Photosensitive resin composition, cured product, barrier, organic electroluminescent device, color filter, image display device, and method for forming a cured product

Abstract

The present invention provides a photosensitive resin composition having high liquid repellency even at low curing temperatures and not causing problems such as ink penetration. The photosensitive resin composition of the present invention is a photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent, wherein the alkali-soluble resin (C) contains a copolymer resin (C1) having repeating units including an aliphatic polycyclic structure in the main chain, and the liquid repellent (D) contains a compound (D1) having a crosslinking group and also having a fluorine atom and / or a siloxane chain.

Description

Technology Field

[0001] The present invention relates to a photosensitive resin composition. The present invention also relates to a cured product obtained by curing a photosensitive resin composition; a partition wall composed of the cured product; an organic electroluminescent device, a color filter, and an image display device having the partition wall. Furthermore, the invention relates to a method for forming a cured product.

[0002] The present application claims priority based on Japanese patent application No. 2021-102054 filed in Japan on June 18, 2021, and incorporates the contents thereof herein by reference. Background Technology

[0003] Recently, color filters formed with pixels using luminescent nanocrystalline particles, such as quantum dots, are being considered to achieve low power consumption and a wide color gamut for displays. Methods for manufacturing color filters include photolithography and inkjet methods, and it is known that the latter can reduce the loss of ink material (see, for example, Patent Document 1).

[0004] When manufacturing a color filter containing luminescent nanocrystalline particles by an inkjet method, a pixel is formed by extruding ink containing luminescent nanocrystalline particles into an area (pixel area) surrounded by a pre-fabricated barrier.

[0005] In addition, organic electroluminescent devices used in organic electroluminescent displays, etc., are manufactured by forming a bank on a substrate and stacking various functional layers within an area enclosed by the bank. An inkjet method is known for stacking functional layers within the bank.

[0006] When discharging ink by an inkjet, it is necessary to prevent mixing of inks between adjacent pixel areas, and thus high ink-repellent properties are required for barriers for color filters containing luminescent nanocrystalline particles and barriers for organic electroluminescent devices.

[0007] Patent Document 2 describes a material for forming a barrier with liquid-repellent properties by photolithography, wherein a colored photosensitive resin composition with high liquid-repellent properties and good linearity is obtained by using two types of specific alkali-soluble resins in combination.

[0008] Typically, when a partition wall as described above is formed by photolithography, a final pattern is formed through a heat curing process of at least 30 minutes at a temperature of 200°C or higher, which is performed after development. In the embodiment described in Patent Document 2, it is also described that the material is heated and cured in an oven at 230°C for 30 minutes.

[0009] Meanwhile, recently, the lowering or shortening of the heat sintering process is being considered in terms of reducing manufacturing costs or addressing substrates with limited heat resistance, such as plastic substrates, and there is a demand for photosensitive resin compositions that have performance no different from conventional ones even in heat sintering processes at lower temperatures or for shorter durations than conventional ones. Regarding such performance requirements, methods using a blocked isocyanate (e.g., Patent Document 3) and methods combining an epoxy-containing material with a heat-activated, delayed fluorescent compound (e.g., Patent Document 4) are known. Prior art literature

[0010] Japanese Published Patent Application No. 2019-086745, International Publication No. 2019 / 146685, Japanese Patent Application No. 5708313, Japanese Published Patent Application No. 2020-30290 The problem to be solved

[0011] In Patent Document 3 or Patent Document 4, the intent is described in the examples that the necessary performance is obtained even when the heat sintering process is performed at 150°C, but liquid repellency is not specifically described. As such, prior art regarding photosensitive resin compositions that have high liquid repellency and can be cured at lower temperatures than conventional ones is not sufficient.

[0012] As a result of the inventors' investigation, it was found that in the colored photosensitive resin composition described in Patent Document 2, when a barrier is formed under conditions where the firing temperature and time are reduced to 90°C and 30 minutes and ink is applied within the barrier using an inkjet, a problem occurs in which the ink penetrates into the barrier. The fact that the ink seeps into the barrier means that, at the same time, certain components move from within the barrier into the ink, and there is a possibility that the inkjet-coated material may be contaminated, which is a problem.

[0013] Meanwhile, patent documents 3 and 4 do not describe a liquid-repellent agent, and the liquid-repellent properties when a liquid-repellent agent is used are unknown.

[0014] Therefore, the present invention aims to provide a photosensitive resin composition that has high liquid repellency even at low curing temperatures and does not cause problems such as ink penetration (hereinafter, such a characteristic may be referred to as "penetration resistance").

[0015] In addition, 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 cause problems such as ink penetration, a barrier composed of the cured product, an organic electroluminescent device having a barrier, a color filter having a barrier, and an image display device having a barrier.

[0016] In addition, the present invention aims to provide a method for manufacturing a cured product using a photosensitive resin composition that has high liquid repellency even at low curing temperatures and does not cause problems such as ink penetration. means of solving the problem

[0017] As a result of careful examination by the inventors, it was discovered that the above problem can be solved by using an alkali-soluble resin containing a specific resin in a photosensitive resin composition containing a liquid-repellent agent, and thus the present invention was completed.

[0018] That is, the gist of the present invention is as follows.

[0019] [1] A photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid-repellent agent, wherein

[0020] The above (C) alkali-soluble resin contains a copolymer resin (C1) having repeating units including an aliphatic polycyclic structure in the main chain, and

[0021] A photosensitive resin composition characterized in that the above (D) liquid-repellent agent contains a compound (D1) having a crosslinking group and also having a fluorine atom and / or a siloxane chain.

[0022] [2] A photosensitive resin composition of [1] in which the copolymer resin (C1) has repeating units (I) represented by the following general formula (I).

[0023] [Chemical Formula 1]

[0024]

[0025] (In Equation (I), R 1 ~ R 4 Each represents independently a hydrogen atom or a hydrocarbon group. n represents an integer from 0 to 2. * represents a bonding hand.)

[0026] [3] The above copolymer resin (C1) has repeating units (II) having carboxyl groups, [1] or [2] photosensitive resin composition.

[0027] [4] A photosensitive resin composition of [3] in which the repeating unit (II) having the above carboxyl group contains the repeating unit represented by the following general formula (II-1).

[0028] [Chemical Formula 2]

[0029]

[0030] (In Equation (II-1), R 5represents a hydrogen atom or an organic group. * represents a bonding hand.)

[0031] [5] A photosensitive resin composition of any one of [1] to [4], wherein the content of the copolymer resin (C1) is 20 mass% or more relative to the total solid content of the photosensitive resin composition.

[0032] [6] A photosensitive resin composition of any one of [1] to [5], wherein the above (C) alkali-soluble resin contains, in addition to the copolymer resin (C1), an alkali-soluble resin.

[0033] [7] A photosensitive resin composition of any one of [1] to [6], additionally containing (E) a coloring agent.

[0034] [8] A photosensitive resin composition of any one of [1] to [7], additionally containing a solvent.

[0035] [9] A photosensitive resin composition of any one of [1] to [8] for heat firing at 140 ℃ or lower.

[0036]

[10] A cured product formed by curing any one of the photosensitive resin compositions [1] to [9].

[0037]

[11]

[10] A bulkhead composed of hardened material.

[0038]

[12]

[11] An organic field light-emitting device having a partition wall.

[0039]

[13]

[11] A color filter equipped with a partition and additionally containing luminescent nanocrystalline particles.

[0040]

[14]

[11] Image display device having a partition wall.

[0041]

[15] A method for forming a cured product using any one of the photosensitive resin compositions [1] to [8] and having at least the following processes (1) to (4).

[0042] Process (1): A process of forming a film by applying the above photosensitive resin composition onto a substrate.

[0043] Process (2): A process of exposing at least a portion of the coating film formed in the above process (1).

[0044] Process (3): A process for developing the film exposed in the above process (2).

[0045] Process (4): A process of firing the coating developed in the above process (3).

[0046]

[16] A method for forming a hardened product of the above process (4) in which the firing temperature is 140 ℃ or lower.

[15]

[0047]

[17] A method for forming a cured product of

[15] or

[16] having a post-exposure process of exposing the developed film in the above process (3) after the above process (3). Effects of the invention

[0048] According to the present invention, a photosensitive resin composition can be provided that has high liquid repellency even at a low curing temperature and does not cause problems such as ink penetration. Brief explanation of the drawing

[0049] FIG. 1 is a schematic cross-sectional view of an example of a color filter having a partition wall according to the present invention. FIG. 2a is a schematic diagram of the ink penetration evaluation results in the present invention. FIG. 2b is a schematic diagram of the ink penetration evaluation results in the present invention. Specific details for implementing the invention

[0050] The present invention will be described in detail below. Furthermore, the following description is merely an example of an embodiment of the present invention, and the present invention is not limited thereto unless it exceeds the gist thereof.

[0051] In the present invention, the following terms have the following meanings.

[0052] "(Meth)acrylic" means "either or both of acrylic and methacrylic."

[0053] "Total solid content" refers to the total amount of components other than the solvent in the photosensitive resin composition. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solid content.

[0054] The numerical range indicated using "~" refers to a range that includes the values ​​listed before and after "~" as lower and upper limits.

[0055] The term “(co)polymer” means including both a single polymer (homopolymer) and a copolymer (copolymer).

[0056] "(Acid) anhydrous" and "(Anhydrous)... acid" mean that it includes both the acid and the anhydrous substance.

[0057] "Bulkhead material" refers to bank material, wall material, and wall material. "Bulkhead" refers to bank, wall, and wall.

[0058] "Weight average molecular weight" means the weight average molecular weight (Mw) of polystyrene equivalent by GPC (gel permeation chromatography).

[0059] "Acid value" refers to the acid value converted to effective solids unless otherwise specified, and is calculated by neutralization titration.

[0060] In the present invention, the partition wall can be used, for example, to partition a functional layer (organic layer, light-emitting part) in an active-driven organic electroluminescent device, and can be used to form a pixel including, for example, a functional layer and a partition wall by ejecting and drying ink, which is a material for constituting the functional layer, in a partitioned area (pixel area). In addition, it can be used to partition a pixel part in a color filter containing luminescent nanocrystalline particles, and can be used to form a pixel by ejecting and drying ink in a partitioned area.

[0061] [1] Photosensitive resin composition

[0062] 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 agent as essential components. Additionally, other components may be included as needed, for example, (E) a colorant and (F) a dispersant.

[0063] [1-1] Components and composition of photosensitive resin composition

[0064] The components constituting the photosensitive resin composition of the present invention and the composition thereof will be described.

[0065] [1-1-1] (A) Photopolymerizable compounds

[0066] The photosensitive resin composition of the present invention contains (A) a photopolymerizable compound. By including (A) the photopolymerizable compound, it is believed that the curability of the coating film is increased and the ink-repellent properties are improved.

[0067] A photopolymerizable compound refers to a compound having one or more ethylenically unsaturated bonds within its molecule. For example, it is preferable to have a compound having two or more ethylenically unsaturated bonds within its molecule, in that it can amplify polymerization, crosslinkability, and the accompanying difference in developer solubility between the exposed and unexposed parts. It is preferable that the ethylenically unsaturated bonds originate from (meth)acryloyloxy groups, and it is even more preferable that the photopolymerizable compound be a (meth)acrylate compound.

[0068] In the present invention, it is particularly preferable to use a polyfunctional ethylene monomer having two or more ethylene unsaturated bonds in one molecule. The number of ethylene unsaturated groups in the polyfunctional ethylene monomer is not particularly limited, but is preferably two or more, more preferably three or more, even more preferably five or more, and preferably 15 or fewer, more preferably 10 or fewer, even more preferably 8 or fewer, and particularly preferably 7 or fewer. The upper and lower limits above may be combined arbitrarily. For example, 2 to 15 are preferred, 2 to 10 are more preferred, 3 to 8 are even more preferred, and 5 to 7 are particularly preferred. By making the value above the lower limit, polymerization is improved, and ink release tends to be higher. By making the value below the upper limit, developability tends to be better.

[0069] Specific examples of photopolymerizable compounds include, for example, esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; and esters obtained by the esterification reaction of a polyhydroxy compound, such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound, and an unsaturated carboxylic acid and a polybasic carboxylic acid.

[0070] As esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, for example, 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 in which the acrylate of these exemplary compounds is replaced with methacrylate; itaconic acid esters in which the acrylate of these exemplary compounds is replaced with itaconate; and crotonic acid esters in which the acrylate of these exemplary compounds is replaced with crotonate. Maleic acid esters in which the acrylate of these example compounds is replaced with maleate can be cited.

[0071] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include, for instance, acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0072] 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 single products, but representative specific examples include, for instance, 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.

[0073] In addition, examples of polyfunctional ethylenetic monomers include urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound 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 are useful.

[0074] Examples of the above urethane (meth)acrylates include, for instance, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoei Chemical Co.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Mitsubishi Chemical Co.).

[0075] In terms of adhesion and ink-repellent properties of the partition wall to the substrate, (A) as a photopolymerizable compound, it is preferable to use an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid or a urethane (meth)acrylate, and more preferable to use a dibasic acid anhydride adduct of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, 2-tris(meth)acryloyloxymethylethylphthalic acid, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate.

[0076] (A) One type of photopolymerizable compound may be used alone, or two or more types may be used in combination.

[0077] (A) The molecular weight of the photopolymerizable compound is not particularly limited, but 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, more preferably 700 or less, in terms of forming ink-repellent and narrow-line-width, high-precision barriers. The upper and lower limits above may be combined arbitrarily. For example, 100 to 1000 is preferred, 150 to 1000 is more preferred, 200 to 1000 is more preferred, 300 to 700 is more preferred, 400 to 700 is particularly preferred, and 500 to 700 is particularly preferred.

[0078] (A) The number of carbon atoms in the photopolymerizable compound is not particularly limited, but from the viewpoint of ink-forming properties 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, and particularly preferably 30 or less. The upper and lower limits above may be combined arbitrarily. For example, 7 to 50 is preferred, 10 to 50 is more preferred, 15 to 40 is more preferred, 20 to 35 is more preferred, and 25 to 30 is particularly preferred.

[0079] In terms of forming a high-precision partition with a narrow line width and ink-like properties, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred, and ester (meth)acrylates with three or more functions such as pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate, and acid anhydride adducts of ester (meth)acrylates with three or more functions such as 2,2,2-tris(meth)acryloyloxymethylethylphthalic acid and dipentaerythritol penta(meth)acrylate are more preferred.

[0080] From the perspective of improving the penetration resistance of the barrier, it is preferable to use ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates having one or more hydroxyl groups in the molecule, and 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, dipentaerythritol di(meth)acrylate, glycidyl (meth)acrylate adducts to glycerol (additional number 1-3), and glycidyl (meth)acrylate adducts to pentaerythritol (additional number 1-4). Glycidyl (meth)acrylate adducts to dipentaerythritol (additional water 1-6), glycidyl (meth)acrylate adducts to sorbitol (additional water 1-6), glycidyl acrylate adducts to 3-butene-1,2-diol (additional water 2), reaction products of diglycidylated compounds of bisphenols and (meth)acrylic acid, and alkylene oxide modified products thereof are more preferred. Two or more of these may be used in combination.

[0081] (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, and particularly preferably 300 g / mol or less. Additionally, it is 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 upper and lower limits above may 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 225 to 300 g / mol is particularly preferred. By making it below the upper limit value, the developmental properties or penetration resistance of the barrier tend to be improved, and by making it above the lower limit value, the ink-repellent properties tend to be improved.

[0082] The content ratio of (A) a photopolymerizable compound in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1 mass% or more, more preferably 5 mass% or more, even more preferably 10 mass% or more, even more preferably 15 mass% or more, particularly preferably 20 mass% or more with respect to the total solid content of the photosensitive resin composition, and is also preferably 90 mass% or less, more preferably 80 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less. The upper and lower limits above may be combined arbitrarily. For example, 1 to 80 mass% is preferred, 5 to 80 mass% is more preferred, 10 to 70 mass% is more preferred, 15 to 60 mass% is more preferred, and 25 to 50 mass% is particularly preferred. By making the value above the lower limit or higher, the ink-repellent properties tend to be improved. By keeping the value below the upper limit mentioned above, there is a tendency to form a fixed bulkhead with a narrow line width.

[0083] (C) The content ratio of (A) the photopolymerizable compound to 100 parts by mass of the 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 particularly 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 may 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. By making it above the lower limit value, ink-repellent properties tend to be improved. By making it below the upper limit value, it tends to be possible to form a high-precision partition with a narrow line width.

[0084] [1-1-2] (B) Photopolymerization initiator

[0085] The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. (B) The photopolymerization initiator is not particularly limited to a compound that polymerizes (A) a photopolymerizable compound by an active light, for example, a compound that polymerizes the ethylenically unsaturated bonds of (A) a photopolymerizable compound.

[0086] The photosensitive resin composition of the present invention may use (B) a photopolymerization initiator commonly used in the field as a photopolymerization initiator. Examples of such photopolymerization initiators include, for instance, metallocene compounds including titanocene compounds described in Japanese Patent Publication No. Sho 59-152396 and Japanese Patent Publication No. Sho 61-151197; hexaarylbiimidazole derivatives 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 described in Japanese Patent Publication No. Hei 10-39503; Examples include oxime ester compounds described in Japanese Published Patent Application No. 2000-80068 and Japanese Published Patent Application No. 2006-36750.

[0087] Examples of metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di(2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), and dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyro-1-yl)-phenyl]. It is possible.

[0088] Examples of non-imidazole 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.

[0089] 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.

[0090] Examples of halomethyl-s-triazine derivatives include, for instance, 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.

[0091] 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.

[0092] As photopolymerization initiators, oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties. For example, when using an alkali-soluble resin containing a phenolic hydroxyl group, sensitivity becomes disadvantageous, so oxime ester compounds with such excellent sensitivity are particularly useful. Since oxime ester compounds have a high quantum yield of photoreaction and high activity of the generated radicals, it is possible to obtain a photosensitive resin composition that is highly sensitive with a small amount, stable against thermal reactions, and highly sensitive with a small amount.

[0093] Examples of oxime ester compounds include, for instance, compounds represented by the following general formula (IV).

[0094] [Chemical Formula 3]

[0095]

[0096] In Equation (IV), R 21a represents a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring that may have a substituent.

[0097] R 21b represents any substituent containing a directional ring.

[0098] R 22a represents an alkanoyl group that may have substituents, or an aroyl group that may have substituents.

[0099] n represents an integer of 0 or 1.

[0100] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the perspective of solubility or sensitivity to a solvent, it is preferably 1 or more, more preferably 2 or more, and also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, and cyclohexylmethyl groups.

[0101] Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl groups, and N-acetyl-N-acetoxyamino groups. From the perspective of ease of synthesis, it is preferable to be unsubstituted.

[0102] R 21a Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic complex ring groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but it is preferable to have 5 or more from the perspective of solubility in the photosensitive resin composition. In addition, from the perspective of developability, it is preferable to have 30 or fewer, more preferable to have 20 or fewer, and even more preferable to have 12 or fewer. For example, 5 to 30 is preferable, 5 to 20 is more preferable, and 5 to 12 is even more preferable.

[0103] Examples of aromatic ring groups include phenyl groups, naphthyl groups, pyridyl groups, and furyl groups. From the perspective of development, phenyl groups or naphthyl groups are preferred, and phenyl groups are more preferred.

[0104] Substituents that may be present in the aromatic ring include, for example, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, alkyl groups, alkoxy groups, and groups to which the substituents are connected. From the perspective of development, alkyl groups, alkoxy groups, and groups to which the substituents are connected are preferred, and connected alkoxy groups are more preferred.

[0105] In terms of sensitivity, R 21a It is preferable that the group be an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.

[0106] R 21bA substituted carbazolyl group, a substituted thioxanthonyl group, a substituted diphenylsulfide group, a substituted fluorenyl group, or a substituted indolyl group is preferred. From the perspective of sensitivity, a substituted carbazolyl group is more preferred.

[0107] R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but from the perspective of solubility or sensitivity to a solvent, it is preferably 2 or more, 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 more preferred, and 2 to 5 is even more preferred.

[0108] Alkanoyl groups include, for example, acetyl groups, ethylyl groups, propanoyl groups, and butanoyl groups.

[0109] Substituents that the alkanoyl group may have include, for example, aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups. From the perspective of ease of synthesis, it is preferable to be unsubstituted.

[0110] R 22a The number of carbon atoms in the aroyl group is not particularly limited, but from the perspective of solubility or sensitivity to a solvent, it is preferably 7 or more, more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. For example, 7 to 20 is preferred, 7 to 15 is more preferred, and 7 to 10 is even more preferred. Examples of aroyl groups include benzoyyl groups and naphthyl groups.

[0111] Substituents that the aroyl group may have include, for example, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and alkyl groups. From the perspective of ease of synthesis, it is preferable to be unsubstituted.

[0112] In terms of sensitivity, R 22a It is preferable that the alkanoyl group be one that may have a substituent, more preferable that it be an unsubstituted alkanoyl group, and even more preferable that it be an acetyl group.

[0113] For example, photopolymerization initiators described in Japanese Patent Publication 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 Publication 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 may be used.

[0114] One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0115] In the photopolymerization initiator, a sensitizing dye and a polymerization promoter according to the wavelength of the image exposure light source may be incorporated as needed to increase sensitivity. Examples of sensitizing dyes include, for instance, the xanthene dyes described in Japanese Patent Publication No. Hei 4-221958 and Japanese Patent Publication No. Hei 4-219756; the coumarin dyes having a complex ring described in Japanese Patent Publication No. Hei 3-239703 and Japanese Patent Publication No. Hei 5-289335; the 3-ketocoumarin compounds described in Japanese Patent Publication No. Hei 3-239703 and Japanese Patent Publication No. Hei 5-289335; and the pyromethene dye described in Japanese Patent Publication No. Hei 6-19240. Examples include pigments having a dialkylaminobenzene backbone described in Japanese Patent Publication No. Sho 47-2528, Japanese Patent Publication No. Sho 54-155292, Japanese Patent Publication No. Sho 45-37377, Japanese Patent Publication No. Sho 48-84183, Japanese Patent Publication No. Sho 52-112681, Japanese Patent Publication No. Sho 58-15503, Japanese Patent Publication No. Sho 60-88005, Japanese Patent Publication No. Sho 59-56403, Japanese Patent Publication No. Hei 2-69, Japanese Patent Publication No. Sho 57-168088, Japanese Patent Publication No. Hei 5-107761, Japanese Patent Publication No. Hei 5-210240, and Japanese Patent Publication No. Hei 4-288818.

[0116] As for the sensitizing dye, an amino group-containing sensitizing dye is preferred, and a compound having an amino group and a phenyl group within the same molecule is more preferred. For example, benzophenone-based compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 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)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, Compounds containing a p-dialkylaminophenyl group, such as (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine, are more preferable, and 4,4'-dialkylaminobenzophenone is particularly preferred.

[0117] One type of sensitizing dye may be used alone, or two or more types may be used in combination.

[0118] As polymerization promoters, for example, aromatic amines such as 4-dimethylaminobenzoate ethyl, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, 4-dimethylaminopropiophenone, etc., and aliphatic amines such as n-butylamine, N-methyldiethanolamine, 2-dimethylaminoethyl benzoate can be used.

[0119] Polymerization promoters may be used as a single type or in combination of two or more types.

[0120] The content ratio of (B) a photopolymerization initiator in the photosensitive resin composition of the present invention is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, it is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, even more preferably 1 mass% or more, even more preferably 2 mass% or more, particularly preferably 3 mass% or more, and also preferably 25 mass% or less, more preferably 20 mass% or less, even more preferably 15 mass% or less, even more preferably 12 mass% or less, particularly preferably 10 mass% or less, and most preferably 8 mass% or less. The above upper and lower limits may be combined arbitrarily. For example, 0.01 to 25 mass% is preferred, 0.01 to 20 mass% is more preferred, 0.1 to 15 mass% is even more preferred, 1 to 10 mass% is more preferred, 2 to 8 mass% is particularly preferred, and 3 to 7 mass% is particularly preferred. By making it above the lower limit value, ink-repellent properties tend to improve. By making it below the upper limit value, residue tends to be reduced.

[0121] The mixing ratio of (B) a photopolymerization initiator to (A) a photopolymerizable compound in a photosensitive resin composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, more preferably 4 parts by mass or more, 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, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less, with respect to 100 parts by mass or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 200 parts by mass is preferred, 3 to 200 parts by mass is more preferred, 5 to 100 parts by mass is more preferred, 8 to 50 parts by mass is more preferred, and 10 to 20 parts by mass is particularly preferred. By exceeding the above lower limit value, the ink-repellent properties tend to be improved. There is a tendency for residue to be reduced by keeping it below the upper limit value mentioned above.

[0122] A chain transfer agent may be used in combination with a photopolymerization initiator. Examples of chain transfer agents include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use mercapto group-containing compounds because they tend to have a high chain transfer effect. This is thought to be because the low SH bond energy facilitates bond cleavage, making it easy to induce hydrogen pull-out reactions or chain transfer reactions. The use of a chain transfer agent is effective for improving sensitivity and surface hardenability.

[0123] As for the mercapto group-containing compound, it may have multiple mercapto groups within the molecule. As for the mercapto group-containing compound, for example, a mercapto group-containing compound having an aromatic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazolin, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene;

[0124] Hexanedithiol, Decandithil, 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-mercaptopropionate), Butanediol bis(3-mercaptobutyrate), Ethylene glycol bis(3-mercaptobutyrate), Trimethylolpropane tris(3-mercaptobutyrate), Pentaerythritol tetrakis(3-mercaptobutyrate), Pentaerythritol tris(3-mercaptobutyrate), Examples of aliphatic mercapto group-containing compounds include 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0125] As mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred. As aliphatic mercapto group-containing compounds, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), pentaerythritoltris(3-mercaptopropionate), trimethylolpropanetris(3-mercaptobutyrate), pentaerythritoltetrakis(3-mercaptobutyrate), pentaerythritoltris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

[0126] In terms of sensitivity, aliphatic mercapto group-containing compounds are preferred, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), pentaerythritoltris(3-mercaptopropionate), trimethylolpropanetris(3-mercaptobutyrate), pentaerythritoltetrakis(3-mercaptobutyrate), pentaerythritoltris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are more preferred, and pentaerythritoltetrakis(3-mercaptopropionate) and pentaerythritoltetrakis(3-mercaptobutyrate) are even more preferred.

[0127] Aliphatic mercapto group-containing compounds may be used alone or in combination of two or more.

[0128] In terms of increasing the taper angle, it is preferable to use a photopolymerization initiator system by combining 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.

[0129] From the perspective 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). Additionally, from the perspective 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.

[0130] 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 with respect to the total solid content of the photosensitive resin composition, it is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, even more preferably 0.5 mass% or more, and even more preferably 0.8 mass% or more, and also preferably 5 mass% or less, more preferably 4 mass% or less, even more preferably 3 mass% or less, and even more preferably 2 mass% or less. The above upper and lower limits may be arbitrarily combined. For example, 0.01 to 5 mass% is preferred, 0.1 to 4 mass% is more preferred, 0.5 to 3 mass% is even more preferred, and 0.8 to 2 mass% is particularly preferred. By making the value above the lower limit, the ink-repellent properties tend to be improved. By making the value below the upper limit, it tends to be possible to form a high-precision barrier with a narrow line width.

[0131] Regarding the content ratio of a chain transfer agent to a photopolymerization initiator (B) in a photosensitive resin composition, with respect to 100 parts by mass of (B) photopolymerization initiator, it is preferable to have 5 parts by mass or more, more preferable to have 10 parts by mass or more, even more preferable to have 15 parts by mass or more, and particularly preferable to have 20 parts by mass or more, and also preferable to have 500 parts by mass or less, more preferable to have 300 parts by mass or less, even more preferable to have 100 parts by mass or less, and particularly preferable to have 50 parts by mass or less. The above upper and lower limits may be combined arbitrarily. For example, 5 to 500 parts by mass is preferable, 10 to 300 parts by mass is more preferable, 15 to 100 parts by mass is even more preferable, and 20 to 50 parts by mass is particularly preferable. By making the value greater than the above lower limit, there is a tendency for the ink-repellent properties to be improved. By making the value less than the above upper limit, there is a tendency to form a high-precision barrier with a narrow line width.

[0132] [1-1-3] (C) Alkali-soluble resin

[0133] The photosensitive resin composition of the present invention comprises (C) an alkali-soluble resin. (C) The alkali-soluble resin comprises a copolymer resin (C1) having repeating units including an aliphatic polycyclic structure in the main chain (hereinafter referred to as “copolymer resin (C1)”).

[0134] It is believed that by having repeating units containing aliphatic polycyclic structures in the main chain, the reaction sites approach each other during photo and / or thermal curing reactions, and thus the curing reaction proceeds without excessively hindering the reaction, and furthermore, after curing, the function of efficiently suppressing the penetration of ink, etc. (hereinafter referred to as penetration resistance) is exhibited due to the large structure.

[0135] The copolymer resin (C1) preferably has a repeating unit represented by the following general formula (I) (hereinafter referred to as “repeating unit (I)”).

[0136] [Chemical Formula 4]

[0137]

[0138] In Equation (I), R 1 ~ R 4 Each represents independently a hydrogen atom or a hydrocarbon group. n represents an integer from 0 to 2. * represents a bond hand.

[0139] <Repetition Unit (I)>

[0140] In Equation (I), R 1 ~ R 4 Each is independently a hydrogen atom or a hydrocarbon group.

[0141] Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aromatic ring groups, and aralkyl groups.

[0142] The alkyl group may be any of the straight-chain, branched-chain, or cyclic types.

[0143] The number of carbon atoms in the alkyl group is not particularly limited, but 1 or more is preferred, 3 or more is more preferred, 6 or more is even more preferred, 15 or less is preferred, and 8 or less is even more preferred. The upper and lower limits above may be combined arbitrarily. For example, 1 to 15 is preferred, 3 to 15 is more preferred, and 6 to 8 is even more preferred. By making the value above the lower limit, the penetration resistance of the ink tends to improve. By making the value below the upper limit, the developability tends to improve.

[0144] Examples of alkyl groups include, for instance, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.

[0145] The number of carbon atoms in the alkenyl group is not particularly limited, but 2 or more is preferred, 3 or more is more preferred, 10 or less is preferred, and 8 or less is more preferred. The above upper and lower limits can be combined arbitrarily. For example, 2 to 10 is preferred, and 3 to 8 is more preferred. Penetration resistance tends to improve when the value is greater than or equal to the above lower limit. Formability tends to improve when the value is less than or equal to the above upper limit.

[0146] Examples of alkenyl groups include vinyl, allyl, butenyl, and pentenyl groups.

[0147] The number of carbon atoms in the alkynyl group is not particularly limited, but 2 or more is preferred, 3 or more is more preferred, 10 or fewer is preferred, and 8 or fewer is more preferred. The upper and lower limits above may be combined arbitrarily. For example, 2 to 10 is preferred, and 3 to 8 is more preferred. Penetration resistance tends to improve when the value is greater than or equal to the lower limit. Formability tends to improve when the value is less than or equal to the upper limit.

[0148] Examples of alkynyl groups include the ethinyl group and the propargyl group.

[0149] Examples of aromatic rings include aromatic hydrocarbon rings and aromatic complex rings.

[0150] The number of carbon atoms in the aromatic ring is not particularly limited, but 4 or more is preferred, 5 or more is more preferred, 6 or more is even more preferred, 20 or less is preferred, 15 or less is more preferred, and 10 or less is even more preferred. 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. By making it above the above lower limit value, penetration resistance tends to improve. By making it below the above upper limit value, the surface properties tend to improve.

[0151] Examples of aromatic ring groups include phenyl groups, naphthyl groups, tolyl groups, and xylyl groups.

[0152] 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. Penetration resistance tends to improve when the value is greater than or equal to the above lower limit. Formability tends to improve when the value is less than or equal to the above upper limit.

[0153] Examples of aralkyl groups include a group in which one hydrogen atom of the alkyl group is substituted with the aromatic ring. Examples include a benzyl group and a phenethyl group.

[0154] R 1 ~ R 4 Each independently represents a hydrogen atom or a hydrocarbon group, but R 1 and R 4 It may be connected to form a ring-shaped structure, and likewise, R 2 and R 3 It is acceptable for this to be connected and form a ring-shaped structure.

[0155] In terms of ease of synthesis, R 1 ~ R 4 It is preferable that one of them is a hydrogen atom, and R 1 ~ R 4 It is more desirable that all of them be hydrogen atoms.

[0156] n represents an integer from 0 to 2, but from the perspective of phenomenology, it is preferable that n be 0.

[0157] As for the repeating unit (I), the repeating unit represented by the following general formulas (I-1) to (I-3) can be used, and the repeating unit represented by the following general formula (I-1) is more desirable in terms of penetration resistance.

[0158] [Chemical Formula 5]

[0159]

[0160] <Repetition Unit (II)>

[0161] It is preferable that the copolymer resin (C1) has a repeating unit (II) having a carboxyl group (hereinafter referred to as "repeating unit (II)").

[0162] The structure of the repeating unit (II) having a carboxyl group is not particularly limited, but, for example, a repeating unit derived from an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride may be used.

[0163] It is desirable to include a repeating unit represented by the following general formula (II-1) (hereinafter referred to as "repeating unit (II-1)") from the perspective of achieving both phenomenality and penetration resistance, and also being able to adjust the strength of these characteristics as needed.

[0164] [Chemical Formula 6]

[0165]

[0166] In Equation (II-1), R 5 represents a hydrogen atom or an organic group. * represents a bonding hand.

[0167] Examples of organic groups include alkyl groups that may have substituents and aryl groups that may have substituents. It is preferable that the number of carbon atoms in the alkyl and aryl groups be 1 to 18.

[0168] R 5 In the case where the alkyl group is an alkyl group, the number of carbon atoms is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 4 or more is even more preferred, 9 or fewer is preferred, and 7 or fewer is even more preferred. The upper and lower limits above may be combined arbitrarily. For example, 1 to 9 is preferred, 2 to 9 is more preferred, and 4 to 7 is even more preferred.

[0169] Examples of alkyl groups include, for instance, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.

[0170] R 5 In the case where α is an aryl group, the number of carbon atoms is not particularly limited, but 6 or more is preferred, 20 or fewer is preferred, 15 or fewer is more preferred, and 10 or fewer is even more preferred. 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.

[0171] Examples of aryl groups include phenyl groups, naphthyl groups, tolyl groups, and xylyl groups.

[0172] Substituents that may be present in alkyl and aryl groups include, for example, hydroxyl groups and (meth)acryloyl groups.

[0173] In terms of penetration resistance, R 5 A unit having a structure represented by the following general formula (II-2) is more preferable.

[0174] [Chemical Formula 7]

[0175]

[0176] In Equation (II-2), R 6 represents a hydrogen atom or a methyl group. e represents an integer from 1 to 5. * represents a bond hand.

[0177] In formula (II-2), e is preferably 1 to 3 in terms of penetration resistance, and more preferably 1 to 2.

[0178] As for the repeating unit (II-1), any of the repeating units represented by the following general formulas (II-3) to (II-6) is more preferable, and the repeating unit represented by the following general formula (II-3) or the following general formula (II-4) is particularly preferred.

[0179] [Chemical Formula 8]

[0180]

[0181] In equations (II-3) to (II-6), * indicates a bond.

[0182] <Other repeating units>

[0183] The copolymer resin (C1) may have repeating units other than repeating unit (I) and repeating unit (II).

[0184] Other repeating units are not limited to, but include, for example, repeating units represented by the following general formulas (III-1) to (III-5) (hereinafter referred to as “repetition units (III-1) to (III-5)”).

[0185] [Chemical Formula 9]

[0186]

[0187] Among equations (III-1) to (III-4), R 5 is equivalent to Equation (II-1), and R 7 represents a hydrogen atom or a methyl group. * represents a bond.

[0188] [Chemical Formula 10]

[0189]

[0190] In Equation (III-5), R 8 * indicates an alkyl group that may have a substituent. * indicates a bond loss.

[0191] By having a repeating unit represented by formula (III-5), the heat resistance of the copolymer resin (C1) tends to be improved.

[0192] R 8 Examples of alkyl groups that may have substituents include methyl, ethyl, propyl, and benzyl groups.

[0193] The copolymer resin (C1) is preferably having repeating units (I), repeating units (II-1) and repeating units (III-1) in terms of surface smoothness and penetration resistance, and is more preferably having repeating units (I), repeating units (II-1), repeating units (III-1) and repeating units (III-4).

[0194] [Method for manufacturing copolymer resin (C1)]

[0195] The method for manufacturing the copolymer resin (C1) is not particularly limited and conventionally known methods may be employed. For example, it can be manufactured by the following (Process i) to (Process iii). In addition, the ring-opening precursor polymer obtained in (Process ii) may be used as the copolymer resin (C1).

[0196] (Process i) A process for preparing a precursor polymer comprising a repeating unit represented by Formula (I) and a repeating unit represented by Formula (III-4).

[0197] (Process ii) A process of reacting an alcohol or water with the above precursor polymer to ring-open the anhydrous backbone in formula (III-4) and to generate a carboxyl group or its ester in the precursor polymer to obtain a ring-opening precursor polymer.

[0198] For the alcohols used in (Process ii), it is more preferable to use a compound represented by the following general formula (II-2-1) from the perspective of penetration resistance.

[0199] [Chemical Formula 11]

[0200]

[0201] In Equation (II-2-1), R6 , e has the same meaning as in Equation (II-2).

[0202] (Process iii) Optionally, a process of reacting a compound having an epoxy group and an ethylenic double bond with the ring-opening precursor polymer obtained in (Process ii).

[0203] Examples of compounds having an epoxy group and an ethylenic double bond include, for instance, glycidyl methacrylate.

[0204] The copolymer resin (C1) may be manufactured, for example, according to the method described in International Publication No. 2016 / 194619 or International Publication No. 2017 / 154439.

[0205] The content ratio of the repeating unit (I) in the copolymer resin (C1) is not particularly limited, but in the copolymer resin (C1), 10 mass% or more is preferred, 20 mass% or more is more preferred, 25 mass% or more is even more preferred, 50 mass% or less is preferred, 40 mass% or less is more preferred, and 30 mass% or less is even more preferred. The above upper and lower limits can be combined arbitrarily. For example, 10 to 50 mass% is preferred, 20 to 40 mass% is more preferred, and 25 to 30 mass% is even more preferred. By making it above the above lower limit value, penetration resistance tends to improve. By making it below the above upper limit value, the formability tends to improve.

[0206] The content ratio of the repeating unit (I) in the copolymer resin (C1) is not particularly limited, but among the total repeating units, 20 mol% or more is preferred, 30 mol% or more is more preferred, 40 mol% or more is even more preferred, 80 mol% or less is preferred, 70 mol% or less is more preferred, and 60 mol% or less is even more preferred. 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. By making it above the above lower limit value, penetration resistance tends to improve. By making it below the above upper limit value, formability tends to improve.

[0207] When the copolymer resin (C1) has repeating units (II-1), the content ratio is not particularly limited, but among the total repeating units, 5 mol% or more is preferred, 10 mol% or more is more preferred, 15 mol% or more is even more preferred, 40 mol% or less is preferred, 30 mol% or less is more preferred, and 20 mol% or less is even more preferred. 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. There is a tendency for the formability to improve by making it above the above lower limit value. There is a tendency for the penetration resistance to improve by making it below the above upper limit value.

[0208] When the copolymer resin (C1) has repeating units (III-1), the content ratio is not particularly limited, but among the total repeating units, 5 mol% or more is preferred, 10 mol% or more is more preferred, 15 mol% or more is even more preferred, 40 mol% or less is preferred, 30 mol% or less is more preferred, and 20 mol% or less is even more preferred. 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. By making the value above the lower limit, penetration resistance tends to improve. By making the value below the upper limit, the formability tends to improve.

[0209] When the copolymer resin (C1) has repeating units (III-4), the content ratio is not particularly limited, but among the total repeating units, 5 mol% or more is preferred, 10 mol% or more is more preferred, 15 mol% or more is even more preferred, 40 mol% or less is preferred, 30 mol% or less is more preferred, and 20 mol% or less is even more preferred. 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. Synthesis tends to become easier when the value is above the above lower limit. Penetration resistance and developability tend to become better when the value is below the above upper limit.

[0210] When the copolymer resin (C1) has repeating unit (II-1), repeating unit (III-1), and repeating unit (III-4), the content ratio of repeating unit (II-1) relative to the sum of the content ratios of repeating unit (II-1), repeating unit (III-1), and repeating unit (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 may 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. There is a tendency for the formability to improve by making it above the above lower limit value. There is a tendency for the penetration resistance to improve by making it below the above upper limit value.

[0211] The acid value of the copolymer resin (C1) is not particularly limited, but is preferably 10 mgKOH / g or higher, more preferably 30 mgKOH / g or higher, even more preferably 50 mgKOH / g or higher, and also preferably 200 mgKOH / g or lower, more preferably 150 mgKOH / g or lower, even more preferably 100 mgKOH / g or lower, and particularly preferably 80 mgKOH / g or lower. The upper and lower limits above may be combined arbitrarily. For example, 10 to 200 mgKOH / g is preferred, 10 to 150 mgKOH / g is more preferred, 30 to 100 mgKOH / g is even more preferred, and 50 to 80 mgKOH / g is particularly preferred. By making it above the lower limit value, developability tends to improve. By making it below the upper limit value, develop adhesion tends to improve.

[0212] 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, and 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 upper and lower limits above may be combined arbitrarily. 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. By making it greater than the lower limit value, the adhesion of the development tends to improve. There is a tendency for the phenomenal properties to improve by keeping the value below the upper limit mentioned above.

[0213] 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, particularly preferably 500 or more, and 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 particularly preferred. There is a tendency for the formability to improve by making it above the above lower limit value. There is a tendency for the penetration resistance to improve by making it below the above upper limit value.

[0214] The content ratio of the copolymer resin (C1) is not particularly limited, but it is preferable to have 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, and 40 mass% or more with respect to the total solid content of the photosensitive resin composition. In addition, it is preferable to have 80 mass% or less, 60 mass% or less, and 50 mass% or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 80 mass% is preferable, 10 to 80 mass% is more preferable, 20 to 60 mass% is more preferable, 30 to 60 mass% is more preferable, and 40 to 50 mass% is particularly preferable. By making it above the above lower limit value, penetration resistance tends to be good. By making it below the above upper limit value, the development form tends to be prone to dissolution.

[0215] (C) The content ratio of copolymer resin (C1) in alkali-soluble resin is not particularly limited, but 20 mass% or more is preferred, 30 mass% or more is more preferred, 40 mass% or more is even more preferred, 45 mass% or more is particularly preferred, and 100 mass% or less is preferred. For example, 20 to 100 mass% is preferred, 30 to 100 mass% is more preferred, 40 to 100 mass% is even more preferred, and 45 to 100 mass% is particularly preferred. By making it above the lower limit value, penetration resistance tends to be good. By making it below the upper limit value, the development form tends to be a dissolution phenomenon.

[0216] In the photosensitive resin composition of the present invention, (C) alkali-soluble resin may additionally contain an alkali-soluble resin other than copolymer resin (C1) (hereinafter referred to as "other alkali-soluble resin"). It is preferable to include other alkali-soluble resins so that additional properties, including improved developability, can be imparted while maintaining the aforementioned penetration resistance.

[0217] Among other alkali-soluble resins, from the perspective of developing solubility, it is preferable to include an epoxy(meth)acrylate resin (C2) other than the copolymer resin (C1) (hereinafter referred to as "epoxy(meth)acrylate resin (C2)"), and an epoxy(meth)acrylate resin (C2) having an aromatic ring in the main chain is more preferable. From the perspective of ink-repellent properties, it is preferable to include an acrylic copolymer resin (C3) having an ethylenically unsaturated group in the side chain (hereinafter referred to as "acrylic copolymer resin (C3)").

[0218] [Epoxy(meth)acrylate resin (C2)]

[0219] The epoxy (meth)acrylate resin (C2) is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or an 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, the carboxyl group of the unsaturated monocarboxylic acid is ring-opened and added to the epoxy group of the epoxy resin, thereby adding an ethylenically unsaturated group to the epoxy resin via an ester bond (-COO-), and the carboxyl group of the polybasic anhydride is added to the hydroxyl group generated at that time. It is also possible to add a polyhydric alcohol simultaneously when adding the polybasic anhydride.

[0220] A resin obtained by reacting a compound having a functional group capable of further reacting with the carboxyl group of the resin obtained by the above reaction is also included in the above epoxy(meth)acrylate resin (C2).

[0221] Examples of epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, biphenyl novolak epoxy resin, trisphenol epoxy resin, polymerization epoxy resin of phenol and dicyclopentadiene, dihydroxyfluorene type epoxy resin, dihydroxyalkylene oxyfluorene type epoxy resin, diglycidyl etheride of 9,9-bis(4'-hydroxyphenyl)fluorene, and diglycidyl etheride of 1,1-bis(4'-hydroxyphenyl)adamantan, and epoxy resins having an aromatic ring in the main chain may be preferably used.

[0222] As for the epoxy resin, in terms of heat resistance, bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene are preferred, and bisphenol A epoxy resin is more preferred.

[0223] As epoxy resins, for example, bisphenol A type epoxy resin (e.g., “jER (registered trademark, hereinafter the same) 828”, “jER1001”, “jER1002”, “jER1004” manufactured by Mitsubishi Chemical, and “NER-1302” manufactured by Nippon Kagaku Co., Ltd. (epoxy equivalent 323, softening point 76°C)), bisphenol F type resin (e.g., “jER807”, “jER4004P”, “jER4005P”, “jER4007P” manufactured by Mitsubishi Chemical, and “NER-7406” manufactured by Nippon Kagaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S type epoxy resin, biphenylglycidyl ether (e.g., “jERYX-4000” manufactured by Mitsubishi Chemical), Phenol novolak type epoxy resin (e.g., "EPPN-201" manufactured by Nippon Kagyaku Co., Ltd., "jER152" and "jER154" manufactured by Mitsubishi Chemical, and "DEN-438" manufactured by Dow Chemical), (o, m, p-) cresol novolak type epoxy resin (e.g., "EOCN (registered trademark, hereinafter the same)-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kagyaku Co., Ltd.), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissin Chemical Co., Ltd.), trisphenolmethane type epoxy resin (e.g., "EPPN (registered trademark, hereinafter the same)-501", "EPPN-502", and "EPPN-503" manufactured by Nippon Kagyaku Co., Ltd.), alicyclic epoxy resin ("Celoxide (registered trademark, hereinafter the same)" manufactured by Daicel Co., Ltd.) 2021P”, “Celoxide EHPE”), epoxy resin obtained by glycidylating a phenol resin by the reaction of dicyclopentadiene and phenol (e.g., “EXA-7200” manufactured by DIC, “NC-7300”, “XD-1000” manufactured by Nippon Hwayaksha Co., Ltd.), biphenyl-type epoxy resin (e.g., “NC-7000” manufactured by Nippon Hwayaksha Co., Ltd.), “E-201” manufactured by Osaka Organic Chemical Industry Co., Ltd., and “XD-1000” manufactured by Nippon Hwayaksha Co., Ltd., “NC-3000” manufactured by Nippon Hwayaksha Co., Ltd., “ESF-300” manufactured by Shin-Nippon Tetsu Steel Chemical Co., Ltd.,"E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. is more preferable.

[0224] Epoxy resin may be used as a single type or in combination with two or more types.

[0225] 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 anhydride succinic acid adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate anhydride succinic acid adduct, dipentaerythritol penta(meth)acrylate anhydride phthalic acid adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and reaction products of (meth)acrylic acid and ε-caprolactone, and (meth)acrylic acid is preferred in terms of sensitivity.

[0226] Ethylenergic unsaturated monocarboxylic acids may be used alone or in combination of two or more types.

[0227] 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, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides; from the perspective 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, Tetrahydrophthalic anhydride is more preferable.

[0228] As for polybasic acids (anhydrous), one type may be used alone, or two or more types may be used in combination.

[0229] By using polyhydric alcohols, the molecular weight of the epoxy(meth)acrylate resin (C2) can be increased, and branches can be introduced into the molecule, and a balance between molecular weight and viscosity can be achieved. In addition, the rate of introduction of acid groups into the molecule can be increased, making it easier to achieve a balance between sensitivity and adhesion.

[0230] As polyhydric alcohols, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol are preferred.

[0231] As for the polyhydric alcohol, one type may be used alone, or two or more types may be used in combination.

[0232] As for the epoxy (meth)acrylate resin (C2), in addition to the resins mentioned above, the resin described in Korean Patent Publication No. 10-2013-0022955 may be cited.

[0233] The epoxy(meth)acrylate resin (C2) preferably comprises at least one selected from the group consisting of an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (i) (hereinafter referred to as "epoxy(meth)acrylate resin (C2-1)"), and an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (ii) (hereinafter referred to as "epoxy(meth)acrylate resin (C2-2)") in terms of developing solubility.

[0234] [Chemical Formula 12]

[0235]

[0236] In Equation (i), R a represents a hydrogen atom or a methyl group. R brepresents a divalent hydrocarbon group that may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may additionally be substituted by any substituent. * represents each bond loss.

[0237] [Chemical Formula 13]

[0238]

[0239] In Equation (ii), R c represents, respectively, a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R e and R f Each represents an independent divalent aliphatic group that may have a substituent. l and m each represent an integer from 0 to 2. * each represents a bonding hand.

[0240] <Epoxy (Met)acrylate Resin (C2-1)>

[0241] [Chemical Formula 14]

[0242]

[0243] In Equation (i), R a represents a hydrogen atom or a methyl group. R b represents a divalent hydrocarbon group that may have a substituent. k represents 1 or 2. The benzene ring in formula (i) may additionally be substituted by any substituent. * represents each bond loss.

[0244] (R b )

[0245] In Equation (i), R b represents a divalent hydrocarbon group that may have a substituent.

[0246] Examples of divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups formed by connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

[0247] 2. Examples of aliphatic groups include straight-chain, branched-chain, and ring-shaped aliphatic groups. Among these, straight-chain aliphatic groups are preferred from the perspective of developing solubility, while ring-shaped aliphatic groups are preferred from the perspective of reducing the penetration of the developer into the exposed area.

[0248] The number of carbon atoms in the 2-valent 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. Film strength tends to improve by making it greater than or equal to the above lower limit value. Ink-repellent properties tend to improve by making it less than or equal to the above upper limit value.

[0249] Examples of 2-valent straight-chain aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene groups. From the perspective of ink-repellent properties or manufacturing costs, methylene groups are preferred.

[0250] As for the divalent branched chain aliphatic group, a structure having one or more side chains, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, can be cited.

[0251] The number of rings of the cyclic aliphatic groups is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 10 or fewer is preferred, and 5 or fewer is more preferred. The upper and lower limits above can be combined arbitrarily. For example, 1 to 10 is preferred, and 2 to 5 is more preferred. By making the value greater than the lower limit, the membrane strength tends to improve. By making the value less than the upper limit, the performance tends to improve.

[0252] Examples of divalent cyclic aliphatic groups having two free valencies include, for instance, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. In terms of film strength and phenotype, an adamantane ring and a dicyclopentane ring having two free valencies are preferred.

[0253] Substituents that may be present on the divalent aliphatic group include, for example, alkoxy groups having 1 to 5 carbon atoms, such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the perspective of ease of synthesis, it is preferable to be unsubstituted.

[0254] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic complex ring groups.

[0255] The number of carbon atoms in the divalent aromatic ring is preferably 4 or more, more preferably 5 or more, more preferably 6 or more, and also preferably 20 or less, more preferably 15 or less, and 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 more preferred. By making it above the above lower limit value, the film strength tends to improve. By making it below the above upper limit value, the formability tends to improve.

[0256] The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.

[0257] Examples of divalent aromatic hydrocarbon ring groups having two free valencies include, for instance, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0258] In an aromatic complex ring, the aromatic complex ring may be a single ring or a condensed ring.

[0259] Examples of divalent aromatic complex ring groups having two free valencies include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazol rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrazol rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, propyrrol rings, furofuran rings, thienofuran rings, benzisooxazole rings, benzisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, synnoline rings, quinoxaline rings, phenanthridine rings, ferrimidine rings, quinazoline rings, quinazolinone rings, and azulene rings. From the perspective of manufacturing costs, a benzene ring with two free valence atoms and a naphthalene ring are preferred, and a benzene ring with two free valence atoms is more preferred.

[0260] Substituents that may be present on the divalent aromatic ring include, for example, hydroxyl groups, methyl groups, methoxy groups, ethyl groups, ethoxy groups, propyl groups, and propoxy groups. From the perspective of curing properties, no substitution is preferred.

[0261] Examples of a group connecting one or more 2-valent aliphatic groups and one or more 2-valent aromatic ring groups include one or more of the aforementioned 2-valent aliphatic groups and one or more of the aforementioned 2-valent aromatic ring groups.

[0262] The number of 2-valent aliphatic groups is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 10 or less is preferred, 5 or less is more preferred, and 3 or less is even more preferred. 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 even more preferred. There is a tendency for the performance to improve by making it greater than the above lower limit value. There is a tendency for the membrane strength to improve by making it less than the above upper limit value.

[0263] The number of 2-valent aromatic rings is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 10 or less is preferred, 5 or less is more preferred, and 3 or less is even more preferred. 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 even more preferred. By making the value greater than or equal to the lower limit, the membrane strength tends to improve. By making the value less than or equal to the upper limit, the performance tends to improve.

[0264] Specific examples of groups formed by connecting 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 perspective of skeletal rigidity and membrane hydrophobicity, the group represented by the following general formula (iA) is preferred.

[0265] [Chemical Formula 15]

[0266]

[0267] The benzene ring in formula (i) may additionally be substituted by any substituent, and 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 and may be one or two or more. From the perspective of curing properties, it is preferable to be unsubstituted.

[0268] The substructure represented by formula (i) is preferably the substructure represented by the following general formula (i-1) in terms of phenotype solubility.

[0269] [Chemical Formula 16]

[0270]

[0271] In Equation (i-1), R a , R b and k is R in Equation (i) a , R b and has the same meaning as k. R Y represents a hydrogen atom or a polybasic acid residue. The benzene ring in formula (i-1) may additionally be substituted by any substituent. * represents each bond loss.

[0272] R in Equation (i-1) Y In this case, a polybasic acid residue means a 1 or 2 valent group obtained by removing 1 or 2 OH groups from a polybasic acid.

[0273] Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorenedic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. In terms of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0274] The benzene ring in formula (i-1) may additionally be substituted with any substituent.

[0275] 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 and may be one or two or more.

[0276] The repeating unit structure represented by formula (i-1) included in one molecule of epoxy(meth)acrylate resin (C2-1) may be one type or two or more types.

[0277] The number of substructures represented by formula (i) included 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 also 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. By making the value greater than or equal to the lower limit, the developability tends to improve. By making the value less than or equal to the upper limit, the ink release tendency tends to improve.

[0278] The number of substructures represented by formula (i-1) included in one molecule of epoxy(meth)acrylate resin (C2-1) is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 3 or more is even more preferred, 10 or fewer is preferred, and 8 or fewer is even more preferred. 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 8 is even more preferred. By making the value greater than the above lower limit, developability tends to improve. By making the value less than the above upper limit, ink release tends to improve.

[0279] Specific examples of epoxy (meth)acrylate resin (C2-1) are given below.

[0280] [Chemical Formula 17]

[0281]

[0282] [Chemical Formula 18]

[0283]

[0284] [Chemical Formula 19]

[0285]

[0286] [Chemical Formula 20]

[0287]

[0288] [Chemical Formula 21]

[0289]

[0290] [Chemical Formula 22]

[0291]

[0292] <Epoxy (Met)Acrylate Resin (C2-2)>

[0293] [Chemical Formula 23]

[0294]

[0295] In Equation (ii), R crepresents, respectively, a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R e and R f Each represents an independent divalent aliphatic group that may have a substituent. l and m each represent an integer from 0 to 2. * each represents a bonding hand.

[0296] (R d )

[0297] In Equation (ii), R d It represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

[0298] Examples of cyclic hydrocarbon groups include aliphatic rings or aromatic rings.

[0299] The number of rings having an aliphatic ring group is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 10 or fewer is preferred, 5 or fewer is more preferred, and 3 or fewer is even more preferred. 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 even more preferred, and 2 to 3 is particularly preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0300] The number of carbon atoms in the aliphatic ring is preferably 4 or more, more preferably 6 or more, even more preferably 8 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 may 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0301] Examples of aliphatic rings include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, and adamantane rings. From the perspective of heat resistance, the adamantane ring is preferred.

[0302] The number of rings having aromatic ring groups is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 3 or more is even more preferred, 10 or fewer is preferred, 5 or fewer is more preferred, and 4 or fewer is even more preferred. 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0303] Examples of aromatic rings include aromatic hydrocarbon rings and aromatic complex rings.

[0304] The number of carbon atoms in the aromatic ring 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 may 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0305] Examples of aromatic rings in the aromatic ring group include, for instance, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. From the perspective of heat resistance, a fluorene ring is preferred.

[0306] In the 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 connecting one or more divalent aliphatic groups and one or more divalent aromatic rings.

[0307] Examples of 2-valent aliphatic groups include straight-chain, branched-chain, and ring-shaped aliphatic groups. From the perspective of improving performance, straight-chain aliphatic groups are preferred. From the perspective of heat resistance, ring-shaped aliphatic groups are preferred.

[0308] The number of carbon atoms in the 2-valent 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 may be combined arbitrarily. For example, 1 to 25 is preferred, 3 to 20 is more preferred, and 6 to 15 is even more preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0309] Examples of 2-valent straight-chain aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene, and n-heptylene groups. From the perspective of heat resistance, methylene groups are preferred.

[0310] As for the divalent branched chain aliphatic group, a structure having one or more methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups as side chains to the aforementioned divalent straight chain aliphatic group can be cited.

[0311] The number of rings of the cyclic aliphatic groups of 2 is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 10 or fewer is preferred, 5 or fewer is more preferred, and 3 or fewer is even more preferred. The upper and lower limits above may be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the lower limit. Developability tends to be improved by making the value less than or equal to the upper limit.

[0312] Examples of divalent cyclic aliphatic groups having two free valencies include, for instance, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the perspective of heat resistance, an adamantane ring having two free valencies is preferred.

[0313] Substituents that may be present on the divalent aliphatic group include, for example, alkoxy groups having 1 to 5 carbon atoms, such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the perspective of ease of synthesis, it is preferable to be unsubstituted.

[0314] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic complex ring groups.

[0315] The number of carbon atoms in the divalent aromatic ring is preferably 4 or more, more preferably 5 or more, more preferably 6 or more, and also preferably 30 or less, more preferably 20 or less, and more preferably 15 or less. The above upper and lower limits may be combined arbitrarily. For example, 4 to 30 is preferred, 5 to 20 is more preferred, and 6 to 15 is more preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0316] The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.

[0317] Examples of divalent aromatic hydrocarbon ring groups having two free valencies include, for instance, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0318] In an aromatic complex ring, the aromatic complex ring may be a single ring or a condensed ring.

[0319] Examples of divalent aromatic complex ring groups having two free valencies include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazol rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrazol rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, propyrrol rings, furofuran rings, thienofuran rings, benzisooxazole rings, benzisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, synnoline rings, quinoxaline rings, phenanthridine rings, ferrimidine rings, quinazoline rings, quinazolinone rings, and azulene rings. From the perspective of manufacturing costs, a benzene ring with two free valence atoms and a naphthalene ring are preferred, and a benzene ring with two free valence atoms is more preferred.

[0320] Substituents that the divalent aromatic ring may have include, for example, hydroxyl groups, methyl groups, methoxy groups, ethyl groups, ethoxy groups, propyl groups, and propoxy groups. From the perspective of curing properties, no substitution is preferred.

[0321] Examples of a group connecting one or more 2-valent aliphatic groups and one or more 2-valent aromatic ring groups include one or more of the aforementioned 2-valent aliphatic groups and one or more of the aforementioned 2-valent aromatic ring groups.

[0322] The number of aliphatic groups of 2 is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 10 or less is preferred, 5 or less is more preferred, and 3 or less is even more preferred. 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 even more preferred, and 2 to 3 is particularly preferred. There is a tendency for the formability to improve by making it greater than or equal to the above lower limit value. There is a tendency for the heat resistance to improve by making it less than or equal to the above upper limit value.

[0323] The number of aromatic ring groups is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, and preferably 10 or less, 5 or less is more preferred, and 3 or less is even more preferred. The upper and lower limits above may be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the lower limit. Developability tends to be improved by making the value less than or equal to the upper limit.

[0324] Groups connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include, for example, groups represented by formulas (iA) to (iF). From the perspective of membrane strength, a group represented by formula (iC) is preferred.

[0325] The bonding mode of the cyclic hydrocarbon group as a side chain to the 2-valent hydrocarbon group is not particularly limited, but examples include a mode in which one hydrogen atom of an aliphatic or aromatic ring group is substituted with the cyclic hydrocarbon group as a side chain, or a mode in which the cyclic hydrocarbon group as a side chain is formed by including one carbon atom of an aliphatic group.

[0326] (R e , R f )

[0327] In Equation (ii), R e and R f Each represents a divalent aliphatic group that may have a substituent, independently.

[0328] Examples of 2-valent aliphatic groups include straight-chain, branched-chain, and ring-shaped aliphatic groups. From the perspective of current solubility, straight-chain aliphatic groups are preferred. From the perspective of heat resistance, ring-shaped aliphatic groups are preferred.

[0329] The number of carbon atoms in the 2-valent aliphatic group is preferably 1 or more, more preferably 3 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and 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 more preferred. By making the value greater than or equal to the above lower limit, adhesion to the substrate and ink release properties tend to improve. By making the value less than or equal to the above upper limit, it is easier to suppress deterioration of sensitivity or film reduction during development, and resolution tends to improve.

[0330] Examples of 2-valent straight-chain aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene groups. From the perspective of skeletal rigidity, methylene groups are preferred.

[0331] As for the divalent branched chain type aliphatic group, there is a structure having, for example, one or more methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, or tert-butyl groups as side chains to the aforementioned divalent straight chain type aliphatic group.

[0332] The number of rings of the cyclic aliphatic groups is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, and preferably 12 or less, and 10 or less is more preferred. The upper and lower limits above 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. By making the value greater than the lower limit above, adhesion to the substrate and ink release properties tend to improve. By making the value less than the upper limit above, it is easier to suppress deterioration of sensitivity or film reduction during development, and resolution tends to improve.

[0333] Examples of divalent cyclic aliphatic groups having two free valencies include, for instance, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a dicyclopentadiene ring. From the perspective of heat resistance, a dicyclopentadiene ring and an adamantane ring having two free valencies are preferred.

[0334] Substituents that may be present on the divalent aliphatic group include, for example, carbon-1 to carbon-5 alkoxy groups such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the perspective of ease of synthesis, it is preferable to be unsubstituted.

[0335] (l, m)

[0336] In Equation (ii), l and m each independently represent integers from 0 to 2. Adhesion to the substrate tends to improve when set above the lower limit value. Formability tends to improve when set below the upper limit value. From the perspective of formability, it is preferable that l and m are 0. From the perspective of adhesion to the substrate, it is preferable that l and m are 1 or greater.

[0337] The substructure represented by formula (ii) is preferably the substructure represented by the following general formula (ii-1) in terms of film strength and ink-repellent properties.

[0338] [Chemical Formula 24]

[0339]

[0340] In Equation (ii-1), R c , R e , R f , l and m have the same meaning as in the above equation (ii). R α represents a monovalent cyclic hydrocarbon group that may have a substituent. n is an integer greater than or equal to 1. The benzene ring in Equation (ii-1) may additionally be substituted by any substituent. * represents each bond loss.

[0341] (R α )

[0342] In Equation (ii-1), R α represents a monovalent cyclic hydrocarbon group that may have a substituent.

[0343] Examples of cyclic hydrocarbon groups include aliphatic rings or aromatic rings.

[0344] The number of rings having an aliphatic ring group is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 6 or fewer is preferred, 4 or fewer is more preferred, and 3 or fewer is even more preferred. 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 even more preferred, and 2 to 3 is particularly preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0345] The number of carbon atoms in the aliphatic ring is preferably 4 or more, more preferably 6 or more, even more preferably 8 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 may 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0346] Examples of aliphatic rings include, for instance, cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, and adamantane rings. From the perspective of the compatibility of ink-forming and developability, the adamantane ring is preferred.

[0347] The number of rings having aromatic ring groups is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 3 or more is even more preferred, 10 or fewer is preferred, and 5 or fewer is even more preferred. 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0348] Examples of aromatic rings include aromatic hydrocarbon rings and aromatic complex rings.

[0349] The number of carbon atoms in the aromatic ring 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0350] Examples of aromatic rings in the aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. From the perspective of compatibility between ink-repellent and developable properties, fluorene rings are preferred.

[0351] Substituents that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as hydroxyl groups, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, amyl groups, and isoamyl groups; alkoxy groups having 1 to 5 carbon atoms, such as methoxy groups and ethoxy groups; nitro groups; cyano groups; and carboxyl groups. From the perspective of ease of synthesis, non-substitution is preferred.

[0352] n represents an integer greater than or equal to 1, preferably greater than or equal to 2, and preferably less than or equal to 3. For example, 1 to 3 is preferable, and 2 to 3 is more preferable. Ink-release properties tend to be improved by making it greater than or equal to the lower limit value. Developability tends to be improved by making it less than or equal to the upper limit value.

[0353] In terms of the compatibility of ink-emitting and phenomenal properties, R α It is preferable that the group be an aliphatic ring, and more preferable that it be an adamantyl group.

[0354] The benzene ring in formula (ii-1) may additionally be substituted with any substituent.

[0355] 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 and may be one or two or more. From the perspective of curing properties, it is preferable to be unsubstituted.

[0356] Specific examples of substructures represented by Equation (ii-1) are given below.

[0357] [Chemical Formula 25]

[0358]

[0359] [Chemical Formula 26]

[0360]

[0361] [Chemical Formula 27]

[0362]

[0363] [Chemical Formula 28]

[0364]

[0365] [Chemical Formula 29]

[0366]

[0367] The substructure represented by formula (ii) is preferably the substructure represented by the following general formula (ii-2) in terms of closeness to the phenomenon.

[0368] [Chemical Formula 30]

[0369]

[0370] In Equation (ii-2), R c , R e , R f , l and m have the same meaning as in the above equation (ii). R βrepresents a divalent cyclic hydrocarbon group that may have a substituent. The benzene ring in formula (ii-2) may additionally be substituted by any substituent. * represents each bond loss.

[0371] (R β )

[0372] In Equation (ii-2), R β It represents a divalent cyclic hydrocarbon group that may have a substituent.

[0373] Examples of cyclic hydrocarbon groups include aliphatic rings or aromatic rings.

[0374] The number of rings in the aliphatic ring group is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 10 or fewer is preferred, and 5 or fewer is more preferred. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, and 2 to 5 is more preferred. There is a tendency for development to improve by making it greater than the above lower limit value. There is a tendency for ink release to improve by making it less than the above upper limit value.

[0375] The number of carbon atoms in the aliphatic ring 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 may be combined arbitrarily. For example, 4 to 40 is preferred, 6 to 35 is more preferred, and 8 to 30 is even more preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0376] Examples of aliphatic rings include, for instance, cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, and adamantane rings. From the perspective of the compatibility of ink-forming and developability, the adamantane ring is preferred.

[0377] The number of rings having aromatic ring groups is not particularly limited, but 1 or more is preferred, 2 or more is more preferred, 3 or more is even more preferred, 10 or fewer is preferred, and 5 or fewer is even more preferred. 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0378] Examples of aromatic rings include aromatic hydrocarbon rings and aromatic complex rings.

[0379] The number of carbon atoms in the aromatic ring 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 may 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. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0380] Examples of aromatic rings in the aromatic ring group include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Fluorene rings are preferred in terms of ink-repellent and developable properties.

[0381] Substituents that the cyclic hydrocarbon group may have include, for example, C1- to C5 alkyl groups such as hydroxyl groups, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, amyl groups, isoamyl groups; C1- to C5 alkoxy groups such as methoxy groups, ethoxy groups; nitro groups; cyano groups; and carboxyl groups. From the perspective of ease of synthesis, non-substitution is preferred.

[0382] In terms of the compatibility of ink-producing and developability and heat resistance, R β It is preferable that α is a divalent aliphatic ring, and more preferable that α is a divalent adamantane ring. In terms of the compatibility of ink-releasing properties and developability, and heat resistance, R β It is preferable that the ring is a divalent aromatic ring, and more preferable that it is a divalent fluorene ring.

[0383] The benzene ring in formula (ii-2) may additionally be substituted with any substituent.

[0384] 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 and may be one or two or more. For the benzene ring in formula (ii-2), it is preferable that it be unsubstituted from the perspective of curability.

[0385] Specific examples of substructures represented by Equation (ii-2) are given below.

[0386] [Chemical Formula 31]

[0387]

[0388] [Chemical Formula 32]

[0389]

[0390] [Chemical Formula 33]

[0391]

[0392] [Chemical Formula 34]

[0393]

[0394] The substructure represented by Equation (ii) is preferably the substructure represented by the following general formula (ii-3) from the perspective of phenomenology.

[0395] [Chemical Formula 35]

[0396]

[0397] In Equation (ii-3), R c , R d , R e , R f , l and m have the same meaning as in the above equation (ii). R Z Each represents, independently, a hydrogen atom or a polybasic acid residue.

[0398] R Z The polybasic acid residue in this case is R in formula (i-1). Y The example provided can be adopted in a desirable manner.

[0399] The substructure represented by formula (ii-3) included in one molecule of epoxy(meth)acrylate resin (C2-2) may be one type or two or more types.

[0400] The number of substructures represented by formula (ii) included 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, 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, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 is even more preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0401] The number of substructures represented by formula (ii-1) included 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, 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 arbitrarily combined. For example, 1 to 20 is preferred, 1 to 15 is more preferred, and 3 to 10 is even more preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0402] The number of substructures represented by formula (ii-2) included 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, more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 15 is more preferred, 1 to 10 is even more preferred, and 3 to 10 is particularly preferred. Ink-repellent properties tend to be improved by making the value greater than or equal to the above lower limit. Developability tends to be improved by making the value less than or equal to the above upper limit.

[0403] The number of substructures represented by formula (ii-3) included 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, 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, 1 to 20 is preferred, 1 to 15 is more preferred, 1 to 10 is even more preferred, and 3 to 10 is particularly preferred. By making the value greater than or equal to the lower limit, the developability tends to improve. By making the value less than or equal to the upper limit, the ink release tendency tends to improve.

[0404] The acid value of the epoxy(meth)acrylate resin (C2) is not particularly limited, but is preferably 10 mgKOH / g or higher, more preferably 30 mgKOH / g or higher, even more preferably 50 mgKOH / g or higher, even more preferably 70 mgKOH / g or higher, particularly preferably 80 mgKOH / g or higher, and also preferably 200 mgKOH / g or lower, more preferably 180 mgKOH / g or lower, even more preferably 150 mgKOH / g or lower, even more preferably 120 mgKOH / g or lower, and particularly preferably 110 mgKOH / g or lower. The above upper and lower limits may be combined arbitrarily. For example, 10 to 200 mgKOH / g is preferred, 30 to 180 mgKOH / g is more preferred, 50 to 150 mgKOH / g is even more preferred, 70 to 120 mgKOH / g is more preferred, and 80 to 110 mgKOH / g is particularly preferred. By making it above the lower limit value, the developability tends to improve. By making it below the upper limit value, the ink release and film strength tend to improve.

[0405] 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 upper and lower limits above may be combined arbitrarily. For example, 1000 to 30000 is preferred, 1000 to 15000 is more preferred, 2000 to 10000 is more preferred, 3000 to 8000 is more preferred, and 3500 to 5000 is particularly preferred. By making it greater than the lower limit value, ink-repellent properties and film strength tend to be improved. There is a tendency for residue to be reduced by keeping it below the upper limit value mentioned above.

[0406] [Acrylic copolymer resin (C3)]

[0407] The acrylic copolymer resin (C3) has ethylenically unsaturated groups in its side chains. By having ethylenically unsaturated groups, it becomes difficult for film reduction to occur due to the alkaline developer during development by photocuring by exposure to light, and thus the surface smoothness is improved. In addition, by having a flexible main framework, the adhesion to the substrate tends to be improved.

[0408] (Repetition unit represented by general formula (1))

[0409] The partial structure of the acrylic copolymer resin (C3) having a side chain having an ethylenically unsaturated group is not particularly limited, but it is preferable to have a repeating unit represented by the following general formula (1) in terms of ease of radical emission accompanying the flexibility of the film and adhesion to the substrate.

[0410] [Chemical Formula 36]

[0411]

[0412] In Equation (1), R a1 and R a2 Each represents, independently, a hydrogen atom or a methyl group. * represents a bonding hand.

[0413] Among the repeating units represented by Equation (1), the repeating unit represented by the following general formula (1') is preferred in terms of sensitivity or alkaline properties.

[0414] [Chemical Formula 37]

[0415]

[0416] In Equation (1'), R a1 and R a2 represents, respectively, a hydrogen atom or a methyl group. R x represents a hydrogen atom or a polybasic acid residue.

[0417] A polybasic acid residue is R in formula (i-1). Y The example provided can be adopted in a desirable manner.

[0418] When the acrylic copolymer resin (C3) includes a repeating unit represented by formula (1), the content ratio is not particularly limited, but is preferably 10 mol% or more with respect to the total repeating unit, 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 may be combined arbitrarily. For example, 10 to 90 mol% is preferred, 20 to 85 mol% is more preferred, 30 to 80 mol% is even more preferred, 40 to 75 mol% is even more preferred, and 50 to 70 mol% is particularly preferred. By making the value above the lower limit, the ink-repellent properties tend to improve. By making the value below the upper limit, the residue tends to be reduced.

[0419] When the acrylic copolymer resin (C3) contains repeating units represented by the general formula (1'), the content ratio is not particularly limited, but among the total repeating units, 10 mol% or more is preferred, 20 mol% or more is more preferred, 25 mol% or more is even more preferred, 30 mol% or more is even more preferred, 35 mol% or more is particularly preferred, 80 mol% or less is preferred, 75 mol% or less is even more preferred, 70 mol% or less is even more preferred, and 65 mol% or less is particularly preferred. 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 35 to 65 mol% is particularly preferred. By making the value greater than the above lower limit, the ink-repellent properties tend to be improved. By keeping it below the upper limit value mentioned above, there is a tendency for the adhesion of the phenomenon to be easily secured.

[0420] (Repetition unit represented by general formula (2))

[0421] When the acrylic copolymer resin (C3) includes a repeating unit represented by the general formula (1), other repeating units included are not particularly limited, but from the perspective of developmental adhesion, it is preferable to have a repeating unit represented by the following general formula (2).

[0422] [Chemical Formula 38]

[0423]

[0424] In Equation (2), R a3 R represents a hydrogen atom or a methyl group. a4 represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent.

[0425] (R a4 )

[0426] In Equation (2), R a4 represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent.

[0427] R a4 Examples of alkyl groups include straight-chain, branched-chain, 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 may be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 18 is more preferred, 3 to 16 is even more preferred, 5 to 14 is even more preferred, and 8 to 12 is particularly preferred. By setting the value above the lower limit, the film strength tends to increase and the adhesion to the developing process tends to improve. By setting the value below the upper limit, the residue tends to be reduced.

[0428] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclofentanyl, and dodecanyl groups. From the perspective of development properties, dicyclofentanyl or dodecanyl groups are preferred, and dicyclofentanyl groups are more preferred.

[0429] Examples of substituents that the alkyl group may have include methoxy groups, ethoxy groups, chloro groups, bromo groups, fluoro groups, hydroxyl groups, amino groups, epoxy groups, oligoethylene glycol groups, phenyl groups, carboxyl groups, acryloyl groups, and methacryloyl groups, and from the perspective of development properties, hydroxyl groups and oligoethylene glycol groups are preferred.

[0430] R a4Examples of aromatic ring groups include monovalent aromatic hydrocarbon ring groups and monovalent aromatic complex ring groups. The number of carbon atoms is preferably 6 or more, 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. The upper and lower limits can be combined arbitrarily. For example, 6 to 24 is preferred, 6 to 22 is more preferred, 6 to 20 is even more preferred, and 6 to 18 is particularly preferred. By making the value greater than or equal to the lower limit, the adhesion of the developing material tends to improve. By making the value less than or equal to the upper limit, the residue tends to be reduced.

[0431] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples include a benzene ring, a naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.

[0432] The aromatic complex ring group in the aromatic complex ring group may be a monoring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazol ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazol ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a propyrrol ring, a furan ring, a thienofuran ring, a benzisooxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a fermidine ring, a quinazolinine ring, a quinazolinone ring, An azulene ring can be cited. From the perspective of phenotype, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

[0433] Substituents that may be present in the aromatic ring include, for example, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group, and from the perspective of development properties, hydroxyl group and oligoethylene glycol group are preferred.

[0434] R a4Examples of alkenyl groups include straight-chain, branched-chain, or ring-type alkenyl groups. The number of carbon atoms is preferably 2 or more, 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, 2 to 20 is more preferred, 2 to 18 is more preferred, 2 to 16 is even more preferred, and 2 to 14 is particularly preferred. By making the value greater than or equal to the lower limit, the adhesion of the developing process tends to improve. By making the value less than or equal to the upper limit, the residue tends to be reduced.

[0435] Substituents that may be present in the alkenyl group include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group, and from the perspective of development properties, hydroxyl group and oligoethylene glycol group are preferred.

[0436] R a4 Among these, alkyl groups and alkenyl groups are preferred in terms of developmentability and film strength, and alkyl groups are more preferred.

[0437] When the acrylic copolymer resin (C3) includes a repeating unit represented by formula (2), the content ratio is not particularly limited, but among the total repeating units, 1 mol% or more is preferred, 5 mol% or more is more preferred, 10 mol% or more is even more preferred, 20 mol% or more is particularly preferred, 70 mol% or less is preferred, 60 mol% or less is more preferred, 50 mol% or less is even more preferred, and 40 mol% or less is particularly preferred. 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 20 to 40 mol% is particularly preferred. By making the value above the lower limit, the adhesion of the development tends to improve. By making the value below the upper limit, the residue tends to be reduced.

[0438] (Repetition unit represented by general formula (3))

[0439] When the acrylic copolymer resin (C3) includes a repeating unit represented by formula (1), it is preferable to include a repeating unit represented by the following general formula (3) as an additional repeating unit, in terms of heat resistance and film strength.

[0440] [Chemical Formula 39]

[0441]

[0442] In the above equation (3), R a5 represents a hydrogen atom or a methyl group. R a6 represents an alkyl group that may have substituents, an alkenyl group that may have substituents, an alkynyl group that may have substituents, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group that may have substituents, a thiol group, or an alkyl sulfide group that may have substituents. t represents an integer from 0 to 5.

[0443] (R a6 )

[0444] R in Equation (3) a6 It represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group that may have a substituent, a thiol group, or an alkyl sulfide group that may have a substituent.

[0445] R a6 Examples of alkyl groups include straight-chain, branched-chain, 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, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 20 is preferred, 1 to 18 is more preferred, 3 to 16 is more preferred, 3 to 14 is even more preferred, and 5 to 12 is particularly preferred. By making the value greater than or equal to the above lower limit, the adhesion of the developing material tends to improve. By making the value less than or equal to the above upper limit, the residue tends to be reduced.

[0446] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclofentanyl, and dodecanyl groups. In terms of developability and film strength, dicyclofentanyl and dodecanyl groups are preferred, and dicyclofentanyl groups are more preferred.

[0447] Examples of substituents that the alkyl group may have include methoxy groups, ethoxy groups, chloro groups, bromo groups, fluoro groups, hydroxyl groups, amino groups, epoxy groups, oligoethylene glycol groups, phenyl groups, carboxyl groups, acryloyl groups, and methacryloyl groups, and from the perspective of development properties, hydroxyl groups and oligoethylene glycol groups are preferred.

[0448] R a6Examples of alkenyl groups include straight-chain, branched-chain, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, 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, 2 to 20 is more preferred, 2 to 18 is even more preferred, 2 to 16 is even more preferred, and 2 to 14 is particularly preferred. By making the value above the lower limit, the adhesion of the developing process tends to improve. By making the value below the upper limit, the residue tends to be reduced.

[0449] Substituents that may be present in the alkenyl group include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group, and from the perspective of development properties, hydroxyl group and oligoethylene glycol group are preferred.

[0450] R a6 Examples of alkynyl groups include straight-chain, branched-chain, or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, 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, 2 to 20 is more preferred, 2 to 18 is even more preferred, 2 to 16 is even more preferred, and 2 to 14 is particularly preferred. By making the value above the lower limit, the adhesion of the developing material tends to improve. By making the value below the upper limit, the residue tends to be reduced.

[0451] Substituents that may be present in the alkynyl group include, for example, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group, and from the perspective of developability, hydroxyl group and oligoethylene glycol group are preferred.

[0452] R a6 Examples of halogen atoms in this include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and from the perspective of phenomenal properties, fluorine atoms are preferred.

[0453] R a6 Examples of alkoxy groups include straight-chain, branched-chain, or ring-type 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. By making the value greater than or equal to the lower limit, the adhesion of the developing process tends to improve. By making the value less than or equal to the upper limit, the residue tends to be reduced.

[0454] Substituents that may be present on the alkoxy group include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, and methacryloyl group, and from the perspective of development properties, hydroxyl group and oligoethylene glycol group are preferred.

[0455] R a6Examples of alkyl sulfide groups include straight-chain, branched-chain, 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. By making the value greater than or equal to the lower limit, the adhesion of the developing material tends to improve. By making the value less than or equal to the upper limit, the residue tends to be reduced.

[0456] Examples of substituents that the alkyl group in the alkyl sulfide group may have include methoxy groups, ethoxy groups, chloro groups, bromo groups, fluoro groups, hydroxyl groups, amino groups, epoxy groups, oligoethylene glycol groups, phenyl groups, carboxyl groups, acryloyl groups, and methacryloyl groups, and from the perspective of development properties, hydroxyl groups and oligoethylene glycol groups are preferred.

[0457] R a6 Among these, from the perspective of phenomenality, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0458] In equation (3), t represents an integer from 0 to 5, and from the perspective of ease of manufacturing, it is preferable that t be 0.

[0459] When the acrylic copolymer resin (C3) includes a repeating unit represented by formula (3), the content ratio is not particularly limited, but among the total repeating units, 0.5 mol% or more is preferred, 1 mol% or more is more preferred, 2 mol% or more is even more preferred, and 5 mol% or more is particularly preferred. Also, 50 mol% or less is preferred, 40 mol% or less is more preferred, 30 mol% or less is even more preferred, 20 mol% or less is even more preferred, and 15 mol% or less is particularly preferred. The above upper and lower limits can be combined arbitrarily. For example, 0.5 to 50 mol% is preferred, 0.5 to 40 mol% is more preferred, 1 to 30 mol% is even more preferred, 2 to 20 mol% is even more preferred, and 5 to 15 mol% is particularly preferred. By making the value greater than the above lower limit, the adhesion of the developing process tends to improve. There is a tendency for residue to be reduced by keeping it below the upper limit value mentioned above.

[0460] (Repetition unit represented by general formula (4))

[0461] When the acrylic copolymer resin (C3) has a repeating unit represented by formula (1), it is preferable to have a repeating unit represented by the following general formula (4) as an additional repeating unit for the sake of appearance.

[0462] [Chemical Formula 40]

[0463]

[0464] In the above equation (4), R a7 It represents a hydrogen atom or a methyl group.

[0465] When the acrylic copolymer resin (C3) includes a repeating unit represented by formula (4), the content ratio is not particularly limited, but among the total repeating units, 5 mol% or more is preferred, 10 mol% or more is more preferred, 20 mol% or more is even more preferred, 80 mol% or less is preferred, 70 mol% or less is even more preferred, and 60 mol% or less is even more preferred. 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. By making it above the lower limit value, the developability tends to improve. By making it below the upper limit value, the developability tends to improve.

[0466] The acid value of the acrylic copolymer resin (C3) is not particularly limited, but is preferably 30 mgKOH / g or higher, more preferably 40 mgKOH / g or higher, even more preferably 50 mgKOH / g or higher, even more preferably 60 mgKOH / g or higher, and also preferably 150 mgKOH / g or lower, more preferably 140 mgKOH / g or lower, even more preferably 130 mgKOH / g or lower, and even more preferably 120 mgKOH / g or lower. The upper and lower limits above may be combined arbitrarily. For example, 30 to 150 mgKOH / g is preferred, 40 to 140 mgKOH / g is more preferred, 50 to 130 mgKOH / g is even more preferred, and 60 to 120 mgKOH / g is particularly preferred. There is a tendency for the developability to be improved by making it above the lower limit value. By keeping it below the upper limit value mentioned above, the adhesion of the phenomenon tends to improve.

[0467] 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 is also preferably 30000 or less, more preferably 20000 or less, even more preferably 15000 or less, and particularly preferably 10000 or less. The upper and lower limits above may be combined arbitrarily. For example, 1000 to 30000 is preferred, 2000 to 30000 is more preferred, 4000 to 20000 is more preferred, 6000 to 20000 is more preferred, 7000 to 15000 is particularly preferred, and 8000 to 10000 is particularly preferred. By making it above the lower limit, the adhesion of the development tends to improve. By making it below the upper limit, the development quality tends to improve.

[0468] As for acrylic copolymer resins (C3), examples include resins described in Japanese Patent Publication No. Hei 8-297366 or Japanese Patent Publication No. 2001-89533.

[0469] In the present invention, (C) alkali-soluble resin may additionally include an alkali-soluble resin other than epoxy (meth)acrylate resin (C2) and acrylic copolymer resin (C3) as other alkali-soluble resins.

[0470] (C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 30 mgKOH / g or higher, more preferably 50 mgKOH / g or higher, more preferably 60 mgKOH / g or higher, more preferably 300 mgKOH / g or lower, more preferably 200 mgKOH / g or lower, even more preferably 100 mgKOH / g or lower, and particularly preferably 80 mgKOH / g or lower. The upper and lower limits above may be combined arbitrarily. For example, 30 to 300 mgKOH / g is preferred, 30 to 200 mgKOH / g is more preferred, 50 to 100 mgKOH / g is even more preferred, and 60 to 80 mgKOH / g is particularly preferred. By making it above the lower limit value, the developability tends to improve. By making it below the upper limit value, the developability tends to improve.

[0471] (C) In the case where the alkali-soluble resin is a mixture of two or more types, the acid value refers to the weighted average value according to the content ratio.

[0472] The content ratio of (C) alkali-soluble resin in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, even more preferably 20 mass% or more, particularly preferably 25 mass% or more, even more particularly preferably 30 mass% or more, particularly preferably 40 mass% or more with respect to the total solid content of the photosensitive resin composition, and is also preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less. The above upper and lower limits may be arbitrarily combined. For example, 5 to 90 mass% is preferred, 10 to 90 mass% is more preferred, 15 to 90 mass% is even more preferred, 20 to 80 mass% is more preferred, 30 to 80 mass% is particularly preferred, 35 to 70 mass% is more particularly preferred, and 40 to 60 mass% is particularly preferred. By making it above the lower limit value, there is a tendency for residue to be reduced. By making it below the upper limit value, there is a tendency for ink-repellent properties to be improved.

[0473] The total content ratio of (A) a photopolymerizable compound and (C) an 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 mass% or more, more preferably 30 mass% or more, even more preferably 60 mass% or more, particularly preferably 80 mass% or more, and also preferably 95 mass% or less, more preferably 92 mass% or less, and even more preferably 90 mass% or less. The above upper and lower limits may be combined arbitrarily. For example, 10 to 95 mass% is preferred, 30 to 95 mass% is more preferred, 60 to 92 mass% is even more preferred, and 80 to 90 mass% is particularly preferred. By making the value greater than or equal to the lower limit, the adhesion of the barrier to the substrate tends to improve. By making the value less than or equal to the upper limit, light-blocking properties or ink-repellent properties tend to improve.

[0474] [1-1-4] (D) Fluid-repellent

[0475] The photosensitive resin composition of the present invention contains (D) a compound (D1) that contains a liquid-repellent agent, has a crosslinking group, and also has a fluorine atom and / or a siloxane chain. By containing a liquid-repellent agent, the upper surface of the resulting barrier can be imparted ink-repellent properties, thereby preventing color mixing between pixels of the resulting barrier.

[0476] Hereinafter, as compound (D1),

[0477] Compound (D1-1): A fluorine atom-containing resin having a crosslinking group, and / or

[0478] Compound (D1-2): Resin containing crosslinking groups and siloxane chains

[0479] It is desirable to include .

[0480] <Compound (D1-1)>

[0481] Examples of crosslinking groups include epoxy groups, ethylenically unsaturated groups, or active groups that generate radicals upon irradiation with active energy rays.

[0482] Examples of active groups that generate radicals upon irradiation with an active energy line include benzophenone groups, acetophenone groups, α-hydroxyketone groups, α-aminoketone groups, α-diketone groups, and α-diketonedialkylacetal groups. Among these, the α-hydroxyketone group is preferred from the perspective of the overlap between the wavelength distribution of the light source used in the exposure and the absorbance spectrum of the active group.

[0483] As for the crosslinking group, an ethylenically unsaturated group is preferred from the perspective of suppressing the outflow of the developer of the liquid-repellent agent.

[0484] It is believed that by using a liquid repellent having a crosslinking group, the crosslinking reaction on the surface of the formed film can be accelerated when the film is exposed to light, making it difficult for the liquid repellent to flow out during the development process, and as a result, the resulting barrier can be made to exhibit high ink repellency.

[0485] A compound (D1-1) containing fluorine atoms is oriented on the surface of the barrier and tends to prevent ink from bleeding or mixing. More specifically, a group having fluorine atoms tends to repel the ink and prevent ink from bleeding or mixing by preventing the ink from crossing the barrier and entering an adjacent area.

[0486] A fluorine atom-containing resin having a crosslinking group preferably has any or two or more of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group. Per or fluoroalkyl groups, per or fluoroalkylene groups, per or fluoroalkylene ether chains, and per or fluoroaromatic groups are preferred, and having perfluoroalkyl groups, perfluoroalkylene groups, perfluoroalkylene ether chains, and perfluoroaromatic groups is more preferred in terms of liquid repellency. By having any or two or more of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group, the fluorine atom-containing resin becomes more oriented on the surface of the partition, exhibiting higher ink repellency and tending to further prevent ink bleeding or color mixing.

[0487] 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.

[0488] 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.

[0489] 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 thereof, and examples of fluoroalkylene ether chains include fluoroalkylene ether chains in which some, not all, of the F of the perfluoroalkylene ether chain is substituted with H.

[0490] Examples of per or fluoro-aromatic groups include per or fluorophenyl groups, per or fluoronaphthyl groups, and per or fluoroanthracyl groups.

[0491] Examples of resins containing fluorine atoms having crosslinking groups include, for instance, an acrylic copolymer resin having epoxy groups and perfluoroalkyl groups, an acrylic copolymer resin having epoxy groups and perfluoroalkylene ether chains, an acrylic copolymer resin having ethylenically unsaturated groups and perfluoroalkyl groups, an acrylic copolymer resin having ethylenically unsaturated groups and perfluoroalkylene ether chains, an epoxy(meth)acrylate resin having epoxy groups and perfluoroalkyl groups, an epoxy(meth)acrylate resin having epoxy groups and perfluoroalkylene ether chains, an epoxy(meth)acrylate resin having ethylenically unsaturated groups and perfluoroalkyl groups, and an epoxy(meth)acrylate resin having ethylenically unsaturated groups and perfluoroalkylene ether chains. In terms of ink-repellent properties, an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkylene ether chain is preferred, and an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkylene ether chain is more preferred.

[0492] Commercially available products of fluorine atom-containing resins having crosslinking groups include, for example, “MegaPac (registered trademark, hereinafter the same) F116”, “MegaPac F120”, “MegaPac F142D”, “MegaPac F144D”, “MegaPac F150”, “MegaPac F160”, “MegaPac F171”, “MegaPac F172”, “MegaPac F173”, “MegaPac F177”, “MegaPac F178A”, “MegaPac F178K”, “MegaPac F179”, “MegaPac F183”, “MegaPac F184”, “MegaPac F191”, “MegaPac F812”, “MegaPac F815”, “MegaPac F824”, “MegaPac F833”, “MegaPac” RS101”, “Megapark RS102”, “Megapark RS105”, “Megapark RS201”, “Megapark RS202”, “Megapark RS301”, “Megapark RS303”, “Megapark RS304”, “Megapark RS401”, “Megapark RS402”, “Megapark RS501”, “Megapark RS502”, “Megapark RS-72-K”, “Megapark RS-78”, “Megapark RS-90”, “DEFENSA (registered trademark, hereinafter the same) MCF300”, “DEFENSA MCF310”, “DEFENSA MCF312”, “DEFENSA MCF323”, “Fluorad FC430” manufactured by 3M Japan, “Fluorad Fluorine-containing organic compounds sold under the trade names “FC431”, “FC-4430”, “FC4432”, “Asahi Guard (registered trademark) AG710” manufactured by AGC, “Suplon (registered trademark, hereinafter the same) S-382”, “Suplon SC-101”, “Suplon SC-102”, “Suplon SC-103”, “Suplon SC-104”, “Suplon SC-105”, and “Suplon SC-106” may be used.

[0493] As an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group, “Megapac RS-72-K”, “Megapac RS-78”, and “Megapac RS-90” may be preferably used.

[0494] The fluorine atom content ratio in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but it is preferable to have 5 mass% or more of the fluorine atom-containing resin having a crosslinking group, 10 mass% or more is more preferable, 15 mass% or more is even more preferable, and 20 mass% or more is even more preferable. In addition, it is preferable to have 50 mass% or less, and more preferable to have 35 mass% or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 50 mass% is preferable, 10 to 50 mass% is more preferable, 15 to 35 mass% is even more preferable, and 20 to 35 mass% is particularly preferable. By setting it above the above lower limit value, leakage into the pixel area tends to be suppressed. By setting it below the above upper limit value, a high contact angle tends to be exhibited.

[0495] The molecular weight of the fluorine atom-containing resin having crosslinking groups is not particularly limited and may be a low molecular weight compound or a high molecular weight compound. A high molecular weight compound is preferred because it suppresses seepage during development and fluidity due to post-baking, thereby suppressing leakage from the partitions. When the fluorine atom-containing resin having crosslinking groups is a high molecular weight compound, the number average molecular weight of the fluorine atom-containing resin having crosslinking groups is preferably 100 or more, more preferably 500 or more, and even more preferably 1000 or more. Additionally, it is 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 may be combined arbitrarily. For example, 100 to 150,000 is preferred, 500 to 130,000 is more preferred, and 1000 to 100,000 is even more preferred.

[0496] In addition, the weight average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. In addition, it is preferably 150,000 or less, and even more preferably 130,000 or less. The above upper and lower limits may be combined arbitrarily. For example, 1,000 to 150,000 is preferred, 5,000 to 130,000 is more preferred, and 10,000 to 130,000 is even more preferred.

[0497] <Compound (D1-2)>

[0498] As a crosslinking group, the crosslinking group described in compound (D1-1) is preferably used.

[0499] The siloxane chain of compound (D1-2) is preferably a polysiloxane represented by the following general formula (d1-2).

[0500] R 61 R 62 R 63 Si-O-(SiR 64 R 65 -O)n-SiR 66 R 67 R 68 (d1-2)

[0501] In equation (d1-2), R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 Each represents an organic group or hydrogen atom independently.

[0502] Preferably as an organic group having 1 to 10 carbon atoms, examples include 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, and these organic groups may have ester bonds.

[0503] n is an integer greater than or equal to 0, preferably 5 or greater, more preferably 10 or greater, also 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 upper and lower limits above may 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. By making the value greater than or equal to the lower limit, the ink-repellent properties tend to increase. By making the value less than or equal to the upper limit, the uniformity of the coating film tends to increase.

[0504] As commercially available resins containing crosslinking groups and siloxane chains, compounds marketed under the trade names "BYK-UV3500 series" manufactured by Big Chem Co., Ltd. and "8SS" series manufactured by Taisei Fine Chemical Co., Ltd. may be used.

[0505] Examples of compounds having a crosslinking group and also having a fluorine atom and a siloxane chain include compounds marketed under the trade names "8FS" series manufactured by Taisei Fine Chemical Co., Ltd. and "KP" series manufactured by Shin-Etsu Chemical Co., Ltd.

[0506] Compound (D1) may be a compound containing both a fluorine atom and a siloxane chain in one molecule, or a mixture of multiple compounds (D1) may be used.

[0507] The content ratio of (D) liquid-repellent agent in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more with respect to the total solid content of the photosensitive resin composition, and is also preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 2 mass% or less. The upper and lower limits above may be arbitrarily combined. For example, 0.01 to 5 mass% is preferred, 0.05 to 3 mass% is more preferred, and 0.1 to 2 mass% is even more preferred. By making the value above the lower limit, the ink-repellent properties tend to improve. By making the value below the upper limit, it tends to be easier to obtain a uniform coating film when applying ink to the pixel portion after forming the barrier.

[0508] The content ratio of compound (D1) in the photosensitive resin composition of the present invention is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, it is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and also preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 2 mass% or less. The upper and lower limits above may be arbitrarily combined. For example, 0.01 to 5 mass% is preferred, 0.05 to 3 mass% is more preferred, and 0.1 to 2 mass% is even more preferred. By making it above the lower limit value, the ink-repellent properties tend to be improved. By making it below the upper limit value, it tends to be easier to obtain a uniform coating film when applying ink to the pixel portion after forming the barrier.

[0509] 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 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more with respect to the total solid content of the photosensitive resin composition, and is also preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 2 mass% or less. The above upper and lower limits may be arbitrarily combined. For example, 0.01 to 5 mass% is preferred, 0.05 to 3 mass% is more preferred, and 0.1 to 2 mass% is even more preferred. By making the value above the lower limit, the ink-repellent properties tend to be improved. By making the value below the upper limit, it tends to be easier to obtain a uniform coating film when applying ink to the pixel portion after forming the barrier.

[0510] 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 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.5 mass% or more with respect to the total solid content of the photosensitive resin composition, and is also preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 2 mass% or less. The above upper and lower limits may be arbitrarily combined. For example, 0.1 to 5 mass% is preferred, 0.2 to 3 mass% is more preferred, and 0.5 to 2 mass% is even more preferred. By making the value above the lower limit, the ink-repellent properties tend to be improved. By making the value below the upper limit, it tends to be easier to obtain a uniform coating film when applying ink to the pixel portion after forming the barrier.

[0511] In the photosensitive resin composition of the present invention, a surfactant may be used together with (D) a liquid-repellent agent. The surfactant may be used, for example, to improve the applicability of the photosensitive resin composition as a coating solution and the developability of the coating film, and examples include fluorine-based surfactants and silicone-based surfactants that do not have crosslinking groups.

[0512] In particular, silicone-based surfactants are preferred, and polyether-modified silicone-based surfactants are even more preferred, in that they have the function of removing residues of the photosensitive resin composition from the unexposed area during development and also have the function of exhibiting wettability.

[0513] As a fluorine-based surfactant that does not have a crosslinking group, a compound having a fluoroalkyl or fluoroalkylene group at least at any of the terminal, main chain, and side chain is preferred.

[0514] Examples of commercially available fluorine-based surfactants that do not have crosslinking groups include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megapac F142D”, “Megapac F172”, “Megapac F173”, “Megapac F183”, “Megapac F470”, “Megapac F475”, “Megapac F554”, and “Megapac F559” manufactured by DIC, “FC430” manufactured by 3M Japan, and “DFX-18” manufactured by Neos.

[0515] Examples of commercially available silicone-based surfactants include “DC3PA,” “SH7PA,” “DC11PA,” “SH21PA,” “SH28PA,” “SH29PA,” “8032Additive,” and “SH8400” manufactured by Toray Dow Corning, and “BYK (registered trademark, hereinafter the same) 323” and “BYK330” manufactured by Big Chem.

[0516] As a surfactant, it may include surfactants other than fluorine-based surfactants and silicone-based surfactants. Examples of surfactants include nonionic, anionic, cationic, and amphoteric surfactants.

[0517] 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, pentaerythritate fatty acid esters, polyoxyethylene pentaerythritate fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0518] Examples of commercially available products of these include polyoxyethylene-based surfactants such as “Mulgen (registered trademark, hereinafter the same) 104P” and “Mulgen A60” manufactured by Kao Co.

[0519] Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic alcohol sulfate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and special polymeric surfactants. Among these, special polymeric surfactants are preferred, and special polycarboxylic acid type polymeric surfactants are even more preferred. Examples of commercially available products of these include, for example, “Emal (registered trademark, hereinafter the same) 10” manufactured by Kao Co., for alkyl sulfate ester salts, “Pelex (registered trademark) NB-L” manufactured by Kao Co., for example, for alkyl naphthalene sulfonate salts, “Pelex (registered trademark) NB-L” manufactured by Kao Co., and for example, “Homogenol (registered trademark, hereinafter the same) L-18” and “Homogenol L-100” manufactured by Kao Co., for special polymer-based surfactants.

[0520] Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are even more preferred.

[0521] Examples of commercially available products of these include, for alkylamine salts, “Acetamine (registered trademark) 24” manufactured by Kao, and for quaternary ammonium salts, “Quotamin (registered trademark, hereinafter the same) 24P” and “Quotamin 86W” manufactured by Kao.

[0522] Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, and amino acids.

[0523] Surfactants may be used as a single type or in combination of two or more types. Examples include a combination of a silicone-based surfactant and a fluorine-based surfactant, a combination of a silicone-based surfactant and a special polymer-based surfactant, and a combination of a fluorine-based surfactant and a special polymer-based surfactant, and a combination of a silicone-based surfactant and a fluorine-based surfactant is preferred.

[0524] Examples of combinations of silicone-based surfactants and fluorine-based surfactants include the combination of “DFX-18” manufactured by Neos, “BYK-300” or “BYK-330” manufactured by Big Chem, and “S-393” manufactured by AGC Seimi Chemical; the combination of “KP340” manufactured by Shin-Etsu Silicon and “F-554” or “F-559” manufactured by DIC; the combination of “SH7PA” manufactured by Toray Dow Corning and “DS-401” manufactured by Daikin; and the combination of “L-77” manufactured by NUC and “FC4430” manufactured by 3M Japan.

[0525] [1-1-5] (E) Colorant

[0526] The photosensitive resin composition of the present invention may additionally contain (E) a coloring agent. By including (E) a coloring agent, suitable light absorption can be obtained, and particularly when used for forming a light-shielding member including a colored barrier, suitable light-shielding properties can be obtained. In addition, when used for an application intended for light scattering, good light scattering properties can be obtained by using a white coloring agent.

[0527] The type of (E) coloring agent used in the present invention is not particularly limited, and pigments or dyes may be used. From the perspective of durability, it is preferable to use pigments.

[0528] (E) The pigment included in the coloring agent may be one type or two or more types. In particular, from the perspective of uniformly blocking light in the visible range, it is preferable to have two or more types.

[0529] (E) The types of pigments that can be used as coloring agents are not particularly limited, but examples include organic pigments and inorganic pigments. When the purpose is light-blocking, it is preferable to use organic pigments from the perspective of efficiently curing by controlling the transmitted wavelength of the photosensitive resin composition.

[0530] Examples of organic pigments include organic coloring pigments and organic black pigments. Here, organic coloring pigments refer to organic pigments that exhibit colors other than black, and examples include red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

[0531] Among organic pigments, it is preferable to use organic coloring pigments in terms of ultraviolet absorption.

[0532] Organic coloring pigments may be used as a single type or in combination of two or more types. When used for light-blocking purposes, it is more preferable to use a combination of organic coloring pigments with different colors, and it is even more preferable to use a combination of organic coloring pigments that exhibit a color close to black.

[0533] The chemical structures of these organic pigments are not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene types. Specific examples of pigments that can be used are indicated by pigment numbers below. Terms such as "CI Pigment Red 2" below refer to the color index (CI).

[0534] As for red pigments, for example, 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, 235, 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, Examples include 275 and 276.

[0535] In terms of light-blocking and dispersibility, CI pigment red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 are preferred, and CI pigment red 177, 209, 224, 254 are more preferred.

[0536] CI Pigment Red 177, 254, and 272 are preferred in terms of dispersibility and light-blocking properties. When curing a photosensitive resin composition with ultraviolet light, it is preferable to use a red pigment with a low ultraviolet absorption rate, and in this regard, CI Pigment Red 254 and 272 are preferred.

[0537] Examples of orange pigments include CI pigments 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, 79.

[0538] In terms of dispersibility or light-blocking properties, CI pigments orange 13, 43, 64, and 72 are preferred, and CI pigments orange 43, 64, and 72 are more preferred. When curing a photosensitive resin composition with ultraviolet light, it is preferable to use an orange pigment with a low ultraviolet absorption rate, and in this regard, CI pigments orange 64 and 72 are preferred.

[0539] 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, 79.

[0540] In terms of light-blocking properties, CI pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and CI pigment blue 15:6 is more preferred.

[0541] In terms of dispersibility or light-blocking properties, CI Pigment Blue 15:6, 16, 60 is preferred, and CI Pigment Blue 15:6, 60 is more preferred. When curing a photosensitive resin composition with ultraviolet light, it is preferable to use a blue pigment with a low ultraviolet absorption rate, and in this regard, CI Pigment Blue 60 is more preferred.

[0542] 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, 50.

[0543] In terms of light-blocking properties, CI pigment violet 19, 23 is preferred, and CI pigment violet 23 is more preferred.

[0544] CI pigment violet 23 and 29 are preferred in terms of dispersibility and light-blocking properties. When curing a photosensitive resin composition with ultraviolet light, it is preferable to use a purple pigment with a low ultraviolet absorption rate, and in this regard, CI pigment violet 29 is preferred.

[0545] Organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include, for example, green pigments and yellow pigments.

[0546] Examples of green pigments include CI Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55, and CI Pigment Greens 7 and 36 are preferred.

[0547] As for yellow pigments, for example, 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, 81, 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, 157, 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, Examples include 189, 190, 191, 191 : 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are more preferable, and CI pigment yellow 83, 138, 139, 150, 180 are even more preferable.

[0548] In terms of light-blocking properties or ink-repellent properties, it is preferable to use at least one type selected from the group consisting of red pigments, orange pigments, blue pigments, and purple pigments.

[0549] It is preferable to include at least one of the following pigments in terms of light-blocking properties or ink-repellent properties.

[0550] Red pigment: CI Pigment Red 177, 254, 272

[0551] Orange pigment: CI pigment orange 64, 72

[0552] Blue pigment: CI pigment blue 15: 6, 16, 60

[0553] Purple pigment: CI pigment violet 23, 29

[0554] When using two or more types of organic coloring pigments in combination, the combination of organic coloring pigments is not particularly limited, but from the perspective of light blocking properties, it is preferable to contain (E) 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.

[0555] While there are no specific limitations on color combinations, from the perspective of light-blocking properties, examples include combinations of red pigment and blue pigment, combinations of blue pigment and orange pigment, and combinations of blue pigment, orange pigment, and purple pigment.

[0556] In terms of blue light blocking properties, (E) it is desirable to contain a purple pigment as a coloring agent.

[0557] In terms of light-blocking properties, it is preferable to use an organic black pigment as a coloring agent (E). In particular, in terms of suppressing the absorption of ultraviolet rays and improving ink-like properties, it is preferable to use an organic black pigment comprising 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)”), geometric isomers of compound (A), salts of compound (A), and salts of geometric isomers of compound (A) (hereinafter referred to as “organic black pigment represented by general formula (A)”).

[0558] [Chemical Formula 41]

[0559]

[0560] In Equation (A), R11 and R 16 Each independently represents a hydrogen atom, CH3, CF3, a fluorine atom, or a chlorine atom;

[0561] R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 Each independently, hydrogen atom, halogen atom, R 21 , COOH, COOR 21 , COO - , CONH2, CONHR 21 , 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 Indicates ;

[0562] R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R19 , and R 19 and R 20 At least one combination selected from the group consisting of may be directly bonded to each other, or an oxygen atom, a sulfur atom, NH or NR 21 They can also be joined to each other by a bridge;

[0563] R 21 and R 22 Each 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.

[0564] Compound (A) and the geometric isomer of compound (A) have the following core structures (wherein the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable.

[0565] [Chemical Formula 42]

[0566]

[0567] If compound (A) is anionic, it is preferable that the charge be compensated by any known suitable cation, for example, a metal, organic, inorganic, or metal-organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organometallic complex. In addition, if the geometric isomer of compound (A) is anionic, it is preferable that it be the same salt.

[0568] Regarding the substituents of general formula (A) and their definitions, the following are preferred in that they tend to increase the shielding rate. This is because the following substituents are thought to have no absorption and do not affect the color of the pigment.

[0569] R 12 , R 14 , R 15, R 17 , R 19 and R 20 Each is independently, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

[0570] R 13 and R 18 Each 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.

[0571] R 11 and R 16 Each is independently, preferably a hydrogen atom, CH3 or CF3, and more preferably a hydrogen atom.

[0572] 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 Same as, and R 12 is R 17 Same as, and R 13 is R 18 Same as, and R 14 is R 19 Same as, and also, R 15 is R 20 It is identical to.

[0573] Alkyl groups having 1 to 12 carbon atoms are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group.

[0574] The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexyl group, a tulyl group, a norbornyl group, a bornyl group, a norcaryl group, a caryl group, a menthyl group, a norpinyl group, a pinyl group, an adamantane-1-yl group, or an adamantane-2-yl group.

[0575] Alkenyl groups having 2 to 12 carbon atoms are, for example, vinyl group, allyl group, 2-propene-2-yl group, 2-butene-1-yl group, 3-butene-1-yl group, 1,3-butadiene-2-yl group, 2-pentene-1-yl group, 3-pentene-2-yl group, 2-methyl-1-butene-3-yl group, 2-methyl-3-butene-2-yl group, 3-methyl-2-butene-1-yl group, 1,4-pentadiene-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group, and dodecenyl group.

[0576] The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobutene-1-yl group, 2-cyclopentene-1-yl group, 2-cyclohexene-1-yl group, 3-cyclohexene-1-yl group, 2,4-cyclohexadiene-1-yl group, 1-p-menten-8-yl group, 4(10)-tugen-10-yl group, 2-norbornene-1-yl group, 2,5-norbornene-1-yl group, 7,7-dimethyl-2,4-norcaradiene-3-yl group, and camphenyl group.

[0577] Alkynyl groups having 2 to 12 carbon atoms are, for example, 1-propin-3-yl group, 1-butin-4-yl group, 1-pentin-5-yl group, 2-methyl-3-butin-2-yl group, 1,4-pentadiene-3-yl group, 1,3-pentadiene-5-yl group, 1-hexine-6-yl group, cis-3-methyl-2-pentene-4-phosph-1-yl group, trans-3-methyl-2-pentene-4-phosph-1-yl group, 1,3-hexadiene-5-yl group, 1-octine-8-yl group, 1-nonine-9-yl group, 1-decine-10-yl group, and 1-dodecine-12-yl group.

[0578] Halogen atoms are, for example, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0579] The organic black pigment represented by general formula (A) is preferably an organic black pigment comprising 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).

[0580] [Chemical Formula 43]

[0581]

[0582] An example of such an organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).

[0583] This organic black pigment is preferably used by dispersing it using a dispersant, solvent, and method described below. Since the dispersibility and preservation properties may be improved when a sulfonic acid derivative of compound (A), particularly a sulfonic acid derivative of compound (B), is present during dispersion, it is desirable for the organic black pigment to include these sulfonic acid derivatives.

[0584] Organic black pigments other than the organic black pigment represented by formula (A) include, for example, aniline black and perylene black.

[0585] Examples of coloring agents other than these organic pigments include inorganic black pigments. In addition to organic pigments, inorganic black pigments may also be used.

[0586] 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 can be preferably used for its light-blocking properties. Examples of carbon black include the following carbon blacks.

[0587] Manufactured by Mitsubishi Chemical Corporation: 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, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

[0588] Manufactured by Degusa Corporation: Printex (registered trademark, hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, 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

[0589] Manufactured by Cabot: Monarch (registered trademark, hereinafter the same) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, hereinafter the same) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL550R, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark)-8

[0590] Manufactured by Birla Co.: RAVEN (Registered Trademark, hereinafter the same.) 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

[0591] Carbon black coated with resin may be used. Using resin-coated carbon black has the effect of improving adhesion to a glass substrate and volume resistivity. As for the resin-coated carbon black, for example, carbon black described in Japanese Patent Publication No. Hei 09-71733 may be preferably used. Resin-coated carbon black is preferably used in terms of volume resistivity and dielectric constant.

[0592] It is preferable to use these organic pigments and inorganic pigments dispersed 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 standard for the average particle size is the number of pigment particles.

[0593] The average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is performed on a sufficiently diluted photosensitive resin composition (typically diluted to prepare a pigment concentration of about 0.005 to 0.2 mass%). However, if there is a concentration recommended by the measuring instrument, that concentration is used) and measured at 25°C.

[0594] In addition to organic pigments and inorganic black pigments, dyes may be used. Examples of dyes that can be used as coloring agents include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, etc.

[0595] 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 Mordaunted Red 7, CI Mordaunted Yellow 5, and CI Mordaunted Black 7.

[0596] Examples of anthraquinone dyes include CI Butt 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.

[0597] As a phthalocyanine dye, for example, CI Bat Blue 5 can be cited.

[0598] Examples of quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9.

[0599] Examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Dispers Yellow 64.

[0600] Examples of nitro dyes include CI acid yellow 1, CI acid orange 3, and CI dispers yellow 42.

[0601] When the photosensitive resin composition of the present invention includes (E) a colorant, the content ratio of (E) the colorant is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, 1 mass% or more is preferred, 2 mass% or more is more preferred, 3 mass% or more is even more preferred, 4 mass% or more is particularly preferred, 50 mass% or less is preferred, 30 mass% or less is more preferred, 20 mass% or less is even more preferred, 15 mass% or less is even more preferred, 12 mass% or less is particularly preferred, and 10 mass% or less is most preferred. The above upper and lower limits may be arbitrarily combined. For example, 1 to 50 mass% is preferred, 1 to 30 mass% is more preferred, 2 to 20 mass% is even more preferred, 2 to 15 mass% is even more preferred, 3 to 12 mass% is particularly preferred, and 4 to 10 mass% is particularly preferred. There is a tendency to secure light-blocking properties by making the value above the lower limit. Since the alkali-soluble resin and photopolymerizable compound can be relatively increased by making the value below the upper limit, the curability and ink-repellent properties of the coating film tend to be improved.

[0602] For the purpose of light scattering, a white pigment (E2) may be used in part or in whole among the (E) coloring agents. Examples of white pigments (E2) include metal oxides such as titanium oxide, zirconium oxide, hafnium oxide, and barium titanate, and inorganic fillers such as calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate.

[0603] White pigment (E2) may be used alone or in combination with two or more types.

[0604] In terms of refractive index and light scattering properties, it is preferable to use metal oxides, titanium oxide, zirconium oxide, and hafnium oxide are more preferable, and titanium oxide is even more preferable.

[0605] When the photosensitive resin composition of the present invention includes a white pigment (E2), with respect to the total solid content of the photosensitive resin composition, 1 mass% or more is preferred, 2 mass% or more is more preferred, 3 mass% or more is even more preferred, 4 mass% or more is particularly preferred, 50 mass% or less is preferred, 30 mass% or less is more preferred, 20 mass% or less is even more preferred, 15 mass% or less is even more preferred, and 10 mass% or less is particularly preferred. The above upper and lower limits may be combined arbitrarily. For example, 1 to 50 mass% is preferred, 1 to 30 mass% is more preferred, 2 to 20 mass% is even more preferred, 3 to 15 mass% is even more preferred, and 4 to 10 mass% is particularly preferred. By exceeding the above lower limit value, there is a tendency for high refractive index and light scattering properties to be improved. By keeping it below the upper limit value, the transmittance of the ultraviolet range can be increased, and the curability and ink-repellent properties of the coating film tend to be improved.

[0606] [1-1-6] (F) Dispersant

[0607] The photosensitive resin composition of the present invention may include (F) a dispersant in order to finely disperse (E) the colorant and also stabilize the dispersed state, when (E) the colorant is included.

[0608] (F) As a dispersant, a polymeric dispersant having functional groups is preferred, and in terms of dispersion stability, a polymeric dispersant having, for example, a carboxyl group, a phosphate group, a sulfonic acid group, or a base thereof; a primary, secondary, or tertiary amino group; a quaternary ammonium base; a nitrogen-containing heterocyclic group such as pyridine, pyrimidine, or pyrazine is preferred. A polymeric dispersant having basic functional groups such as a primary, secondary, or tertiary amino group; a quaternary ammonium base; a nitrogen-containing heterocyclic group such as pyridine, pyrimidine, or pyrazine is particularly preferred in terms of being able to disperse pigments with a small amount of dispersant.

[0609] Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of monomers having amino groups and macromonomers, 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.

[0610] Examples of such dispersants include, for instance, EFKA (registered trademark. Manufactured by BASF), DISPERBYK (registered trademark. Manufactured by Bic Chem), Dyspalon (registered trademark. Manufactured by Kusumoto Kasei), SOLSPERSE (registered trademark. Manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), PolyFlow (manufactured by Kyoei Chemical Co., Ltd.), and Azisper (registered trademark. Manufactured by Ajinomoto Co., Ltd.) by trade name.

[0611] Polymer dispersants may be used as a single type or in combination of two or more types.

[0612] The weight average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1000 or more, and also preferably 100,000 or less, more preferably 50,000 or less. The upper and lower limits may be any combination. For example, 700 to 100,000 is preferred, and 1000 to 50,000 is more preferred.

[0613] In terms of the dispersibility of the pigment, (F) the dispersant preferably comprises either or both of a urethane-based polymer dispersant and an acrylic-based polymer dispersant having functional groups, and it is particularly preferable to comprise an acrylic-based polymer dispersant.

[0614] In terms of dispersibility and preservation, a polymeric dispersant having basic functional groups and either or both of polyester and polyether bonds is preferred.

[0615] Examples of urethane-based and acrylic-based polymer dispersants include the DISPERBYK-160 to 167 and 182 series (all urethane-based), DISPERBYK-2000, 2001, and BYK-LPN21116 (all acrylic-based) (all manufactured by Big Chem Co.).

[0616] Examples of urethane-based polymer dispersants include, for instance, a dispersion resin having 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, for example, benzyl chloride, all or part of the tertiary amino groups can be converted into quaternary ammonium bases.

[0617] Polyisocyanate compounds include aromatic diisocyanates such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidin diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; Examples include alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), ω,ω'-diisocyanate-dimethylcyclohexane, aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate, 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; their trimers, their water adducts, and their polyol adducts. As for the polyisocyanate, an organic diisocyanate trimer is preferred, and a tolylene diisocyanate trimer and an isophorone diisocyanate trimer are particularly preferred.

[0618] Polyisocyanate compounds may be used alone or in combination of two or more types.

[0619] A method for producing a tripmer of isocyanates can be described as a method of partially trimerizing isocyanate groups of polyisocyanates using a suitable trimerizing catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, or carboxylates, stopping the trimerization by adding a catalyst poison, and then removing the unreacted polyisocyanate by solvent extraction and thin-film distillation to obtain the desired polyisocyanate containing isocyanurate groups.

[0620] Examples of compounds having one or two hydroxyl groups within the same molecule and a number average molecular weight of 300 to 10000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., compounds in which the terminal hydroxyl groups of these compounds are alkoxylated with alkyl groups having 1 to 25 carbon atoms, and mixtures of two or more of these types.

[0621] 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 copolymerizing alkylene oxides alone or by copolymerization, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of two or more of these.

[0622] Examples of polyether ester diols include polyether ester diols obtained by reacting a mixture with an ether-containing diol or another glycol with a dicarboxylic acid or their anhydride, or by reacting an alkylene oxide with a polyester glycol, such as poly(polyoxytetramethylene) adipate. The most preferred polyether glycol is a compound in which the terminal hydroxyl group of polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound thereof is alkoxylated to an alkyl group having 1 to 25 carbon atoms.

[0623] As polyester glycols, 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, Polyester glycols obtained by polycondensing (such as 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, aliphatic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol, bishydroxyethoxybenzene, and N-alkyldialkanolamines such as N-methyldiethanolamine), e.g., polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate; or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, e.g., polycaprolactone glycol, polymethylvalerolactone, and mixtures of two or more of these) There are. As polyester glycols, polycaprolactone glycol and polycaprolactone having an alcohol having 1 to 25 carbon atoms as an initiator are particularly preferred.

[0624] Examples of polycarbonate glycols include poly(1,6-hexylene)carbonate, poly(3-methyl-1,5-pentylene)carbonate, etc. Examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol.

[0625] Compounds having one or two hydroxyl groups within the same molecule and a number average molecular weight of 300 to 10000 may be used as a single type or two or more types may be used in combination.

[0626] The number average molecular weight of a compound 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.

[0627] In a compound having an active hydrogen and a tertiary amino group within the same molecule, the hydrogen atom directly bonded to the active hydrogen, that is, an oxygen atom, a nitrogen atom, or a sulfur atom, may be, for example, a hydrogen atom in the functional group of a hydroxyl group, an amino group, or a thiol group, and among these, a hydrogen atom of an amino group, particularly a primary amino group, is preferred.

[0628] The tertiary amino group is not particularly limited, but may include, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, and examples of heterocyclic structures may include, for example, an imidazole ring or a triazole ring.

[0629] Examples of compounds having an 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.

[0630] Examples of nitrogen-containing heterocyclic rings in which the tertiary amino group has a nitrogen-containing heterocyclic structure include, for instance, nitrogen-containing heterocyclic 5-membered rings such as pyrazol ring, imidazole ring, triazole ring, tetrazol ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, and benzothiadiazole ring, nitrogen-containing heterocyclic 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring, and imidazole ring and triazole ring are preferred.

[0631] Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole.

[0632] 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.

[0633] 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.

[0634] Compounds having an imidazole ring or a triazole ring and an amino group may be used alone or in combination of two or more.

[0635] The preferred mixing ratio of raw materials when manufacturing a urethane-based polymer dispersant is, for every 100 parts by mass of a 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 an active hydrogen and a tertiary amino group in the same molecule.

[0636] The preparation of a urethane-based polymer dispersant can be carried out according to known methods for preparing polyurethane resins. As a solvent for preparation, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone; esters such as ethyl acetate, butyl acetate, cellosolve acetate; hydrocarbons such as benzene, toluene, xylene, hexane; some alcohols such as diacetone alcohol, isopropanol, dis-butanol, ter-butanol; chlorides such as methylene chloride, chloroform; ethers such as tetrahydrofuran, diethyl ether; and non-protonic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide are used.

[0637] One type of solvent may be used alone, or two or more types may be used in combination.

[0638] For example, a urethane reaction catalyst is used in the manufacture of urethane-based polymer dispersants. Examples of urethane reaction catalysts include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoeate, and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine.

[0639] One type of urethane reaction catalyst may be used alone, or two or more types may be used in combination.

[0640] The amount of compound introduced having an active hydrogen and a tertiary amino group within the same molecule is preferably controlled by the amine value after reaction, preferably within the range of 1 to 100 mgKOH / g, and more preferably within 5 to 95 mgKOH / g. The amine value is a value expressed as the number of mg of KOH corresponding to the acid value after neutralizing the basic amino group with an acid. Dispersion ability tends to be improved by setting it above the lower limit value. Development performance tends to be improved by setting it below the upper limit value.

[0641] If isocyanate groups remain in the polymer dispersant, it is desirable to inactivate the isocyanate groups with an alcohol or an amino compound, as this increases the time-dependent stability of the product.

[0642] The weight average molecular weight (Mw) of the urethane-based 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. By making it above the lower limit value, dispersibility and dispersion stability tend to improve. By making it below the upper limit value, solubility is improved and dispersibility tends to improve.

[0643] 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 a functional group contained in the polymer dispersant and is the aforementioned functional group) and an unsaturated group-containing monomer not having a functional group. These copolymers can be manufactured by known methods.

[0644] Examples of monomers containing unsaturated groups having functional groups include, for instance, unsaturated monomers having carboxyl groups such as (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, and acrylic acid dimers, and unsaturated monomers having tertiary amino groups and quaternary ammonium bases such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternary compounds thereof.

[0645] One type of monomer containing an unsaturated group having a functional group may be used alone, or two or more types may be used in combination.

[0646] Unsaturated group-containing monomers that do not have functional groups include, for example, 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, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, Examples of macromonomers include N-substituted maleimides such as N-phenylmaleimide and N-benzylmaleimide, 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.

[0647] One type of unsaturated monomer that does not have a functional group may be used alone, or two or more types may be used in combination.

[0648] The acrylic polymer dispersant is, particularly preferably, an AB or BAB block copolymer comprising an A block having functional groups and a B block not having functional groups. In this case, the A block may contain, in addition to a partial structure derived from an unsaturated group-containing monomer containing said functional groups, a partial structure derived from an unsaturated group-containing monomer not containing said functional groups, and these may be contained in the A block in either a random copolymerization or a block copolymerization.

[0649] The content of the A block of the partial structure that does not contain functional groups is preferably 80 mass% or less, more preferably 50 mass% or less, and even more preferably 30 mass% or less.

[0650] The B block is composed of a substructure derived from an unsaturated group-containing monomer that does not contain the above functional group, and a single B block may contain substructures derived from two or more monomers, and these may be contained in the B block in either a random copolymer or a block copolymer.

[0651] AB or BAB block copolymers are prepared, for example, by the living polymerization method shown below.

[0652] Living polymerization methods include anionic living polymerization, cationic living polymerization, and radical living polymerization.

[0653] When synthesizing this acrylic polymer dispersant, for example, Japanese Patent Publication No. Hei 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B.C. Anderson, G.D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), Polym. J. 18, 1037 (1986), Koichi Ute, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. The method described in Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985), and DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987) may be adopted.

[0654] The acrylic polymer dispersant that can be used in the present invention may be 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 particularly more preferably 5 / 95 to 60 / 40 (mass ratio). By keeping it within the above range, it tends to be possible to secure a balance of dispersibility and storage stability.

[0655] The amount of quaternary ammonium base in 1 g of AB block copolymer and BAB block copolymer usable in the present invention is preferably 0.1 to 10 mmol. By keeping it within the above range, good dispersibility can be secured.

[0656] In the case where an amino group generated during the manufacturing process is contained in the block copolymer, the amine value is preferably 1 to 100 mgKOH / g, and from the perspective of dispersibility, preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, even more preferably 50 mgKOH / g or more, also preferably 90 mgKOH / g or less, more preferably 80 mgKOH / g or less, and even more preferably 75 mgKOH / g or less. The upper and lower limits above may be combined arbitrarily. For example, 1 to 100 mgKOH / g is preferred, 10 to 90 mgKOH / g is more preferred, 30 to 80 mgKOH / g is even more preferred, and 50 to 75 mgKOH / g is particularly preferred.

[0657] The amine value of a dispersant such as a block copolymer is expressed as the mass of an equivalent amount of KOH and the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.

[0658] 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 titration apparatus equipped with a pH electrode, neutralize this solution with a 0.1 mol / L HClO4 acetic acid solution. Set the inflection point of the titration pH curve as the endpoint of the titration, determine the amine value using the following equation.

[0659] Amine number [mgKOH / g] = (561 × V) / (W × S) [where W: weighed amount of dispersant sample [g], V: titration amount at the endpoint [mL], S: solid content concentration of dispersant sample [mass%]]

[0660] The acid value of the block copolymer varies depending on the presence and type of acidic group that forms the basis of the acid value, but it is preferable for it to be low, and preferably 10 mgKOH / g or less.

[0661] The weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. By keeping it within the above range, good dispersibility can be secured.

[0662] When having a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited, but from the perspective of dispersibility, it is desirable to have a repeating unit represented by the following general formula (ri) (hereinafter referred to as "repeating unit (ri)").

[0663] [Chemical Formula 44]

[0664]

[0665] Among the formula (ri), R 31 ~ R 33 Each independently represents a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or an aralkyl group that may have substituents;

[0666] R 31 ~ R 33 Middle school students in grades 2 or higher may combine with each other to form a ring-shaped structure;

[0667] R 34 is a hydrogen atom or a methyl group;

[0668] X is a 2-valent connector and ;

[0669] Y - is a counter noon.

[0670] R of equation (ri) 31 ~ R 33 In the above, the number of carbon atoms of the alkyl group that may have a substituent 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.

[0671] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. The alkyl group may be either a straight-chain type or a branched type. In addition, it may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0672] R of equation (ri) 31 ~ R 33 In the above, the number of carbon atoms in the aryl group that may have a substituent is not particularly limited, but it 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.

[0673] Examples of aryl groups include phenyl groups, methylphenyl groups, ethylphenyl groups, dimethylphenyl groups, diethylphenyl groups, naphthyl groups, and anthracenyl groups; phenyl groups, methylphenyl groups, ethylphenyl groups, dimethylphenyl groups, and diethylphenyl groups are preferred, and phenyl groups, methylphenyl groups, and ethylphenyl groups are more preferred.

[0674] R of equation (ri) 31 ~ R 33 In the above, the number of carbon atoms in the aralkyl group that may have a substituent 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.

[0675] Examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenylyl group), phenylpropyl group, phenylbutyl group, and phenylisopropyl group; phenylmethyl group, phenylethyl group, phenylpropyl group, and phenylbutyl group are preferred, and phenylmethyl group and phenylethyl group are more preferred.

[0676] In terms of variance, R 31 ~ R33 It is preferable that each of these independently is an alkyl group or an aralkyl group, and R 31 and R 33 Each of these is independently a methyl group or an ethyl group, and also, R 32 It is more preferable that is a phenylmethyl group or a phenylethyl group, and R 31 and R 33 This is a methyl group, and also, R 32 It is more preferable that the group be a phenylmethyl group.

[0677] When a polymeric dispersant has a tertiary amine as a functional group, it is desirable to have a repeating unit represented by the following general formula (r-ii) (hereinafter referred to as "repeating unit (r-ii)") for the sake of dispersibility.

[0678] [Chemical Formula 45]

[0679]

[0680] In equation (r-ii), R 35 and R 36 Each is independently a hydrogen atom, an alkyl group that may have substituents, an aryl group that may have substituents, or an aralkyl group that may have substituents;

[0681] R 35 and R 36 These may combine to form a ring-shaped structure;

[0682] R 37 is a hydrogen atom or a methyl group;

[0683] Z is a 2-fold connector.

[0684] R of equation (r-ii) 35 and R 36 In this case, the alkyl group that may have a substituent is R of formula (ri). 31 ~ R 33 As such, the example can be adopted in a desirable manner.

[0685] R of equation (r-ii) 35 and R36 In this case, the aryl group that may have a substituent is R of formula (ri). 31 ~ R 33 As such, the example can be adopted in a desirable manner.

[0686] R of equation (r-ii) 35 and R 36 In this case, the aralkyl group that may have a substituent is R of formula (ri). 31 ~ R 33 As such, the example can be adopted in a desirable manner.

[0687] R 35 and R 36 It is preferable that each of these independently be an alkyl group that may have a substituent, and more preferable that it be a methyl group or an ethyl group.

[0688] R of equation (ri) 31 ~ R 33 and R of equation (r-ii) 35 and R 36 Examples of substituents that may be present in the alkyl group, aralkyl group, or aryl group include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.

[0689] In formulas (ri) and (r-ii), the divalent linkers X and Z are, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 - Gi, -COOR 44 - Unit (R 43 and R 44 Examples include a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, and preferably -COO-R 44 - It is.

[0690] In equation (ri), the Y of the counter-anon - Ro, for example, Cl - , Br - , I- , ClO4 - , BF4 - , CH3COO - , PF6 - ...can be cited.

[0691] The content ratio of the repeating unit represented by formula (ri) is not particularly limited, but with respect to dispersibility, with respect to the sum of the content ratio of the repeating unit represented by formula (ri) and the content ratio of the repeating unit represented by formula (r-ii), 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. The above upper and lower limits may 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.

[0692] The content ratio of the repeating unit represented by formula (ri) in the total repeating unit of the polymer dispersant is not particularly limited, but from the perspective of dispersibility, 1 mol% or more is preferred, 5 mol% or more is more preferred, 10 mol% or more is even more preferred, 50 mol% or less is preferred, 30 mol% or less is more preferred, 20 mol% or less is even more preferred, and 15 mol% or less is particularly preferred. 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.

[0693] The content ratio of the repeating unit represented by the above formula (r-ii) in the total repeating unit of the polymer dispersant is not particularly limited, but from the perspective of dispersibility, it is preferable that it be 5 mol% or more, more preferable that it be 10 mol% or more, even more preferable that it be 15 mol% or more, particularly preferable that it be 20 mol% or more, and also preferable that it be 60 mol% or less, more preferable that it be 40 mol% or less, even more preferable that it be 30 mol% or less, and particularly preferable that it be 25 mol% or less. The above upper and lower limits may be combined arbitrarily. For example, 5 to 60 mol% is preferable, 10 to 40 mol% is more preferable, 15 to 30 mol% is even more preferable, and 20 to 25 mol% is particularly preferable.

[0694] In order to increase compatibility with binder components such as solvents and to improve dispersion stability, it is desirable for a polymer dispersant to have a repeating unit represented by the following general formula (r-iii) (hereinafter referred to as "repeating unit (r-iii)").

[0695] [Chemical Formula 46]

[0696]

[0697] In equation (r-iii), R 40 is an ethylene group or a propylene group;

[0698] R 41 It is an alkyl group that may have substituents;

[0699] R 42 is a hydrogen atom or a methyl group;

[0700] n is an integer from 1 to 20.

[0701] R in equation (r-iii) 41In the above, the number of carbon atoms in the alkyl group that may have a substituent is not particularly limited, but is preferably 1 or more, more preferably 2 or more, more preferably 10 or fewer, and more preferably 6 or fewer. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, and 2 to 6 is more preferred.

[0702] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and methyl, ethyl, propyl, butyl, pentyl, or hexyl groups are preferred, and methyl, ethyl, propyl, or butyl groups are more preferred. The alkyl group may be either a straight-chain type or a branched type. In addition, it may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

[0703] In formula (r-iii), n is preferably 1 or more, more preferably 2 or more, more preferably 10 or less, and more preferably 5 or less, from the perspective of compatibility and dispersibility with respect to the solvent or binder component. The above upper and lower limits may be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 5 is even more preferred.

[0704] The content ratio of the repeating unit represented by formula (r-iii) in the total repeating unit of the polymer dispersant is not particularly limited, but 1 mol% or more is preferred, 2 mol% or more is more preferred, 4 mol% or more is even more preferred, 30 mol% or less is preferred, 20 mol% or less is more preferred, and 10 mol% or less is even more preferred. The upper and lower limits above 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, compatibility with solvent or binder components and dispersion stability tend to be achieved.

[0705] It is desirable for a polymer dispersant to have a repeating unit represented by the following general formula (r-iv) (hereinafter referred to as "repeating unit (r-iv)") in order to increase compatibility of the dispersant with the solvent or binder component and to improve dispersion stability.

[0706] [Chemical Formula 47]

[0707]

[0708] In equation (r-iv), R 38 is an alkyl group that may have substituents, an aryl group that may have substituents, or an aralkyl group that may have substituents;

[0709] R 39 is a hydrogen atom or a methyl group.

[0710] R of equation (r-iv) 38In the above, the number of carbon atoms in the alkyl group that may have a substituent is not particularly limited, but is preferably 1 or more, more preferably 2 or more, more preferably 4 or more, more preferably 10 or less, and more preferably 8 or less. The above upper and lower limits may be combined arbitrarily. For example, 1 to 10 is preferred, 2 to 8 is more preferred, and 4 to 8 is even more preferred.

[0711] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. The alkyl group may be either straight-chain or branched. In addition, it may include a cyclic structure, such as a cyclohexyl group or a cyclohexylmethyl group.

[0712] R of equation (r-iv) 38 In the above, the number of carbon atoms of the aryl group that may have a substituent is not particularly limited, but is preferably 6 or more, and 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.

[0713] Examples of aryl groups include phenyl groups, methylphenyl groups, ethylphenyl groups, dimethylphenyl groups, diethylphenyl groups, naphthyl groups, and anthracenyl groups; phenyl groups, methylphenyl groups, ethylphenyl groups, dimethylphenyl groups, and diethylphenyl groups are preferred, and phenyl groups, methylphenyl groups, and ethylphenyl groups are more preferred.

[0714] R of equation (r-iv) 38In the above, the number of carbon atoms of the aralkyl group that may have a substituent is not particularly limited, but is preferably 7 or more, and 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.

[0715] Examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenylyl group), phenylpropyl group, phenylbutyl group, and phenylisopropyl group; phenylmethyl group, phenylethyl group, phenylpropyl group, and phenylbutyl group are preferred, and phenylmethyl group and phenylethyl group are more preferred.

[0716] In terms of solvent compatibility and dispersion stability, R 38 An alkyl group or an aralkyl group is preferred, and a methyl group, ethyl group, or phenylmethyl group is more preferred.

[0717] R 38 Examples of substituents that the alkyl group may have include, for instance, halogen atoms and alkoxy groups.

[0718] R 38 Examples of substituents that may be present in the aryl or aralkyl group include chain-type alkyl groups, halogen atoms, and alkoxy groups.

[0719] R 38 The chain-type alkyl groups represented by include both straight-chain and branched-chain types.

[0720] The content ratio of the repeating unit represented by the above formula (r-iv) in the total repeating unit of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, more preferably 50 mol% or more, and also preferably 80 mol% or less, and more preferably 70 mol% or less, from the perspective of dispersibility. The above upper and lower limits may be arbitrarily combined. For example, 30 to 80 mol% is preferred, 40 to 80 mol% is more preferred, and 50 to 70 mol% is more preferred.

[0721] Polymer dispersants may have repeating units other than repeating units (ri), repeating unit (r-ii), repeating unit (r-iii), and repeating unit (r-iv). Examples of such repeating units include repeating units derived from styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylate chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allylglycidyl ether; glycidyl crotonic acid ether; and N-methacryloylmorpholine.

[0722] In order to further enhance dispersibility, the polymeric dispersant is preferably a block copolymer having a block A having repeating unit (ri) and repeating unit (r-ii) and a block B not having repeating unit (ri) and repeating unit (r-ii). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing tertiary amino groups as well as quaternary ammonium bases into block A, the dispersion ability of the dispersant tends to be significantly improved. It is preferable for block B to have a repeating unit (r-iii), and it is even more preferable for it to additionally have a repeating unit (r-iv).

[0723] In block A, repeating unit (ri) and repeating unit (r-ii) may be contained in either a random copolymer or a block copolymer. One or more types of repeating unit (ri) and repeating unit (r-ii) may each be contained in block A, and in that case, each repeating unit may be contained in either a random copolymer or a block copolymer.

[0724] 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 instance, repeating units derived from the aforementioned (meth)acrylic acid ester-based monomer. 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 0 mol% is particularly preferred.

[0725] Repeating units other than repeating units (r-iii) and (r-iv) may be contained in the B block, and examples of such repeating units include repeating units derived from styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylate chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allylglycidyl ether; glycidyl crotonic acid; and N-methacryloylmorpholine. The content of repeating units other than repeating units (r-iii) and (r-iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and 0 mol% is particularly preferred.

[0726] When the photosensitive resin composition of the present invention contains a (F) dispersant, the content ratio is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, 0.1 mass% or more is preferred, 0.5 mass% or more is more preferred, 8 mass% or less is preferred, 5 mass% or less is more preferred, 3 mass% or less is even more preferred, and 2 mass% or less is particularly preferred. The above upper and lower limits may be arbitrarily combined. For example, 0.1 to 8 mass% is preferred, 0.1 to 5 mass% is more preferred, 0.5 to 3 mass% is even more preferred, and 0.5 to 2 mass% is particularly preferred. By setting the value above the lower limit, there is a tendency to suppress the generation of residues caused by aggregates. By setting the value below the upper limit, there is a tendency to improve ink release properties or developability.

[0727] [1-1-7] UV absorber

[0728] 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 a specific wavelength of the light source used for exposure. By adding the ultraviolet absorber, effects such as forming a high-precision barrier with a narrow linewidth or eliminating residue remaining in the unexposed area after development are obtained.

[0729] As an ultraviolet absorber, (B) a compound having an absorption maximum between a wavelength of 250 nm and 400 nm can be used in terms of inhibiting light absorption of the photopolymerization initiator.

[0730] As for the UV absorber, it is preferable to include either or both of benzotriazole-based compounds and triazine-based compounds. It is believed that by including either or both of benzotriazole-based compounds and triazine-based compounds, the light absorption rate at the bottom of the initiator film is reduced, and the line width at the bottom of the film is reduced, thereby enabling the formation of a narrow, high-precision barrier.

[0731] Benzotriazole compounds include, for example, 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, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, Examples include ester compounds of 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 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionic acid and C7-9 straight-chain and branched alkyl alcohols.

[0732] Commercially available benzotriazole compounds include, for example, Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry), TINUVIN (registered trademark, hereinafter the same) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, Examples include EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Yongguang Chemical Industry), Tomysorb (registered trademark, hereinafter the same) 100, Tomysorb 600 (manufactured by API Corporation), SEESORB (registered trademark, hereinafter the same) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Cipro Chemical), and RUVA-93 (Otsuka Chemical Co., Ltd.).

[0733] Examples of triazine-based 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, the reaction product 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, and hydroxyphenyltriazine compounds are preferred in terms of ink-like properties and forming a narrow, high-precision barrier.

[0734] Examples of commercially available triazine compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

[0735] 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.

[0736] For example, benzophenone compounds such as Smisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongguang Chemical Industry), Tomisov 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Cipro Chemical); benzoate compounds such as Smisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate; cinnamon acid derivatives such as 2-ethylhexyl cinnamonate, 2-ethylhexyl paramethoxycinnamonate, isopropyl methoxycinnamonate, and isoamyl methoxycinnamonate; Naphthalene derivatives such as α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; anthracene and derivatives such as anthracene, 9,10-dihydroxyanthracene; Examples of dyes include azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, etc. From the perspective of ink-blotting properties, cinnamon acid derivatives and naphthalene derivatives are preferred, and cinnamon acid derivatives are particularly preferred.

[0737] In terms of tapered shape, either or both of benzotriazole compounds and hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are particularly preferred.

[0738] As for the ultraviolet absorber, one type may be used alone, or two or more types may be used in combination.

[0739] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content ratio is not particularly limited, but with respect to the total solid content of the photosensitive resin composition, it is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, even more preferably 0.5 mass% or more, particularly preferably 1 mass% or more, and also preferably 15 mass% or less, more preferably 10 mass% or less, even more preferably 5 mass% or less, and particularly preferably 3 mass% or less. The above upper and lower limits may be arbitrarily combined. For example, 0.01 to 15 mass% is preferred, 0.05 to 15 mass% is more preferred, 0.1 to 10 mass% is more preferred, 0.5 to 5 mass% is more preferred, and 1 to 3 mass% is particularly preferred. By making it greater than the above lower limit value, there is a tendency to form a high-precision barrier with a narrow line width. By keeping it below the upper limit value mentioned above, there is a tendency for the ink-repellent properties to increase.

[0740] When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the mixing ratio with respect to (B) the photopolymerization initiator is, as the amount of ultraviolet absorber mixed with respect to 100 parts by mass of (B) the photopolymerization initiator, 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 upper and lower limits above may be arbitrarily combined. 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 more preferred, 50 to 200 parts by mass is more preferred, and 80 to 100 parts by mass is particularly preferred. By making the value greater than the lower limit mentioned above, there is a tendency to form a high-precision bulkhead with a narrow line width. By making the value less than the upper limit mentioned above, there is a tendency for the ink-repellent properties to increase.

[0741] [1-1-8] Polymerization Inhibitor

[0742] The photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the taper angle of the resulting barrier tends to be increased in that it inhibits radical polymerization.

[0743] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). In terms of polymerization inhibitory ability, hydroquinone, methoxyphenol, and methylhydroquinone are preferred, and methylhydroquinone is more preferred.

[0744] Polymerization inhibitors may be used as a single type or in combination of two or more types.

[0745] (C) Depending on the method of manufacturing the alkali-soluble resin, the manufactured alkali-soluble resin may contain a polymerization inhibitor. In such cases, the alkali-soluble resin may be used as is, even if it contains the polymerization inhibitor, or, in addition to the polymerization inhibitor contained in the resin, a polymerization inhibitor identical to or different from it may be additionally added during the preparation of the photosensitive resin composition.

[0746] When a photosensitive resin composition contains a polymerization inhibitor, the content ratio is not particularly limited, but is preferably 0.0005 mass% or more, more preferably 0.001 mass% or more, even more preferably 0.01 mass% or more with respect to the total solid content of the photosensitive resin composition, and is also preferably 0.1 mass% or less, more preferably 0.08 mass% or less, and even more preferably 0.05 mass% or less. The above upper and lower limits may be arbitrarily combined. For example, 0.0005 to 0.1 mass% is preferred, 0.001 to 0.08 mass% is more preferred, and 0.01 to 0.05 mass% is even more preferred. By setting the value above the lower limit, there is a tendency to increase the taper angle. By setting the value below the upper limit, there is a tendency to increase the ink release properties.

[0747] [1-1-9] Thermal polymerization initiator

[0748] The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, the degree of crosslinking of the film tends to be increased. Examples of such thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide.

[0749] These may be used as a single type or in combination with two or more types.

[0750] When a thermal polymerization initiator is used in combination with a photopolymerization initiator to improve ink-repellent properties or increase the crosslinking density of the film, it is desirable that the sum of the content ratios of these initiators equals the content ratio of the photopolymerization initiator in the aforementioned photosensitive resin composition, and also, regarding the combined ratio of the photopolymerization initiator and the thermal polymerization initiator, from the perspective of ink-repellent properties, it is desirable to have 5 to 300 parts by mass of the thermal polymerization initiator for every 100 parts by mass of the photopolymerization initiator.

[0751] [1-1-10] Amino compounds

[0752] The photosensitive resin composition of the present invention may contain an amino compound to promote thermal curing. When an amino compound is included in the photosensitive resin composition of the present invention, the content ratio of the amino compound is preferably 40 mass% or less, more preferably 30 mass% or less, with respect to the total solid content of the photosensitive resin composition, and is also preferably 0.5 mass% or more, more preferably 1 mass% or more. The upper and lower limits above may be arbitrarily combined. For example, 0.5 to 40 mass% is preferred, and 1 to 30 mass% is more preferred. By keeping the value below the upper limit, storage stability tends to be maintained. By keeping the value above the lower limit, sufficient thermal curability tends to be secured.

[0753] Examples of amino compounds include, for instance, amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups modified by alcohol condensation having 1 to 8 carbon atoms. Specifically, for instance, melamine resin obtained by polycondensing melamine and formaldehyde; benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde; glycoluryl resin obtained by polycondensing glycoluryl and formaldehyde; urea resin obtained by polycondensing urea and formaldehyde; and a resin obtained by polycondensing two or more of melamine, benzoguanamine, glycoluryl, or urea with formaldehyde. Examples include modified resins in which the methylol groups of the resin described above are modified by alcohol condensation, and melamine resin and its modified resin are preferred. Among the modified resins, a modified resin with a modification ratio of 70% or more of methylol groups is more preferred, and a modified resin with a modification ratio of 80% or more is even more preferred.

[0754] One type of amino compound may be used alone, or two or more types may be used in combination.

[0755] Examples of melamine resins and modified resins thereof include “Simel” (registered trademark, hereinafter the same) manufactured by Cytech Co., Ltd., 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nikarak” (registered trademark, hereinafter the same) manufactured by Sanwa Chemical Co., Ltd., MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302.

[0756] Examples of benzoguanamine resins and modified resins thereof include "Symel" 1123, 1125, and 1128 manufactured by SciTech Co., Ltd.

[0757] Examples of glycoluryl resins and modified resins thereof include "Symel" 1170, 1171, 1174, and 1172 manufactured by Cytech, and "Nikarak" MX-270 manufactured by Sanwa Chemical.

[0758] Examples of urea resins and their modified resins include “UFR” (registered trademark) 65, 300 manufactured by SciTech Co., and “Nikarak” MX-290 manufactured by Sanwa Chemical Co.

[0759] [1-1-11] Silane coupling agent

[0760] The photosensitive resin composition of the present invention may contain a silane coupling agent to improve adhesion to a substrate.

[0761] As for silane coupling agents, for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used, and epoxy-based and imidazole-based silane coupling agents are preferred from the perspective of improving adhesion.

[0762] When the photosensitive resin composition of the present invention contains a silane coupling agent, the content thereof is preferably 20 mass% or less, more preferably 15 mass% or less, with respect to the total solid content of the photosensitive resin composition in terms of adhesion.

[0763] [1-1-12] Weapon Filler

[0764] The photosensitive resin composition of the present invention may contain an inorganic filler for the purpose of improving the strength as a cured product, as well as improving the excellent verticality and taper angle of the coating film through appropriate interaction with an alkali-soluble resin (formation of a matrix structure).

[0765] Examples of inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, or these surface-treated with various silane coupling agents. In particular, silica sol and silica sol modified products are preferred because they tend to have excellent effects in improving the taper angle along with dispersion stability.

[0766] 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 is a value measured by a laser diffraction scattering particle size distribution measuring device manufactured by Beckmann Coulter or similar.

[0767] When the photosensitive resin composition of the present invention includes an inorganic filler, the content thereof is preferably 5 mass% or more, more preferably 10 mass% or more, and preferably 80 mass% or less, more preferably 70 mass% or less, with respect to the total solid content of the photosensitive resin composition, from the perspective of ink-repellent properties. The upper and lower limits above may be arbitrarily combined. For example, 5 to 80 mass% is preferred, and 10 to 70 mass% is more preferred.

[0768] [1-1-13] Adhesion enhancer

[0769] The photosensitive resin composition of the present invention may contain an adhesion enhancer for the purpose of imparting adhesion to a substrate. Examples of adhesion enhancers include phosphate-based ethylene monomers.

[0770] As for the phosphate-based ethylene monomer, (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.

[0771] [Chemical Formula 48]

[0772]

[0773] 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.

[0774] Phosphate-based ethylenetic monomers may be used as a single type or in combination of two or more types.

[0775] When the photosensitive resin composition of the present invention includes a phosphate-based ethylenetic monomer as an adhesion enhancer, the content ratio thereof is preferably 0.02 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, particularly preferably 0.2 mass% or more, and also preferably 4 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and particularly preferably 1 mass% or less, based on the total solid content of the photosensitive resin composition. The upper and lower limits above may be arbitrarily combined. For example, 0.02 to 4 mass% is preferred, 0.05 to 3 mass% is more preferred, 0.1 to 2 mass% is even more preferred, and 0.2 to 1 mass% is particularly preferred. By setting the value above the lower limit, the effect of improving adhesion to the substrate tends to become sufficient. By setting the value below the upper limit, it tends to be easier to suppress the deterioration of adhesion to the substrate.

[0776] [1-1-14] Solvent

[0777] The photosensitive resin composition of the present invention typically contains a solvent and is used in a state where each component contained in the photosensitive resin composition is dissolved or dispersed in the solvent. The solvent is not particularly limited, but examples include the organic solvents described below.

[0778] 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;

[0779] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0780] 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;

[0781] Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanol diacetate, etc.;

[0782] Alkyl acetates such as cyclohexanol acetate;

[0783] Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

[0784] 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;

[0785] Monovalent or polyvalent 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;

[0786] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0787] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0788] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0789] Chain or cyclic esters such as amylformate, ethylformate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, ethyl benzoate, methyl ethoxypropionate, ethyl ethoxypropionate, methyl methoxypropionate, ethyl methoxypropionate, propyl methoxypropionate, butyl methoxypropionate, and γ-butyrolactone;

[0790] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0791] Halogenated hydrocarbons such as butyl chloride and amyl chloride;

[0792] Etherketones such as methoxymethylpentanone;

[0793] Nitriles such as acetonitrile and benzonitrile;

[0794] Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

[0795] Examples of commercially available solvents include, for instance, Mineral Spirit, Barsol No. 2, Afco No. 18 Solvent, Afco Thinner, Socal Solvent No. 1 and No. 2, Solvesso No. 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, and Deglaim (all trade names).

[0796] The solvent is capable of dissolving or dispersing 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 perspective of coating properties, the boiling point of the solvent under 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.

[0797] One type of solvent may be used alone, or two or more types may be used in combination.

[0798] It is preferable to use a solvent such that the content ratio of the total solid content in the photosensitive resin composition solution is preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 20 mass% or more, particularly preferably 25 mass% or more, and also preferably 90 mass% or less, more preferably 50 mass% or less, even more preferably 40 mass% or less, and particularly preferably 35 mass% or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferable to use a solvent such that the content is preferably 10 to 90 mass%, more preferably 15 to 50 mass%, even more preferably 20 to 40 mass%, and particularly preferably 25 to 35 mass%. By setting the content above the lower limit, the occurrence of non-uniform coating tends to be suppressed. By setting the content below the upper limit, the occurrence of foreign substances, cratering, etc. tends to be suppressed.

[0799] [1-2] Method for preparing a photosensitive resin composition

[0800] The photosensitive resin composition of the present invention is prepared by mixing each component contained in the photosensitive resin composition with a stirrer.

[0801] For example, (E) if the colorant contains solvent-free components such as pigments, it is preferable to perform dispersion treatment using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc., in advance. Because the (E) colorant is micronized by dispersion treatment, the coating properties of the photosensitive resin composition are improved.

[0802] It is preferable to carry out the dispersion treatment in a system that typically uses (E) a coloring agent, a solvent, and (F) a dispersant, or optionally in a system that uses (C) some or all of an alkali-soluble resin in combination with them (hereinafter, the mixture provided for the dispersion treatment and the composition obtained from the dispersion treatment may be referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as (F) the dispersant because the dispersion stability of the obtained ink and photosensitive resin composition is excellent and thickening over time is suppressed.

[0803] Thus, in the process of manufacturing a photosensitive resin composition, it is preferable to prepare a pigment dispersion containing at least (E) a coloring agent, a solvent, and (F) a dispersant.

[0804] As for (E) the colorant, organic solvent, and (F) the dispersant that can be used in the pigment dispersion, the ones described as usable in the photosensitive resin composition may be preferably adopted. As for the content ratio of each colorant (E) in the pigment dispersion, the ones described as the content ratio in the photosensitive resin composition may be preferably adopted.

[0805] When dispersing the (E) coloring agent with a sand grinder, glass beads or zirconia beads with a particle size of about 0.1 to 8 mm are preferably used. The temperature at which the dispersion treatment is performed is preferably 0°C to 100°C, and more preferably in the range from room temperature to 80°C. The dispersion time is appropriately adjusted as the optimal time varies depending on the composition of the liquid and the size of the dispersion treatment device. The standard for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.

[0806] The dispersion 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.

[0807] Next, the ink obtained by the dispersion treatment is mixed with other components included in the photosensitive resin composition to form 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.

[0808] [2] Bulkhead and method of forming it

[0809] By curing the photosensitive resin composition of the present invention, a cured product of the present invention can be obtained. The photosensitive resin composition of the present invention can be used to form a barrier, and for example, it can be preferably used to form a barrier for partitioning an organic layer of an organic electroluminescent device or a barrier for partitioning a pixel portion in a color filter containing luminescent nanocrystalline particles. The barrier of the present invention is composed of the cured product of the present invention.

[0810] The method of forming a barrier using the photosensitive resin composition of the present invention is not particularly limited, and conventionally known methods may be employed. The formation of a cured product using the photosensitive resin composition of the present invention preferably comprises at least the following processes (1) to (4).

[0811] Process (1): A process of forming a film by applying the photosensitive resin composition of the present invention onto a substrate.

[0812] Process (2): A process of exposing at least a portion of the film formed in Process (1).

[0813] Process (3): A process for developing the film exposed in Process (2).

[0814] Process (4): A process for firing the coating developed in Process (3).

[0815] <Process (1): A process of forming a film by applying a photosensitive resin composition onto a substrate>

[0816] Methods for supplying a photosensitive resin composition to a substrate include, for example, inkjet and photolithography.

[0817] In the inkjet method, a photosensitive resin composition with viscosity adjusted by dilution with a solvent, etc., is used as ink, and the photosensitive resin composition is applied to a substrate by extruding ink droplets onto the substrate along a predetermined pattern of barriers using the inkjet method to form a pattern of uncured barriers. Then, the pattern of uncured barriers is exposed to light to form cured barriers on the substrate. The exposure of the pattern of uncured barriers is performed in the same manner as the exposure process in the photolithography method described later, except that a mask is not used.

[0818] In the photolithography method, a photosensitive resin composition is applied to the entire surface of the area where the partition is to be formed on the substrate to form a photosensitive resin composition layer. After exposing the formed photosensitive resin composition layer to light according to a predetermined partition pattern, the exposed photosensitive resin composition layer is developed to form a partition on the substrate.

[0819] In the coating process of applying a photosensitive resin composition onto a substrate in a photolithography method, the photosensitive resin composition is applied onto the substrate on which a barrier is to be formed using a contact transfer type coating device such as a roll coater, reverse coater, or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or curtain flow coater.

[0820] After supplying a photosensitive resin composition onto a substrate, a coating film is formed by preferably performing drying. Drying is preferably performed using a drying method that utilizes a hot plate, an IR oven, or a convection oven. A vacuum drying method may also be combined, in which drying is performed within a vacuum chamber without raising the temperature.

[0821] The drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. The drying time is typically selected in the range of 15 seconds to 5 minutes at a temperature of 40°C to 100°C, depending on the type of solvent component and the performance of the dryer used, and preferably in the range of 30 seconds to 3 minutes at a temperature of 50°C to 80°C. In addition, it is preferable to carry out the process within a range that does not exceed the firing temperature described below.

[0822] <Process (2): A process of exposing at least a portion of the film formed in Process (1)>

[0823] In the photolithography process, an active energy line, such as ultraviolet light or excimer laser light, is irradiated onto a photosensitive resin composition using a negative-type mask, and the photosensitive resin composition layer is partially exposed according to a bank pattern. For the exposure, a light source emitting ultraviolet light, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp, may be used. The amount of exposure varies depending on the composition of the photosensitive resin composition; for example, approximately 10 to 400 mJ / ㎠ is preferred.

[0824] <Process (3): Process of developing the film exposed in Process (2)>

[0825] In the development process, a barrier is formed by developing a photosensitive resin composition layer exposed according to the barrier pattern with a developer. The development method is not particularly limited and may use methods such as immersion or spraying. Specific examples of the developer include organic agents such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Additionally, an antifoaming agent or a surfactant may be added to the developer.

[0826] After the development process, an additional exposure process (post-exposure process) is performed as needed. An active energy line, such as ultraviolet light or excimer laser light, is irradiated onto the barrier after development to perform exposure. At this time, partial exposure using a mask may be performed. For exposure, a light source emitting ultraviolet light, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, or a UV-FL (ultraviolet-emitting fluorescent lamp), may be used. The amount of exposure varies depending on the composition of the photosensitive resin composition, but it is preferably 10 mJ / ㎠ or more, more preferably 100 mJ / ㎠ or more, more preferably 500 mJ / ㎠ or more, particularly preferably 800 mJ / ㎠ or more, and also preferably 10,000 mJ / ㎠ or less, more preferably 5,000 mJ / ㎠ or less, and more preferably 2,000 mJ / ㎠ or less. For example, 10 to 10,000 mJ / ㎠ is preferable, 100 to 10,000 mJ / ㎠ is more preferable, 500 to 5,000 mJ / ㎠ is even more preferable, and 800 to 2,000 mJ / ㎠ is particularly preferable. Penetration resistance tends to improve when the value is above the lower limit. It is preferable to keep the value below the upper limit so that penetration resistance can be achieved and productivity can be secured by keeping the irradiation time from being excessively long.

[0827] <Process (4): Process of firing the coating developed in Process (3)>

[0828] After development, or after post-exposure following development, a post-baking, i.e., heat curing treatment, is performed on the partition. The conditions for the post-baking are preferably 80°C or higher, more preferably 90°C or higher, and 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 to 250°C is preferred, 80 to 200°C is more preferred, 80 to 180°C is even more preferred, 80 to 140°C is more preferred, 80 to 120°C is particularly preferred, 80 to 100°C is more particularly preferred, and 90 to 100°C is particularly preferred. Penetration resistance and heat resistance tend to improve above the lower limit. By keeping it below the upper limit, the impact on manufacturing costs, substrates with heat resistance limits such as plastic substrates, and devices tends to decrease.

[0829] The firing time is preferably 5 to 120 minutes.

[0830] The substrate used for forming the barrier is not particularly limited and is appropriately selected according to the type of organic electroluminescent device or color filter manufactured using the substrate with the barrier formed thereon. Preferred substrate materials include glass or various resin materials. Resin materials include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonates; poly(meth)acrylic resins; polysulfones; and polyimides. Glass and polyimides are preferred due to their excellent heat resistance. Depending on the type of organic electroluminescent device or color filter being manufactured, a transparent electrode layer such as ITO or ZnO may be formed in advance on the surface of the substrate where the barrier is formed. Additionally, a barrier for the color filter may be formed on the substrate having the device.

[0831] On the substrate, to improve surface properties such as adhesion, treatment such as corona discharge, ozone treatment, or thin film formation treatment of various resins such as silane coupling agents or urethane-based resins may be performed as needed.

[0832] The film thickness of the barrier 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 upper and lower limits above may be arbitrarily combined. For example, 0.1 μm to 1 mm is preferred, 0.1 to 100 μm is more preferred, 1 to 50 μm is more preferred, 5 to 30 μm is more preferred, and 10 to 20 μm is particularly preferred. Light-blocking performance tends to be improved by making it greater than the lower limit value. Adhesion tends to be improved by making it less than the upper limit value.

[0833] The film thickness of the barrier is measured using a step, surface roughness, and micro-shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.

[0834] [3] Organic field light-emitting diode

[0835] The organic electroluminescent device of the present invention comprises the barrier of the present invention.

[0836] Various organic electroluminescent devices are manufactured using a substrate having a barrier pattern manufactured by the method described above. Although the method of forming the organic electroluminescent device is not particularly limited, preferably, after forming a barrier pattern on the substrate by the above method, an organic electroluminescent device is manufactured by injecting ink into the area enclosed by the barrier on the substrate to form an organic layer such as a pixel.

[0837] Examples of organic electroluminescent device types include bottom emission type and top emission type.

[0838] In the bottom emission type, for example, a partition is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are laminated in the opening surrounded by the partition to manufacture it.

[0839] In the top emission type, for example, a partition is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer are laminated in the opening surrounded by the partition to manufacture it.

[0840] When the partition wall has a gently sloping shape, the ink for forming the organic layer bounces off the lower part of the partition wall, so the area enclosed by the partition wall may not be sufficiently covered by the ink for forming the organic layer. In contrast, by making it a good shape without a gently sloping shape, the area enclosed by the partition wall can be sufficiently covered by the ink for forming the organic layer. By doing so, for example, the problem of halation in an organic EL display device can be resolved.

[0841] Water, organic solvents, and mixtures thereof may be used as solvents when forming an ink for forming an organic layer.

[0842] Organic solvents are not particularly limited as long as they can be removed from the film formed after the ink injection. 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.

[0843] Surfactants, antioxidants, viscosity modifiers, UV absorbers, etc., may be added to the ink.

[0844] As a method for injecting ink into an area enclosed by a partition, an inkjet method is preferred in that a small amount of ink can be easily injected at a predetermined point. The ink used to form the organic layer is appropriately selected according to the type of organic electroluminescent device being manufactured. When injecting ink by an 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.

[0845] As for the light-emitting layer, the organic electroluminescent layer described in Japanese Patent Publication No. 2009-146691 or Japanese Patent Publication No. 5734681 may be used. The quantum dots described in Japanese Patent Publication No. 5653387 or Japanese Patent Publication No. 5653101 may also be used.

[0846] [4] Color filter containing luminescent nanocrystalline particles

[0847] A color filter comprising luminescent nanocrystalline particles related to the present invention is not particularly limited as long as it has the partition of the present invention, and may include a pixel formed in an area partitioned by the partition.

[0848] FIG. 1 is a schematic cross-sectional view of an example of a color filter having a partition according to the present invention. As shown in FIG. 1, the color filter (100) comprises a substrate (10), a partition (20) formed on the substrate, a red pixel (30), a green pixel (40), and a blue pixel (50). The red pixel (30), the green pixel (40), and the blue pixel (50) are arranged in a grid pattern to repeat in this order. The partition (20) is formed between adjacent pixels. In other words, adjacent pixels are separated by the partition (20).

[0849] The red pixel (30) contains red-emitting nanocrystalline particles (2), and the green pixel (40) contains green-emitting nanocrystalline particles (1). The blue pixel (50) is a pixel that transmits blue light from a light source.

[0850] These nanocrystalline particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and are crystals with a maximum particle size of 100 nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope.

[0851] The 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 particles (2) emit light (red light) having a peak wavelength of emission in the range of 605 to 665 nm, and green luminescent nanocrystalline particles (1) emit light (green light) having a peak wavelength of emission in the range of 500 to 560 nm.

[0852] According to the solution of the Schrödinger wave equation of the well-type potential model, the wavelength of light (emission color) emitted by luminescent nanocrystalline particles depends on the size (e.g., particle diameter) of the luminescent nanocrystalline particles, but also depends 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.

[0853] The method for manufacturing a color filter containing luminescent nanocrystalline particles is not particularly limited, but may include a method of preparing a substrate having a partition formed by the cured material of the present invention and forming a layer containing luminescent nanocrystalline particles in the area partitioned by the partition. The method for forming a layer containing luminescent nanocrystalline particles is not particularly limited, but may be manufactured, for example, by a method of selectively attaching an ink composition containing luminescent nanocrystalline particles by an inkjet method and curing the ink composition by irradiation with an active energy line or heating.

[0854] [5] Image display device

[0855] The image display device of the present invention comprises the partition wall of the present invention.

[0856] As an image display device of the present invention, for example, an image display device comprising an organic electroluminescent element of the present invention may be provided. As long as it includes an organic electroluminescent element, there are no particular restrictions on the form or structure of the image display device, and for example, it may be assembled according to conventional methods using an active-drive type organic electroluminescent element. For example, an image display device of the present invention may be formed in the manner described in "Organic EL Display" (Ohm Co., published August 20, 2004, authored by Shizuo 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.

[0857] As an image display device of the present invention, for example, an image display device comprising a color filter including luminescent nanocrystalline particles related to the present invention may be cited.

[0858] Examples of types of image display devices include liquid crystal display devices and image display devices including organic electroluminescent elements. In the case of a liquid crystal display device, examples include a light source equipped with a blue LED and a liquid crystal layer equipped with an electrode that controls the blue light emitted from the light source for each pixel.

[0859] On the other hand, in an image display device including an organic electroluminescent element, a blue-emitting organic electroluminescent element is placed at a position corresponding to each pixel portion of the color filter. Specifically, a method described in Japanese Patent Publication No. 2019-87746 can be cited.

[0860] Examples

[0861] Hereinafter, the photosensitive resin composition of the present invention will be described with reference to specific examples. The present invention is not limited to the following examples, provided that it does not exceed the gist thereof.

[0862] <Alkali-Soluble Resin-1>

[0863] (Synthesis of precursor resins)

[0864] In a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, 2-norbornene (75 mass% toluene solution, manufactured by Maruzen Petrochemical Co., Ltd., 125.5 g, 1.00 mol) and dimethyl 2,2'-azobis(2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industry Co., Ltd., 9.2 g, 40 mmol) were weighed and dissolved in methyl ethyl ketone (MEK, 196.1 g). After removing oxygen by passing nitrogen through the solution for 10 minutes, the solution was heated to 80°C while stirring. While maintaining the solution at 80°C, a pre-prepared solution of maleic anhydride (manufactured by Nippon Catalytic Co., Ltd., 98.1 g, 1.00 mol) dissolved in 119.9 g of MEK was added dropwise at 1.5 hours, and the reaction was carried out at that temperature for an additional 8 hours. This reaction mixture was added dropwise to a large amount of methanol, and the polymer was precipitated. After filtration using a Nuche filter, the solid was further washed with methanol and vacuum dried at 70 °C. The weight-average molecular weight Mw of the obtained precursor resin was 6900.

[0865] (Synthesis of Alkali-Soluble Resin-1)

[0866] In a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, the precursor resin described above (50.0 g) was weighed and dissolved in MEK (90 g). Additionally, 2-hydroxyethyl methacrylate (manufactured by Nippon Catalytic 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. Glycidyl methacrylate (11.1 g, 78 mmol) was added to this reaction mixture, and the mixture was further stirred at 70°C for 4 hours. Formic acid was added to the reaction mixture for acid treatment, and then the mixture was dropped into a large volume of pure water to precipitate a 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. Also, the double bond equivalent was 540 g / mol.

[0867] Alkali-soluble resin-1 corresponds to copolymer resin (C1).

[0868] <Alkali-Soluble Resin-2>

[0869] An alkali-soluble acrylic copolymer resin comprising dicyclofentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.02 / 0.045 / 0.935) as constituent monomers, to which an equivalent amount of acrylic acid is added to glycidyl methacrylate, and additionally, tetrahydrophthalic anhydride is added at a molar ratio of 0.096 to 1 mole of the copolymer resin. The weight average molecular weight (Mw) of polystyrene equivalent measured by GPC is 8900, and the solid dispersion value is 27 mgKOH / g. Alkali-soluble resin-2 corresponds to an alkali-soluble resin (acrylic copolymer resin (C3)) other than copolymer resin (C1).

[0870] <Alkali-Soluble Resin-3>

[0871] An alkali-soluble acrylic copolymer resin comprising a copolymer resin having tricyclodecane methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6) as constituent monomers, to which acrylic acid is reacted in an equal amount with glycidyl methacrylate, and additionally, tetrahydrophthalic anhydride is added at a molar ratio of 0.39 per 1 mole of the copolymer resin. The weight average molecular weight (Mw) equivalent to polystyrene measured by GPC is 9000, and the solid dispersion value is 80 mgKOH / g.

[0872] Alkali-soluble resin-3 corresponds to an alkali-soluble resin (acrylic copolymer resin (C3)) other than copolymer resin (C1).

[0873] <Alkali-Soluble Resin-4>

[0874] "ZCR-8024H" manufactured by Nippon Explosives Co., Ltd. (Mw = 3100, acid value = 60 mgKOH / g).

[0875] Alkali-soluble resin-4 corresponds to an alkali-soluble resin (epoxy(meth)acrylate resin (C2)) other than the copolymer resin (C1).

[0876] <Photopolymerizable Compounds>

[0877] In Examples 1 to 9 and Comparative Example 1, one of the following was selected and blended. The selection and blending of the photopolymerizable compound (photopolymerizable monomer) are as shown in Table 2 below.

[0878] <Photopolymerizable Monomer-1>

[0879] ·DPHA: Manufactured by Nippon Gunpowder Co.

[0880] A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

[0881] <Photopolymerizable Monomer-2>

[0882] · A-9570W: Manufactured by Shinnakamura Chemical Industry Co., Ltd.

[0883] A mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0884] <Photopolymerizable Monomer-3>

[0885] · Mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid half ester of dipentaerythritol pentaacrylate (molar ratio 50 / 25 / 25%).

[0886] <Photopolymerizable Monomer-4>

[0887] · Light Acrylate PE-4A: Pentaerythritol tetraacrylate manufactured by Kyoei Chemical Co., Ltd.

[0888] <Photopolymerizable Monomer-5>

[0889] · M-933: A mixture of pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate manufactured by Toa Synthetic Fiber

[0890] <Dispersant>

[0891] A high-molecular-weight acrylic AB block copolymer comprising an A block having a quaternary ammonium base and a tertiary amino group in the side chain, and a B block not having a quaternary ammonium base and a tertiary amino group. The amine value is 70 mgKOH / g. The acid value is 1 mgKOH / g or less.

[0892] Block A of the dispersant contains repeating units of the following formulas (1a) and (2a), and Block B contains repeating units of the following formula (3a). The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of the dispersant are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[0893] [Chemical Formula 49]

[0894]

[0895] <Solvent-1>

[0896] PGMEA: Propylene glycol monomethyl ether acetate

[0897] <Yongje-2>

[0898] MB : 3-Methoxybutanol

[0899] <Solvent-3>

[0900] PGME: Propylene glycol monomethyl ether

[0901] <Photopolymerization Initiator>

[0902] A compound having the following chemical structure was used. The following compound can be prepared by the synthesis method described in International Publication No. 2009 / 131189.

[0903] [Chemical Formula 50]

[0904]

[0905] <Foot Fluid>

[0906] Acrylic copolymer resin having a constituent unit having a perfluoroalkyl group, a constituent unit having an ethylenic double bond, and a constituent unit having a carboxyl group. Mw 90000, fluorine atom content 20 mass%.

[0907] This antiperspirant corresponds to compound (D1).

[0908] <Surfactants>

[0909] F-559 manufactured by DIC (nonionic surfactant, oligomer containing fluorinated, hydrophilic, and lipophilic groups).

[0910] Since this surfactant does not have a crosslinking group, it does not correspond to compound (D1).

[0911] <Additive-1>

[0912] Showa Denkosha manufactured Carens MT PE1 (Pentaerythritol Tetrakis(3-Mercaptobutyrate))

[0913] <Additive-2>

[0914] KAYAMER PM-21 (methacryloyl group containing phosphate) manufactured by Nippon Hwayakusha

[0915] <Additive-3>

[0916] XIAMETER OFS-6040Silane (Glycidoxypropyltrimethoxysilane) manufactured by Dow & Toray

[0917] <Preparation of Pigment Dispersion>

[0918] The pigment, dispersant, alkali-soluble resin, and solvent listed in Table 1 were mixed in the mass ratios listed in Table 1. This solution was subjected to dispersion treatment using a paint shaker at a temperature ranging from 25 to 45°C for 3 hours. Zirconia beads with a diameter of 0.5 mmφ were used, and 2.5 times the mass of the dispersion was added. After dispersion was completed, the beads and the dispersion were separated by a filter to prepare the pigment dispersion.

[0919]

[0920] [Examples 1 to 10 and Comparative Examples 1 and 2]

[0921] Using the pigment dispersion prepared above, each component was added such that the content ratio of each component in the total solid content was the value listed in Table 2, and additionally, PGMEA was added such that the content ratio of PGME in the total solvent was 20 mass% and the content ratio of the total solid content was 31 mass%, and the mixture was stirred and dissolved to prepare a photosensitive resin composition. Using the obtained photosensitive resin composition, an evaluation was performed using the method described below.

[0922]

[0923] The method for performance evaluation is explained below.

[0924] <Manufacture of Evaluation Bulkheads>

[0925] A photosensitive resin composition was applied to a glass substrate using a spinner to achieve a thickness of 10.0 μm after heat curing. Subsequently, a drying treatment was performed using a vacuum dryer for 60 seconds. Next, the film was heat-dried for 120 seconds on a hot plate heated to 90°C. The obtained film was exposed using a photomask. A mirror projection type exposure machine (MPA-600FA) manufactured by Canon was used, and exposure was performed for 25 seconds with an exposure amount of 100 mJ / cm². The illuminance was 500 mW / cm², and the slit width was 1.6 mm. A photomask was used that had an opening of 10 mm by 10 mm and a grid-like opening (a covering of 100 μm × 300 μm, and a plurality of the coverings were formed by interposing an exposure area of ​​100 μm in the long axis direction and an exposure area of ​​10 μm in the short axis direction). Subsequently, a 0.033% KOH aqueous solution was used, and a development treatment was performed for a development time of 70 seconds using a shower with a pressure of 0.05 MPa, followed by washing with pure water for 10 seconds. Afterward, post-exposure of 1000 mJ / cm² was performed using UV light with an illuminance of 60 mW / cm² with an ND60 filter (60% photosensitive filter) by a proxy exposure machine (MA-1100) manufactured by Dainippon Kayeon Co., Ltd. Finally, by subjecting this substrate to heat treatment at 90°C for 30 minutes in an oven, a substrate having a film for measuring contact angles corresponding to a 10 mm x 10 mm opening of a photomask and a barrier for evaluating ink penetration was obtained.

[0926] <Measurement of Contact Angle>

[0927] <Measurement Liquid Sample>

[0928] PGMEA: Propylene glycol monomethyl ether acetate

[0929] <Usage Device>

[0930] Kyowa Kaimen Kagakusha manufactured DMo-502

[0931] <Measurement>

[0932] The liquid volume was set to 0.7 μL using the droplet method, and the contact angle was derived using the θ / 2 method.

[0933] <Ink Penetration Evaluation>

[0934] <Ink Used>

[0935] YED216D (1,6-hexanedyl diglycidyl ether) manufactured by Mitsubishi Chemical Corporation

[0936] <Usage Device>

[0937] Fujifilm DMP-2831

[0938] For inkjet coating, a 10 pL corresponding head was used.

[0939] <Application of Ink>

[0940] Using the above DMP-2831, the above ink was applied in an amount of 24 drops each to a total of 15 openings of 5 columns × 3 rows of 100 μm × 300 μm openings in the evaluation partition.

[0941] <Observation and Evaluation of Penetration>

[0942] Among the 15 openings where ink was applied, the penetration of ink into the partition wall surrounding the central opening in the 3rd column, 2nd row was observed using an optical microscope. When ink penetration occurs, abnormalities are observed in the form of discoloration of the partition wall or the occurrence of spot-like shapes. Observations were conducted over time 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 a part of the partition wall, it was evaluated as B; and if penetration occurred in the entire partition wall, it was evaluated as C, with evaluations A and B set as acceptable levels. Figures 2a and 2b show a schematic diagram of the ink penetration observation results and the evaluation results.

[0943] From Examples 1 to 5, it can be seen that when using the copolymer resin (C1), it has resistance to penetration in combination with various photopolymerizable compounds. This is because the copolymer resin (C1) used has repeating units containing an aliphatic polycyclic structure in its main chain, and specifically, as a structure represented by Formula (I), it has a norbornane backbone that is stereo-volume and not as rigid as aromatic hydrocarbons, and exhibits a certain degree of flexibility. Therefore, during the photo and / or thermal curing reaction of the photosensitive resin composition, the reaction sites of photopolymerizable compounds approach each other and do not excessively hinder the progress of the curing reaction, and after curing, due to its bulky structure, it effectively suppresses the penetration of ink.

[0944] From Examples 6 to 10, it can be seen that resistance to penetration is maintained even when another alkali-soluble resin is used in combination with the copolymer resin (C1). When intending to impart properties other than resistance to penetration, such as liquid repellency, adhesion, and resolution, to the photosensitive resin composition in addition to the performance of Examples 1 to 5, it is important that resistance to penetration is not lost even when an alkali-soluble resin that imparts such properties is used in combination.

[0945] By comparing the example and comparative example 1, it can be seen that if the copolymer resin (C1) is not used, resistance to penetration is not exhibited.

[0946] In addition, from Examples 6 to 8, it can be understood that using a photopolymerizable compound containing more hydroxyl groups, such as dipentaerythritol tetraacrylate, results in higher resistance to penetration than using a photopolymerizable compound that does not. It is considered that in Examples 1 to 5, which contain the same photopolymerizable compound, no such difference was observed, given that the copolymer resin (C1) itself provides strong resistance to penetration.

[0947] The reason for the increased resistance to penetration when using a photopolymerizable compound having many hydroxyl groups is that when the copolymer resin (C1) contains many highly polar substituents (carboxyl groups and hydroxyl groups in this embodiment) represented in formulas (II-1) and (II-2), the hydroxyl groups of the photopolymerizable compound and these substituents form a non-covalent network such as hydrogen bonds, thereby preventing the penetration of the ink more efficiently.

[0948] By comparing the Example and Comparative Example 2, it can be seen that if the compound (D1) having a crosslinking group and also having fluorine atoms and / or siloxane chains is not used, the PGMEA contact angle is significantly lower than others, and liquid repellency is not exhibited, and additionally, penetration resistance is also impaired. Furthermore, by comparing with Comparative Example 1, it can be seen that even if the compound (D1) is used, penetration resistance is not obtained unless it is used in combination with the copolymer resin (C1). The liquid repellent exhibits liquid repellency by segregating on the surface. When combined with a resin that has repeating units containing an aliphatic polycyclic structure in the main chain, such as copolymer resin (C1), and is difficult for ink to penetrate, the ink-repelling function of the repellent itself can be used to reinforce penetration resistance, but when combined with a resin that does not have repeating units containing an aliphatic polycyclic structure in the main chain, such as copolymer resin (C1), it is inferred that although the ink is repelled macroscopically (=the contact angle is increased), it does not show an effect in inhibiting ink penetration at the molecular level. Explanation of the symbols

[0949] 1: Green luminescent nanocrystalline particles 2: Red-emitting nanocrystalline particles 10 : Substrate 20: Bulkhead 30: Red pixel 40: Green pixel 50: Blue pixels 100 : Color filter

Claims

Claim 1 A photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid-repellent agent, wherein the alkali-soluble resin (C) comprises a copolymer resin (C1) having repeating units comprising an aliphatic polycyclic structure in its main chain, and the copolymer resin (C1) comprises repeating units (I) represented by the following general formula (I), and the liquid-repellent agent (D) comprises a compound (D1) having a crosslinking group and also having a fluorine atom and / or a siloxane chain. (In Equation (I), R 1 ~ R 4 Each represents independently a hydrogen atom or a hydrocarbon group. n represents an integer from 0 to 2. * represents a bonding hand.) Claim 2 A photosensitive resin composition according to claim 1, wherein the copolymer resin (C1) has repeating units (II) having carboxyl groups. Claim 3 A photosensitive resin composition according to claim 2, wherein the repeating unit (II) having the carboxyl group comprises a repeating unit represented by the following general formula (II-1). (In Equation (II-1), R 5 represents a hydrogen atom or an organic group. * represents a bonding hand.) Claim 4 A photosensitive resin composition according to claim 1, additionally containing (E) a coloring agent. Claim 5 In claim 2, a photosensitive resin composition additionally containing (E) a coloring agent. Claim 6 In claim 3, a photosensitive resin composition additionally containing (E) a coloring agent. Claim 7 A photosensitive resin composition according to any one of claims 1 to 6, wherein the content ratio of the copolymer resin (C1) is 20 mass% or more with respect to the total solid content of the photosensitive resin composition. Claim 8 A photosensitive resin composition according to any one of claims 1 to 6, wherein the alkali-soluble resin (C) further comprises an alkali-soluble resin in addition to the copolymer resin (C1). Claim 9 A photosensitive resin composition according to any one of claims 1 to 6, additionally containing a solvent. Claim 10 A photosensitive resin composition for heat-sintering at 140°C or lower, in any one of claims 1 to 6. Claim 11 A cured product formed by curing a photosensitive resin composition described in any one of claims 1 to 6. Claim 12 A bulkhead composed of the hardened material described in claim 11. Claim 13 An organic electroluminescent device having a partition wall as described in claim 12. Claim 14 A color filter having the partition wall described in claim 12 and additionally comprising luminescent nanocrystalline particles. Claim 15 An image display device having a partition wall as described in Clause 12. Claim 16 A method for forming a cured product using a photosensitive resin composition described in any one of claims 1 to 6, and having at least the following processes (1) to (4). Process (1): A process of applying the photosensitive resin composition onto a substrate to form a coating film. Process (2): A process of exposing at least a portion of the coating film formed in process (1). Process (3): A process of developing the coating film exposed in process (2). Process (4): A process of firing the coating film developed in process (3). Claim 17 A method for forming a hardened product according to claim 16, wherein the firing temperature of the above process (4) is 140 ℃ or lower. Claim 18 A method for forming a cured product according to claim 16, having a post-exposure process for exposing the developed film in the above process (3) after the above process (3). Claim 19 A method for forming a cured product according to claim 17, having a post-exposure process for exposing the developed film in the process (3) after the process (3).

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