "Megafac F554," and "Megafac F559," 3M Japan's "FC430," and Neos' "DFX-18."

[0317] Examples of commercially available silicone-based surfactants include "DC3PA," "SH7PA," "DC11PA," "SH21PA," "SH28PA," "SH29PA," "8032Additive," and "SH8400" from Toray Dow Corning, and "BYK(registered trademark, hereinafter the same) 323" and "BYK330" from BIC Chemie.

[0318] The surfactant may include surfactants other than fluorine-based surfactants and silicone-based surfactants. Examples of surfactants include nonionic, anionic, cationic, and amphoteric surfactants.

[0319] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin 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. Examples of these commercially available products include polyoxyethylene-based surfactants such as Kao Corporation's "Emulgen (registered trademark, hereinafter the same) 104P" and "Emulgen A60".

[0320] 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 polymer surfactants. Among these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are even more preferred. Examples of commercially available products include, among alkyl sulfate salts, Kao Corporation's "Emal (registered trademark, hereinafter the same) 10", among alkylnaphthalene sulfonates, Kao Corporation's "Perex (registered trademark) NB-L", and among special polymer surfactants, Kao Corporation's "Homogenol (registered trademark, hereinafter the same) L-18" and "Homogenol L-100".

[0321] Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are even more preferred. Examples of commercially available products include, for alkylamine salts, "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and for quaternary ammonium salts, "Cotamin (registered trademark, hereinafter the same) 24P" and "Cotamin 86W" manufactured by Kao Corporation. Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, and amino acids.

[0322] Surfactants may be used individually or in combination of two or more types. For example, combinations include a silicone-based surfactant and a fluorine-based surfactant, a silicone-based surfactant and a special polymer-based surfactant, and a fluorine-based surfactant and a special polymer-based surfactant, with the combination of a silicone-based surfactant and a fluorine-based surfactant being preferred.

[0323] Examples of combinations of silicone-based surfactants and fluorine-based surfactants include: combinations of Neos' "DFX-18", Big Chemie's "BYK-300" or "BYK-330" with AGC Seimi Chemical's "S-393"; combinations of Shin-Etsu Silicone's "KP340" with DIC's "F-554" or "F-559"; combinations of Toray Dow Corning's "SH7PA" with Daikin's "DS-401"; and combinations of NUC's "L-77" with 3M Japan's "FC4430".

[0324] [1-1-5](E) Coloring agent The photosensitive resin composition of the present invention may further contain (E) a coloring agent. By including (E) a coloring agent, appropriate light absorption can be obtained, and in particular, appropriate light shielding can be obtained when used in applications to form light-shielding members including colored partitions. Furthermore, when used in applications where light scattering is the objective, good light scattering can be obtained by using a white coloring agent.

[0325] The type of colorant (E) used in the present invention is not particularly limited, and pigments or dyes may be used. From the viewpoint of durability, it is preferable to use pigments.

[0326] (E) The colorant may contain one or more pigments. In particular, from the viewpoint of uniformly blocking light in the visible region, it is preferable to have two or more pigments. (E) The types of pigments that can be used as colorants are not particularly limited, but examples include organic pigments and inorganic pigments. When light shielding is the objective, it is preferable to use organic pigments from the viewpoint of controlling the transmission wavelength of the photosensitive resin composition to cure it efficiently. Examples of organic pigments include organic colored pigments and organic black pigments. Here, organic colored pigments refer to organic pigments that exhibit colors other than black, such as red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

[0327] Among organic pigments, it is preferable to use organic coloring pigments from the viewpoint of ultraviolet absorption. Organic coloring pigments may be used individually or in combination of two or more. When used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments of different colors, and even more preferable to use a combination of organic coloring pigments that produce a color close to black.

[0328] The chemical structures of these organic pigments are not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolon, isoindolinone, dioxazine, indanthrene, and perylene pigments. Specific examples of usable pigments are shown below by their pigment numbers. Terms such as "CI Pigment Red 2" below refer to the Color Index (CI).

[0329] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53 :3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 2 We can list 35, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, and 276. From the viewpoint of light-shielding and dispersive properties, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254 are preferred, and CI Pigment Red 177, 209, 224, and 254 are more preferred. In terms of dispersibility and light-shielding properties, CI Pigment Red 177, 254, and 272 are preferred. When curing a photosensitive resin composition with ultraviolet light, it is preferable to use a red pigment with a low ultraviolet absorption rate, and from this viewpoint, CI Pigment Red 254 and 272 are preferred.

[0330] Examples of orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. From the viewpoint of dispersibility and light-shielding properties, CI pigment oranges 13, 43, 64, and 72 are preferred, and CI pigment oranges 43, 64, and 72 are more preferred. When curing the photosensitive resin composition with ultraviolet light, it is preferable to use an orange pigment with a low ultraviolet absorption rate, and from this viewpoint, CI pigment oranges 64 and 72 are preferred.

[0331] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. From the viewpoint of light-blocking properties, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, with CI Pigment Blue 15:6 being more preferred. In terms of dispersibility and light-shielding properties, CI Pigment Blue 15:6, 16, and 60 are preferred, with CI Pigment Blue 15:6 and 60 being more preferred. When curing the photosensitive resin composition with ultraviolet light, it is preferable to use a blue pigment with a low ultraviolet absorption rate, and from this viewpoint, CI Pigment Blue 60 is more preferred.

[0332] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. From the viewpoint of light-shielding properties, CI pigment violet 19 and 23 are preferred, and CI pigment violet 23 is more preferred. In terms of dispersibility and light-shielding properties, CI pigment violet 23 and 29 are preferred. When curing the photosensitive resin composition with ultraviolet light, it is preferable to use a purple pigment with a low ultraviolet absorption rate, and from this viewpoint, CI pigment violet 29 is preferred.

[0333] In addition to red, orange, blue, and purple pigments, other organic coloring pigments that can be used include, for example, green and yellow pigments.

[0334] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55, with CI Pigment Green 7 and 36 being preferred.

[0335] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 8 1, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 15 7, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, Examples include 198, 199, 200, 202, 203, 204, 205, 206, 207, and 208, with CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 being more preferred, and CI Pigment Yellow 83, 138, 139, 150, and 180 being even more preferred.

[0336] From the viewpoint of light-shielding properties and ink-repellent properties, it is preferable to use at least one pigment selected from the group consisting of red pigment, orange pigment, blue pigment, and purple pigment.

[0337] From the viewpoint of light-shielding properties and ink-repellent properties, it is preferable to include at least one of the following pigments. Red pigments: CI Pigment Red 177, 254, 272 Orange pigment: CI Pigment Orange 64, 72 Blue pigment: CI Pigment Blue 15: 6, 16, 60 Purple pigment: CI Pigment Violet 23, 29

[0338] When two or more organic coloring pigments are used in combination, there are no particular limitations on the combination of organic coloring pigments, but from the viewpoint of light shielding, it is preferable that (E) the coloring agent contains at least one selected from the group consisting of red pigments and orange pigments, and at least one selected from the group consisting of blue pigments and purple pigments. While there are no particular limitations on the color combinations, from the standpoint of light-blocking properties, examples include combinations of red and blue pigments, blue and orange pigments, and blue, orange, and purple pigments.

[0339] From the viewpoint of blocking blue light, it is preferable that (E) the coloring agent contains a purple pigment.

[0340] From the viewpoint of light shielding, it is preferable to use an organic black pigment as the (E) coloring agent. In particular, from the viewpoint of suppressing the absorption of ultraviolet light and improving ink repellency, it is preferable to use an organic black pigment (hereinafter sometimes referred to as "organic black pigment represented by general formula (A)") that includes at least one selected from the group consisting of a compound represented by the following general formula (A) (hereinafter also referred to as "compound (A)"), a geometric isomer of compound (A), a salt of compound (A), and a salt of a geometric isomer of compound (A).

[0341] [ka]

[0342] In formula (A), R 11 and R 16 Each of these independently represents a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom; R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 Each of them independently consists of a hydrogen atom, a halogen atom, and R 21 COOH, COOR 21 COO - CONH2, CONHR21 CONR 21 R 22 , CN, OH, OR 21 COCR 21 , OOCNH2, OOCNHR 21 , OOCNR 21 R 22 NO2, NH2, NHR 21 , NR 21 R 22 , NHCOR 22 , NR 21 COR 22 N=CH2, N=CHR 21 N=CR 21 R 22 SH, SR 21 SOR 21 SO2R 21 SO3R 21 SO3H, SO3 - SO2NH2, SO2NHR 21 Or SO2NR 21 R 22 It represents; R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 At least one combination selected from the group consisting of these elements may be directly bonded to each other, or it may consist of an oxygen atom, a sulfur atom, NH, or NR. 21 They can also be connected to each other by bridges; R 21 and R 22 Each of these is independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

[0343] Compound (A) and its geometric isomers have the following core structure (with substituents omitted from the structural formulas), and the trans-trans isomer is probably the most stable.

[0344] [ka]

[0345] If compound (A) is anionic, it is preferable that its charge is compensated by any known suitable cation, such as a metal, organic, inorganic, or metal-organic cation, specifically alkali metals, alkaline earth metals, transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Furthermore, if the geometric isomer of compound (A) is anionic, it is preferable that it be a similar salt.

[0346] In the substituents of general formula (A) and their definitions, the following are preferred because they tend to increase the shielding rate. This is because the following substituents do not absorb and are not thought to affect the hue of the pigment. R 12 , R 14 , R 15 , R 17 , R 19 and R 20 Each of these atoms is independently preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom. R 13 and R 18 Each of these is independently preferably a hydrogen atom, NO2, OCH3, OC2H5, a bromine atom, a chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H, or SO3 - It is more preferably a hydrogen atom or SO3H, and particularly preferably a hydrogen atom.

[0347] R 11 and R 16Each of these is independently preferably a hydrogen atom, CH3, or CF3, and more preferably a hydrogen atom. Preferably, R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 At least one combination selected from the group consisting of is identical, and more preferably, R 11 is R 16 It is identical to R 12 is R 17 It is identical to R 13 is R 18 It is identical to R 14 is R 19 It is identical to and R 15 is R 20 It is identical to [the other one].

[0348] Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl, and dodecyl groups.

[0349] Examples of cycloalkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thuzyl, norbornyl, bornyl, norcalyl, calyl, menthyl, norpinyl, pinyl, adamantane-1-yl, and adamantane-2-yl groups.

[0350] Alkenyl groups having 2 to 12 carbon atoms include, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadiene-3-yl, hexenyl, octenyl, nonenyl, decenyl, and dodecenyl groups.

[0351] Examples of cycloalkenyl groups having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadiene-1-yl, 1-p-menten-8-yl, 4(10)-thujen-10-yl, 2-norbornene-1-yl, 2,5-norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaladien-3-yl, and camphenyl.

[0352] Alkynyl groups having 2 to 12 carbon atoms include, for example, 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butyne-2-yl group, 1,4-pentadiiin-3-yl group, 1,3-pentadiiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-in-1-yl group, trans-3-methyl-2-penten-4-in-1-yl group, 1,3-hexadiiin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decine-10-yl group, and 1-dodecine-12-yl group.

[0353] Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

[0354] The organic black pigment represented by general formula (A) is preferably an organic black pigment that includes at least one selected from the group consisting of a compound represented by the following general formula (B) (hereinafter also referred to as "compound (B)") and geometric isomers of compound (B).

[0355] [ka]

[0356] An example of such an organic black pigment is Irgaphor® Black S 0100 CF (manufactured by BASF). This organic black pigment is preferably dispersed and used by a dispersant, solvent, and method described later. The presence of sulfonic acid derivatives of compound (A), particularly sulfonic acid derivatives of compound (B), during dispersion may improve dispersibility and storage properties; therefore, it is preferable that the organic black pigment contains these sulfonic acid derivatives.

[0357] Examples of organic black pigments other than the organic black pigment represented by formula (A) include aniline black and perylene black.

[0358] Other colorants besides these organic pigments include inorganic black pigments. In addition to organic pigments, inorganic black pigments may also be used.

[0359] Examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black is preferably used from the viewpoint of light-shielding properties. Examples of carbon black include the following:

[0360] Mitsubishi Chemical Corporation products: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, # 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #31 50, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Manufactured by Degussa: Printex (registered trademark, same hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 Cabot Corporation: Monarch (registered trademark, same applies hereafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 13 00, Monarch1400, Monarch4630, REGAL (registered trademark, same hereinafter) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL550R, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, same hereinafter) XC72R, ELFTEX (registered trademark)-8 Biller Co., Ltd.: RAVEN (registered trademark, same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0361] Carbon black coated with resin may be used. Using resin-coated carbon black has the effect of improving adhesion to the glass substrate and volume resistivity. Suitable resin-coated carbon black includes, for example, the carbon black described in Japanese Patent Publication No. 09-71733. Resin-coated carbon black is preferred in terms of volume resistivity and dielectric constant.

[0362] These organic and inorganic pigments are preferably used in a dispersed manner such that the average particle size is typically 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the criterion for the average particle size is the number of pigment particles. The average particle size of the pigment is determined from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is performed on a sufficiently diluted photosensitive resin composition (usually diluted to a pigment concentration of approximately 0.005-0.2% by mass; however, if a concentration is recommended by the measuring instrument, that concentration should be followed) and measured at 25°C.

[0363] In addition to organic pigments and inorganic black pigments, dyes may also be used. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0364] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0365] Examples of anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60. An example of a phthalocyanine-based dye is CI Bat Blue 5. Examples of quinone imine dyes include CI Basic Blue 3 and CI Basic Blue 9. Examples of quinoline-based dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64. Examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0366] When the photosensitive resin composition of the present invention contains (E) a colorant, the content ratio of (E) the colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 4% by mass or more, and also preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, particularly preferably 12% by mass or less, and most preferably 10% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 50% by mass is preferred, 1 to 30% by mass is more preferred, 2 to 20% by mass is even more preferred, 2 to 15% by mass is even more preferred, 3 to 12% by mass is especially preferred, and 4 to 10% by mass is particularly preferred. Setting it above the lower limit tends to ensure light-shielding properties. Setting it below the upper limit tends to improve the curability and ink-repellent properties of the coating film because the alkali-soluble resin and photopolymerizable compound can be relatively increased.

[0367] For the purpose of light scattering, (E) a white pigment (E2) may be used in part or in whole. Examples of white pigments (E2) include metal oxides such as titanium dioxide, zirconium oxide, hafnium oxide, and barium titanate, as well as inorganic fillers such as calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate. White pigment (E2) may be used alone or in combination of two or more types.

[0368] From the viewpoint of refractive index and light scattering properties, it is preferable to use metal oxides, with titanium oxide, zirconium oxide, and hafnium oxide being more preferable, and titanium oxide being even more preferable.

[0369] When the photosensitive resin composition of the present invention contains a white pigment (E2), the amount is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 4% by mass or more, and also preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less, based on the total solid content of the photosensitive resin composition. The above upper and lower limits can be combined arbitrarily. For example, 1 to 50% by mass is preferred, 1 to 30% by mass is more preferred, 2 to 20% by mass is even more preferred, 3 to 15% by mass is even more preferred, and 4 to 10% by mass is particularly preferred. Setting the value above the lower limit tends to improve refractive index and light scattering properties. Setting the value below the upper limit can increase the transmittance in the ultraviolet range, and tends to improve the curability and ink repellency of the coating film.

[0370] [1-1-6](F) Dispersant If the photosensitive resin composition of the present invention contains (E) a coloring agent, it may also contain (F) a dispersant in order to finely disperse the (E) coloring agent and stabilize its dispersion state. (F) As a dispersant, polymeric dispersants having functional groups are preferred, and from the viewpoint of dispersion stability, polymeric dispersants having, for example, carboxyl groups, phosphate groups, sulfonic acid groups or their bases; primary, secondary, or tertiary amino groups; quaternary ammonium bases; or nitrogen-containing heterocycle-derived groups such as pyridine, pyrimidine, and pyrazine are preferred. From the viewpoint that pigments can be dispersed with a small amount of dispersant, polymeric dispersants having basic functional groups such as primary, secondary, or tertiary amino groups; quaternary ammonium bases; or nitrogen-containing heterocycle-derived groups such as pyridine, pyrimidine, and pyrazine are particularly preferred.

[0371] Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of monomers and macromonomers having amino groups, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants.

[0372] Examples of such dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Bic Chemie), Disparon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Adisper (registered trademark, manufactured by Ajinomoto Co., Ltd.). The polymer dispersant may be used alone or in combination of two or more types.

[0373] The weight-average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1000 or more, and also preferably 100000 or less, and more preferably 50000 or less. The above upper and lower limits can be combined arbitrarily. For example, 700 to 100000 is preferred, and 1000 to 50000 is more preferred.

[0374] From the viewpoint of pigment dispersibility, the (F) dispersant preferably contains either one or both of a urethane-based polymer dispersant and an acrylic-based polymer dispersant having functional groups, and is particularly preferably an acrylic-based polymer dispersant. From the standpoint of dispersibility and storage properties, polymeric dispersants having basic functional groups and having either polyester bonds or polyether bonds, or both, are preferred.

[0375] Examples of urethane-based and acrylic polymer dispersants include the DISPERBYK-160~167 and 182 series (all urethane-based), and DISPERBYK-2000, 2001, and BYK-LPN21116 (all acrylic-based) (all manufactured by Bic Chemie Co., Ltd.). Examples of urethane-based polymer dispersants include dispersion resins with a weight-average molecular weight of 1,000 to 200,000, obtained by reacting a polyisocyanate compound with a compound having one or two hydroxyl groups in the same molecule and a number-average molecular weight of 300 to 10,000, and a compound having active hydrogen and a tertiary amino group in the same molecule. By treating these with a quaternizing agent, such as benzyl chloride, all or part of the tertiary amino groups can be converted into quaternary ammonium bases.

[0376] Polyisocyanate compounds include aromatic diisocyanates such as paraphenylenediisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate, naphthalene-1,5-diisocyanate, and tolidinediisocyanate; aliphatic diisocyanates such as hexamethylenediisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylenediisocyanate, and dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and ω,ω'-diisocyanate dimethylcyclo Examples include alicyclic diisocyanates such as hexane, aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate; triisocyanates such as lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate-methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanate-phenylmethane), and tris(isocyanate-phenyl)thiophosphate; trimers of these, hydrate adducts of these, and polyol adducts of these. As for polyisocyanates, trimers of organic diisocyanates are preferred, and trimers of tolylene diisocyanate and trimers of isophorone diisocyanate are particularly preferred. Polyisocyanate compounds may be used individually or in combination of two or more.

[0377] One method for producing isocyanate trimers involves partially trimerizing the isocyanate groups of polyisocyanates using a suitable trimerizing catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, or carboxylate salts. After stopping the trimerization by adding a catalyst poison, the unreacted polyisocyanate is removed by solvent extraction or thin-film distillation to obtain the desired isocyanurate-containing polyisocyanate.

[0378] Compounds with a number-average molecular weight of 300 to 10000 that have one or two hydroxyl groups in the same molecule include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols, and compounds in which one of the terminal hydroxyl groups of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms, as well as mixtures of two or more of these. Examples of polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols include polyether diols obtained by polymerization of alkylene oxides alone or copolymerized, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more of these.

[0379] Examples of polyether ester diols include polyether ester diols obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or its anhydride, or by reacting a polyester glycol with an alkylene oxide, such as poly(polyoxytetramethylene) adipate. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds of these compounds in which one terminal hydroxyl group is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

[0380] Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol) Polyester glycols obtained by polycondensation of aliphatic glycols such as 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and N-alkyldialkanolamines such as N-methyldiethanolamine, for example polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or polylactone diols or polylactone monools obtained using the aforementioned diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, for example polycaprolactone glycol, polymethylvalerolactone, and mixtures of two or more of these. Polycaprolactone glycol and polycaprolactone initiated with alcohols having 1 to 25 carbon atoms are particularly preferred as polyester glycols.

[0381] Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, while examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol.

[0382] Compounds having one or two hydroxyl groups within the same molecule and a number-average molecular weight of 300 to 10000 may be used individually or in combination of two or more.

[0383] The number-average molecular weight of compounds having one or two hydroxyl groups within the same molecule is preferably 300 to 10000, more preferably 500 to 6000, and even more preferably 1000 to 4000.

[0384] In compounds having active hydrogen and a tertiary amino group within the same molecule, examples of hydrogen atoms directly bonded to the active hydrogen, i.e., the oxygen atom, nitrogen atom, or sulfur atom, include hydrogen atoms in functional groups such as hydroxyl groups, amino groups, and thiol groups, with hydrogen atoms of amino groups, particularly primary amino groups, being preferred.

[0385] The tertiary amino group is not particularly limited, but examples include an amino group having an alkyl group with 1 to 4 carbon atoms, or a heterocyclic structure. Examples of heterocyclic structures include an imidazole ring and a triazole ring.

[0386] Examples of compounds having active hydrogen and a tertiary amino group within the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, and N,N-dibutyl-1,4-butanediamine.

[0387] Examples of nitrogen-containing heterocyclic rings when the tertiary amino group has a nitrogen-containing heterocyclic structure include five-membered nitrogen-containing rings such as pyrazole rings, imidazole rings, triazole rings, tetrazole rings, indole rings, carbazole rings, indazole rings, benzimidazole rings, benzotriazole rings, benzoxazole rings, benzothiazole rings, and benzothiadiazole rings, as well as six-membered nitrogen-containing rings such as pyridine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, acridine rings, and isoquinoline rings, with imidazole rings and triazole rings being preferred.

[0388] Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole. Examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, and 3-amino-1-benzyl-1H-2,4-triazole. N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole are preferred. Compounds having an imidazole ring or a triazole ring and an amino group may be used individually or in combination of two or more.

[0389] The preferred blending ratio of raw materials when manufacturing a urethane polymer dispersant is 100 parts by mass of polyisocyanate compound, 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, of a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10000, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, of a compound having active hydrogen and a tertiary amino group in the same molecule.

[0390] The urethane polymer dispersant can be manufactured according to known methods for the manufacture of polyurethane resins. Suitable solvents for this manufacture include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; hydrocarbons such as benzene, toluene, xylene, and hexane; certain alcohols such as diacetone alcohol, isopropanol, decantorhinol, and tertianorhinol; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. The solvent may be used alone or in combination of two or more solvents.

[0391] In the production of urethane polymer dispersants, for example, a urethane reaction catalyst is used. Examples of urethane reaction catalysts include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stanus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine. The urethane reaction catalyst may be used alone or in combination of two or more types.

[0392] The amount of compound containing active hydrogen and a tertiary amino group within the same molecule should be controlled by the amine value after the reaction, preferably in the range of 1 to 100 mg KOH / g, more preferably in the range of 5 to 95 mg KOH / g. The amine value is the value obtained by titrating the basic amino group with an acid and expressing it in mg of KOH corresponding to the acid value. Setting it above the lower limit tends to improve dispersion ability. Setting it below the upper limit tends to improve developability.

[0393] If isocyanate groups remain in the polymer dispersant, it is preferable to deactivate the isocyanate groups with an alcohol or amino compound, as this improves the long-term stability of the product.

[0394] The weight-average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. Setting it above the lower limit tends to improve dispersibility and dispersion stability. Setting it below the upper limit tends to improve solubility and dispersibility.

[0395] As an acrylic polymer dispersant, it is preferable to use a random copolymer, graft copolymer, or block copolymer of an unsaturated group-containing monomer having a functional group (the functional group referred to here is the functional group described above as a functional group contained in the polymer dispersant) and an unsaturated group-containing monomer without a functional group. These copolymers can be produced by known methods.

[0396] Examples of unsaturated monomers containing functional groups include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, acrylate dimers, and other unsaturated monomers having carboxyl groups, as well as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and their quaternary derivatives, and other unsaturated monomers having tertiary amino groups and quaternary ammonium bases. Monomers containing functional groups and unsaturated groups may be used individually or in combination of two or more.

[0397] Examples of unsaturated monomers without functional groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecane (meth)acrylate. Examples of macromonomers include acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-substituted maleimides such as N-cyclohexyl maleimide, N-phenyl maleimide, and N-benzyl maleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly-2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, and polycaprolactone macromonomers. Monomers containing unsaturated groups but lacking functional groups may be used individually or in combination of two or more.

[0398] The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block not having a functional group. In this case, the A block may contain not only substructures derived from unsaturated group-containing monomers containing the above-mentioned functional groups, but also substructures derived from unsaturated group-containing monomers not containing the above-mentioned functional groups, and these may be contained in the A block in either a random copolymerization or a block copolymerization. The content of functional group-free substructures in block A is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0399] Block B consists of substructures derived from unsaturated monomers that do not contain the above-mentioned functional groups, but a single Block B may contain substructures derived from two or more monomers, and these may be contained in Block B in either a random copolymerization or a block copolymerization manner.

[0400] AB or BAB block copolymers are prepared, for example, by the living polymerization method described below. Living polymerization methods include anionic living polymerization, cationic living polymerization, and radical living polymerization.

[0401] When synthesizing this acrylic polymer dispersant, for example, Japanese Patent Application Publication No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GDAndrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977(1985), Polym. J. 18, 1037(1986), Koichi Miji, Koichi Hatada, Polymer Processing, 36, 366(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189(1989), M.Kuroki, T.Aida, J. Am. Chem. Soc, 109, The methods described in 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985), and DYSogoh, WRHertler et al, Macromolecules, 20, 1473 (1987) can be employed.

[0402] The acrylic polymer dispersant that can be used in the present invention may be either an AB block copolymer or a BAB block copolymer, and the A block / B block ratio constituting the copolymer is preferably 1 / 99 to 80 / 20 (mass ratio), and more preferably 5 / 95 to 60 / 40 (mass ratio). By keeping it within the above range, it tends to be possible to ensure a balance between dispersibility and storage stability. The amount of quaternary ammonium base in 1 g of the AB block copolymer or BAB block copolymer used in the present invention is preferably 0.1 to 10 mmol. Keeping it within this range tends to ensure good dispersibility.

[0403] If the block copolymer contains amino groups generated during the manufacturing process, the amine value is preferably 1 to 100 mg KOH / g, and from the viewpoint of dispersibility, preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 50 mg KOH / g or more, and also preferably 90 mg KOH / g or less, more preferably 80 mg KOH / g or less, and even more preferably 75 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 100 mg KOH / g is preferred, 10 to 90 mg KOH / g is more preferred, 30 to 80 mg KOH / g is even more preferred, and 50 to 75 mg KOH / g is particularly preferred. The amine value of dispersants such as block copolymers is expressed as the amount of base and the equivalent amount of KOH per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Accurately weigh 0.5 to 1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, neutralize and titrate this solution with 0.1 mol / L HClO4 acetic acid solution. The inflection point of the titration pH curve is defined as the titration endpoint, and the amine value is determined by the following formula.

[0404] Amine value [mgKOH / g] = (561 × V) / (W × S) [where W: amount of dispersant sample weighed [g], V: titration volume at the titration endpoint [mL], and S: solid content concentration of the dispersant sample [mass%]].

[0405] The acid value of the block copolymer depends on the presence and type of acidic groups that give rise to the acid value, but a lower value is preferable, and preferably 10 mg KOH / g or less. The weight-average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. Keeping it within this range tends to ensure good dispersibility.

[0406] When a quaternary ammonium base is used as a functional group, the specific structure of the polymeric dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferable to have a repeating unit represented by the following general formula (ri) (hereinafter sometimes referred to as "repeating unit (ri)").

[0407] [ka]

[0408] In equation (ri), R 31 ~R 33 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; R 31 ~R 33 Two or more of these may be joined together to form a ring structure; R 34 is a hydrogen atom or a methyl group; X is a divalent linking group; Y - It is an anti-anion.

[0409] R in equation (ri) 31 ~R 33 The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is preferably 1 or more, preferably 10 or less, and more preferably 6 or less. For example, 1 to 10 is preferred, and 1 to 6 is more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, with methyl, ethyl, propyl, butyl, pentyl, and hexyl groups being preferred, and methyl, ethyl, propyl, and butyl groups being more preferred. Alkyl groups may be linear or branched. They may also include cyclic structures, such as cyclohexyl and cyclohexylmethyl groups.

[0410] R in equation (ri) 31 ~R 33 The number of carbon atoms in the aryl group, which may have substituents, is not particularly limited, but is preferably 6 or more, preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 is preferred, and 6 to 12 is more preferred. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl groups being preferred, and phenyl, methylphenyl, and ethylphenyl groups being more preferred.

[0411] R in equation (ri) 31 ~R 33 The number of carbon atoms in the aralkyl group, which may have substituents, is not particularly limited, but is preferably 7 or more, preferably 16 or less, and more preferably 12 or less. For example, 7 to 16 is preferred, and 7 to 12 is more preferred. Examples of aralkyl groups include phenylmethyl (benzyl) group, phenylethyl (phenethyl) group, phenylpropyl group, phenylbutyl group, and phenylisopropyl group, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl groups being preferred, and phenylmethyl and phenylethyl groups being more preferred.

[0412] From the perspective of variance, R 31 ~R 33 Each of these is preferably an alkyl group or an aralkyl group, 31and R 33 Each of them is independently a methyl group or an ethyl group, and R 32 It is more preferable that R is a phenylmethyl group or a phenylethyl group. 31 and R 33 is a methyl group, and R 32 It is even more preferable that the group is a phenylmethyl group.

[0413] When a polymeric dispersant has a tertiary amine as a functional group, it is preferable from the viewpoint of dispersibility to have a repeating unit represented by the following general formula (r-ii) (hereinafter sometimes referred to as "repeating unit (r-ii)").

[0414] [ka]

[0415] In formula (r-ii), R 35 and R 36 Each of these is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; R 35 and R 36 They may also combine with each other to form a ring structure; R 37 is a hydrogen atom or a methyl group; Z is a divalent linking group.

[0416] R in equation (r-ii) 35 and R 36 In this context, an alkyl group which may have substituents is R of formula (ri). 31 ~R 33 The examples provided can be preferably adopted. R in equation (r-ii) 35 and R 36 In this, the optionally substituted aryl group is R of formula (ri). 31 ~R 33 The examples provided can be preferably adopted. R in equation (r-ii)35 and R 36 In this, the aralkyl group which may have substituents is R of formula (ri). 31 ~R 33 The examples provided can be preferably adopted.

[0417] R 35 and R 36 Each of these is preferably an alkyl group which may have substituents, and more preferably a methyl group or an ethyl group.

[0418] R in equation (ri) 31 ~R 33 and R in equation (r-ii) 35 and R 36 Examples of substituents that the alkyl group, aralkyl group, or aryl group in the compound may have include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups.

[0419] In formulas (ri) and (r-ii), the divalent linking groups X and Z are, for example, alkylene groups having 1 to 10 carbon atoms, arylene groups having 6 to 12 carbon atoms, and -CONH-R 43 -group, -COOR 44 -Base (however, R 43 and R 44 The group is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms. Examples include -COO-R 44 - It is the basis. In equation (ri), the pair anion Y - For example, Cl - , Br - , I - ClO4 - BF4 - CH3COO - PF6 - These are some examples.

[0420] The content of the repeating units represented by formula (ri) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 35 mol% or less, and also preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and particularly preferably 30 mol% or more, relative to the sum of the content of the repeating units represented by formula (ri) and the content of the repeating units represented by formula (r-ii). The above upper and lower limits can be combined arbitrarily. For example, 5 to 60 mol% is preferred, 10 to 50 mol% is more preferred, 20 to 40 mol% is even more preferred, and 30 to 35 mol% is particularly preferred.

[0421] The proportion of repeating units represented by formula (ri) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and also preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 50 mol% is preferred, 1 to 30 mol% is more preferred, 5 to 20 mol% is even more preferred, and 10 to 15 mol% is particularly preferred.

[0422] The proportion of the repeating unit represented by formula (r-ii) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20 mol% or more, and also preferably 60 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 25 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 60 mol% is preferred, 10 to 40 mol% is more preferred, 15 to 30 mol% is even more preferred, and 20 to 25 mol% is particularly preferred.

[0423] From the viewpoint of improving compatibility with binder components such as solvents and enhancing dispersion stability, polymer dispersants preferably have repeating units represented by the following general formula (r-iii) (hereinafter sometimes referred to as "repeating unit (r-iii)").

[0424] [ka]

[0425] In formula (r-iii), R 40 is an ethylene group or a propylene group; R 41 is an alkyl group which may have substituents; R 42 is a hydrogen atom or a methyl group; n is an integer between 1 and 20.

[0426] R in equation (r-iii) 41 The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, and more preferably 6 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, and 2 to 6 is more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, with methyl, ethyl, propyl, butyl, pentyl, or hexyl groups being preferred, and methyl, ethyl, propyl, or butyl groups being more preferred. The alkyl group may be linear or branched. It may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups.

[0427] In formula (r-iii), n is preferably 1 or greater, more preferably 2 or greater, preferably 10 or less, and more preferably 5 or less, from the viewpoint of compatibility and dispersibility with the solvent and binder components. The above 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.

[0428] The proportion of repeating units represented by formula (r-iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and also preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 4 to 10 mol% is even more preferred. Within the above range, it tends to be possible to achieve both compatibility with the solvent and binder components and dispersion stability.

[0429] From the viewpoint of improving the compatibility of the dispersant with the solvent and binder components and enhancing dispersion stability, it is preferable that the polymeric dispersant has a repeating unit represented by the following general formula (r-iv) (hereinafter sometimes referred to as "repeating unit (r-iv)").

[0430] [ka]

[0431] In formula (r-iv), R 38 is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; R 39 This is either a hydrogen atom or a methyl group.

[0432] R in equation (r-iv) 38The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is preferably 1 or more, more preferably 2 or more, more preferably 4 or more, and preferably 10 or less, and more preferably 8 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 2 to 8 is more preferred, and 4 to 8 is even more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, with methyl, ethyl, propyl, butyl, pentyl, and hexyl groups being preferred, and methyl, ethyl, propyl, and butyl groups being more preferred. Alkyl groups may be linear or branched. They may also include cyclic structures, such as cyclohexyl and cyclohexylmethyl groups.

[0433] R in equation (r-iv) 38 The number of carbon atoms in the optionally substituted aryl group is not particularly limited, but is preferably 6 or more, more preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. For example, 6 to 16 is preferred, 6 to 12 is more preferred, and 6 to 8 is even more preferred. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl groups being preferred, and phenyl, methylphenyl, and ethylphenyl groups being more preferred.

[0434] R in equation (r-iv) 38 The number of carbon atoms in the aralkyl group, which may have substituents, is not particularly limited, but is preferably 7 or more, more preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. For example, 7 to 16 is preferred, 7 to 12 is more preferred, and 7 to 10 is even more preferred. Examples of aralkyl groups include phenylmethyl (benzyl) group, phenylethyl (phenethyl) group, phenylpropyl group, phenylbutyl group, and phenylisopropyl group, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl groups being preferred, and phenylmethyl and phenylethyl groups being more preferred.

[0435] From the viewpoint of solvent compatibility and dispersion stability, R 38 Alkyl or aralkyl groups are preferred, and methyl, ethyl, and phenylmethyl groups are more preferred.

[0436] R 38 Examples of substituents that the alkyl group may have include halogen atoms and alkoxy groups. R 38 Examples of substituents that the aryl group or aralkyl group may have include a chain-like alkyl group, a halogen atom, and an alkoxy group. R 38 The linear alkyl groups shown include both linear and branched alkyl groups.

[0437] From the viewpoint of dispersibility, the content of the repeating unit represented by formula (r-iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 80 mol% or less, and even more preferably 70 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 30 to 80 mol% is preferred, 40 to 80 mol% is more preferred, and 50 to 70 mol% is even more preferred.

[0438] The polymer dispersant may have repeating units other than repeating units (ri), (r-ii), (r-iii), and (r-iv). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylate chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; glycidyl ether crotonic acid; and N-methacryloylmorpholine.

[0439] From the viewpoint of further improving dispersibility, the polymeric dispersant is preferably a block copolymer having an A block having repeating units (ri) and repeating units (r-ii), and a B block not having repeating units (ri) and repeating units (r-ii). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Introducing not only a quaternary ammonium base but also a tertiary amino group into the A block tends to significantly improve the dispersing ability of the dispersant. It is preferable that the B block has repeating units (r-iii), and more preferably has repeating units (r-iv).

[0440] In block A, repeating units (ri) and (r-ii) may be contained in either random copolymerization or block copolymerization. Repeating units (ri) and (r-ii) may each be contained in one or more types in a single block A, in which case each repeating unit may be contained in block A in either random copolymerization or block copolymerization.

[0441] Repeating units other than repeating unit (ri) and repeating unit (r-ii) may be contained in block A, and examples of such repeating units include, for example, the repeating units derived from the (meth)acrylic acid ester monomers mentioned above. The content of repeating units other than repeating unit (ri) and repeating unit (r-ii) in block A is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and particularly preferably 0 mol%.

[0442] Repeating units other than repeating units (r-iii) and (r-iv) may be contained in block B. Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylate chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; glycidyl ether crotonic acid; and N-methacryloylmorpholine. The content of repeating units other than repeating units (r-iii) and (r-iv) in block B is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and particularly preferably 0 mol%.

[0443] If the photosensitive resin composition of the present invention contains a dispersant (F), the proportion of the dispersant is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less, relative to the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 0.1 to 8% by mass is preferred, 0.1 to 5% by mass is more preferred, 0.5 to 3% by mass is even more preferred, and 0.5 to 2% by mass is particularly preferred. Setting the value above the lower limit tends to suppress the generation of residue due to aggregates. Setting the value below the upper limit tends to improve ink repellency and developability.

[0444] [1-1-7] UV absorber The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing specific wavelengths of the light source used for exposure. The addition of an ultraviolet absorber can, for example, form fine, narrow-line-width partitions or eliminate residue remaining in unexposed areas after development. As an ultraviolet absorber, (B) from the viewpoint of inhibiting the light absorption of the photopolymerization initiator, for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used.

[0445] It is desirable that the ultraviolet absorber contains either a benzotriazole compound or a triazine compound, or both. It is thought that by including either a benzotriazole compound or a triazine compound, the light absorption rate at the bottom of the initiator film decreases, and the line width at the bottom of the coating film becomes smaller, thereby enabling the formation of fine, narrow septa.

[0446] Examples of benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethylhexyl propionate, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5 Examples include chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 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, and ester compounds of C7-9 linear and branched alkyl alcohols.

[0447] Examples of commercially available benzotriazole compounds include Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry), TINUVIN (registered trademark, hereinafter the same) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN Examples include 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Yongguang Chemical Industry Co., Ltd., Taiwan), Tomisorb (registered trademark, same applies hereinafter) 100, Tomisorb 600 (manufactured by API Corporation), SEESORB (registered trademark, same applies hereinafter) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Cipro Chemical Co., Ltd.), and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0448] Examples of triazine compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazine-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, reaction products of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-ethylhexylglycidyl ether, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine. Hydroxyphenyl triazine compounds are preferred from the viewpoint of ink repellency and the formation of fine, high-definition septa with narrow line widths.

[0449] Examples of commercially available triazine compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

[0450] Other ultraviolet absorbers include, for example, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes. For example, benzophenone compounds such as Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB 10, EVERSORB 11, EVERSORB 12 (manufactured by Yongguang Chemical Industry, Taiwan), Tomisorb 800 (manufactured by API Corporation), SEESORB 100, SEESORB 101, SEESORB 101S, SEESORB 102, SEESORB 103, SEESORB 105, SEESORB 106, SEESORB 107, SEESORB 151 (manufactured by Cipro Chemical); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; α-naphthol, β-naphthol, α- Examples include naphthalene derivatives such as 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; anthracenes such as anthracenes and 9,10-dihydroxyanthracenes and their derivatives; and dyes such as azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, and p-aminobenzoic acid dyes. From the viewpoint of ink repellency, cinnamic acid derivatives and naphthalene derivatives are preferred, and cinnamic acid derivatives are particularly preferred.

[0451] From the viewpoint of tapered shape, either or both of benzotriazole compounds and hydroxyphenyltriazine compounds are preferred, with benzotriazole compounds being particularly preferred.

[0452] As for UV absorbers, one type may be used alone, or two or more types may be used in combination.

[0453] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the percentage of the absorber is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, relative to the total solid content of the photosensitive resin composition, and also preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 15% by mass is preferred, 0.05 to 15% by mass is more preferred, 0.1 to 10% by mass is even more preferred, 0.5 to 5% by mass is even more preferred, and 1 to 3% by mass is particularly preferred. Setting the value above the lower limit tends to form fine-lined, high-definition partitions. Setting the value below the upper limit tends to increase ink repellency.

[0454] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio to (B) photopolymerization initiator is preferably 1 part by mass or more, more preferably 10 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, also preferably 500 parts by mass or less, more preferably 300 parts by mass or less, even more preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 500 parts by mass is preferred, 10 to 500 parts by mass is more preferred, 30 to 300 parts by mass is even more preferred, 50 to 200 parts by mass is even more preferred, and 80 to 100 parts by mass is particularly preferred. Setting the amount above the lower limit tends to form fine-lined, high-definition partitions. Setting the amount below the upper limit tends to increase ink repellency.

[0455] [1-1-8] Polymerization inhibitors The photosensitive resin composition of the present invention may contain a polymerization inhibitor. The presence of a polymerization inhibitor inhibits radical polymerization, which tends to increase the taper angle of the resulting septum. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of polymerization inhibitory ability, hydroquinone, methoxyphenol, and methylhydroquinone are preferred, and methylhydroquinone is more preferred. Polymerization inhibitors may be used individually or in combination of two or more.

[0456] (C) Depending on the method of producing the alkali-soluble resin, the produced alkali-soluble resin may contain a polymerization inhibitor. In that case, the alkali-soluble resin may be used as is, or in addition to the polymerization inhibitor contained in the resin, the same or a different polymerization inhibitor may be further added during the production of the photosensitive resin composition.

[0457] If the photosensitive resin composition contains a polymerization inhibitor, the content ratio is not particularly limited, but is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and also preferably 0.1% by mass or less, more preferably 0.08% by mass or less, and even more preferably 0.05% by mass or less, relative to the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 0.0005 to 0.1% by mass is preferred, 0.001 to 0.08% by mass is more preferred, and 0.01 to 0.05% by mass is even more preferred. Setting the value above the lower limit tends to increase the taper angle. Setting the value below the upper limit tends to increase the ink repellency.

[0458] [1-1-9] Thermal polymerization initiator The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. The inclusion of a thermal polymerization initiator tends to increase the degree of crosslinking of the film. Examples of such thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide. These may be used individually or in combination of two or more types.

[0459] When a thermal polymerization initiator is used in combination with a photopolymerization initiator to improve ink repellency or increase the crosslinking density of the film, it is preferable that the total proportion of these initiators equals the proportion of the photopolymerization initiator in the aforementioned photosensitive resin composition. Furthermore, from the viewpoint of ink repellency, the preferred ratio of the photopolymerization initiator to the thermal polymerization initiator is 5 to 300 parts by mass of the thermal polymerization initiator per 100 parts by mass of the photopolymerization initiator.

[0460] [1-1-10] Amino compounds The photosensitive resin composition of the present invention may contain an amino compound to promote thermosetting. When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the total solid content of the photosensitive resin composition. The above upper and lower limits can be combined arbitrarily. For example, 0.5 to 40% by mass is preferred, and 1 to 30% by mass is more preferred. Keeping the content below the upper limit tends to maintain storage stability. Keeping the content above the lower limit tends to ensure sufficient thermosetting properties.

[0461] Examples of amino compounds include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by alcohol condensation modification of the methylol group having 1 to 8 carbon atoms. Specifically, examples include melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluryl resin obtained by polycondensation of glycoluryl and formaldehyde; urea resin obtained by polycondensation of urea and formaldehyde; resin obtained by co-polycondensation of two or more of the above-mentioned resins such as melamine, benzoguanamine, glycoluryl, or urea with formaldehyde; and modified resin obtained by alcohol condensation modification of the methylol group of the above-mentioned resins. Melamine resin and its modified resin are preferred, and among the modified resins, modified resins with a methylol group modification rate of 70% or more are more preferred, and modified resins with a modification rate of 80% or more are even more preferred. One amino compound may be used alone, or two or more may be used in combination.

[0462] Examples of melamine resins and their modified resins include 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 Cytech Co., Ltd., and Nikalac (registered trademark, hereinafter the same) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, and MX-302 manufactured by Sanwa Chemical Co., Ltd. Examples of benzoguanamine resins and their modified resins include Cymel 1123, 1125, and 1128 manufactured by Cytec. Examples of glycoluryl resins and their modified resins include Cymel 1170, 1171, 1174, and 1172 manufactured by Cytech, and Nikalac MX-270 manufactured by Sanwa Chemical. Examples of urea resins and their modified resins include "UFR" (registered trademark) 65 and 300 manufactured by Cytec Corporation, and "Nikalac" MX-290 manufactured by Sanwa Chemical Co., Ltd.

[0463] [1-1-11] Silane coupling agent The photosensitive resin composition of the present invention may contain a silane coupling agent to improve adhesion to the substrate. As silane coupling agents, for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used, and from the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are preferred. If the photosensitive resin composition of the present invention contains a silane coupling agent, the amount thereof is preferably 20% by mass or less, and more preferably 15% by mass or less, relative to the total solid content of the photosensitive resin composition, from the viewpoint of adhesion.

[0464] [1-1-12] Inorganic fillers The photosensitive resin composition of the present invention may contain an inorganic filler for the purpose of improving the strength of the cured product, as well as for improving the excellent verticality and taper angle of the coating film through appropriate interaction with the alkali-soluble resin (formation of a matrix structure). Examples of inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, or these materials surface-treated with various silane coupling agents. In particular, silica sols and silica sol-modified materials are preferred because they tend to exhibit excellent dispersion stability and taper angle improvement effects.

[0465] The average particle size of the inorganic filler is preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm. The average particle size was measured using a laser diffraction scattering particle size distribution analyzer such as those manufactured by Beckman Coulter.

[0466] If the photosensitive resin composition of the present invention contains an inorganic filler, its content is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the total solid content of the photosensitive resin composition, from the viewpoint of ink repellency. The above upper and lower limits can be arbitrarily combined. For example, 5 to 80% by mass is preferred, and 10 to 70% by mass is more preferred.

[0467] [1-1-13] Adhesion enhancer The photosensitive resin composition of the present invention may contain an adhesion enhancer for the purpose of providing adhesion to a substrate. Examples of adhesion enhancers include phosphate-based ethylenic monomers. As phosphate-based ethylenic monomers, (meth)acryloyloxy group-containing phosphates are preferred, and (meth)acryloyloxy group-containing phosphates represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0468] [ka]

[0469] In equations (g1), (g2), and (g3), R 51 ' represents a hydrogen atom or a methyl group, l and l' are integers from 1 to 10, and m is 1, 2, or 3.

[0470] Phosphate-based ethylenic monomers may be used individually or in combination of two or more types.

[0471] When the photosensitive resin composition of the present invention contains a phosphate-based ethylenic monomer as an adhesion improver, the content is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and also preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less, based on the total solid content of the photosensitive resin composition. The above upper and lower limits can be arbitrarily combined. For example, 0.02 to 4% by mass is preferred, 0.05 to 3% by mass is more preferred, 0.1 to 2% by mass is even more preferred, and 0.2 to 1% by mass is particularly preferred. Setting the value above the lower limit tends to provide a sufficient improvement in adhesion to the substrate. Setting the value below the upper limit tends to suppress deterioration of adhesion to the substrate.

[0472] [1-1-14] Solvent The photosensitive resin composition of the present invention typically contains a solvent, and is used in a state in which each component contained in the photosensitive resin composition is dissolved or dispersed in the solvent. There are no particular restrictions on the solvent, but examples include the organic solvents described below.

[0473] Glycol monoalkyl ethers such as 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 t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; Glycol alkyl ether acetates such as ethylene glycol monomethyl 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, 3-methoxy-1-butyl 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, and 3-methyl-3-methoxybutyl acetate; Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, and methoxymethylpentanone; Monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain-like or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, propyl acetate, propyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile; Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

[0474] Examples of commercially available solvents include Mineral Spirit, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, and Digrime (all brand names).

[0475] The solvent can dissolve or disperse each component contained in the photosensitive resin composition and is selected according to the method of use of the photosensitive resin composition of the present invention. From the viewpoint of coatability, the boiling point of the solvent at atmospheric pressure is preferably 60 to 280°C, and more preferably 70 to 260°C. Among these, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.

[0476] The solvent may be used alone or in combination of two or more types. The solvent is preferably used such that its content in the total solid content of the photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably used so that it is 10 to 90% by mass, more preferably 15 to 50% by mass, even more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass. Setting it above the lower limit tends to suppress the occurrence of uneven coating. Setting it below the upper limit tends to suppress the occurrence of foreign matter, repellency, etc.

[0477] [1-2] Method for preparing a photosensitive resin composition The photosensitive resin composition of the present invention is prepared by mixing each component contained in the photosensitive resin composition with a stirrer. For example, if (E) the colorant contains solvent-free components such as pigments, it is preferable to disperse it beforehand using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. The dispersion treatment makes the (E) colorant into fine particles, which improves the coating properties of the photosensitive resin composition.

[0478] Dispersion treatment is usually preferably carried out using a system that combines (E) a colorant, a solvent, and (F) a dispersant, or optionally a system that combines these with some or all of (C) an alkali-soluble resin (hereinafter, the mixture subjected to dispersion treatment and the composition obtained by dispersion treatment may be referred to as "ink" or "pigment dispersion"). In particular, using a polymer dispersant as the (F) dispersant is preferable because it provides excellent dispersion stability for the obtained ink and photosensitive resin composition and suppresses thickening over time. Thus, in the process of manufacturing the photosensitive resin composition, it is preferable to manufacture a pigment dispersion containing at least (E) a colorant, a solvent, and (F) a dispersant. The (E) colorants, organic solvents, and (F) dispersants that can be used in the pigment dispersion are preferably those described as usable in the photosensitive resin composition. The content ratio of each colorant in the (E) colorant in the pigment dispersion is preferably the same as the content ratio described in the photosensitive resin composition.

[0479] When dispersing the colorant (E) with a sand grinder, glass beads or zirconia beads with a particle size of approximately 0.1 to 8 mm are preferably used. The temperature during the dispersion treatment is preferably between 0°C and 100°C, and more preferably between room temperature and 80°C. The dispersion time should be adjusted as appropriate, as the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The guideline for dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.

[0480] The particle size of the pigment dispersed in the ink is preferably 0.03 to 0.3 μm, and is measured, for example, by dynamic light scattering. Next, the ink obtained by the dispersion process is mixed with other components contained in the photosensitive resin composition to obtain a homogeneous solution or dispersion. Since fine dust may be mixed into the liquid during the manufacturing process of the photosensitive resin composition, it is desirable to filter the obtained photosensitive resin composition using a filter or the like.

[0481] [2] Partition wall and method for forming the same A cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention can be used to form partitions, and can be suitably used to form partitions for partitioning the organic layer of an organic electroluminescent device, or partitions for partitioning the pixel portion in a color filter containing luminescent nanocrystalline particles. The partition of the present invention is composed of the cured product of the present invention. The method for forming a partition using the photosensitive resin composition of the present invention is not particularly limited, and conventionally known methods can be employed. The formation of a cured product using the photosensitive resin composition of the present invention preferably comprises at least the following steps (1) to (4). Step (1): A step of applying the photosensitive resin composition of the present invention onto a substrate to form a coating film. Step (2): A step of exposing at least a portion of the coating film formed in step (1). Step (3): A step to develop the coating film exposed in step (2). Step (4): A step in which the coating developed in step (3) is fired.

[0482] <Step (1): Applying a photosensitive resin composition to a substrate to form a coating film> Examples of methods for supplying the photosensitive resin composition to the substrate include inkjet printing and photolithography.

[0483] In the inkjet method, a photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent is used as an ink, and ink droplets are ejected onto the substrate by the inkjet method along a predetermined partition pattern to coat the substrate and form an uncured partition pattern. Then, the uncured partition pattern is exposed to light to form cured partitions on the substrate. The exposure of the uncured partition pattern is carried out in the same way as the exposure process in the photolithography method described later, except that a mask is not used.

[0484] In photolithography, a photosensitive resin composition is applied to the entire surface of the substrate where the partition walls are to be formed to form a photosensitive resin composition layer. After the formed photosensitive resin composition layer is exposed according to a predetermined partition wall pattern, the exposed photosensitive resin composition layer is developed to form partition walls on the substrate.

[0485] In the photolithography process, the coating step involves applying a photosensitive resin composition to a substrate. This coating step uses contact transfer type coating devices such as roll coaters, reverse coaters, and bar coaters, or non-contact type coating devices such as spinners (rotary coating devices) and curtain flow coaters, to coat the substrate on which partition walls are to be formed. After supplying the photosensitive resin composition onto the substrate, drying is preferably performed to form a coating film. Drying is preferably done using a hot plate, IR oven, or convection oven. A vacuum drying method, in which drying is performed in a reduced-pressure chamber without raising the temperature, may also be used. Drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. Drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40°C to 100°C, preferably in the range of 30 seconds to 3 minutes at a temperature of 50°C to 80°C, etc. It is preferable to carry out the drying within a range that does not exceed the firing temperature described later.

[0486] <Step (2): A step of exposing at least a portion of the coating film formed in Step (1)> In the exposure process, a negative-type mask is used to irradiate the photosensitive resin composition with active energy rays such as ultraviolet light or excimer laser light, partially exposing the photosensitive resin composition layer according to the bank pattern. For exposure, ultraviolet light sources such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and carbon arc lamps can be used. The exposure amount varies depending on the composition of the photosensitive resin composition, but is, for example, 10 to 400 mJ / cm². 2 A certain degree is desirable.

[0487] <Step (3): Step to develop the coating film exposed in Step (2)> In the developing process, the partitions are formed by developing a photosensitive resin composition layer exposed according to the partition pattern with a developer. The developing method is not particularly limited, and methods such as immersion or spraying can be used. Specific examples of developers include organic compounds such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, as well as aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Antifoaming agents and surfactants can also be added to the developer.

[0488] After the development process, a further exposure process (post-exposure process) is performed as needed. The developed partition is exposed by irradiating it with active energy rays such as ultraviolet light or excimer laser light. Partial exposure using a mask may also be performed. For exposure, ultraviolet light sources such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, and UV-FL (ultraviolet fluorescent lamps) can be used. The exposure amount varies depending on the composition of the photosensitive resin composition, but is generally 10 mJ / cm². 2 The above is preferable, and 100 mJ / cm² is preferred. 2 The above is more preferable, 500 mJ / cm² 2 The above is even more preferable, 800 mJ / cm² 2 The above is particularly preferable, and also 10,000 mJ / cm². 2 The following is preferable: 5000 mJ / cm² 2 The following is more preferable: 2000 mJ / cm² 2 The following is even more preferable: for example, 10 to 10,000 mJ / cm² 2 Preferably, 100 to 10000 mJ / cm² 2 More preferably, 500-5000 mJ / cm² 2 More preferably, 800-2000 mJ / cm² 2 This is particularly preferable. Setting it above the lower limit tends to improve penetration resistance. Setting it below the upper limit is preferable because it allows for both achieving penetration resistance and ensuring productivity by not making the irradiation time too long.

[0489] <Step (4): A step in which the coating developed in step (3) is fired> After development, or after post-exposure following development, the partition wall is subjected to post-bake, i.e., heat hardening treatment. The conditions for post-bake are preferably 80°C or higher, more preferably 90°C or higher, preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 140°C or lower, particularly preferably 120°C or lower, and most preferably 100°C or lower. The above upper and lower limits can be combined arbitrarily. For example, 80-250°C is preferred, 80-200°C is more preferred, 80-180°C is even more preferred, 80-140°C is even more preferred, 80-120°C is particularly preferred, 80-100°C is even more preferred, and 90-100°C is particularly preferred. Above the lower limit, the penetration resistance and heat resistance tend to be good. Below the upper limit, the impact on manufacturing costs and compatibility with substrates and elements with limited heat resistance, such as plastic substrates, tends to be reduced. The baking time is preferably between 5 and 120 minutes.

[0490] The substrate used to form the partition wall is not particularly limited and is appropriately selected according to the type of organic electroluminescent device or color filter manufactured using the substrate on which the partition wall is formed. Suitable substrate materials include glass and various resin materials. Examples of resin materials include polyester such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resin; polysulfone; and polyimide. Glass and polyimide are preferred due to their excellent heat resistance. Depending on the type of organic electroluminescent device or color filter to be manufactured, a transparent electrode layer such as ITO or ZnO may be provided on the surface of the substrate on which the partition wall is formed. Alternatively, a partition wall for a color filter may be formed on a substrate having the element. To improve surface properties such as adhesion, the substrate may be subjected to treatments as needed, such as corona discharge treatment, ozone treatment, or thin-film formation of various resins, including silane coupling agents and urethane-based resins.

[0491] The thickness of the partition wall of the present invention is preferably 0.1 μm or more, more preferably 1 μm or more, even more preferably 5 μm or more, particularly preferably 10 μm or more, and also preferably 1 mm or less, more preferably 100 μm or less, even more preferably 50 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The above upper and lower limits can be combined arbitrarily. For example, 0.1 μm to 1 mm is preferred, 0.1 to 100 μm is more preferred, 1 to 50 μm is even more preferred, 5 to 30 μm is even more preferred, and 10 to 20 μm is particularly preferred. Light shielding tends to improve when the thickness is above the lower limit. Adhesion tends to improve when the thickness is below the upper limit. The thickness of the partition wall is measured using a step / surface roughness / micro-shape measuring device, a scanning white light interference microscope, an ellipsometer, a reflection spectrometer, and an electron microscope.

[0492] [3] Organic electroluminescent element The organic electroluminescent element of the present invention is equipped with the partition wall of the present invention. Various organic electroluminescent devices are manufactured using a substrate equipped with a partition pattern manufactured by the method described above. The method for forming the organic electroluminescent device is not particularly limited, but preferably, after forming a partition pattern on the substrate by the method described above, an organic electroluminescent device is manufactured by injecting ink into the region surrounded by the partitions on the substrate to form an organic layer such as a pixel.

[0493] Examples of organic electroluminescent devices include bottom-emission and top-emission types. In bottom emission type systems, for example, a partition wall is formed on a glass substrate with stacked transparent electrodes, and a hole transport layer, light-emitting layer, electron transport layer, and metal electrode layer are stacked in the opening surrounded by the partition wall. In top-emission type devices, for example, a partition wall is formed on a glass substrate with stacked metal electrode layers, and an electron transport layer, light-emitting layer, hole transport layer, and transparent electrode layer are stacked in the opening surrounded by the partition wall.

[0494] When the partition wall has a tapered shape, the ink for forming the organic layer is repelled at the bottom of the partition wall, which can result in the area enclosed by the partition wall not being sufficiently covered with the ink. In contrast, by creating a good shape without a tapered bottom, the area enclosed by the partition wall can be sufficiently covered with the ink for forming the organic layer. This can resolve problems such as halation in organic EL display elements.

[0495] Water, organic solvents, and mixtures thereof can be used as solvents when forming the ink for organic layer formation. The organic solvent is not particularly limited as long as it can be removed from the film formed after the ink is injected. Examples of organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, and 3-phenoxytoluene. The ink may contain surfactants, antioxidants, viscosity modifiers, UV absorbers, and other additives.

[0496] As a method for injecting ink into an area enclosed by a partition wall, the inkjet method is preferred because it allows for easy injection of small amounts of ink into predetermined locations. The ink used to form the organic layer is appropriately selected depending on the type of organic electroluminescent device to be manufactured. When injecting ink by the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected well from the inkjet head, but 4 to 20 mPa·s is preferred, and 5 to 10 mPa·s is more preferred. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, etc.

[0497] Examples of light-emitting layers include organic electroluminescent layers as described in Japanese Patent Publication No. 2009-146691 and Japanese Patent No. 5734681. Quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[0498] [4] Color filter containing luminescent nanocrystalline particles A color filter containing luminescent nanocrystalline particles according to the present invention is not particularly limited as long as it is equipped with the partition wall of the present invention, and includes a filter in which pixels are formed in a region partitioned by the partition wall.

[0499] Figure 1 is a schematic cross-sectional view of an example of a color filter equipped with a partition wall according to the present invention. As shown in Figure 1, the color filter 100 comprises a substrate 10, a partition wall 20 provided on the substrate, red pixels 30, green pixels 40, and blue pixels 50. The red pixels 30, green pixels 40, and blue pixels 50 are arranged in a grid pattern, repeating in this order. The partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are separated from each other by the partition wall 20.

[0500] The red pixels 30 contain red-emitting nanocrystalline particles 2, and the green pixels 40 contain green-emitting nanocrystalline particles 1. The blue pixels 50 are pixels that transmit blue light from the light source.

[0501] These nanocrystalline particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, for example, crystals with a maximum particle diameter of 100 nm or less as measured by a transmission electron microscope or scanning electron microscope.

[0502] Luminescent nanocrystalline particles can emit light of a different wavelength (fluorescence or phosphorescence) by absorbing light of a predetermined wavelength. For example, red-luminescent nanocrystalline particle 2 emits light (red light) with an emission peak wavelength in the range of 605 to 665 nm, and green-luminescent nanocrystalline particle 1 emits light (green light) with an emission peak wavelength in the range of 500 to 560 nm.

[0503] The wavelength (emission color) of light emitted by luminescent nanocrystalline particles depends on the size (e.g., particle diameter) of the luminescent nanocrystalline particles, according to the solution to the Schrödinger wave equation in the square-well model, but also on the energy gap of the luminescent nanocrystalline particles. Therefore, the emission color can be selected by changing the constituent material and size of the luminescent nanocrystalline particles used. Examples of luminescent nanocrystalline particles include quantum dots.

[0504] The method for manufacturing a color filter containing luminescent nanocrystalline particles is not particularly limited, but one method involves preparing a substrate with partitions formed from the cured product of the present invention, and forming a layer containing luminescent nanocrystalline particles in the region partitioned by the partitions. The method for forming the layer containing luminescent nanocrystalline particles is not particularly limited, but for example, it can be manufactured by selectively attaching an ink composition containing luminescent nanocrystalline particles using an inkjet method, and curing the ink composition by irradiation with active energy rays or heating.

[0505] [5] Image display device The image display device of the present invention is equipped with the partition wall of the present invention. An example of the image display device of the present invention is an image display device that includes the organic electroluminescent element of the present invention. As long as it includes an organic electroluminescent element, there are no particular restrictions on the type or structure of the image display device, and it can be assembled according to conventional methods using, for example, an actively driven organic electroluminescent element. For example, the image display device of the present invention can be formed by a method such as that described in "Organic EL Display" (Ohmsha, published August 20, 2004, by Shizuka Tokito, Chihaya Adachi, and Hideyuki Murata). For example, an image may be displayed by combining an organic electroluminescent element that emits white light with a color filter, or an image may be displayed by combining organic electroluminescent elements with different emission colors such as RGB.

[0506] An example of an image display device of the present invention is an image display device equipped with a color filter containing luminescent nanocrystalline particles according to the present invention. Examples of image display devices include liquid crystal displays and image display devices that include organic electroluminescent elements. In the case of liquid crystal displays, examples include those that include a liquid crystal layer equipped with a light source with blue LEDs and electrodes that control the blue light emitted from the light source for each pixel. On the other hand, an image display device including an organic electroluminescent element may be one in which a blue-emitting organic electroluminescent element is arranged at a position corresponding to each pixel of the color filter. Specifically, the method described in Japanese Patent Publication No. 2019-87746 is an example. [Examples]

[0507] The photosensitive resin composition of the present invention will be described below with reference to specific examples. The present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0508] <Alkali-soluble resin-1> (Synthesis of precursor resins) In a reaction vessel of appropriate size equipped with a stirrer and condenser, 2-norbornene (75% by mass toluene solution, Maruzen Petrochemical Co., Ltd., 125.5 g, 1.00 mol) and dimethyl 2,2'-azobis(2-methylpropionate) (V-601, Wako Pure Chemical Industries, Ltd., 9.2 g, 40 mmol) were weighed and dissolved in methyl ethyl ketone (MEK, 196.1 g). After removing oxygen from this solution by passing nitrogen through it for 10 minutes, the mixture was heated to 80°C with stirring. While maintaining the solution at 80°C, a pre-prepared solution of maleic anhydride (Nippon Shokubai Co., Ltd., 98.1 g, 1.00 mol) dissolved in 119.9 g of MEK was added dropwise over 1.5 hours, and the reaction was continued at that temperature for a further 8 hours. This reaction mixture was added dropwise to a large amount of methanol to precipitate the polymer. After filtration using a Nutsche filter, the solid was washed with methanol and vacuum-dried at 70°C. The weight-average molecular weight Mw of the obtained precursor resin was 6900.

[0509] (Synthesis of alkali-soluble resin-1) In a reaction vessel of appropriate size equipped with a stirrer and condenser, the aforementioned precursor resin (50.0 g) was weighed and dissolved in MEK (90 g). Then, 2-hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd., 21.2 g, 163 mmol) and triethylamine (5.0 g) were added, and the mixture was heated at 70°C for 6 hours. To this reaction solution, glycidyl methacrylate (11.1 g, 78 mmol) was added, and the mixture was stirred at 70°C for another 4 hours. Formic acid was added to the reaction solution for acid treatment, and then the solution was dropped into a large amount of pure water to precipitate the polymer. The filtered solid was dried in a vacuum dryer at 40°C for 16 hours to obtain alkali-soluble resin-1. The weight-average molecular weight Mw was 7800. The double bond equivalent was 540 g / mol. Alkali-soluble resin-1 corresponds to copolymer resin (C1).

[0510] <Alkali-soluble resin-2> This alkali-soluble acrylic copolymer resin is obtained by adding acrylic acid in an equal amount to glycidyl methacrylate to a copolymer resin composed of dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.02 / 0.045 / 0.935), and then adding tetrahydrophthalic anhydride in a molar ratio of 0.096 per mole of the copolymer resin. The weight-average molecular weight (Mw) in polystyrene equivalent, measured by GPC, is 8900, and the solid content acid value is 27 mgKOH / g. Alkali-soluble resin-2 corresponds to an alkali-soluble resin other than copolymer resin (C1) (acrylic copolymer resin (C3)).

[0511] <Alkali-soluble resin-3> This alkali-soluble acrylic copolymer resin is obtained by adding acrylic acid in an equal amount to glycidyl methacrylate to a copolymer resin composed of tricyclodecane methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6), and then adding tetrahydrophthalic anhydride in a molar ratio of 0.39 per mole of the copolymer resin. The weight-average molecular weight (Mw) in polystyrene equivalent, measured by GPC, is 9000, and the solid content acid value is 80 mgKOH / g. Alkali-soluble resin-3 corresponds to alkali-soluble resins other than copolymer resin (C1) (acrylic copolymer resin (C3)).

[0512] <Alkali-soluble resin-4> "ZCR-8024H" manufactured by Nippon Kayaku Co., Ltd. (Mw=3100, Acid value=60mgKOH / g). Alkali-soluble resin-4 corresponds to alkali-soluble resins other than copolymer resins (C1) (epoxy (meth)acrylate resins (C2)).

[0513] <Photopolymerizable compound> In Examples 1-9 and Comparative Example 1, one of the following was selected and incorporated. The selection and incorporation of the photopolymerizable compound (photopolymerizable monomer) are as shown in Table 2 below.

[0514] <Photopolymerizable monomer-1> • DPHA: Manufactured by Nippon Kayaku Co., Ltd. A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. <Photopolymerizable monomer-2> ·A-9570W: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. A mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. <Photopolymerizable monomer-3> A mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid half-esters of dipentaerythritol pentaacrylate. (Molar ratio: 50 / 25 / 25%) <Photopolymerizable monomer-4> • Light Acrylate PE-4A: Pentaerythritol tetraacrylate, manufactured by Kyoeisha Chemical Co., Ltd. <Photopolymerizable monomer-5> • M-933: A mixture of pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate manufactured by Toagosei Co., Ltd.

[0515] <Dispersant> A polymeric acrylic AB-block copolymer consisting of block A, which has a quaternary ammonium base and a tertiary amino group in its side chain, and block B, which does not have a quaternary ammonium base or a tertiary amino group. The amine value is 70 mgKOH / g. The acid value is 1 mgKOH / g or less. Block A of the dispersant contains repeating units of formulas (1a) and (2a) below, and block B contains repeating units of formula (3a) below. The content percentages of the repeating units of formulas (1a), (2a), and (3a) below in the total repeating units of the dispersant are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[0516] [ka]

[0517] <Solvent-1> PGMEA: Propylene glycol monomethyl ether acetate <Solvent-2> MB: 3-Methoxybutanol <Solvent-3> PGME: Propylene glycol monomethyl ether

[0518] <Photopolymerization initiator> The following compounds were used. These compounds can be prepared by the synthesis method described in International Publication No. 2009 / 131189.

[0519] [ka]

[0520] <Liquid repellent> An acrylic copolymer resin having a perfluoroalkyl group, a perfluoroalkyl group, and a carboxyl group. Mw 90000, fluorine atom content 20% by mass. This liquid repellent corresponds to compound (D1).

[0521] <Surfactants> DIC Corporation's F-559 (nonionic surfactant, oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups). Since this surfactant does not have a crosslinking group, it does not fall under compound (D1).

[0522] <Additive-1> Showa Denko Corporation's Karenz MT PE1 (Pentaerythritol Tetrakis (3-Mercaptobutyrate)) <Additive-2> KAYAMER PM-21 (methacryloyl group-containing phosphate) manufactured by Nippon Kayaku Co., Ltd. <Additive-3> XIAMETER OFS-6040Silane (Glycidoxypropyltrimethoxysilane) manufactured by Dow Toray Corporation

[0523] <Preparation of Pigment Dispersion> The pigments, dispersants, alkali-soluble resins, and solvents listed in Table 1 were mixed in the mass ratios shown in Table 1. This solution was dispersed using a paint shaker at a temperature of 25-45°C for 3 hours. 0.5 mm diameter zirconia beads were used as beads, added in an amount equal to 2.5 times the mass of the dispersion. After dispersion, the beads and dispersion were separated by filter to prepare the pigment dispersion.

[0524] [Table 1]

[0525] [Examples 1-10 and Comparative Examples 1 and 2] Using the pigment dispersion prepared above, each component was added so that the proportion of each component's solid content in the total solid content was as shown in Table 2. Furthermore, PGMEA was added so that the proportion of PGME in the total solvent was 20% by mass and the proportion of PGME in the total solid content was 31% by mass. The mixture was then stirred and dissolved to prepare a photosensitive resin composition. The obtained photosensitive resin composition was evaluated using the method described later.

[0526] [Table 2]

[0527] The performance evaluation method is described below.

[0528] <Creation of evaluation partitions> A photosensitive resin composition was applied to a glass substrate using a spinner to a thickness of 10.0 μm after heat curing. The substrate was then dried in a vacuum dryer for 60 seconds. Subsequently, it was heated and dried on a hot plate at 90°C for 120 seconds. The resulting coating was exposed to light using a photomask. A Canon mirror projection type exposure unit (MPA-600FA) was used, with an exposure dose of 100 mJ / cm². 2 To achieve this result, an exposure time of 25 seconds was used. The illuminance was 500 mW / cm². 2The slit width was 1.6 mm. The photomask used was a mask with a 10 mm square opening and a grid-like opening (having a 100 μm × 300 μm covering area, with multiple such covering areas separated by a 100 μm exposure area in the long axis direction and a 10 μm exposure area in the uniaxial direction). Next, development was performed using a 0.033% KOH aqueous solution with a shower at a pressure of 0.05 MPa for a development time of 70 seconds, followed by rinsing with pure water for 10 seconds. After that, development was performed using a proxy exposure machine (MA-1100) manufactured by Dainippon Kaken Co., Ltd. with an ND60 filter (60% neutral density filter) at an illuminance of 60 mW / cm². 2 UV light at 1000 mJ / cm² 2 Post-exposure was performed. Finally, by heating this substrate in an oven at 90°C for 30 minutes, a substrate was obtained having a coating film for contact angle measurement corresponding to the 10 mm square opening of the photomask and a partition wall for ink penetration evaluation.

[0529] <Measuring Contact Angle> <Measurement liquid sample> PGMEA: Propylene glycol monomethyl ether acetate <Equipment used> DMo-502 manufactured by Kyowa Interface Science Co., Ltd. <Measurement> The liquid volume was set to 0.7 μL using the droplet method, and the contact angle was derived using the θ / 2 method.

[0530] <Ink absorption evaluation> <Ink used> YED216D (1,6-Hexanediol Diglycidyl Ether) manufactured by Mitsubishi Chemical Corporation <Equipment used> Fujifilm DMP-2831 A 10pL compatible inkjet print head was used for coating. <Ink application> Using the DMP-2831 mentioned above, 24 drops of the ink used were applied to each of the 15 openings (5 rows x 3 columns) of the evaluation partition, each measuring 100 μm x 300 μm.

[0531] <Observation and evaluation of staining> Of the 15 openings to which ink was applied, the ink penetration into the septum surrounding the central 3x2 opening was observed using an optical microscope. When ink penetration occurred, abnormalities were observed in the form of discoloration of the septum or the appearance of spotted patterns. Observations were made immediately after application, and at 1 hour, 2 hours, and 3 hours. If no abnormalities were observed, it was evaluated as A; if penetration occurred in part of the septum, it was evaluated as B; and if penetration occurred throughout the septum, it was evaluated as C. Evaluations A and B were considered acceptable levels. Schematic diagrams of the ink penetration observation results and evaluation results are shown in Figures 2A and 2B.

[0532] Examples 1-5 show that when copolymer resin (C1) is used, it exhibits resistance to penetration in combination with various photopolymerizable compounds. This is because the copolymer resin (C1) used has repeating units containing aliphatic polycyclic structures in its main chain, specifically, it has a norbornane skeleton represented by formula (I) that is sterically bulky and not as rigid as aromatic hydrocarbons, exhibiting a certain degree of flexibility. Therefore, during the photo- and / or thermosetting reaction of the photosensitive resin composition, the reaction sites of photopolymerizable compounds and other elements come into close proximity, preventing excessive inhibition of the curing reaction. Furthermore, after curing, its bulky structure effectively suppresses ink penetration.

[0533] Examples 6-10 show that resistance to penetration is maintained even when other alkali-soluble resins are used in combination with the copolymer resin (C1). In addition to the performance shown in Examples 1-5, if it is desired to impart properties other than resistance to penetration, such as liquid repellency, adhesion, and resolution, to the photosensitive resin composition, it is important that resistance to penetration is not lost even when alkali-soluble resins that impart such properties are used in combination.

[0534] A comparison of the example with Comparative Example 1 shows that resistance to penetration is not achieved without the use of copolymer resin (C1). Furthermore, from Examples 6-8, it can be seen that using a photopolymerizable compound containing more hydroxyl groups, such as dipentaerythritol tetraacrylate, results in higher resistance to penetration compared to using a photopolymerizable compound that does not contain more hydroxyl groups. It is considered that this difference was not observed in Examples 1-5, which also contained similar photopolymerizable compounds, because the copolymer resin (C1) itself provides strong resistance to penetration. The reason why using a photopolymerizable compound with many hydroxyl groups increases resistance to ink penetration is thought to be that when the copolymer resin (C1) contains many highly polar substituents (carboxyl groups and hydroxyl groups in this example) as represented by formulas (II-1) and (II-2), these substituents and the hydroxyl groups of the photopolymerizable compound form a non-covalent network, such as hydrogen bonds, which more efficiently prevents ink penetration.

[0535] A comparison of the example with Comparative Example 2 reveals that without compound (D1), which has a crosslinking group and contains fluorine atoms and / or siloxane chains, the PGMEA contact angle is significantly lower than in other examples, resulting in a lack of liquid repellency and impaired penetration resistance. Furthermore, a comparison with Comparative Example 1 shows that even with compound (D1), penetration resistance cannot be obtained unless it is used in combination with copolymer resin (C1). Liquid repellents exhibit liquid repellency by segregating on the surface. When used in combination with a copolymer resin (C1), which has repeating units containing aliphatic polycyclic structures in its main chain and is resistant to ink penetration, the liquid repellent's own ink-repellent function can reinforce penetration resistance. However, when combined with a resin that does not have repeating units containing aliphatic polycyclic structures in its main chain, such as copolymer resin (C1), it is presumed that while the ink is repelled macroscopically (= the contact angle increases), it does not show any effect in suppressing ink penetration at the molecular level. [Explanation of Symbols]

[0536] 1. Green-emitting nanocrystalline particles 2. Red-emitting nanocrystalline particles 10 circuit boards 20 Bulkhead 30 red pixels 40 green pixels 50 blue pixels 100 Color Filters

Claims

1. A photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent, The (C) alkali-soluble resin contains a copolymer resin (C1) having repeating units containing an aliphatic polycyclic structure in its main chain. The copolymer resin (C1) has repeating units (I) represented by the following general formula (I) and repeating units represented by the following general formula (II-1), A photosensitive resin composition characterized in that the (D) liquid repellent contains a compound (D1) having a crosslinking group and having a fluorine atom and / or a siloxane chain. 【Chemistry 1】 (In formula (I), R1 to R4 each independently represent a hydrogen atom or a hydrocarbon group. n represents an integer from 0 to 2. * represents a bond.) 【Chemistry 2】 (In formula (II-1), R5 represents an organic group containing the structure shown in the general formula (II-2) below. * represents a bond.) 【Transformation 3】 (In formula (II-2), R6 represents a hydrogen atom or a methyl group. e represents an integer from 1 to 5. * represents a bond.)

2. The photosensitive resin composition according to claim 1, wherein the content ratio of the copolymer resin (C1) with respect to the total solid content of the photosensitive resin composition is 20% by mass or more.

3. The photosensitive resin composition according to claim 1, wherein the (C) alkali-soluble resin further contains an alkali-soluble resin in addition to the copolymer resin (C1).

4. The photosensitive resin composition according to claim 1, further comprising (E) a coloring agent.

5. The photosensitive resin composition according to claim 3, further comprising (E) a coloring agent.

6. The photosensitive resin composition according to claim 1, further containing a solvent.

7. The photosensitive resin composition according to claim 3, further containing a solvent.

8. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 7.

9. A partition wall composed of the cured product described in claim 8.

10. An organic electroluminescent element comprising a partition wall as described in claim 9.

11. A color filter comprising the partition wall described in claim 9, further containing luminescent nanocrystalline particles.

12. An image display device comprising a partition wall as described in claim 9.

13. A method for forming a cured product, comprising at least the following steps (1) to (4), using the photosensitive resin composition described in any one of claims 1 to 7. Step (1): A step of applying the photosensitive resin composition onto a substrate to form a coating film. Step (2): A step of exposing at least a portion of the coating film formed in step (1). Step (3): A step of developing the coating film exposed in step (2). Step (4): A step of firing the coating film developed in step (3).

14. The method for forming a cured product according to claim 13, wherein the firing temperature in step (4) is 140°C or lower.

15. A method for forming a cured product according to claim 13, further comprising a post-exposure step of exposing the coating film developed in step (3) after step (3).

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