Colored photosensitive resin composition, partition wall, organic electroluminescent element, image display device, and illumination

Abstract

The invention provides a colored photosensitive resin composition with high ink repellency and good linearity. The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent, and (E) a colorant, the content ratio of the (E) colorant being 20% by mass or less in the total solid content of the colored photosensitive resin composition, and the content ratio of the (E) colorant being 20% by mass or less in the total solid content of the colored photosensitive resin composition. The alkali-soluble resin (C) contains (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain and (c2) an epoxy (meth) acrylate resin.

Description

[0001] The present application is a divisional application of an application filed on January 24, 2019, with application number 201980007828.0 and invention name “Colored photosensitive resin composition, partition, organic electroluminescent element, image display device and lighting”. Technical Field

[0002] The present invention relates to a colored photosensitive resin composition for forming partition walls, and further relates to partition walls composed of the colored photosensitive resin composition, an organic electroluminescent element having the partition walls, and an image display device and lighting including the organic electroluminescent element.

[0003] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2018-011096 filed with the Japan Patent Office on January 26, 2018, and part or all of the contents disclosed in the documents cited in this specification are cited here and are incorporated as the disclosed contents of this specification. Background Art

[0004] Conventionally, organic electroluminescent elements included in organic electroluminescent displays and organic electroluminescent lighting are manufactured by forming partition walls (dams) on a substrate and then laminating various functional layers in the region surrounded by the partition walls. As a method for easily forming such partition walls, a method of forming the partition walls by photolithography using a photosensitive resin composition is known.

[0005] In addition, as a method for stacking various functional layers in a region surrounded by partition walls, there is known a method of first preparing ink containing materials constituting the functional layers and then injecting the prepared ink into the region surrounded by partition walls. In this method, since it is easy to accurately inject a given amount of ink into a given location, an inkjet method is often used.

[0006] Furthermore, when the functional layer is formed using ink, it is sometimes required to impart ink repellency (liquid repellency) to the partition walls for the purpose of preventing the ink from adhering to the partition walls and preventing the ink injected between adjacent regions from mixing.

[0007] In addition, in recent years, for the partition wall, in addition to requiring ink repellency, various characteristics are also required, and various photosensitive resin compositions have been developed. For example, from the viewpoint of improving contrast and anti-reflection, a colored partition wall is required. Patent document 1 describes a negative photosensitive resin composition, which is formed by using a black organic pigment and a specific alkali-soluble resin, and the solid component acid value of the composition is set to a specific range, and a partition wall having a fine line pattern and a tiny contact hole can be formed at the same time, and the contained black organic pigment has good dispersibility for the alkaline developer used for development, and storage stability also becomes good.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: International Publication No. 2013 / 069789 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] In recent years, the development of coloring partition walls has been intensively carried out. For example, in order to form a functional layer of a given film thickness using an ink containing a component with low solvent solubility, a large amount of thin ink needs to be injected into the area surrounded by the coloring partition walls, and thick film coloring partition walls are naturally required. Since the light-shielding property required for the coloring partition walls is equivalent to the property of the total film thickness, the light-shielding property per unit film thickness in the thick film partition walls is reduced, that is, there is a tendency for the content ratio of the colorant to decrease.

[0013] In such a thick film colored partition wall, sufficient ink repellency is required to be displayed in order to prevent the mixing of inks between adjacent regions. In addition, although the functional layer of the region surrounded by the partition wall should become a pixel of the image display device, if the edge of the partition wall is not straight or there is residue and the linearity is insufficient, the functional layer cannot be uniformly formed and becomes the cause of uneven light emission, therefore, the linearity of the edge of the partition wall is also required to be good.

[0014] The present inventors have conducted studies and found that, in the colored photosensitive resin composition described in Patent Document 1, when the content ratio of the colorant is small, the linearity is good, but it is difficult to obtain sufficient ink repellency.

[0015] Then, an object of this invention is to provide the colored photosensitive resin composition which has high ink repellency and good linearity.

[0016] Another object of the present invention is to provide partition walls formed using the above-mentioned colored photosensitive resin composition, an organic electroluminescent element including the partition walls, and an image display device and lighting including the organic electroluminescent element.

[0017] Solutions to the problem

[0018] As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a specific alkali-soluble resin in combination in a colored photosensitive resin composition containing a liquid repellent agent even when the content ratio of the colorant is small, thereby completing the present invention.

[0019] That is, the gist of the present invention is as follows.

[0020] [1] A colored photosensitive resin composition comprising: (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent, and (E) a colorant, wherein:

[0021] The content ratio of the (E) colorant in the total solid content of the colored photosensitive resin composition is 20 mass % or less,

[0022] The (C) alkali-soluble resin includes (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain, and (c2) an epoxy (meth)acrylate resin.

[0023] [2] The colored photosensitive resin composition according to the above [1], wherein the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the following general formula (I).

[0024] [Chemical formula 1]

[0025]

[0026] (In formula (I), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group, and * represents a bonding position. )

[0027] [3] The colored photosensitive resin composition described in [1] or [2] above, wherein the (c2) epoxy (meth)acrylate resin 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), an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii), and an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii).

[0028] [Chemical formula 2]

[0029]

[0030] (In formula (i), R a represents a hydrogen atom or a methyl group, R b represents a divalent hydrocarbon group optionally having a substituent, the benzene ring in formula (i) may be further substituted by an arbitrary substituent, and * represents a bonding position. )

[0031] [Chemical formula 3]

[0032]

[0033] (In formula (ii), R c Each independently represents a hydrogen atom or a methyl group, R drepresents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and * represents a bonding position. )

[0034] [Chemical formula 4]

[0035]

[0036] (In formula (iii), R e represents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent, the benzene ring in formula (iii) may be further substituted by any substituent, and * represents a bonding position. )

[0037] [4] The colored photosensitive resin composition according to any one of [1] to [3] above, wherein the (D) liquid repellent has a crosslinking group.

[0038] [5] The colored photosensitive resin composition according to any one of [1] to [4], further comprising a chain transfer agent.

[0039] [6] A partition wall composed of the colored photosensitive resin composition according to any one of [1] to [5].

[0040] [7] An organic electroluminescent element comprising the partition wall according to [6] above.

[0041] [8] An image display device comprising the organic electroluminescent element described in [7] above.

[0042] [9] A lighting device comprising the field electroluminescent element described in [7] above.

[0043] Effects of the Invention

[0044] According to the present invention, a colored photosensitive resin composition having high ink repellency and good linearity can be provided. DETAILED DESCRIPTION

[0045] Hereinafter, the present invention will be described in detail. It should be noted that the following description is an example of an embodiment of the present invention, and the present invention is not limited to these examples within the scope of the gist thereof.

[0046] It should be noted that, in the present invention, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid", and "total solid content" means all components other than the solvent in the colored photosensitive resin composition. In addition, in the present invention, the numerical range represented by "~" means a range including the numerical values ​​described before and after "~" as the lower limit and upper limit.

[0047] In the present invention, the term "(co)polymer" includes both a single polymer (homopolymer) and a copolymer (copolymer), and the term "(acid) anhydride" or "acid (anhydride)" includes both an acid and its anhydride.

[0048] In the present invention, the partition wall material refers to a dam material, a wall material, or a wall material, and similarly, the partition wall refers to a dam, a wall, or a wall.

[0049] In the present invention, the weight average molecular weight refers to a polystyrene-equivalent weight average molecular weight (Mw) based on GPC (gel permeation chromatography).

[0050] [1] Colored photosensitive resin composition

[0051] The colored photosensitive resin composition of the present invention is a colored photosensitive resin composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent, and (E) a colorant, characterized in that, in the total solid content, the content of the (E) colorant is less than 20% by mass, and the (C) alkali-soluble resin contains (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain, and (c2) an epoxy (meth) acrylate resin. In addition, other components may be further contained as needed, for example, a solvent or a chain transfer agent may be contained.

[0052] In the present invention, the partition wall is, for example, a portion used to divide the functional layer (organic layer, light-emitting portion) in an actively driven organic electroluminescent element, and is used to form pixels including the functional layer and the partition wall by spraying ink as a material for constituting the functional layer into the divided area (pixel area) and drying the ink.

[0053] [1-1] Components and compositions of colored photosensitive resin compositions

[0054] The components and compositions constituting the colored photosensitive resin composition of the present invention will be described.

[0055] The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent, and (E) a colorant, and usually further contains a solvent.

[0056] [1-1-1] Component (A): Ethylenically unsaturated compound

[0057] The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound. It is considered that high sensitivity can be obtained by containing (A) an ethylenically unsaturated compound.

[0058] The ethylenically unsaturated compound used herein refers to a compound having one or more ethylenically unsaturated bonds in the molecule, but from the perspective of being able to expand the polymerizability, crosslinking properties, and the accompanying difference in solubility in the developer between the exposed portion and the non-exposed portion, a compound having two or more ethylenically unsaturated bonds in the molecule is preferred, and it is further preferred that the unsaturated bond is an unsaturated bond derived from a (meth)acryloyloxy group, that is, it is further preferred to be a (meth)acrylate compound.

[0059] In the present invention, it is particularly preferred to use a multifunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule. The number of ethylenic unsaturated groups possessed by the multifunctional ethylenic monomer is not particularly limited, and is preferably more than 2, more preferably more than 3, and further preferably more than 5. In addition, it is preferably less than 15, more preferably less than 10, further preferably less than 8, and particularly preferably less than 7. By being above the above lower limit, there is a tendency that polymerizability is improved and high sensitivity can be obtained, and by being below the above upper limit, there is a tendency that developability becomes better. The number of ethylenic unsaturated groups possessed by the multifunctional ethylenic monomer is, for example, 2 to 15, preferably 2 to 10, more preferably 3 to 8, and further preferably 5 to 7.

[0060] Specific examples of ethylenically unsaturated compounds include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; esters obtained by esterification of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids; and the like.

[0061] Examples of the esters of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include acrylates 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; methacrylates obtained by replacing the acrylates of the above-mentioned compounds with methacrylates; itaconates obtained by replacing the acrylates with itaconates; crotonates obtained by replacing the crotonates with crotonates; and maleates obtained by replacing the crotonates with maleates.

[0062] Examples of the esters of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0063] The esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids are not necessarily single substances. Representative specific examples include: condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol and glycerol, etc.

[0064] In addition, as examples of the multifunctional olefinic monomer used in the present invention, useful examples include urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate, or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with a hydroxyl-containing (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate, etc.

[0065] Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Nippon Synthetic Chemical Co., Ltd.), and the like.

[0066] Among these, from the viewpoint of an appropriate taper angle and sensitivity, as the (A) ethylenically unsaturated compound, ester (meth)acrylates or urethane (meth)acrylates are preferably used, and dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-tri(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate dibasic acid anhydride adducts, and dipentaerythritol tri(meth)acrylate dibasic acid anhydride adducts are more preferably used.

[0067] These compounds may be used alone or in combination of two or more.

[0068] In the present invention, the molecular weight of the ethylenically unsaturated compound (A) is not particularly limited, but from the viewpoint of sensitivity, ink repellency, and taper angle, it is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, further preferably 300 or more, particularly preferably 400 or more, and most preferably 500 or more, and preferably 1000 or less, more preferably 700 or less. The molecular weight of the ethylenically unsaturated compound (A) is, for example, 100 to 1000, preferably 150 to 700, more preferably 200 to 700, further preferably 300 to 700, further preferably 400 to 700, and particularly preferably 500 to 700.

[0069] In addition, the number of carbon atoms of the (A) ethylenically unsaturated compound is not particularly limited, but from the viewpoint of sensitivity, ink repellency, and taper angle, it is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, further preferably 20 or more, and particularly preferably 25 or more, and is preferably 50 or less, more preferably 40 or less, further preferably 35 or less, and particularly preferably 30 or less. The number of carbon atoms of the (A) ethylenically unsaturated compound is, for example, 7 to 50, preferably 10 to 40, more preferably 15 to 35, further preferably 20 to 30, and further preferably 25 to 30.

[0070] In addition, from the viewpoints of sensitivity, ink repellency, and taper angle, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferred. Among them, from the viewpoints of sensitivity, ink repellency, and taper angle, trifunctional or higher ester (meth) acrylates such as pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and acid anhydride adducts of trifunctional or higher ester (meth) acrylates such as 2,2,2-tri (meth) acryloyloxymethylethyl phthalate and dipentaerythritol penta (meth) acrylate are more preferred.

[0071] The content ratio of the (A) ethylenically unsaturated compound in the colored photosensitive resin composition of the present invention is not particularly limited, and is generally 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass or more in the total solid content, and is generally 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass or less, and more preferably 20% by mass or less. By being above the above lower limit, there is a tendency for the sensitivity and cone angle during exposure to become good, and by being below the above upper limit, there is a tendency for the developability to become good. As the content ratio of the (A) ethylenically unsaturated compound in the total solid content of the colored photosensitive resin composition, for example, 1 to 80% by mass, preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and more preferably 15 to 20% by mass.

[0072] In addition, the content ratio of (A) ethylenically unsaturated compounds relative to 100 parts by mass of (C) alkali-soluble resin is not particularly limited, and is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, and is usually 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 70 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less. By being above the above lower limit, there is a tendency that the sensitivity becomes good and the cone angle becomes good during exposure, and by being below the above upper limit, there is a tendency that the developability becomes good. As the content ratio of (A) ethylenically unsaturated compounds relative to 100 parts by mass of (C) alkali-soluble resin, for example, it is 1 to 150 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, further preferably 15 to 50 parts by mass, and further preferably 20 to 30 parts by mass.

[0073] [1-1-2] Component (B): Photopolymerization initiator

[0074] The colored photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that can polymerize the ethylenically unsaturated bond of the above-mentioned (A) ethylenically unsaturated compound by active light, and a known photopolymerization initiator can be used.

[0075] The colored photosensitive resin composition of the present invention can use a photopolymerization initiator commonly used in the field as the (B) photopolymerization initiator. Examples of such photopolymerization initiators include metallocene compounds including titanocene compounds described in Japanese Unexamined Patent Publication No. 59-152396 and Japanese Unexamined Patent Publication No. 61-151197; hexaarylbiimidazole derivatives described in Japanese Unexamined Patent Publication No. 2000-56118; and halomethylated derivatives described in Japanese Unexamined Patent Publication No. 10-39503. Oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, free radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester compounds described in Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2006-36750, etc.

[0076] Specifically, for example, as titanocene derivatives, there can be listed: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorobenzene)titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorobenzene)titanium, dicyclopentadienyl bis(2,4,6-trifluorobenzene)titanium, dicyclopentadienyl bis(2,6-difluorobenzene)titanium, dicyclopentadienyl bis(2,4-difluorobenzene)titanium, di(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene)titanium, di(methylcyclopentadienyl)bis(2,6-difluorobenzene)titanium, dicyclopentadienyl[2,6-difluoro-3-(prop-1-yl)-benzene]titanium, and the like.

[0077] Examples of the biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-di(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.

[0078] In addition, as halomethyl Oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4- Oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4- Diazole, etc.

[0079] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0080] Examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0081] As a photopolymerization initiator, oxime ester compounds are effective from the viewpoint of sensitivity and platemaking properties. In the case of using an alkali-soluble resin containing a phenolic hydroxyl group, the sensitivity is disadvantageous, so such oxime ester compounds with excellent sensitivity are particularly useful. Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates free radicals in their structure. Therefore, even in a small amount, the sensitivity is high and the reaction to heat is stable. A small amount of oxime ester compounds can obtain a highly sensitive colored photosensitive resin composition.

[0082] Examples of the oxime ester compounds include compounds represented by the following general formula (IV).

[0083] [Chemical formula 5]

[0084]

[0085] In the above formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0086] R 21b represents an arbitrary substituent containing an aromatic ring.

[0087] R 22a It represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent.

[0088] n represents an integer 0 or 1.

[0089] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of solubility and sensitivity to solvents. Specific examples of the alkyl group include methyl, ethyl, propyl, cyclopentylethyl, and propyl.

[0090] Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl, and N-acetyl-N-acetoxyamino. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0091] As R 21a The aromatic ring group in the photosensitive resin composition may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored photosensitive resin composition. In addition, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.

[0092] Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like. Among these, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred, from the viewpoint of developability.

[0093] Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group formed by linking these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group formed by linking these substituents are preferred, and a linked alkoxy group is more preferred.

[0094] Among these, R 21a An alkyl group which may have a substituent or an aromatic ring group which may have a substituent is preferred.

[0095] In addition, as R 21b , preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthone group or an optionally substituted diphenyl sulfide group. Among these, an optionally substituted carbazolyl group is preferred from the viewpoint of sensitivity.

[0096] In addition, R 22a The number of carbon atoms of the alkanoyl group in is not particularly limited, but is usually 2 or more, preferably 3 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in solvents and sensitivity. Specific examples of the alkanoyl group include acetyl, acetyl, propionyl, butyryl, and the like.

[0097] Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.

[0098] In addition, R 22a The number of carbon atoms of the aromatic acyl group in is not particularly limited, but is usually 7 or more, preferably 8 or more, and is usually 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of solubility and sensitivity to solvents. Specific examples of the aromatic acyl group include benzoyl and naphthoyl.

[0099] Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, the aroyl group is preferably unsubstituted.

[0100] Among these, R 22a An alkanoyl group which may have a substituent is preferred, an unsubstituted alkanoyl group is more preferred, and an acetyl group is further preferred.

[0101] The photopolymerization initiator may be used alone or in combination of two or more.

[0102] In order to improve the sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be added to the photopolymerization initiator as needed. Examples of the sensitizing dye include those described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Laid-Open No. 4-219756. Ton pigment, coumarin pigment with heterocyclic ring described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, 3-oxocoumarin compound described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, methylpyrrole pigment described in Japanese Patent Laid-Open No. 6-19240, and Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 54-37 ... Pigments having a dialkylaminobenzene skeleton as described in JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818.

[0103] Among these sensitizing dyes, sensitizing dyes containing an amino group are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. Particularly preferred are benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzophenone oxazole, 2-(p-diethylaminophenyl)benzo oxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo oxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo oxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4- Compounds containing p-dialkylaminophenyl groups such as 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, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. Among them, 4,4'-dialkylaminobenzophenone is most preferred.

[0104] The sensitizing dye may be used alone or in combination of two or more.

[0105] As the polymerization accelerator, for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine can be used. The polymerization accelerators can be used alone or in combination of two or more.

[0106] The containing ratio of (B) photopolymerization initiator in the colored photosensitive resin composition of the present invention is not particularly limited, in the total solid content of the colored photosensitive resin composition, usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 3% by mass or more, and usually 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, more preferably 7% by mass or less, particularly preferably 5% by mass or less.By being set to more than the above-mentioned lower limit, there is a tendency to form a coating film without film reduction during development, and to produce enough ink repellency, in addition, by being set to less than the above-mentioned upper limit, there is a tendency to easily form a desired pattern shape. The content ratio of the (B) photopolymerization initiator in the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 25 mass %, preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, further preferably 1 to 10 mass %, further preferably 2 to 7 mass %, particularly preferably 3 to 5 mass %.

[0107] In addition, as the mixing ratio of the (B) photopolymerization initiator to the (A) ethylenically unsaturated compound in the colored photosensitive resin composition, it is preferably 1 mass part or more, more preferably 5 mass parts or more, more preferably 10 mass parts or more, more preferably 15 mass parts or more, and particularly preferably 20 mass parts or more relative to 100 mass parts of the (A) ethylenically unsaturated compound, and preferably 200 mass parts or less, more preferably 100 mass parts or less, more preferably 50 mass parts or less, and particularly preferably 30 mass parts or less. By setting it to above the lower limit, there is a tendency to obtain appropriate sensitivity, and by setting it to below the upper limit, there is a tendency to easily form a desired pattern shape. As the mixing ratio of the (B) photopolymerization initiator to 100 mass parts of the (A) ethylenically unsaturated compound, for example, it is 1 to 200 mass parts, preferably 5 to 100 mass parts, more preferably 10 to 100 mass parts, more preferably 15 to 50 mass parts, and further preferably 20 to 30 mass parts.

[0108] In addition, it is preferred to use a chain transfer agent in combination with the above-mentioned photopolymerization initiator. As the chain transfer agent, sulfhydryl-containing compounds, carbon tetrachloride, etc. can be listed. Due to the tendency of high chain transfer effect, it is more preferred to use a compound with a sulfhydryl group. It is believed that this is because sulfhydryl-containing compounds are prone to bond cleavage, hydrogen abstraction reaction, and chain transfer reaction due to low SH bond energy, which is effective for increasing sensitivity and surface curing.

[0109] Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzo azole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other thiol-containing compounds with aromatic rings; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol dimercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyl trimercaptopropionate, pentaerythritol tetra(3-mercapto Aliphatic mercapto group-containing compounds, particularly compounds having multiple mercapto groups, such as trimethylolpropane tris(3-mercaptobutyrate), 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), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc.

[0110] Among them, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred among the mercapto-containing compounds having an aromatic ring, and trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred among the mercapto-containing compounds of aliphatic type.

[0111] In addition, from the viewpoint of sensitivity, aliphatic mercapto-containing compounds are preferred, and specifically, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.

[0112] These various substances may be used alone or in combination of two or more.

[0113] Among these, from the viewpoint of increasing the taper angle, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzo One or more of the azoles are preferably used in combination with a photopolymerization initiator as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, or a combination of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole can be used.

[0114] In addition, from the viewpoint of sensitivity, it is preferred to use one or more selected from pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). In addition, from the viewpoint of sensitivity, it is preferred to use one or more selected from 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole. One or more of the azoles, one or more of the azoles selected from pentaerythritoltetrakis(3-mercaptopropionate) and pentaerythritoltetrakis(3-mercaptobutyrate), and a photopolymerization initiator are used in combination.

[0115] The content ratio of the chain transfer agent in the colored photosensitive resin composition of the present invention is not particularly limited, and is generally 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 0.8% by mass or more in the total solid content of the colored photosensitive resin composition, and is generally 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, and more preferably 2% by mass or less. By setting it to more than the above lower limit, there is a tendency for the sensitivity to increase, and by setting it to less than the above upper limit, there is a tendency to easily form a desired pattern. As the content ratio of the chain transfer agent in the total solid content of the colored photosensitive resin composition, for example, 0.01~5% by mass, preferably 0.1~4% by mass, more preferably 0.5~3% by mass, and more preferably 0.8~2% by mass.

[0116] In addition, as the content ratio of the chain transfer agent in the colored photosensitive resin composition relative to the photopolymerization initiator (B), it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more relative to 100 parts by mass of the photopolymerization initiator (B), and it is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. By setting it to be above the lower limit, there is a tendency to become highly sensitive, and by setting it to be below the upper limit, there is a tendency to easily form a desired pattern. As the content ratio of the chain transfer agent relative to 100 parts by mass of the photopolymerization initiator (B), for example, it is 5 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 15 to 100 parts by mass, and further preferably 20 to 50 parts by mass.

[0117] [1-1-3] Component (C): Alkali-soluble resin

[0118] The colored photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. In the present invention, the alkali-soluble resin (C) is not particularly limited as long as it is a resin that can be developed in a developer, but since the developer is preferably an alkaline developer, it is preferred to use a carboxyl- or hydroxyl-containing resin, and from the viewpoint of excellent developability, a carboxyl-containing resin is preferred.

[0119] An alkali-soluble resin having an ethylenically unsaturated group is preferred because a partition wall having an appropriate taper angle can be obtained and outflow of the liquid repellent agent due to development or thermal melting of the partition wall can be suppressed to maintain ink repellency.

[0120] The (C) alkali-soluble resin of the colored photosensitive resin composition of the present invention includes an acrylic copolymer resin having an ethylenically unsaturated group in the side chain of (c1) (hereinafter, sometimes referred to as "(c1) acrylic copolymer resin"). It can be considered that the acrylic copolymer resin having an ethylenically unsaturated group in the side chain of (c1) has a high degree of freedom in the film due to the soft skeleton, and the free radicals generated during exposure have a high degree of freedom in the film, which can suppress the deactivation of the free radicals caused by oxygen on the film surface, and the curability of the film surface is improved, so that the liquid repellent is easily captured near the surface. It can be further considered that the liquid repellent oriented on the film surface can be fully captured by the ethylenically unsaturated group of the side chain. It can be considered that the ink repellency is improved by the liquid repellent fully captured on the film surface, and the ink adhesion to the partition wall and the mixing of the ink injected into the adjacent regions are suppressed, so that the organic electroluminescent element emits light uniformly at each pixel.

[0121] On the other hand, the (C) alkali-soluble resin of the colored photosensitive resin composition of the present invention further comprises (c2) epoxy (meth) acrylate resin. It can be considered that (c2) epoxy (meth) acrylate resin will not make the adhesion with the substrate too high due to the rigid skeleton, the residue of the edge of the partition wall is suppressed, and then the hemming is also suppressed, and the edge of the partition wall is formed into a straight line. In this way, it can be considered that if the linearity of the edge of the partition wall can become good, it is considered that the area surrounded by the partition wall can uniformly form a functional layer, thereby suppressing uneven luminescence. It can be further considered that impedance unevenness can also be suppressed, and therefore, current concentration, which is the cause of life degradation, is not easy to occur.

[0122] Therefore, it is considered that the colored photosensitive resin composition of the present invention can achieve both ink repellency and linearity by containing both (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain and (c2) an epoxy (meth)acrylate resin as (C) an alkali-soluble resin.

[0123] The (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain will be described in detail below.

[0124] [(c1) Acrylic copolymer resin having an ethylenically unsaturated group in the side chain]

[0125] (c1) The acrylic copolymer resin has an ethylenically unsaturated group in the side chain. It is believed that the copolymer resin having an ethylenically unsaturated group can be photocured by exposure to light, forming a stronger film and preventing the liquid repellent from flowing out during development.

[0126] (Partial structure represented by general formula (I))

[0127] The partial structure of the acrylic copolymer resin (c1) containing a side chain having an ethylenically unsaturated group is not particularly limited, but preferably has a partial structure represented by the following general formula (I) from the viewpoint of ease of emission of free radicals accompanying film flexibility.

[0128] [Chemical formula 6]

[0129]

[0130] In formula (I), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group, and * represents a bonding position.

[0131] Among the partial structures represented by the above formula (I), the partial structures represented by the following general formula (I′) are preferred from the viewpoints of sensitivity and alkali developability.

[0132] [Chemical formula 7]

[0133]

[0134] In formula (I'), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group, R X represents a hydrogen atom or a polyacid residue.

[0135] The polyacid residue refers to a monovalent group obtained by removing one OH group from a polyacid or its anhydride. Examples of the polyacid include one or more selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexachloronadic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0136] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0137] (c1) side chain has the acrylic copolymer resin of ethylenically unsaturated group contained in the above-mentioned general formula (I) represented by the partial structure containing ratio is not particularly limited, but preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, in addition, preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, most preferably 70 mol% or less. By being set to more than the above-mentioned lower limit, there is a tendency for ink repellency to improve, and in addition, by being set to below the above-mentioned upper limit, there is a tendency for residue to decrease. The content ratio of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is, for example, 10 to 95 mol %, preferably 20 to 85 mol %, more preferably 30 to 80 mol %, further preferably 40 to 75 mol %, and further preferably 50 to 70 mol %.

[0138] (c1) The content ratio of the partial structure represented by the general formula (I') contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 65 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting it to be above the lower limit, there is a tendency to facilitate alkali development, and by setting it to be below the upper limit, there is a tendency to ensure development adhesion. The content ratio of the partial structure represented by the general formula (I') contained in the acrylic copolymer resin (c1) having an ethylenically unsaturated group in the side chain is, for example, 10 to 95 mol %, preferably 20 to 80 mol %, more preferably 30 to 75 mol %, further preferably 40 to 70 mol %, and further preferably 50 to 65 mol %.

[0139] (Partial structure represented by general formula (II))

[0140] When the acrylic copolymer resin (c1) having an ethylenically unsaturated group in the side chain contains the partial structure represented by the above-mentioned general formula (I), there is no particular limitation on the other partial structures contained, but from the viewpoint of development adhesion, it is preferred that it also contains a partial structure represented by the following general formula (II), for example.

[0141] [Chemical formula 8]

[0142]

[0143] In the above formula (II), R 3 represents a hydrogen atom or a methyl group, R 4 It represents an alkyl group which may have a substituent, an aryl group (aromatic ring group) which may have a substituent, or an alkenyl group which may have a substituent.

[0144] (R 4 )

[0145] In the above formula (II), R 4 It represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent.

[0146] As R 4 The alkyl group in the formula (a) may be a linear, branched or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. By setting the value to be equal to or greater than the lower limit, the film strength tends to be high and the development adhesion tends to be improved, and by setting the value to be equal to or less than the upper limit, the residue tends to be reduced.

[0147] Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, a dodecyl group, etc. Among these, from the viewpoint of developability, a dicyclopentyl group or a dodecyl group is preferred, and a dicyclopentyl group is more preferred.

[0148] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0149] As R 4The aryl group (aromatic ring group) in the formula (A) may be a monovalent aromatic hydrocarbon ring group or a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When the value is set to be equal to or greater than the lower limit, the developing adhesion tends to be improved, and when the value is set to be equal to or less than the upper limit, the residue tends to be reduced.

[0150] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

[0151] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzisocyanate ring azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferred, and a benzene ring group is more preferred.

[0152] Examples of the substituent which the aryl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0153] As R 4 The alkenyl group in the formula (a) may be a linear, branched or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the value is set to be equal to or greater than the lower limit, the developing adhesion tends to be improved, and when the value is set to be equal to or less than the upper limit, the residue tends to be reduced.

[0154] Specific examples of alkenyl groups include vinyl, allyl, 2-propylene-2-yl, 2-butene-1-yl, 3-butene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Among these, from the viewpoint of developability, vinyl or allyl is preferred, and vinyl is more preferred.

[0155] Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0156] In this way, R 4 It represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent, and among these, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred, from the viewpoint of developability and film strength.

[0157] The content ratio of the partial structure represented by the general formula (II) in the acrylic copolymer resin (c1) having an ethylenically unsaturated group in the side chain is not particularly limited, and is preferably 1 mol % or more, more preferably 5 mol % or more, further preferably 10 mol % or more, and particularly preferably 20 mol % or more, and is preferably 70 mol % or less, more preferably 60 mol % or less, further preferably 50 mol % or less, and particularly preferably 40 mol % or less. By setting it to be above the lower limit, there is a tendency to improve the developing adhesion, and by setting it to be below the upper limit, there is a tendency to reduce the residue.

[0158] (Partial structure represented by general formula (III))

[0159] (c1) When the acrylic copolymer resin contains the partial structure represented by the above general formula (I), it is preferred that the partial structure contained elsewhere contains a partial structure represented by the following general formula (III) from the viewpoint of heat resistance and film strength.

[0160] [Chemical formula 9]

[0161]

[0162] In the above formula (III), R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkylthio group optionally having a substituent, and t represents an integer of 0 to 5.

[0163] (R 6 )

[0164] In the above formula (III), R 6 It represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylthio group which may have a substituent.

[0165] As R 6 The alkyl group in the formula (a) may be a linear, branched or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and further preferably 5 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the value is set to be equal to or greater than the lower limit, the developing adhesion tends to be improved, and when the value is set to be equal to or less than the upper limit, the residue tends to be reduced.

[0166] Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, a dodecyl group, etc. Among these, from the viewpoint of developability and film strength, a dicyclopentyl group or a dodecyl group is preferred, and a dicyclopentyl group is more preferred.

[0167] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0168] As R 6 The alkenyl group in the formula (a) may be a linear, branched or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the value is set to be equal to or greater than the lower limit, the developing adhesion tends to be improved, and when the value is set to be equal to or less than the upper limit, the residue tends to be reduced.

[0169] Specific examples of alkenyl groups include vinyl, allyl, 2-propylene-2-yl, 2-butene-1-yl, 3-butene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc. Among these, from the viewpoint of developability, vinyl or allyl is preferred, and vinyl is more preferred.

[0170] Examples of the substituent which the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0171] As R6 The alkynyl group in the alkynyl group may be a linear, branched or cyclic alkynyl group. The number of carbon atoms is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the value is set to be equal to or greater than the lower limit, the developing adhesion tends to be improved, and when the value is set to be equal to or less than the upper limit, the residue tends to be reduced.

[0172] Specific examples of the alkynyl group include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, and 1-hexyn-6-yl.

[0173] Examples of the substituent which the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0174] As R 6 The halogen atom in the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom is preferred from the viewpoint of ink repellency.

[0175] As R 6 The alkoxy group in the formula (a) may be a linear, branched or cyclic alkoxy group. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the value is set to be equal to or greater than the lower limit, the developing adhesion tends to be improved, and when the value is set to be equal to or less than the upper limit, the residue tends to be reduced.

[0176] Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.

[0177] Examples of the substituent which the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0178] As R 6The alkylthio group in the formula (a) may be a linear, branched or cyclic alkylthio group. The number of carbon atoms is preferably 2 or more, and preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the value is set to be equal to or greater than the lower limit, the developing adhesion tends to be improved, and when the value is set to be equal to or less than the upper limit, the residue tends to be reduced.

[0179] Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, etc. Among these, a methylthio group or an ethylthio group is preferred from the viewpoint of developability.

[0180] Examples of the substituent which the alkyl group in the alkylthio group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

[0181] In this way, R 6 It represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkylthio group optionally having a substituent, among which, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0182] In the above formula (III), t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of production.

[0183] The content ratio of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, and particularly preferably 8 mol% or more. In addition, it is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less. By setting it to be above the above lower limit, there is a tendency for the development adhesion to be improved, and by setting it to be below the above upper limit, there is a tendency for the residue to be reduced. The content ratio of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is, for example, 1 to 50 mol%, preferably 2 to 40 mol%, more preferably 5 to 30 mol%, and further preferably 8 to 20 mol%.

[0184] (Partial structure represented by general formula (IV))

[0185] When the acrylic copolymer resin (c1) having an ethylenically unsaturated group in a side chain contains the partial structure represented by the above general formula (I), it is also preferred that the partial structure contained therein further contains a partial structure represented by the following general formula (IV) from the viewpoint of developability.

[0186] [Chemical formula 10]

[0187]

[0188] In the above formula (IV), R 7 represents a hydrogen atom or a methyl group.

[0189] The content ratio of the partial structure represented by the general formula (IV) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more, and is preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less. By setting it to be above the above lower limit, there is a tendency for the developability to be improved, and by setting it to be below the above upper limit, there is a tendency for the developability to be improved. The content ratio of the partial structure represented by the general formula (IV) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is, for example, 5 to 80 mol%, preferably 10 to 70 mol%, and more preferably 20 to 60 mol%.

[0190] On the other hand, the acid value of the acrylic copolymer resin (c1) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and particularly preferably 60 mgKOH / g or more, and is preferably 150 mgKOH / g or less, more preferably 140 mgKOH / g or less, further preferably 130 mgKOH / g or less, and further preferably 120 mgKOH / g or less. By setting it to be above the lower limit, there is a tendency for the developability to be improved, and by setting it to be below the upper limit, there is a tendency for the developable adhesion to be improved. The acid value of the acrylic copolymer resin (c1) is, for example, 10 to 150 mgKOH / g, preferably 30 to 140 mgKOH / g, more preferably 50 to 130 mgKOH / g, and further preferably 60 to 120 mgKOH / g.

[0191] The weight average molecular weight (Mw) of the (c1) acrylic copolymer resin is not particularly limited, and is generally 1000 or more, preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, further preferably 7000 or more, and particularly preferably 8000 or more, and is generally 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10000 or less. When the weight average molecular weight is set to be above the lower limit, there is a tendency for the development adhesion to be improved, and when the weight average molecular weight is set to be below the upper limit, there is a tendency for the residue to be reduced. The weight average molecular weight (Mw) of the (c1) acrylic copolymer resin is, for example, 1000 to 30000, preferably 2000 to 20000, more preferably 4000 to 15000, further preferably 6000 to 15000, further preferably 7000 to 10000, and particularly preferably 8000 to 10000.

[0192] (C) The ratio of the acrylic copolymer resin (c1) contained in the alkali-soluble resin is not particularly limited, preferably 10% by mass or more, more preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 70% by mass or more, in addition, preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 85% by mass or less. By setting it to more than the above-mentioned lower limit, there is a tendency for ink repellency to improve, and in addition, by setting it to less than the above-mentioned upper limit, there is a tendency for residue to decrease. As the ratio of the acrylic copolymer resin (c1) contained in the alkali-soluble resin (C), for example, 10~95% by mass, preferably 30~90% by mass, more preferably 50~85% by mass, and more preferably 70~85% by mass.

[0193] In addition, for the content ratio of (c1) acrylic copolymer resin, relative to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth) acrylate resin, preferably more than 10% by mass, more preferably more than 30% by mass, more preferably more than 50% by mass, particularly preferably more than 70% by mass, in addition, preferably less than 95% by mass, more preferably less than 90% by mass, more preferably less than 85% by mass. By being set to more than the above-mentioned lower limit, there is a tendency for ink repellency to improve, and in addition, by being set to less than the above-mentioned upper limit, there is a tendency for residue to decrease. As the content ratio of the total mass of (c1) acrylic copolymer resin relative to (c1) acrylic copolymer resin and (c2) epoxy (meth) acrylate resin, for example, 10~95% by mass, preferably 30~90% by mass, more preferably 50~85% by mass, more preferably 70~85% by mass.

[0194] Specific examples of the (c1) acrylic copolymer resin are described in detail below. Examples of the (c1) acrylic copolymer resin include (c1-a) carboxyl group-containing copolymers having an ethylenically unsaturated group in a side chain.

[0195] (c1-a) Carboxyl-containing copolymer having ethylenically unsaturated groups in the side chains

[0196] (c1-a-1) Copolymer of an unsaturated carboxylic acid and a compound containing two or more ethylenically unsaturated groups

[0197] Examples of the carboxyl group-containing copolymer having an ethylenically unsaturated group in a side chain include copolymers obtained by copolymerizing a compound having two or more ethylenically unsaturated groups such as allyl (meth)acrylate, 3-allyloxy-2-hydroxypropyl (meth)acrylate, cinnamyl (meth)acrylate, crotyl (meth)acrylate, methallyl (meth)acrylate, N,N-diallyl (meth)acrylamide, or a compound having two or more ethylenically unsaturated groups such as vinyl (meth)acrylate, 1-vinyl (meth)acrylate, 2-phenylvinyl (meth)acrylate, 1-propylene (meth)acrylate, vinyl crotonate, vinyl (meth)acrylamide, with an unsaturated carboxylic acid such as (meth)acrylic acid, or further with an unsaturated carboxylic acid ester, so that the proportion of the former compound having two or more ethylenically unsaturated groups in the whole is about 10 to 90 mol%, preferably about 30 to 80 mol%.

[0198] In addition, from the viewpoint of developability, the acid value of the copolymer is preferably 30 to 250 mgKOH / g, and from the viewpoint of developable solubility, the weight average molecular weight (Mw) thereof is preferably 1,000 to 30,000.

[0199] (c1-a-2) Carboxyl-containing copolymer modified by epoxy-containing unsaturated compound

[0200] Examples of the carboxyl-containing copolymer having an ethylenically unsaturated group in the side chain include a modified carboxyl-containing copolymer obtained by reacting an epoxy-containing unsaturated compound with the carboxyl-containing copolymer to add epoxy groups of the epoxy-containing unsaturated compound to part of the carboxyl groups of the carboxyl-containing copolymer.

[0201] As the carboxyl group-containing copolymer, from the viewpoint of patterning properties, a (meth)acrylate-(meth)acrylic acid copolymer, a styrene-(meth)acrylate-(meth)acrylic acid copolymer, and the like are preferred carboxyl group-containing copolymers.

[0202] Examples of the epoxy-containing unsaturated compound include aliphatic epoxy-containing unsaturated compounds such as allyl glycidyl ether, glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, glycidyl crotonate, glycidyl isocrotonic acid, crotyl glycidyl ether, itaconate monoalkyl monoglycidyl ester, fumarate monoalkyl monoglycidyl ester, and maleate monoalkyl monoglycidyl ester; and alicyclic epoxy-containing unsaturated compounds such as 3,4-epoxycyclohexylmethyl (meth)acrylate, 2,3-epoxycyclopentylmethyl (meth)acrylate, and 7,8-epoxy[tricyclo[5.2.1.0]dec-2-yl]oxyethyl (meth)acrylate.

[0203] The epoxy-containing unsaturated compound can be obtained by reacting about 5 to 90 mol %, preferably about 30 to 70 mol % of the carboxyl groups in the carboxyl-containing copolymer. The reaction can be carried out by a known method.

[0204] The epoxy-containing unsaturated compound-modified carboxyl-containing copolymer preferably has an acid value of 30 to 250 mgKOH / g from the viewpoint of developability, and preferably has a weight average molecular weight (Mw) of 1,000 to 300,000 from the viewpoint of developability and film strength.

[0205] (c1-a-3) Unsaturated carboxylic acid-modified copolymer containing epoxy and carboxyl groups

[0206] In addition, examples of carboxyl-containing copolymers having ethylenically unsaturated groups in side chains include: copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with the aforementioned aliphatic epoxy-containing unsaturated compound or alicyclic epoxy-containing unsaturated compound, or further with an unsaturated carboxylic acid ester, styrene, etc., in such a manner that the proportion of the former carboxyl-containing unsaturated compound in the whole is about 10 to 90 mol %, preferably about 30 to 80 mol %, and the resulting copolymer is reacted with an unsaturated carboxylic acid such as (meth) acrylic acid to modify the copolymer by adding the carboxyl group of the unsaturated carboxylic acid to the epoxy group of the copolymer.

[0207] The unsaturated carboxylic acid-modified epoxy and carboxyl group-containing copolymer preferably has an acid value of 30 to 250 mgKOH / g from the viewpoint of developability, and preferably has a weight average molecular weight (Mw) of 1,000 to 300,000 from the viewpoint of developability and film strength.

[0208] (c1-a-4) Acid-modified epoxy-containing copolymer

[0209] In addition, examples of carboxyl-containing (co)polymers having ethylenically unsaturated groups in side chains include acid-modified epoxy-containing (co)polymers obtained by adding an ethylenically unsaturated monocarboxylic acid to at least a portion of the epoxy groups possessed by a copolymer of an epoxy-containing (meth)acrylate and an ethylenically unsaturated compound, and further adding a polyacid (anhydride) to at least a portion of the hydroxyl groups generated by the addition.

[0210] Specifically, examples include: an acid-modified epoxy-containing (co)polymer obtained by adding usually 10 to 100 mol % of an ethylenically unsaturated monocarboxylic acid to epoxy groups contained in the copolymer, and further adding usually 10 to 100 mol % of a polybasic acid (anhydride) to hydroxy groups generated during the addition, relative to a copolymer of 5 to 99 mol % of an epoxy-containing (meth)acrylate such as glycidyl (meth)acrylate and usually 1 to 95 mol % of an ethylenically unsaturated compound such as (meth)acrylate.

[0211] Here, the copolymerization ratio of epoxy-containing (meth) acrylate in the above-mentioned copolymer is not particularly limited, usually 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, more preferably 40 mol% or more, particularly preferably 50 mol% or more, and usually 90 mol% or less, preferably 85 mol% or less, more preferably 80 mol% or less.By being set to more than the above-mentioned lower limit, there is a tendency that ink repellency improves, and in addition, by being set to less than the above-mentioned upper limit, there is a tendency that residue reduces.As the copolymerization ratio of epoxy-containing (meth) acrylate in the above-mentioned copolymer, for example, 5~90 ​​mol%, preferably 10~90 mol%, more preferably 20~85 mol%, more preferably 30~85 mol%, more preferably 40~80 mol%, particularly preferably 50~80 mol%.

[0212] On the other hand, the copolymerization ratio of the ethylenically unsaturated compound in the above-mentioned copolymer is not particularly limited, usually 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 20 mol% or more, particularly preferably 30 mol% or more, and usually 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, more preferably 60 mol% or less, particularly preferably 50 mol% or less.By being set to more than the above-mentioned lower limit, there is a tendency that film strength improves, in addition, by being set to below the above-mentioned upper limit, there is a tendency that ink repellency, developability improve.As the copolymerization ratio of the ethylenically unsaturated compound in the above-mentioned copolymer, for example, 1~90 mol%, preferably 5~80 mol%, more preferably 10~70 mol%, more preferably 20~60 mol%, more preferably 30~50 mol%.

[0213] Examples of the epoxy group-containing (meth)acrylate include aliphatic epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and α-ethyl glycidyl (meth)acrylate; and alicyclic epoxy group-containing (meth)acrylates such as 3,4-epoxycyclohexylmethyl (meth)acrylate, 2,3-epoxycyclopentylmethyl (meth)acrylate, and 7,8-epoxy[tricyclo[5.2.1.0]dec-2-yl]oxyethyl (meth)acrylate.

[0214] Here, as the ethylenically unsaturated compound such as (meth)acrylate, for example, one or two or more mono(meth)acrylates having a partial structure represented by the following general formula (V) are preferably used.

[0215] [Chemical formula 11]

[0216]

[0217] In formula (V), R 1d ~R 4d Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 5d and R 6d Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 5d With R 6d They may also be linked to form a ring. 5d With R 6d The ring formed by the connection is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

[0218] R 1d ~R 4d The number of carbon atoms of the alkyl group in is usually 1 or more and usually 10 or less, preferably 8 or less, more preferably 5 or less. When it is equal to or less than the above upper limit, there is a tendency that suitable developing solubility is obtained.

[0219] Among these, R 1d ~R 4d A hydrogen atom.

[0220] R 5d and R 6d The number of carbon atoms of the alkyl group in is usually 1 or more, and is usually 10 or less, preferably 8 or less, and more preferably 5 or less. When it is equal to or more than the above lower limit, there is a tendency for the development adhesion to be improved, and when it is equal to or less than the above upper limit, there is a tendency for the film strength to be improved.

[0221] Among these, R 5d and R 6d is a hydrogen atom, or R5d With R 6d They are linked to form an aliphatic ring having 5 to 6 carbon atoms.

[0222] In the above formula (V), mono(meth)acrylates having structures represented by the following formulas (Va), (Vb) or (Vc) are preferred. By introducing these partial structures, the heat resistance and strength of the mono(meth)acrylate can be enhanced. It should be noted that these mono(meth)acrylates can be used alone or in any combination and ratio.

[0223] [Chemical formula 12]

[0224]

[0225] As the mono(meth)acrylate having a partial structure represented by the above formula (V), various known mono(meth)acrylates can be used, but from the viewpoint of film strength, a mono(meth)acrylate represented by the following general formula (VI) is particularly preferred.

[0226] [Chemical formula 13]

[0227]

[0228] In formula (VI), R 7d represents a hydrogen atom or a methyl group, R 8d It represents a partial structure of the above formula (V).

[0229] On the other hand, examples of the ethylenically unsaturated compound include ethylenically unsaturated compounds other than the mono(meth)acrylate having a partial structure represented by the above formula (V), for example, styrenes such as α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, and t-butyl (meth)acrylate. acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, anthraquinone (meth)acrylate, piperonyl (meth)acrylate, salicyl (meth)acrylate, furanyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, propylene (meth)acrylate, (Meth)acrylates such as pyranyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, toluene (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, isopropyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate; (meth)acrylic acid amide, N,N-dimethyl (meth)acrylate amide, N,N-diethyl (meth)acrylate amide, N,N-dipropyl (meth)acrylate (Meth)acrylic acid amides such as (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenamide; vinyl compounds such as (meth)acrylaniide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; free radical polymerizable compounds such as N-(meth)acryloylphthalimide.

[0230] Among these, from the viewpoint of film strength, at least one selected from styrene, benzyl (meth)acrylate and monomaleimide is preferably used as the ethylenically unsaturated compound. In this case, from the viewpoint of film strength and developability, the copolymerization ratio of at least one selected from styrene, benzyl (meth)acrylate and monomaleimide is usually 1 mol% or more, preferably 3 mol% or more, and usually 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, and further preferably 10 mol% or less.

[0231] As the ethylenically unsaturated monocarboxylic acid added with the epoxy group contained in the copolymer of epoxy-containing (meth) acrylate and ethylenically unsaturated compounds, known ones can be used, and from the viewpoint of curability, (meth) acrylic acid is preferably used. The amount of the ethylenically unsaturated monocarboxylic acid added on the epoxy group contained in the above-mentioned copolymer is usually more than 10 mol %, preferably more than 30 mol %, more preferably more than 50 mol %, more preferably more than 70 mol %, and usually less than 100 mol %. By making the addition ratio of the ethylenically unsaturated monocarboxylic acid more than the above-mentioned lower limit, there is a tendency to improve curability. It should be noted that, as a method for adding the ethylenically unsaturated monocarboxylic acid to the above-mentioned copolymer, a known method can be used. As the amount of the epoxy group added to the ethylenically unsaturated monocarboxylic acid contained in the above-mentioned copolymer, for example, 10~100 mol %, preferably 30~100 mol %, more preferably 50~100 mol %, more preferably 70~100 mol % of the epoxy group contained in the copolymer.

[0232] The polyacid (anhydride) to which the hydroxyl group generated when the ethylenically unsaturated monocarboxylic acid is added is not particularly limited, and any known one may be used alone, or two or more may be used in any combination and ratio. By adding such a component, alkali solubility can be imparted to the copolymer.

[0233] The addition amount of the polyacid (anhydride) is usually more than 1 mol % of the hydroxyl group generated when the ethylenically unsaturated monocarboxylic acid is added to the above-mentioned copolymer, preferably more than 5 mol %, more preferably more than 10 mol %, further preferably more than 30 mol %, further preferably more than 50 mol %, particularly preferably more than 60 mol %, and in addition, it is usually less than 100 mol %, preferably less than 90 mol %, more preferably less than 80 mol %, and more preferably less than 70 mol %. By setting it to more than the above-mentioned lower limit, there is a tendency to improve the developability, and in addition, by setting it to less than the above-mentioned upper limit, there is a tendency to improve the film strength. It should be noted that as a method for adding the hydroxyl group generated when the polyacid (anhydride) and the ethylenically unsaturated monocarboxylic acid are added to the above-mentioned copolymer, any known method can be adopted. The amount of the polybasic acid (anhydride) added to the hydroxyl group generated when the ethylenically unsaturated monocarboxylic acid is added to the copolymer is, for example, 1 to 100 mol%, preferably 5 to 90 mol%, more preferably 10 to 80 mol%, further preferably 30 to 80 mol%, further preferably 50 to 70, particularly preferably 60 to 70.

[0234] For the modified products of the above epoxy-containing copolymers based on ethylenically unsaturated monocarboxylic acids and polyacids (anhydrides), the photosensitivity can be further improved by adding a part of the carboxyl groups generated by adding glycidyl (meth)acrylate or a glycidyl ether compound having an ethylenically unsaturated group to the polyacid (anhydride). In addition, the developability can also be improved by adding a part of the carboxyl groups generated by adding a glycidyl ether compound not having an ethylenically unsaturated group to the polyacid (anhydride). Furthermore, the above two can be added after the addition of the polyacid (anhydride).

[0235] It should be noted that, as the above-mentioned acid-modified epoxy-containing copolymer, for example, resins described in Japanese Patent Laid-Open No. 8-297366 and Japanese Patent Laid-Open No. 2001-89533 can be cited. In addition, the weight average molecular weight (Mw) of the above-mentioned modified product is not particularly limited, and is usually more than 3000, preferably more than 5000, and is usually less than 100000, preferably less than 50000, more preferably less than 30000, further preferably less than 20000, and particularly preferably less than 15000. By setting it to more than the above-mentioned lower limit, there is a tendency for film strength to improve, and by setting it to less than the above-mentioned upper limit, there is a tendency for residue to decrease. As the weight average molecular weight (Mw) of the above-mentioned modified product, for example, it is 3000~100000, preferably 3000~50000, more preferably 5000~30000, further preferably 5000~20000, and further preferably 5000~15000.

[0236] From the viewpoint of curability, the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 2.0 to 5.0.

[0237] In addition, the acid value of the acid-modified epoxy-containing copolymer is not particularly limited, and is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and further preferably 50 mgKOH / g or more. In addition, it is preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less, further preferably 120 mgKOH / g or less, further preferably 110 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less. By setting it to be above the lower limit, there is a tendency for the developability to be improved, and by setting it to be below the upper limit, there is a tendency for the film strength to be improved. The acid value of the acid-modified epoxy-containing copolymer is, for example, 30 to 150 mgKOH / g, preferably 40 to 130 mgKOH / g, more preferably 40 to 120 mgKOH / g, further preferably 50 to 110 mgKOH / g, and further preferably 50 to 100 mgKOH / g.

[0238] Next, (c2) epoxy (meth)acrylate resin will be described in detail.

[0239] [(c2) Epoxy (meth)acrylate resin]

[0240] (c2) Epoxy (meth) acrylate resin is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin, optionally reacting an isocyanate group-containing compound, and then further reacting a polybasic acid or an anhydride thereof. For example, a resin obtained by adding an ethylenically unsaturated bond to an epoxy resin via an ester bond (-COO-) by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, and simultaneously adding a hydroxyl group generated at this time to a carboxyl group of a polybasic acid anhydride. In addition, a resin obtained by simultaneously adding a polyol to the addition of a polybasic acid anhydride can also be mentioned.

[0241] Furthermore, a resin obtained by further reacting the carboxyl group of the resin obtained in the above reaction with a compound having a reactive functional group is also included in the above (c2) epoxy (meth)acrylate resin.

[0242] As described above, epoxy (meth)acrylate resin does not substantially have an epoxy group in its chemical structure and is not limited to "(meth)acrylate" resins, but is named according to convention because epoxy compounds (epoxy resins) are raw materials and "(meth)acrylate" is a representative example.

[0243] Here, the name of epoxy resin also includes the raw material compound before forming resin by heat curing, and as the epoxy resin, it can be appropriately selected from known epoxy resins. In addition, the epoxy resin can use a compound obtained by reacting a phenolic compound with epichlorohydrin. As the phenolic compound, it is preferably a compound with a phenolic hydroxyl group of more than 2 yuan, which can be a monomer or a polymer.

[0244] Specific examples include: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, dihydroxyfluorene type epoxy resin, dihydroxyalkyleneoxyfluorene type epoxy resin, diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene, diglycidyl ether of 1,1-bis(4'-hydroxyphenyl)adamantane, etc. It is preferred to use compounds having an aromatic ring in the main chain.

[0245] Among them, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, diglycidyl ether of 9,9-bis(4′-hydroxyphenyl)fluorene, etc. are preferred from the viewpoint of high cured film strength, and bisphenol A epoxy resin is more preferred.

[0246] As specific examples of epoxy resins, bisphenol A type epoxy resins (e.g., "jER (registered trademark, hereinafter the same) 828", "jER 1001", "jER 1002", "jER 1004", etc. manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting alcoholic hydroxyl groups of bisphenol A type epoxy resins with epichlorohydrin (e.g., "NER-1302" (epoxy equivalent 323, softening point 76° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resins (e.g., "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin The obtained epoxy resins (e.g., "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66°C)), bisphenol S type epoxy resins, biphenyl glycidyl ether (e.g., "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins (e.g., "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, Dow Chemical Co., Ltd.), (o-, m-, p-) cresol novolac type epoxy resins (e.g., "EOCN (registered trademark, hereinafter the same) -102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenol methane type epoxy resins (e.g., "EPPN (registered trademark, hereinafter the same) -501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resins (e.g., "Celloxide (registered trademark, hereinafter the same) 2021P", "Celloxide Epoxy resins such as "EXA-7200" manufactured by DIC Corporation and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.", epoxy resins represented by the following general formulas (C1) to (C4), etc. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (C1), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (C2), and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. as an epoxy resin represented by the following general formula (C4).

[0247] [Chemical formula 14]

[0248]

[0249] In the above general formula (C1), a is an average value, representing a number from 0 to 10, and R 111 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. 111 Can be the same or different.

[0250] [Chemical formula 15]

[0251]

[0252] In the above general formula (C2), b is an average value, representing a number from 0 to 10, and R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. 121 Can be the same or different.

[0253] [Chemical formula 16]

[0254]

[0255] In the above general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2), wherein the molecular structure contains one or more adamantane structures, and c represents an integer of 2 or 3.

[0256] [Chemical formula 17]

[0257]

[0258] In the above general formulas (C3-1) and (C3-2), R 131 ~R 134 and R 135 ~R 137 Each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bonding position.

[0259] [Chemical formula 18]

[0260]

[0261] In the above general formula (C4), p and q each independently represent an integer of 0 to 4, and R 141 and R 142 Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R 143 and R 144Each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer greater than 0.

[0262] Among these, the epoxy resin represented by any one of the general formulas (C1) to (C4) is preferably used.

[0263] Examples of the ethylenically unsaturated monocarboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and a reaction product of (meth)acrylic acid and ε-caprolactone. Among them, (meth)acrylic acid is preferred from the viewpoint of sensitivity.

[0264] Examples of the polyacid (anhydride) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Among these, from the viewpoint of degassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is preferred, and succinic anhydride or tetrahydrophthalic anhydride is more preferred.

[0265] By using a polyol, there is a tendency to increase the molecular weight of the epoxy (meth)acrylate resin (c2), introduce branches into the molecule, and thus achieve a balance between the molecular weight and the viscosity. In addition, there is a tendency to increase the introduction rate of the acid group into the molecule, and to easily achieve a balance between sensitivity and adhesion.

[0266] The polyol is preferably one or more polyols selected from, for example, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.

[0267] Examples of the epoxy (meth)acrylate resin include epoxy (meth)acrylate resins described in Korean Patent Publication No. 10-2013-0022955 in addition to those described above.

[0268] (c2) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more, and is preferably 200 mgKOH / g or less, more preferably 180 mgKOH / g or less, further preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, and particularly preferably 110 mgKOH / g or less. By setting the acid value to be above the lower limit, developability tends to be improved, and by setting the acid value to be below the upper limit, film strength tends to be improved. The acid value of the epoxy (meth)acrylate resin (c2) is, for example, 10 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, more preferably 50 to 150 mgKOH / g, further preferably 70 to 120 mgKOH / g, and further preferably 80 to 110 mgKOH / g.

[0269] The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (c2) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, further preferably 5000 or more, particularly preferably 6000 or more, and most preferably 7000 or more, and is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10000 or less. When the weight average molecular weight is set to be equal to or more than the above lower limit, the film strength tends to be improved, and when the weight average molecular weight is set to be equal to or less than the above upper limit, the residue tends to be reduced. The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (c2) is, for example, 1,000 to 30,000, preferably 2,000 to 20,000, more preferably 3,000 to 20,000, further preferably 4,000 to 15,000, further preferably 5,000 to 15,000, particularly preferably 6,000 to 10,000, and most preferably 7,000 to 10,000.

[0270] (C) The ratio of the epoxy (meth) acrylate resin contained in (c2) alkali-soluble resin is not particularly limited, preferably more than 5% by mass, more preferably more than 10% by mass, more preferably more than 15% by mass, particularly preferably more than 18% by mass, in addition, preferably less than 90% by mass, more preferably less than 70% by mass, more preferably less than 50% by mass, particularly preferably less than 30% by mass. By being set to more than the above-mentioned lower limit, there is a tendency that the residue is reduced, and in addition, by being set to less than the above-mentioned upper limit, there is a tendency that ink repellency is improved. As the ratio of the epoxy (meth) acrylate resin contained in (c2) alkali-soluble resin (C), for example, 5~90% by mass, preferably 10~70% by mass, more preferably 15~50% by mass, further preferably 18~30% by mass.

[0271] In addition, for the content ratio of (c2) epoxy (meth) acrylate resin, relative to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth) acrylate resin, preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, in addition, preferably 90% by mass or less, more preferably 70% by mass or less, more preferably 50% by mass or less, particularly preferably 30% by mass or less, further particularly preferably 25% by mass or less. By being set to more than the above lower limit, there is a tendency for residue to decrease, and in addition, by being set to less than the above upper limit, there is a tendency for ink repellency to improve. As the content ratio of the total mass of (c2) epoxy (meth) acrylate resin relative to (c1) acrylic copolymer resin and (c2) epoxy (meth) acrylate resin, for example, 5~90% by mass, preferably 5~70% by mass, more preferably 10~50% by mass, more preferably 15~30% by mass, and more preferably 20~25% by mass.

[0272] (c2) The epoxy (meth)acrylate resin can be synthesized by a conventionally known method. Specifically, the following method can be used: dissolving the epoxy resin in an organic solvent, adding the acid or ester compound having an ethylenically unsaturated bond in the presence of a catalyst and a thermal inhibitor to carry out an addition reaction, and further adding a polyacid or anhydride thereof to continue the reaction.

[0273] Here, as the organic solvent used for the reaction, one or more of organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, etc. can be cited. In addition, as the above-mentioned catalyst, one or more of tertiary amines such as triethylamine, benzyldimethylamine, tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride, etc., quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, antimony such as triphenylantimony, etc. can be cited. Further, as the thermal inhibitor, one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, etc. can be cited.

[0274] In addition, the acid or ester compound having an ethylenically unsaturated bond can be used in an amount of generally 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin. In addition, the temperature during the addition reaction can be generally 60 to 150° C., preferably 80 to 120° C. Further, the amount of the polyacid (anhydride) used can be generally 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl group generated in the above addition reaction.

[0275] (c2) The epoxy (meth)acrylate resin preferably contains at least one selected from an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i), an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii), and an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii), from the viewpoint of film strength and linearity.

[0276] [Chemical formula 19]

[0277]

[0278] In formula (i), R a represents a hydrogen atom or a methyl group, R b represents a divalent hydrocarbon group which may have a substituent, the benzene ring in the formula (i) may be further substituted with an arbitrary substituent, and * represents a bonding position.

[0279] [Chemical formula 20]

[0280]

[0281] In formula (ii), R c Each independently represents a hydrogen atom or a methyl group, R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and * represents a bonding position.

[0282] [Chemical formula 21]

[0283]

[0284] In formula (iii), R e represents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent, the benzene ring in formula (iii) may be further substituted with an arbitrary substituent, and * represents a bonding position.

[0285] Among these, first, an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i) (hereinafter, sometimes referred to as “epoxy (meth)acrylate resin (c2-1)”) will be described in detail.

[0286] [Chemical formula 22]

[0287]

[0288] In formula (i), R a represents a hydrogen atom or a methyl group, R b represents a divalent hydrocarbon group which may have a substituent, the benzene ring in the formula (i) may be further substituted with an arbitrary substituent, and * represents a bonding position.

[0289] (R b )

[0290] In the above formula (i), R b It represents a divalent hydrocarbon group which may have a substituent.

[0291] Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked to each other.

[0292] The divalent aliphatic group may be a linear, branched, or cyclic group. Among these, from the viewpoint of developing solubility, a linear group is preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed portion, a cyclic divalent aliphatic group is preferred. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. By setting it to above the lower limit, there is a tendency for film strength to be improved, and by setting it to below the upper limit, there is a tendency for sensitivity to be improved.

[0293] Specific examples of the divalent straight-chain aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, etc. Among these, a methylene group is preferred from the viewpoint of sensitivity and production cost.

[0294] Specific examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent straight-chain aliphatic group has a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group or the like as a side chain.

[0295] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, and is generally more than 1, preferably more than 2, and is generally less than 10, preferably less than 5. By setting it to more than the above lower limit, there is a tendency for film strength to improve, and by setting it to less than the above upper limit, there is a tendency for developability to improve. As a specific example of the divalent cyclic aliphatic group, there can be listed: a group formed by removing 2 hydrogen atoms from a ring of a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, etc. Among these groups, from the viewpoint of film strength and developability, it is preferably a group formed by removing 2 hydrogen atoms from an adamantane ring.

[0296] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups, etc. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0297] In addition, as the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group can be mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When it is set to be above the lower limit, there is a tendency for the film strength to be improved, and when it is set to be below the upper limit, there is a tendency for the developability to be improved.

[0298] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, A group having two free valences such as a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0299] In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzisocyanate ring azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, A group having two free valences such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Among these, a benzene ring or a naphthalene ring having two free valences is preferred from the viewpoint of production cost, and a benzene ring having two free valences is more preferred.

[0300] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, etc. Among these, unsubstituted groups are preferred from the viewpoint of curability.

[0301] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups in which one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are linked.

[0302] The number of the divalent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it to be above the lower limit, there is a tendency for the developability to be improved, and by setting it to be below the upper limit, there is a tendency for the film strength to be improved.

[0303] The number of the divalent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the number is set to be above the lower limit, there is a tendency for the film strength to be improved, and when the number is set to be below the upper limit, there is a tendency for the developability to be improved.

[0304] Specific examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic ring groups include groups represented by the following formulae (iA) to (iF), etc. Among these groups, from the perspective of rigidity of the skeleton and hydrophobization of the membrane, groups represented by the following formula (iA) are preferred.

[0305] [Chemical formula 23]

[0306]

[0307] As described above, the benzene ring in formula (i) may be further substituted by any substituent. Examples of the substituent include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, etc. The number of substituents is also not particularly limited, and may be 1 or more than 2.

[0308] Among these, unsubstituted is preferred from the viewpoint of curability.

[0309] In addition, from the viewpoint of development solubility, the partial structure represented by the above formula (i) is preferably a partial structure represented by the following formula (i-1).

[0310] [Chemical formula 24]

[0311]

[0312] In formula (i-1), R a and R b and R in the above formula (i) a and R b Synonymous. Y represents a hydrogen atom or a polyacid residue, and * represents a bonding position. The benzene ring in formula (i-1) may be further substituted by any substituent.

[0313] The polyacid residue refers to a monovalent group obtained by removing one OH group from a polyacid or its anhydride. Examples of the polyacid include one or more selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexachloronadic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0314] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0315] The repeating structural unit represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-1) may be one type or two or more types.

[0316] The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (c2-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, and is preferably 10 or less, and more preferably 8 or less. When the number is equal to or greater than the lower limit, developability tends to be improved, and when the number is equal to or less than the upper limit, film strength tends to be improved.

[0317] The number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, and is preferably 10 or less, and more preferably 8 or less. When the number is equal to or greater than the lower limit, developability tends to be improved, and when the number is equal to or less than the upper limit, film strength tends to be improved.

[0318] Specific examples of the epoxy (meth)acrylate resin (c2-1) are listed below.

[0319] [Chemical formula 25]

[0320]

[0321] [Chemical formula 26]

[0322]

[0323] [Chemical formula 27]

[0324]

[0325] [Chemical formula 28]

[0326]

[0327] [Chemical formula 29]

[0328]

[0329] [Chemical formula 30]

[0330]

[0331] [Chemical formula 31]

[0332]

[0333] Next, the epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii) (hereinafter, sometimes referred to as “epoxy (meth)acrylate resin (c2-2)”) will be described in detail.

[0334] [Chemical formula 32]

[0335]

[0336] In formula (ii), R c Each independently represents a hydrogen atom or a methyl group, R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and * represents a bonding position.

[0337] (R d )

[0338] In the above formula (ii), R d It represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

[0339] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0340] The number of rings possessed by the aliphatic cyclic group is not particularly limited, and is generally 1 or more, preferably 2 or more, and generally 10 or less, preferably 5 or less, and more preferably 3 or less. By setting the number to be greater than the above lower limit, there is a tendency for film strength to be improved, and by setting the number to be less than the above upper limit, there is a tendency for developability to be improved.

[0341] The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the carbon number is equal to or more than the above lower limit, the film strength tends to be improved, and when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0342] Specific examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, etc. Among these, adamantane ring is preferred from the viewpoint of film strength and developability.

[0343] On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less, more preferably 4 or less. When the number is set to be equal to or greater than the above lower limit, there is a tendency for film strength to be improved, and when the number is set to be equal to or less than the above upper limit, there is a tendency for developability to be improved.

[0344] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more, and is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. By setting the value to be greater than the lower limit, there is a tendency for film strength to be improved, and by setting the value to be less than the upper limit, there is a tendency for developability to be improved.

[0345] Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Among these, the fluorene ring is preferred from the viewpoint of pattern characteristics.

[0346] The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

[0347] The divalent aliphatic group may be a straight-chain, branched, or cyclic group. Among these, from the viewpoint of improving the developability, a straight-chain divalent aliphatic group is preferred, and from the viewpoint of film strength, a cyclic divalent aliphatic group is preferred. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. By setting it to above the lower limit, there is a tendency to improve film strength, and by setting it to below the upper limit, there is a tendency to improve developability.

[0348] Specific examples of the divalent straight-chain aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, etc. Among these, a methylene group is preferred from the viewpoint of sensitivity.

[0349] Specific examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent straight-chain aliphatic group has a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group or the like as a side chain.

[0350] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the number is equal to or more than the above lower limit, the film strength tends to be improved, and when the number is equal to or less than the above upper limit, the developability tends to be improved.

[0351] Specific examples of the divalent cyclic aliphatic group include groups formed by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, etc. Among these, groups formed by removing two hydrogen atoms from an adamantane ring are preferred from the viewpoint of film strength.

[0352] Examples of the substituent that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups, etc. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0353] In addition, as the divalent aromatic ring group, a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group can be mentioned. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. When it is set to be equal to or more than the above lower limit, there is a tendency for film strength to be improved, and when it is set to be equal to or less than the above upper limit, there is a tendency for developability to be improved.

[0354] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, A group having two free valences such as a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0355] In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thienofuran ring, benzisocyanate ring azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, A group having two free valences such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Among these, from the viewpoint of production cost, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0356] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, etc. Among these, unsubstituted groups are preferred from the viewpoint of curability.

[0357] Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups in which one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic ring groups are linked.

[0358] The number of the divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the number is set to be above the lower limit, there is a tendency for the developability to be improved, and when the number is set to be below the upper limit, there is a tendency for the film strength to be improved.

[0359] The number of the divalent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the number is set to be above the lower limit, there is a tendency for the film strength to be improved, and when the number is set to be below the upper limit, there is a tendency for the developability to be improved.

[0360] Specific examples of the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include: the groups represented by the above formulas (iA) to (iF), etc. Among these groups, the group represented by the above formula (iC) is preferred from the viewpoint of both film strength and sensitivity.

[0361] The bonding form of the cyclic hydrocarbon group as a side chain relative to these divalent hydrocarbon groups is not particularly limited, and examples thereof include a form in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain, and a form in which a cyclic hydrocarbon group as a side chain is constituted by including one carbon atom of an aliphatic group.

[0362] In addition, from the viewpoint of sensitivity, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-1).

[0363] [Chemical formula 33]

[0364]

[0365] In formula (ii-1), R c Same as above formula (ii), R α represents a monovalent cyclic hydrocarbon group which may have a substituent, n is an integer of 1 or more, the benzene ring in formula (ii-1) may be further substituted with an arbitrary substituent, and * represents a bonding position.

[0366] (R α )

[0367] In the above formula (ii-1), R α It represents a monovalent cyclic hydrocarbon group which may have a substituent.

[0368] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0369] The number of rings possessed by the aliphatic cyclic group is not particularly limited, and is generally 1 or more, preferably 2 or more, and generally 6 or less, preferably 4 or less, and more preferably 3 or less. By setting the number to be greater than the above lower limit, there is a tendency for film strength to be improved, and by setting the number to be less than the above upper limit, there is a tendency for developability to be improved.

[0370] The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the carbon number is equal to or more than the above lower limit, the film strength tends to be improved, and when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0371] Specific examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, etc. Among these, adamantane ring is preferred from the viewpoint of achieving both film strength and developability.

[0372] On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the number is set to be equal to or more than the above lower limit, there is a tendency for film strength to be improved, and when the number is set to be equal to or less than the above upper limit, there is a tendency for developability to be improved.

[0373] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. By setting the carbon number to be above the lower limit, there is a tendency for the film strength to be improved, and by setting the carbon number to be below the upper limit, there is a tendency for the developability to be improved.

[0374] Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, etc. Among these, a fluorene ring is preferred from the viewpoint of achieving both film strength and developability.

[0375] Examples of the substituents that the cyclic hydrocarbon group may optionally have include alkyl groups having 1 to 5 carbon atoms, such as hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; nitro; cyano; carboxyl, etc. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

[0376] n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When it is at least the above lower limit, developability tends to be improved, and when it is at most the above upper limit, film strength tends to be improved.

[0377] Among these, R α It is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

[0378] As mentioned above, the phenyl ring in formula (ii-1) is optionally further substituted by any substituent. As the substituent, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy etc. can be listed. The number of substituents is not particularly limited either, and can be 1 or more than 2. Among these, from the viewpoint of curability, it is preferably unsubstituted.

[0379] Specific examples of the partial structure represented by the above formula (ii-1) are listed below.

[0380] [Chemical formula 34]

[0381]

[0382] [Chemical formula 35]

[0383]

[0384] [Chemical formula 36]

[0385]

[0386] [Chemical formula 37]

[0387]

[0388] [Chemical formula 38]

[0389]

[0390] In addition, from the viewpoint of development adhesion, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-2).

[0391] [Chemical formula 39]

[0392]

[0393] In formula (ii-2), R c Same as above formula (ii), R β represents a divalent cyclic hydrocarbon group which may have a substituent, the benzene ring in the formula (ii-2) may be further substituted with an arbitrary substituent, and * represents a bonding position.

[0394] (R β )

[0395] In the above formula (ii-2), R β It represents a divalent cyclic hydrocarbon group which may have a substituent.

[0396] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0397] The number of rings possessed by the aliphatic cyclic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. When the number is set to be above the lower limit, there is a tendency for the film strength to be improved, and when the number is set to be below the upper limit, there is a tendency for the developability to be improved.

[0398] The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and further preferably 30 or less. When the carbon number is equal to or more than the above lower limit, the film strength tends to be improved, and when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0399] Specific examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, etc. Among these, adamantane ring is preferred from the viewpoint of achieving both film strength and developability.

[0400] On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the number is set to be equal to or greater than the above lower limit, there is a tendency for film strength to be improved, and when the number is set to be equal to or less than the above upper limit, there is a tendency for developability to be improved.

[0401] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and further preferably 10 or more, and further preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. By setting the carbon number to be greater than the above lower limit, there is a tendency for film strength to be improved, and by setting the carbon number to be less than the above upper limit, there is a tendency for developability to be improved.

[0402] Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, etc. Among these, a fluorene ring is preferred from the viewpoint of achieving both film strength and developability.

[0403] Examples of the substituents that the cyclic hydrocarbon group may optionally have include alkyl groups having 1 to 5 carbon atoms, such as hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; nitro; cyano; carboxyl, etc. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

[0404] Among these, R βIt is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.

[0405] On the other hand, from the viewpoint of balancing film strength and developability, R β It is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

[0406] As mentioned above, the phenyl ring in formula (ii-2) is optionally further substituted by any substituent. As the substituent, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy etc. can be listed. The number of substituents is not particularly limited either, and can be 1 or more than 2. Among these, from the viewpoint of curability, it is preferably unsubstituted.

[0407] Specific examples of the partial structure represented by the above formula (ii-2) are listed below.

[0408] [Chemical formula 40]

[0409]

[0410] [Chemical formula 41]

[0411]

[0412] [Chemical formula 42]

[0413]

[0414] [Chemical formula 43]

[0415]

[0416] On the other hand, from the viewpoint of developability, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-3).

[0417] [Chemical formula 44]

[0418]

[0419] In formula (ii-3), R c and R d Same as above formula (ii), R Z represents a hydrogen atom or a polyacid residue.

[0420] The polyacid residue refers to a monovalent group obtained by removing one OH group from a polyacid or its anhydride. Examples of the polyacid include one or more selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexachloronadic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0421] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0422] The repeating structural unit represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) may be one type or two or more types.

[0423] In addition, the number of partial structures represented by the above formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (c2-2) is not particularly limited, and is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. By setting it to be above the above lower limit, there is a tendency for the sensitivity to be improved, and by setting it to be below the above upper limit, there is a tendency for the developability to be improved. The number of partial structures represented by the above formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, and more preferably 3 to 10.

[0424] In addition, the number of partial structures represented by the above formula (ii-1) contained in one molecule of epoxy (meth) acrylate resin (c2-2) is not particularly limited, and is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. By setting it to be greater than the above lower limit, there is a tendency for the sensitivity to be improved, and by setting it to be less than the above upper limit, there is a tendency for the developability to be improved. The number of partial structures represented by the above formula (ii-1) contained in one molecule of epoxy (meth) acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, and more preferably 3 to 10.

[0425] In addition, the number of partial structures represented by the above formula (ii-2) contained in one molecule of epoxy (meth) acrylate resin (c2-2) is not particularly limited, and is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. By setting it to be greater than the above lower limit, there is a tendency for the sensitivity to be improved, and by setting it to be less than the above upper limit, there is a tendency for the developability to be improved. The number of partial structures represented by the above formula (ii-2) contained in one molecule of epoxy (meth) acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, and more preferably 3 to 10.

[0426] In addition, the number of partial structures represented by the above formula (ii-3) contained in one molecule of epoxy (meth) acrylate resin (c2-2) is not particularly limited, and is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. By setting it to be greater than the above lower limit, there is a tendency for the sensitivity to be improved, and by setting it to be less than the above upper limit, there is a tendency for the developability to be improved. The number of partial structures represented by the above formula (ii-3) contained in one molecule of epoxy (meth) acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, and more preferably 3 to 10.

[0427] Next, the epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii) (hereinafter, sometimes referred to as “epoxy (meth)acrylate resin (c2-3)”) will be described in detail.

[0428] [Chemical formula 45]

[0429]

[0430] In formula (iii), R e represents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent, the benzene ring in formula (iii) may be further substituted with an arbitrary substituent, and * represents a bonding position.

[0431] (γ)

[0432] In the above formula (iii), γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.

[0433] The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain from the viewpoint of developer solubility, and is preferably a branched chain from the viewpoint of developer adhesion. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less. By setting the number to be above the lower limit, there is a tendency for the film strength to be improved, and by setting the number to be below the upper limit, there is a tendency for the developability to be improved.

[0434] Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group. From the viewpoint of achieving both film strength and developability, an ethylene group or a propylene group is preferred, and a propylene group is more preferred.

[0435] Examples of the substituent that the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups, etc. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0436] Examples of the divalent cyclic hydrocarbon group include a divalent aliphatic ring group and a divalent aromatic ring group.

[0437] The number of rings possessed by the aliphatic cyclic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. When the number is set to be above the lower limit, there is a tendency for the film strength to be improved, and when the number is set to be below the upper limit, there is a tendency for the developability to be improved.

[0438] The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and further preferably 30 or less. When the carbon number is equal to or more than the above lower limit, the film strength tends to be improved, and when the carbon number is equal to or less than the above upper limit, the developability tends to be improved.

[0439] Specific examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, etc. Among these, adamantane ring is preferred from the viewpoint of achieving both film strength and developability.

[0440] On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the number is set to be equal to or greater than the above lower limit, there is a tendency for film strength to be improved, and when the number is set to be equal to or less than the above upper limit, there is a tendency for developability to be improved.

[0441] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. By setting the carbon number to be greater than the above lower limit, there is a tendency for film strength to be improved, and by setting the carbon number to be less than the above upper limit, there is a tendency for developability to be improved.

[0442] Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, etc. Among these, a fluorene ring is preferred from the viewpoint of achieving both film strength and developability.

[0443] Examples of the substituents that the cyclic hydrocarbon group may optionally have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; carboxyl groups, etc. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0444] Moreover, among these, from the viewpoint of developability, γ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.

[0445] As mentioned above, the phenyl ring in formula (iii) is optionally further substituted by any substituent. As the substituent, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy etc. can be listed. The number of substituents is not particularly limited either, and can be 1 or more than 2. Among these, from the viewpoint of curability, it is preferably unsubstituted.

[0446] On the other hand, from the viewpoint of development solubility, the partial structure represented by the above formula (iii) is preferably a partial structure represented by the following formula (iii-1).

[0447] [Chemical formula 46]

[0448]

[0449] In formula (iii-1), R e and γ are synonymous with those in the above formula (iii), R W represents a hydrogen atom or a polyacid residue, * represents a bonding position, and the benzene ring in the formula (iii-1) may be further substituted by any substituent.

[0450] The polyacid residue refers to a monovalent group obtained by removing one OH group from a polyacid or its anhydride. Examples of the polyacid include one or more selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexachloronadic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0451] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0452] The number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (c2-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and further preferably 10 or more, and preferably 18 or less, and more preferably 15 or less. By setting the number to be greater than the lower limit, the sensitivity tends to be improved, and by setting the number to be less than the upper limit, the developability tends to be improved. The number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (c2-3) is, for example, 1 to 18, preferably 5 to 18, and more preferably 10 to 15.

[0453] The number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (c2-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 5 or more, and preferably 18 or less, and more preferably 15 or less. By setting the number to be greater than the lower limit, the sensitivity tends to be improved, and by setting the number to be less than the upper limit, the developability tends to be improved. The number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (c2-3) is, for example, 1 to 18, preferably 3 to 18, and more preferably 5 to 15.

[0454] Specific examples of the epoxy (meth)acrylate resin (c2-3) are listed below.

[0455] [Chemical formula 47]

[0456]

[0457] [Chemical formula 48]

[0458]

[0459] As described above, the (C) alkali-soluble resin in the present invention includes (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain and (c2) an epoxy (meth)acrylate resin, and may also include other alkali-soluble resins.

[0460] In addition, the average acid value of the alkali-soluble resin of the component (C) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and further preferably 30 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 100 mgKOH / g or less, further preferably 70 mgKOH / g or less, and particularly preferably 50 mgKOH / g or less. By setting it to be above the lower limit, there is a tendency for the developability to be improved, and by setting it to be below the upper limit, there is a tendency for the developability to be improved. The average acid value of the alkali-soluble resin of the component (C) can be measured by neutralization titration. The average acid value of the alkali-soluble resin as the component (C) is, for example, 10 to 200 mgKOH / g, preferably 10 to 150 mgKOH / g, more preferably 20 to 100 mgKOH / g, further preferably 20 to 70 mgKOH / g, and further preferably 30 to 50 mgKOH / g.

[0461] The content ratio of (C) alkali-soluble resin in the colored photosensitive resin composition of the present invention is not particularly limited, and is generally 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more, and generally 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less. By setting it to more than the above lower limit, there is a tendency that the shape of the partition wall becomes good, and by setting it to less than the above upper limit, there is a tendency to improve sensitivity. As the content ratio of (C) alkali-soluble resin in the total solid content of the colored photosensitive resin composition, for example, 5~90% by mass, preferably 10~90% by mass, more preferably 20~80% by mass, more preferably 30~80% by mass, more preferably 40~80% by mass, particularly preferably 50~70% by mass, and most preferably 60~70% by mass.

[0462] In addition, the sum of the proportions of (A) ethylenically unsaturated compounds and (C) alkali-soluble resins in the total solid content is preferably 10% by mass or more, more preferably 30% by mass or more, more preferably 60% by mass or more, particularly preferably 80% by mass or more, and in addition, preferably 100% by mass or less, more preferably 95% by mass or less, and more preferably 90% by mass or less. By setting it to more than the above-mentioned lower limit, there is a tendency for the sensitivity to increase, and in addition, by setting it to less than the above-mentioned upper limit, there is a tendency for the shape of the partition wall to become good. As the sum of the proportions of (A) ethylenically unsaturated compounds and (C) alkali-soluble resins in the total solid content of the colored photosensitive resin composition, for example, 10 to 100% by mass, preferably 30 to 95% by mass, more preferably 60 to 95% by mass, and more preferably 80 to 90% by mass.

[0463] [1-1-4] (D) Component: Liquid repellent

[0464] The colored photosensitive resin composition of the present invention contains (D) a liquid repellent. By containing the (D) liquid repellent, ink repellency can be imparted to the surface of the obtained partition wall, so it is considered that the obtained partition wall can prevent color mixing of each light-emitting portion (pixel) of the organic layer.

[0465] As the liquid repellent, silicone-containing compounds and fluorine compounds can be listed, and liquid repellents having crosslinking groups (hereinafter also referred to as "liquid repellents containing crosslinking groups") can be preferably listed. As the crosslinking group, epoxy groups or ethylenically unsaturated groups can be listed, and ethylenically unsaturated groups are preferred from the viewpoint of suppressing the outflow of liquid repellent components into the developer.

[0466] It is considered that when a liquid repellent containing a crosslinking group is used, the crosslinking reaction on the surface of the formed coating film can be accelerated when the formed coating film is exposed to light, and the liquid repellent is less likely to flow out during development treatment, resulting in the obtained partition walls showing high ink repellency.

[0467] When a fluorine compound is used as a liquid repellent, there is a tendency that the fluorine compound is oriented on the surface of the partition wall and plays a role in preventing the ink from seeping out and mixing colors. More specifically, there is a tendency that the group having a fluorine atom can play a role in repelling the ink and preventing the ink from seeping out and mixing colors due to the ink crossing the partition wall into the adjacent area.

[0468] Specific examples of fluorine compounds used as liquid repellents include perfluoroalkyl sulfonic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl olefin oxide adducts, perfluoroalkyl trialkyl ammonium salts, oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, carbamates containing perfluoroalkyl groups and hydrophilic groups, perfluoroalkyl esters, perfluoroalkyl phosphates and other fluorine-containing organic compounds.

[0469] In addition, these compounds preferably have an epoxy group or an ethylenically unsaturated group as a crosslinking group.

[0470] As commercially available products of these fluorine-containing compounds having a crosslinking group, “Megafac (registered trademark, hereinafter the same) F116”, “Megafac F120”, “Megafac F142D”, “Megafac F144D”, “Megafac F150”, “Megafac F160”, “Megafac F171”, “Megafac F172”, “Megafac F173”, “Megafac F177”, “Megafac F178A”, “Megafac F178K”, “Megafac F179”, “Megafac F183”, “Megafac F184”, “Megafac F191”, “Megafac F812”, “Megafac F815”, “Megafac F824”, “Megafac F833”, “Megafac RS101”, “Megafac RS102”, “Megafac "Megafac RS105", "Megafac RS201", "Megafac RS202", "Megafac RS301", "Megafac RS303", "Megafac RS304", "Megafac RS401", "Megafac RS402", "Megafac RS501", "Megafac RS502", "Megafac RS-72-K", "DEFENSA (registered trademark, hereinafter the same) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", "Fluorad FC430", "Fluorad FC431", "FC-4430", "FC4432" manufactured by 3M Japan, "Asahi Guard (registered trademark) AG710" manufactured by AGC, "Surfron (registered trademark, hereinafter the same) S-382", "Surfron A fluorine-containing organic compound commercially available under trade names such as "Surfron SC-101", "Surfron SC-102", "Surfron SC-103", "Surfron SC-104", "Surfron SC-105", "Surfron SC-106", and "Optool (registered trademark) DAC-HP" manufactured by Daikin Industries, Ltd.

[0471] Like this, when using fluorine compounds as liquid repellents, there is no particular restriction on the fluorine atom content in the liquid repellent, and the fluorine atom content is preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 25% by mass or less. By setting it to above the above lower limit, there is a tendency to show a high contact angle, and by setting it to below the above upper limit, there is a tendency to suppress the outflow of the liquid repellent to the pixel portion. As the fluorine atom content ratio in the liquid repellent, for example, 1~50% by mass, preferably 5~25% by mass.

[0472] The molecular weight of the liquid repellent is not particularly limited, and it can be a low molecular weight compound or a high molecular weight body. The high molecular weight liquid repellent can suppress the fluidity of the liquid repellent caused by post-baking, thereby suppressing the outflow of the liquid repellent from the dam, so it is preferred that, from such a viewpoint, the number average molecular weight of the liquid repellent is preferably 100 or more, more preferably 500 or more, preferably 100,000 or less, more preferably 10,000 or less. As the molecular weight of the liquid repellent, for example, the number average molecular weight is 100 to 100,000, preferably 500 to 10,000.

[0473] The content ratio of (D) liquid repellent in the colored photosensitive resin composition of the present invention is not particularly limited, and is generally 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the total solids, and in addition, is generally 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less. By being set to more than the above-mentioned lower limit, there is a tendency to show high ink repellency, and in addition, by being set to less than the above-mentioned upper limit, there is a tendency to suppress the outflow of liquid repellent to pixel portion. As the content ratio of (D) liquid repellent in the total solids of the colored photosensitive resin composition, for example, 0.01~5% by mass, preferably 0.1~3% by mass, more preferably 0.5~2% by mass.

[0474] On the other hand, the colored photosensitive resin composition of the present invention may also use a surfactant while using the liquid repellent (D), and may also use a surfactant instead of the liquid repellent (D). The surfactant may be used for the purpose of improving the coating properties of the coating liquid as the colored photosensitive resin composition and the developability of the coating film, and is preferably a fluorine-based or silicone-based surfactant.

[0475] In particular, since the residue of the colored photosensitive resin composition is removed from the unexposed portion during development and the wettability is expressed, a silicone-based surfactant is preferred, and a polyether-modified silicone-based surfactant is more preferred.

[0476] As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group at least at any one of the terminal, the main chain and the side chain is preferred. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. can be cited. Examples of commercially available products thereof include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafac F142D”, “Megafac F172”, “Megafac F173”, “Megafac F183”, “Megafac F470” and “Megafac F475” manufactured by DIC Corporation, “FC430” manufactured by 3M Japan Co., Ltd., and “DFX-18” manufactured by Neos Corporation.

[0477] Examples of the silicone surfactant include commercially available products such as “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032 Additive”, and “SH8400” manufactured by Dow Corning Toray Co., Ltd. and “BYK323” and “BYK330” manufactured by BYK Chemie.

[0478] The surfactant may include surfactants other than fluorine-based surfactants and silicone-based surfactants. Examples of other surfactants include nonionic, anionic, cationic, and amphoteric surfactants.

[0479] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerol fatty acid esters, polyoxyethylene glycerol fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, etc. Examples of commercially available products thereof include polyoxyethylene surfactants such as "EMULGEN (registered trademark, hereinafter the same) 104P" and "EMULGEN A60" manufactured by Kao Corporation.

[0480] In addition, examples of the anionic surfactant include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants, etc. Among them, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred. As such anionic surfactants, commercially available products can be used, for example, alkyl sulfate ester salts include "Emal (registered trademark) 10" manufactured by Kao Corporation, alkyl naphthalene sulfonates include "Perex (registered trademark) NB-L" manufactured by Kao Corporation, and special polymer surfactants include "Homogenol (registered trademark, hereinafter the same) L-18" and "Homogenol L-100" manufactured by Kao Corporation.

[0481] Furthermore, examples of the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts, and the like. Examples of the amphoteric surfactants include betaine compounds, imidazoles, Salts, imidazolines, amino acids, etc. Among these, quaternary ammonium salts are preferred, and stearyl trimethyl ammonium salts are more preferred. As commercially available products, for example, alkylamine salts include "Acetamin (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts include "KOTAMIN (registered trademark, hereinafter the same) 24P" and "KOTAMIN 86W" manufactured by Kao Corporation.

[0482] In addition, the surfactant can also be used in combination of two or more, for example: silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer surfactant combination, etc. Among them, preferably a combination of silicone surfactant / fluorine surfactant. In the combination of silicone surfactant / fluorine surfactant, for example: Neos "DFX-18", BYK Chemie "BYK-300" or "BYK-330" / AGC SEIMI CHEMICAL "S-393", Shin-Etsu Silicone "KP340" / DIC "F-478" or "F-475", Dow Corning Toray "SH7PA" / Daikin Co., Ltd. "DS-401", NUC "L-77" / 3M Japan "FC4430" and the like.

[0483] [1-1-5] (E) Colorant

[0484] The colored photosensitive resin composition of the present invention contains (E) a colorant. By containing the (E) colorant, appropriate light absorption can be obtained, and in particular, when used for forming a light shielding member such as a colored partition wall, appropriate light shielding property can be obtained.

[0485] The type of the colorant (E) used in the present invention is not particularly limited, and a pigment or a dye may be used. Among these, a pigment is preferably used from the viewpoint of durability.

[0486] The pigment contained in the (E) colorant may be a single type or two or more types. In particular, two or more types are preferred from the viewpoint of uniformly shielding light in the visible region.

[0487] The type of pigment that can be used as the (E) colorant is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, organic pigments are preferably used from the viewpoint of controlling the transmission wavelength of the colored photosensitive resin composition and curing it efficiently.

[0488] Examples of organic pigments include organic coloring pigments and organic black pigments. Here, the organic coloring pigment refers to an organic pigment that exhibits a color other than black, and examples thereof include red pigments, orange pigments, blue pigments, violet pigments, green pigments, and yellow pigments.

[0489] Among organic pigments, organic coloring pigments are preferably used from the viewpoint of light-shielding property and ultraviolet absorption property.

[0490] The organic coloring pigment may be used alone or in combination of two or more. In particular, when used for light-shielding purposes, it is more preferred to use a combination of organic coloring pigments of different colors, and it is further preferred to use a combination of organic coloring pigments that present a color close to black.

[0491] The chemical structure of these organic pigments is not particularly limited, and examples thereof include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, diisocyanate, Oxazine, indanthrene, perylene, etc. Specific examples of pigments that can be used are shown below by pigment number. The terms "CI Pigment Red 2" and the like listed below refer to the Pigment Index (CI).

[0492] Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149 , 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 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, 275, 276. Among them, from the viewpoint of light blocking property and dispersibility, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 are preferably used, and CI Pigment Red 177, 209, 224, 254 is more preferably used. It should be noted that from the perspective of dispersibility and light-shielding properties, CI Pigment Red 177, 254, and 272 are preferably used. When the colored photosensitive resin composition is cured by ultraviolet light, a red pigment with a low ultraviolet absorption rate is preferably used as the red pigment. From the above viewpoints, CI Pigment Red 254 and 272 are more preferably used.

[0493] Examples of orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Among them, CI Pigment Orange 13, 43, 64, and 72 are preferably used from the viewpoints of dispersibility and light-shielding properties. When the colored photosensitive resin composition is cured by ultraviolet rays, an orange pigment having a low ultraviolet absorption rate is preferably used as the orange pigment. From the above viewpoints, CI Pigment Orange 64 and 72 are more preferably used.

[0494] Examples of the blue pigment include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, from the viewpoint of light-shielding properties, preferably, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are used, and more preferably, CI Pigment Blue 15:6 is used.

[0495] It should be noted that from the perspective of dispersibility and light-shielding properties, CI Pigment Blue 15:6, 16, and 60 are preferably used. When the colored photosensitive resin composition is cured by ultraviolet light, a blue pigment with a low ultraviolet absorption rate is preferably used as the blue pigment. From the above viewpoint, CI Pigment Blue 60 is more preferably used.

[0496] Examples of the violet pigment include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, from the viewpoint of light-shielding properties, CI Pigment Violet 19 and 23 are preferably used, and CI Pigment Violet 23 is more preferably used.

[0497] It should be noted that from the perspective of dispersibility and light-shielding properties, CI Pigment Violet 23 and 29 are preferably used. When the colored photosensitive resin composition is cured by ultraviolet light, a purple pigment with a low ultraviolet absorption rate is preferably used as the purple pigment. From this viewpoint, CI Pigment Violet 29 is more preferably used.

[0498] Examples of organic coloring pigments that can be used in addition to the red pigment, the orange pigment, the blue pigment, and the violet pigment include a green pigment and a yellow pigment.

[0499] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55. Among them, CI Pigment Green 7 and 36 are preferably used.

[0500] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 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 4, 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, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferably used, and CI Pigment Yellow 83, 138, 139, 150, and 180 are more preferably used.

[0501] Among these, from the viewpoint of light-shielding property and shape control, it is preferred to use at least one selected from a red pigment, an orange pigment, a blue pigment, and a violet pigment.

[0502] Among these, from the viewpoint of light-shielding property and shape control, it is preferred to contain at least one or more of the following pigments.

[0503] Red pigment: CI Pigment Red 177, 254, 272

[0504] Orange pigment: CI Pigment Orange 43, 64, 72

[0505] Blue pigment: CI Pigment Blue 15:6, 60

[0506] Violet Pigment: CI Pigment Violet 23, 29

[0507] When two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding properties, it is preferred that at least one selected from red pigments and orange pigments and at least one selected from blue pigments and violet pigments be contained.

[0508] The combination of colors is not particularly limited, and examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a violet pigment from the viewpoint of light-shielding properties.

[0509] In addition to the above-mentioned organic coloring pigments, a black pigment may be used. In addition to the above-mentioned organic coloring pigments, a black pigment may be used.

[0510] Examples of the black pigment include inorganic black pigments and organic black pigments. From the viewpoint of light-shielding properties, it is preferred that carbon black and / or an organic black pigment be contained.

[0511] Among black pigments, organic black pigments are preferably used from the viewpoint of suppressing the absorption of ultraviolet rays and facilitating the control of shape and height difference. In particular, from the viewpoint of light-shielding properties, it is preferred to use an organic black pigment comprising at least one selected from the group consisting of a compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”), a geometric isomer of compound (1), a salt of compound (1), and a salt of a geometric isomer of compound (1) (hereinafter sometimes referred to as “organic black pigment represented by general formula (1)”).

[0512] [Chemical formula 49]

[0513]

[0514] In formula (1), R 11 and R 16 Each independently represents a hydrogen atom, CH 3 CF 3 , fluorine atom or chlorine atom;

[0515] R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom, R21 、COOH、COOR 21 、COO - ,CONH 2 ,CONHR 21 ,CONR 21 R 22 、CN、OH、OR 21 、COCR 21 、OOCNH 2 ,OOCNHR 21 、OOCNR 21 R 22 、NO 2 NH 2 、NHR 21 NR 21 R 22 、NHCOR 22 NR 21 COR 22 、N=CH 2 、N=CHR 21 、N=CR 21 R 22 , SH, SR 21 、SOR 21 、SO 2 R 21 、SO 3 R 21 、SO 3 H.SO 3 - 、SO 2 NH 2 、SO 2 NHR 21 or SO 2 NR 21 R 22 ; and, selected from R 12 With R 13 , R 13 With R 14 , R 14 With R 15 , R 17 With R 18 , R 18 With R 19 , and R 19 With R 20 At least one combination of is optionally directly bonded to each other, or bonded to each other through an oxygen atom, a sulfur atom, NH or NR 21 Bridged and mutually bonded; R 21 and R 22Each 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.

[0516] Compound (1) and the geometrical isomers of compound (1) have the following core structure (wherein the substituents in the structural formula are omitted), and the trans-trans isomer is likely to be the most stable.

[0517] [Chemical formula 50]

[0518]

[0519] Shun-Shun-Reverse-Reverse

[0520] When compound (1) is anionic, it is preferably a salt obtained by compensating its charge with any known suitable cation, such as metal, organic, inorganic or metal organic cation, specifically alkali metal, alkaline earth metal, transition metal, primary amine, secondary amine, tertiary amine such as trialkylamine, quaternary ammonium such as tetraalkylammonium or organometallic coordination compound. In addition, when the geometrical isomers of compound (1) are anionic, they are preferably the same salts.

[0521] Among the substituents in the general formula (1) and their definitions, the following substituents are preferred because they tend to increase the shielding rate. This is because the following substituents are considered to have no absorption and have no influence on the hue of the pigment.

[0522] R 12 , R 14 , R 15 , R 17 , R 19 and R 20 Each independently is preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.

[0523] R 13 and R 18 are each independently preferably a hydrogen atom, NO 2 、OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 、N(CH 3 ) 2 、N(CH 3 )(C 2 H 5 )、N(C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO3 H or SO 3 - , more preferably a hydrogen atom or SO 3 H is particularly preferably a hydrogen atom.

[0524] R 11 and R 16 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.

[0525] Preferably selected from R 11 With R 16 , R 12 With R 17 , R 13 With R 18 , R 14 With R 19 , and R 15 With R 20 At least one combination is the same, preferably R 11 With R 16 Same, R 12 With R 17 Same, R 13 With R 18 Same, R 14 With R 19 Same, and R 15 With R 20 same.

[0526] The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.

[0527] Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, norbornenyl, bornyl, norcaryl, caryl, The alkyl group may be alkyl, norpinenyl, pinanyl, 1-adamantyl or 2-adamantyl.

[0528] Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2- 1-Buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

[0529] The cycloalkenyl group having 3 to 12 carbon atoms is exemplified by 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-cyclohexadien-1-yl, The 2-n-butylene group may be 1,4-dimethyl-2,4-dicarbazyl, 1,2-dimethyl-2,4-dicarbazyl, 1,2-dimethyl-3-nitropropene, 1,2-dimethyl-4-nitropropene, 1,2-dimethyl-2,4-dicarbazyl, 1,2-dimethyl-3 ...

[0530] The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

[0531] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0532] The organic black pigment represented by the general formula (1) is preferably an organic black pigment comprising at least one selected from a compound represented by the following general formula (2) (hereinafter also referred to as “compound (2)”) and geometric isomers of the compound (2).

[0533] [Chemical formula 51]

[0534]

[0535] Specific examples of such organic black pigments include organic black pigments with a trade name of Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).

[0536] The organic black pigment is preferably dispersed in a dispersant or solvent by the method described below. In addition, if a sulfonic acid derivative of compound (1), particularly a sulfonic acid derivative of compound (2), is present during dispersion, dispersibility and storage properties may be improved. Therefore, the organic black pigment preferably contains these sulfonic acid derivatives.

[0537] Examples of organic black pigments other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.

[0538] On the other hand, inorganic black pigments include carbon black, acetylene black, lamp black, bone charcoal, graphite, iron black, cyanine black, titanium black, etc. Among these, carbon black can be preferably used from the viewpoint of light shielding and image characteristics. Examples of carbon black include the following carbon blacks.

[0539] Made 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, #31 50, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

[0540] Made by Degussa: Printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, ColorBlack S160, Color Black S170

[0541] Made by Cabot Corporation: Monarch (registered trademark, the same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, the same below) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark) -8

[0542] Made by Birla: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN100 0. RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0543] Carbon black coated with resin may also be used. When carbon black coated with resin is used, the adhesion to the glass substrate and the volume resistivity are improved. As carbon black coated with resin, for example, carbon black described in Japanese Patent Publication No. 09-71733 may be preferably used. From the perspective of volume resistivity and dielectric constant, resin coated carbon black is preferably used.

[0544] As carbon black for coating treatment using resin, the total content of Na and Ca is preferably 100 ppm or less. Carbon black usually contains ash, and the composition of the ash is Na mixed from raw oil, fuel oil (or gas), reaction termination water and granulation water, and furnace materials of the reactor during manufacturing, as well as Ca, K, Mg, Al, Fe, etc. Among them, Na and Ca usually contain more than several hundred ppm respectively. By reducing Na and Ca, the penetration into the transparent electrode (ITO) and other electrodes can be suppressed, and there is a tendency to prevent electrical short circuits.

[0545] As a method for reducing the content of ash containing Na and Ca, it is possible to strictly select materials with extremely low Na and Ca contents as raw oil, fuel oil (or gas) and reaction termination water when manufacturing carbon black, and to minimize the amount of alkaline substances added for adjusting the structure. As another method, it is possible to wash the carbon black produced from the furnace with water, hydrochloric acid, etc. to dissolve and remove Na and Ca.

[0546] Specifically, carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide water, and then a solvent that is hardly soluble in water is added. At this time, the carbon black is transferred to the solvent side and completely separated from the water. At the same time, almost all the Na and Ca present in the carbon black are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to less than 100 ppm, although it may be achieved by a single carbon black manufacturing process with strictly selected raw materials or a single dissolution in water or acid, it is easier to reduce the total amount of Na and Ca to less than 100 ppm by combining the two methods.

[0547] In addition, the resin-coated carbon black is preferably the so-called acidic carbon black with a pH below 6. Since the dispersion diameter (agglomerate size) in water becomes smaller, it is possible to coat even fine units, so it is preferred. More preferably, the carbon black has an average particle diameter of 40 nm or less and a dibutyl phthalate (DBP) absorption of 140 ml / 100 g or less. By being within the above range, there is a tendency to obtain a coating film with good light-shielding properties. The average particle size refers to the number-average particle size, which refers to the equivalent circle diameter obtained by particle image analysis, and the particle image analysis is to use an electron microscope to observe and take pictures at tens of thousands times to obtain pictures of several fields of view, and measure about 2000 to 3000 particles in these pictures by an image processing device.

[0548] The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, the following method can be used:

[0549] 1. Mix the resin with a solvent such as cyclohexanone, toluene, or xylene, and heat to dissolve the mixture to prepare a resin solution, mix carbon black with water to prepare a suspension, mix and stir the resin solution and the suspension to separate the carbon black from the water, remove the water, heat and knead to obtain a composition, shape the obtained composition into a sheet, crush it, and then dry it;

[0550] 2. Mix and stir the resin solution and suspension prepared in the same manner as above, granulate the carbon black and resin, separate and heat the obtained granules, and remove the remaining solvent and water;

[0551] 3. Carboxylic acids such as maleic acid and fumaric acid are dissolved in the above-mentioned solvents, carbon black is added and mixed, and the solvent is removed after drying to obtain the added adhesion ( ) carbon black having carboxylic acid, to which resin is then added and dry-blended;

[0552] 4. Prepare a suspension by stirring the monomer component containing reactive groups constituting the resin to be coated with water at high speed, cool it after polymerization, obtain a resin containing reactive groups from the polymer suspension, add carbon black to it and mix it, react the carbon black with the reactive groups (graft the carbon black), and then cool and pulverize it; etc.

[0553] The type of resin to be coated is not particularly limited, and is generally a synthetic resin. From the perspective of dispersibility and dispersion stability, a resin further having a benzene nucleus in its structure is preferred because it has a stronger function as an amphoteric surfactant.

[0554] As specific synthetic resin, thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphthalate resin, epoxy resin, alkylbenzene resin, and thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, poly-p-phenylene terephthalamide, polyamide-imide, polyimide, polyamino bismaleimide, polyether sulfone polyphenyl sulfone, polyarylate, polyether ether ketone can be used. The amount of the coated resin is preferably 1 to 30% by mass relative to the total amount of carbon black and resin. By making the amount of the coated resin more than the above lower limit, there is a tendency to form fully coated carbon black. On the other hand, by making the amount of the coated resin less than the above upper limit, there is a tendency to prevent the adhesion between resins and make dispersibility good.

[0555] The carbon black formed by coating with resin in this way can be made into the shading material of colored spacer according to the usual method and can be used by making the coloring agent of colored partition wall by the usual method. If such carbon black is used, there is the tendency of colored partition wall that can realize high shading rate and low surface reflectivity at low cost. In addition, by coating the carbon black surface with resin, it is inferred that the ash content comprising Na and Ca is enclosed in the carbon black.

[0556] These pigments are preferably used after being dispersed to an average particle size of usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard of the average particle size is the number of pigment particles.

[0557] The average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). The particle size measurement is usually performed on a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2 mass %, but if there is a recommended concentration depending on the measuring instrument, it is used) and measured at 25°C.

[0558] In addition, in addition to the above-mentioned organic coloring pigment and black color material, dyes can also be used. As dyes that can be used as color materials, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, etc. can be listed.

[0559] Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0560] Examples of the anthraquinone dye include CI Vat 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.

[0561] In addition, as phthalocyanine dyes, for example, CI Vat Blue 5, etc. can be listed, as quinoneimine dyes, for example, CI Basic Blue 3, CI Basic Blue 9, etc. can be listed, as quinoline dyes, for example, CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, etc. can be listed, and as nitro dyes, for example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, etc. can be listed.

[0562] For the content ratio of (E) colorant in the colored photosensitive resin composition of the present invention, it is less than 20 mass % in all solid components.Therefore it can be considered that, in the case where the content ratio of colorant is few, colorant will not hinder the orientation of liquid repellent to the surface, and when coating is dried, more liquid repellents are oriented on the coating surface, and the most of the liquid repellents that cannot be fully combined with the film surface can flow during development, and in addition, even if heat curing is carried out, liquid repellent cannot be supplemented from the inside of the film to the surface, so that there is a tendency that the ink repellency of the partition obtained is reduced.Therefore it can be considered that, in the case where the content ratio of colorant is few, by using specific alkali-soluble resin as described above, it is possible to utilize chemical bonds to supplement the liquid repellent that has been oriented on the coating surface, so that ink repellency can be improved.

[0563] In addition, when the content ratio of the colorant is high, there is a situation where a rough surface is generated. It can be considered that this is because, due to the large amount of colorants, the amount of ultraviolet rays reaching the coating surface and the inside of the coating is different, so that the photocurability is different, and the shrinkage of the surface and the inside is different during post-baking, thereby generating a rough surface on the coating surface. When the surface is rough, it is difficult to make a uniform layer when stacking electrodes and other organic layers on the partition wall, so it is preferred to suppress the rough surface, but for the colored photosensitive resin composition of the present invention, it can be considered that due to the low content ratio of the colorant, the difference between the photocurability of the coating surface and the inside of the coating is reduced, and the rough surface can be suppressed.

[0564] The content ratio of (E) colorant in the colored photosensitive resin composition of the present invention is not particularly limited as long as it is less than 20% by mass in all solid components, preferably less than 18% by mass, more preferably less than 15% by mass, more preferably less than 12% by mass, particularly preferably less than 10% by mass, in addition, preferably more than 2% by mass, more preferably more than 3% by mass, more preferably more than 4% by mass, particularly preferably more than 5% by mass. By being set to below the above-mentioned upper limit, due to the relative increase of alkali-soluble resins and ethylenically unsaturated compounds, there is a tendency that the curability of the coating film and the ink repellency are improved, in addition, by being set to more than the above-mentioned lower limit, there is a tendency that can ensure light-shielding. As the content ratio of (E) colorant in all solid components of colored photosensitive resin composition, for example, 2~20% by mass, preferably 2~18% by mass, more preferably 3~15% by mass, more preferably 4~12% by mass, and more preferably 5~10% by mass.

[0565] [1-1-6] (F) Dispersant

[0566] The colored photosensitive resin composition of the present invention preferably contains a dispersant (F) for the purpose of finely dispersing the colorant (E) and stabilizing the dispersion state thereof.

[0567] As the dispersant (F), a polymer dispersant having a functional group is preferred. In addition, from the viewpoint of dispersion stability, a polymer dispersant having functional groups such as a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary amino group, a secondary amino group, or a tertiary amino group; a quaternary ammonium salt group; or a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine is preferred. Among them, a polymer dispersant having a basic functional group such as a primary amino group, a secondary amino group, or a tertiary amino group; a quaternary ammonium salt group; or a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, or pyrazine is particularly preferred from the viewpoint that a small amount of dispersant can be used when dispersing the pigment.

[0568] In addition, examples of polymer dispersants include carbamate dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants formed by monomers having an amino group and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like.

[0569] Specific examples of such dispersants include trade names EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.), and the like.

[0570] These polymer dispersants may be used alone or in combination of two or more.

[0571] The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and is usually 100,000 or less, preferably 50,000 or less.

[0572] Among these, from the viewpoint of pigment dispersibility, the dispersant (F) preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group, and particularly preferably contains an acrylic polymer dispersant.

[0573] In addition, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferred.

[0574] Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116, etc. (all acrylic-based) (all manufactured by BYK-Chemie).

[0575] If the preferred chemical structure of the carbamate polymer dispersant is specifically exemplified, for example, a dispersing resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule and having 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, etc. By treating the above dispersing resin with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted into quaternary ammonium salt groups.

[0576] Examples of the polyisocyanate compound include aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω′-diisocyanate, and the like. The present invention also includes alicyclic diisocyanates such as ester dimethylcyclohexane, aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate and α,α,α′,α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, undecane-1,6,11-triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, hexamethylene-1,3,6-triisocyanate, dicycloheptane triisocyanate, triphenylmethane triisocyanate, triphenylphosphothioate triisocyanate and other triisocyanates, and trimers, hydrides and polyol adducts thereof. As the polyisocyanate, trimers of organic diisocyanates are preferred, and trimers of toluene diisocyanate and trimers of isophorone diisocyanate are most preferred.

[0577] These may be used alone or in combination of two or more.

[0578] As a method for producing a trimer of isocyanate, the following method can be cited: using an appropriate trimerization catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., to partially trimerize the isocyanate group of the above-mentioned polyisocyanates, terminating the trimerization by adding a catalyst poison, and then removing the unreacted polyisocyanate by solvent extraction and thin film distillation, thereby obtaining the target polyisocyanate containing a trimerized isocyanate group.

[0579] Examples of the compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule include polyether diols, polyester diols, polycarbonate diols, polyolefin diols, and compounds obtained by alkoxylating one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more thereof.

[0580] Examples of the polyether diol include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing oxyalkylenes, such as polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxybutylene glycol, polyoxyhexylene glycol, polyoxyoctylene glycol, and mixtures of two or more thereof.

[0581] Examples of the polyetherester diol include those obtained by reacting a diol containing an ether group or a mixture with other diols with a dicarboxylic acid or an anhydride thereof, or by reacting an alkylene oxide with a polyester diol, such as poly(polyoxybutylene) adipate, etc. The most preferred polyether diols are polyethylene glycol, polypropylene glycol, polyoxybutylene glycol, or compounds in which one terminal hydroxyl group of these compounds is alkoxylated by an alkyl group having 1 to 25 carbon atoms.

[0582] Examples of the polyester diol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and diols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3- The polyester diol is preferably a product obtained by polycondensation of aliphatic diols such as bis(hydroxymethyl)cyclohexane, aromatic diols such as benzyl alcohol and bis(hydroxyethoxy)benzene, and N-alkyldialkanolamines such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, poly1,6-hexanediol adipate, and polyethylene adipate propylene glycol, or a polylactone diol or polylactone monool obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, such as polycaprolactone diol, polymethylvalerolactone, and a mixture of two or more thereof. As the polyester diol, the most preferred is polycaprolactone diol or polycaprolactone obtained by using an alcohol having 1 to 25 carbon atoms as an initiator.

[0583] Examples of the polycarbonate diol include poly(1,6-hexanediol) carbonate and poly(3-methyl-1,5-pentanediol) carbonate. Examples of the polyolefin diol include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol.

[0584] These may be used alone or in combination of two or more.

[0585] The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.

[0586] The compound having active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.

[0587] Examples of active hydrogen, that is, hydrogen atoms directly bonded to oxygen, nitrogen or sulfur atoms include hydrogen atoms in functional groups such as hydroxyl, amino and mercapto groups. Among them, hydrogen atoms in amino groups, particularly primary amino groups, are preferred.

[0588] The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

[0589] Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, N,N-dipropyl-1,3-propylenediamine, N,N-dibutyl-1,3-propylenediamine, 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.

[0590] In addition, examples of the nitrogen-containing heterocyclic ring structure in the case where the tertiary amino group is a nitrogen-containing heterocyclic ring include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzo oxazole ring, benzothiazole ring, benzothiadiazole ring and other nitrogen-containing 5-membered heterocyclic rings, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing 6-membered heterocyclic rings. Among these nitrogen-containing heterocyclic rings, imidazole ring or triazole ring is preferred.

[0591] Specific examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole, etc. Specific 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. Among them, N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole are preferred.

[0592] These may be used alone or in combination of two or more.

[0593] The preferred mixing ratio of the raw materials when producing the carbamate polymer dispersant is as follows: relative to 100 parts by mass of the polyisocyanate compound, the compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass.

[0594] The manufacture of carbamate polymer dispersants is carried out according to the known method for the manufacture of polyurethane resins. As solvents during manufacture, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone are generally used; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, sec-butyl alcohol, and tert-butyl alcohol, chlorinated products such as dichloromethane and chloroform; ethers such as tetrahydrofuran and diethyl ether; polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide, etc. They can be used alone or in combination of two or more.

[0595] In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and tin octoate, iron-based catalysts such as ferric acetylacetonate and ferric chloride, and tertiary amines such as triethylamine and triethylenediamine. These catalysts may be used alone or in combination of two or more.

[0596] The amount of the compound having active hydrogen and tertiary amino groups in the same molecule is preferably such that the amine value after the reaction is controlled within the range of 1 to 100 mgKOH / g, and more preferably within the range of 5 to 95 mgKOH / g. The amine value is a value corresponding to the acid value expressed as mg of KOH by neutralization titration of the basic amino group with an acid. By setting the amount to be greater than the lower limit, there is a tendency for the dispersibility to be improved, and by setting the amount to be less than the upper limit, there is a tendency for the developability to be improved.

[0597] In addition, when isocyanate groups remain in the polymer dispersant in the above reaction, it is preferred to further destroy the isocyanate groups with an alcohol or an amino compound because the stability of the product over time becomes high.

[0598] The weight average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1000 to 200000, preferably 2000 to 100000, and more preferably 3000 to 50000. When it is equal to or greater than the above lower limit, dispersibility and dispersion stability tend to be improved, and when it is equal to or less than the above upper limit, solubility tends to be improved and dispersibility tends to be improved.

[0599] As the acrylic polymer dispersant, it is preferred to use a random copolymer, a graft copolymer, or a block copolymer formed by a monomer having a functional group (the functional group referred to here is the functional group mentioned above as the functional group contained in the polymer dispersant) and containing an unsaturated group and a monomer having no functional group but containing an unsaturated group. These copolymers can be produced by a known method.

[0600] As the monomer having a functional group and containing an unsaturated group, unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, acrylic acid dimer, and unsaturated monomers having a tertiary amino group and a quaternary ammonium salt group such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternary compounds thereof can be cited as specific examples. These can be used alone or in combination of two or more.

[0601] Examples of the monomer having no functional group but containing an unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and methacrylic acid. Isobornyl ester, tricyclodecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinyl pyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide and other N-substituted maleimides, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomer, polystyrene macromonomer, poly(meth)acrylate 2-hydroxyethyl macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer and other macromonomers, etc. These can be used alone or in combination of two or more.

[0602] The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. In this case, in addition to the partial structure derived from the above-mentioned monomer containing a functional group and an unsaturated group, the A block may also contain a partial structure derived from the above-mentioned monomer containing no functional group but containing an unsaturated group, and these structures may be contained in the A block in any form of random copolymerization or block copolymerization. In addition, the content of the partial structure without a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

[0603] The B block includes a partial structure derived from the above-mentioned monomer having no functional group but having an unsaturated group. One B block may contain partial structures derived from two or more monomers. These structures may be contained in the B block in any form of random copolymerization or block copolymerization.

[0604] The AB or BAB block copolymer can be prepared, for example, by the living polymerization method shown below.

[0605] Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and free radical living polymerization methods. Among them, in the anionic living polymerization method, the polymerization active species is an anion, which is represented by the following synthesis route, for example.

[0606] [Chemical formula 52]

[0607]

[0608] In the above synthetic route, Ar 1 is a monovalent organic group, Ar 2 Different from Ar 1 A monovalent organic group wherein M is a metal atom, and s and t are each an integer greater than 1.

[0609] The polymerization active species in the radical living polymerization method is a radical, which is represented by the following synthesis scheme, for example.

[0610] [Chemical formula 53]

[0611]

[0612] In the above synthetic route, Ar 1 is a monovalent organic group, Ar 2 Different from Ar 1 wherein j and k are each an integer greater than 1, and R a is a hydrogen atom or a monovalent organic group, R b With R a Different from, it is a hydrogen atom or a monovalent organic group.

[0613] When synthesizing the acrylic polymer dispersant, the following may be used: Japanese Patent Application Laid-Open No. 9-62002, P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Yusuke, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis Collection, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, The known methods are described in, for example, Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertleret al, Macromolecules, 20, 1473 (1987), etc.

[0614] The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer. The A block / B block ratio constituting the copolymer is preferably 1 / 99 to 80 / 20, particularly preferably 5 / 95 to 60 / 40 (mass ratio). By setting it within this range, there is a tendency to ensure a good balance between dispersibility and storage stability.

[0615] The amount of the quaternary ammonium salt group in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol. By setting the amount within this range, good dispersibility tends to be ensured.

[0616] It should be noted that such a block copolymer may contain amino groups generated during the production process, and the amine value is about 1 to 100 mgKOH / g. From the viewpoint of dispersibility, it is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, and further preferably 50 mgKOH / g or more, and is preferably 90 mgKOH / g or less, more preferably 80 mgKOH / g or less, and further preferably 75 mgKOH / g or less.

[0617] Here, the amine value of the dispersant such as these block copolymers is expressed as the mass of KOH equivalent to the alkali amount per 1 g of the solid content excluding the solvent in the dispersant sample, and is measured by the following method.

[0618] Accurately weigh 0.5-1.5 g of the dispersant sample in a 100 mL beaker, dissolve it in 50 mL of acetic acid, and use an automatic titration device equipped with a pH electrode to titrate it with 0.1 mol / L HClO 4 The solution was neutralized and titrated with acetic acid solution, the inflection point of the titration pH curve was taken as the titration end point, and the amine value was calculated according to the following formula.

[0619] Amine value [mgKOH / g] = (561×V) / (W×S)

[0620] [W: represents the amount of dispersant sample weighed [g], V: represents the titration amount at the titration endpoint [mL], S: represents the solid content concentration of the dispersant sample [mass %].]

[0621] In addition, the amine value of the block copolymer depends on the presence or absence of the acidic group as the basis of the acid value and its type, and generally, the acid value is preferably lower, usually 10 mgKOH / g or less, and its weight average molecular weight (Mw) is preferably in the range of 1000 to 100,000. By making it within the above range, there is a tendency to ensure good dispersibility.

[0622] When the polymer dispersant has a quaternary ammonium salt group as a functional group, the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably one having a repeating unit represented by the following formula (i) (hereinafter, sometimes referred to as "repeating unit (i)").

[0623] [Chemical formula 54]

[0624]

[0625] In the above formula (i), R 31 ~R 33 Each is independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent;

[0626] R 31 ~R 33 Two or more of them can be bonded to each other to form a ring structure;

[0627] R 34 is a hydrogen atom or a methyl group;

[0628] X is a divalent linking group;

[0629] Y - as counter anion.

[0630] R in the above formula (i) 31 ~R 33The carbon number of the alkyl group optionally having a substituent is not particularly limited, and is more than 1, and preferably less than 10, and more preferably less than 6. As a specific example of the alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. can be listed, among which methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. In addition, any form in a straight chain or a branched shape can be used. In addition, cyclic structures such as cyclohexyl and cyclohexylmethyl can also be contained.

[0631] R in the above formula (i) 31 ~R 33 The number of carbon atoms of the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, etc. Among these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl or diethylphenyl is preferred, and phenyl, methylphenyl or ethylphenyl is more preferred.

[0632] R in the above formula (i) 31 ~R 33 The number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include phenylmethyl (benzyl), phenylethyl (phenethyl), phenylpropyl, phenylbutyl, phenylisopropyl, etc. Among these, phenylmethyl, phenylethyl, phenylpropyl or phenylbutyl is preferred, and phenylmethyl or phenylethyl is more preferred.

[0633] Among these, R 31 ~R 33 Each independently represents an alkyl group or an aralkyl group. Specifically, R 31 and R 33 are each independently methyl or ethyl, and R 32 is phenylmethyl or phenylethyl, more preferably R 31 and R 33 is methyl, and R 32 It is phenylmethyl.

[0634] When the acrylic polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following formula (ii) (hereinafter, sometimes referred to as "repeating unit (ii)") from the viewpoint of dispersibility.

[0635] [Chemical formula 55]

[0636]

[0637] In the above formula (ii), R 35 and R 36 are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent;

[0638] R 35 and R 36 They can bond with each other to form a ring structure;

[0639] R 37 is a hydrogen atom or a methyl group;

[0640] Z is a divalent linking group.

[0641] As R in the above formula (ii) 35 and R 36 The alkyl group optionally having a substituent can preferably be used as R in the above formula (i): 31 ~R 33 And the example group.

[0642] As R in the above formula (ii) 35 and R 36 The aryl group optionally having a substituent can preferably be used as R in the above formula (i): 31 ~R 33 And the example group.

[0643] As R in the above formula (ii) 35 and R 36 The aralkyl group optionally having a substituent may preferably be used as R in the above formula (i): 31 ~R 33 And the example group.

[0644] Among these, R 35 and R 36 Each independently is preferably an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

[0645] As R of the above formula (i) 31 ~R 33 and R of the above formula (ii) 35 and R 36 Examples of the substituent that the alkyl group, aralkyl group or aryl group in the formula (a) include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

[0646] In the above formulae (i) and (ii), examples of the divalent linking groups X and Z include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 -base, -COOR 44 -base [where R 43 and R44 is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, etc., preferably -COO-R 44 -base.

[0647] In the above formula (i), Y as a counter anion is - , Cl can be listed - Br - ,I - , ClO 4 - , BF 4 - , CH 3 COO - PF 6 - wait.

[0648] The content ratio of the repeating unit represented by the above formula (i) is not particularly limited. From the viewpoint of dispersibility, it is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, and particularly preferably 35 mol% or less, relative to the total content ratio of the repeating unit represented by the above formula (i) and the repeating unit represented by the above formula (ii). In addition, it is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more.

[0649] The content ratio of the repeating unit represented by the above formula (i) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol % or more, more preferably 5 mol % or more, and further preferably 10 mol % or more, and is preferably 50 mol % or less, preferably 30 mol % or less, more preferably 20 mol % or less, and particularly preferably 15 mol % or less from the viewpoint of dispersibility.

[0650] The content ratio of the repeating unit represented by the above formula (ii) in all the repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol % or more, more preferably 10 mol % or more, further preferably 15 mol % or more, particularly preferably 20 mol % or more, and is preferably 60 mol % or less, more preferably 40 mol % or less, further preferably 30 mol % or less, particularly preferably 25 mol % or less.

[0651] From the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter sometimes referred to as "repeating unit (iii)").

[0652] [Chemical formula 56]

[0653]

[0654] In the above formula (iii), R 40 is ethylene or propylene; R 41 is an alkyl group which may have a substituent; R 42 is a hydrogen atom or a methyl group; n is an integer from 1 to 20.

[0655] R in the above formula (iii) 41 The carbon number of the alkyl group optionally having a substituent is not particularly limited, and is 1 or more, preferably 2 or more, and preferably 10 or less, and more preferably 6 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. In addition, any form of straight chain or branched can be used. In addition, cyclic structures such as cyclohexyl and cyclohexylmethyl can also be contained.

[0656] In addition, from the viewpoint of compatibility and dispersibility with a binder component such as a solvent, n in the above formula (iii) is 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less.

[0657] In addition, the content ratio of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. In the case of the above range, there is a tendency to achieve both compatibility and dispersion stability with respect to binder components such as solvents.

[0658] From the viewpoint of improving the compatibility of the dispersant with the binder component such as the solvent and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iv) (hereinafter sometimes referred to as "repeating unit (iv)").

[0659] [Chemical formula 57]

[0660]

[0661] In the above formula (iv), R 38 is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, and R 39 A hydrogen atom or a methyl group.

[0662] R in the above formula (iv)38 The number of carbon atoms of the alkyl group optionally having a substituent is not particularly limited, and is 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. In addition, any form of straight chain or branched can be used. In addition, cyclic structures such as cyclohexyl and cyclohexylmethyl can also be contained.

[0663] R in the above formula (iv) 38 The number of carbon atoms of the aryl group which may have a substituent is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, etc. Among these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl or diethylphenyl is preferred, and phenyl, methylphenyl or ethylphenyl is more preferred.

[0664] R in the above formula (iv) 38 The number of carbon atoms of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, and further preferably 10 or less. Specific examples of the aralkyl group include phenylmethyl (benzyl), phenylethyl (phenethyl), phenylpropyl, phenylbutyl, phenylisopropyl, etc. Among these, phenylmethyl, phenylethyl, phenylpropyl or phenylbutyl is preferred, and phenylmethyl or phenylethyl is more preferred.

[0665] Among these, R 38 It is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethyl group.

[0666] As R 38 The substituents that the alkyl group in the formula (R) may optionally have include halogen atoms, alkoxy groups, and the like. In addition, the substituents that the aryl group or aralkyl group may optionally have include chain alkyl groups, halogen atoms, alkoxy groups, and the like. In addition, R 38 The chain alkyl group shown includes both straight-chain and branched ones.

[0667] In addition, from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mol % or more, more preferably 40 mol % or more, further preferably 50 mol % or more, and is preferably 80 mol % or less, more preferably 70 mol % or less.

[0668] The polymer dispersant may also have repeating units other than the repeating units (i), (ii), (iii) and (iv). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylic chloride monomers such as (meth)acrylic chloride; (meth)acrylamide monomers such as N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine.

[0669] From the viewpoint of further improving dispersibility, the polymer dispersant is preferably a block copolymer having an A block and a B block, wherein the A block has repeating units (i) and repeating units (ii), and the B block does not have repeating units (i) and repeating units (ii). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing a quaternary ammonium salt group and a tertiary amino group into the A block, there is unexpectedly a tendency to significantly improve the dispersibility of the dispersant. In addition, the B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).

[0670] In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization or block copolymerization. In addition, two or more repeating units (i) and repeating units (ii) may be contained in one A block, respectively. In this case, each repeating unit may be contained in the A block in any form of random copolymerization or block copolymerization.

[0671] In addition, the A block may contain repeating units other than the repeating units (i) and (ii), and examples of such repeating units include the repeating units derived from the above-mentioned (meth) acrylic acid ester monomers, etc. The content of the repeating units other than the repeating units (i) and (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably, the A block does not contain such repeating units.

[0672] The B block may contain repeating units other than repeating units (iii) and (iv), and examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylic chloride monomers such as (meth)acrylic chloride; (meth)acrylamide, N-methylol acrylamide and other (meth)acrylamide monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloyl morpholine and other monomers. The content of repeating units other than repeating units (iii) and repeating units (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably, the B block does not contain such repeating units.

[0673] When the colored photosensitive resin composition of the present invention contains (F) a dispersant, the content ratio thereof is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 1.5% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 2% by mass or less. By setting it to above the lower limit, there is a tendency to suppress the generation of residues due to agglomerates, and by setting it to below the upper limit, there is a tendency to improve sensitivity and developability. When the colored photosensitive resin composition contains (F) a dispersant, the content ratio of the (F) dispersant in the total solid content of the colored photosensitive resin composition is, for example, 0.1 to 8% by mass, preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, and further preferably 1.5 to 2% by mass.

[0674] [1-1-7] Ultraviolet light absorbers

[0675] The colored photosensitive resin composition of the present invention may also contain an ultraviolet absorber. The ultraviolet absorber is added for the following purpose: by utilizing the ultraviolet absorber to absorb the specific wavelength of the light source used for exposure, the photocuring distribution is controlled. By adding the ultraviolet absorber, the effects of improving the cone angle and shape after development or eliminating the residue remaining in the non-exposed part after development can be obtained. As the ultraviolet absorber, from the viewpoint of hindering the light absorption of the (B) photopolymerization initiator, for example, a compound with a maximum absorption between wavelengths of 250nm and 400nm can be used.

[0676] As the ultraviolet absorber, benzotriazole compounds and / or triazine compounds are preferred. It is believed that by including benzotriazole compounds and / or triazine compounds, the light absorption rate of the initiator at the bottom of the film is reduced, and the bottom size is reduced, thereby obtaining an effect of increasing the cone angle.

[0677] Among benzotriazole compounds, a benzotriazole compound represented by the following general formula (Z1) is preferred from the viewpoint of the cone shape.

[0678] [Chemical formula 58]

[0679]

[0680] In the above formula (Z1), R 1e and R 2e Each independently represents a hydrogen atom, an alkyl group which may have a substituent, a group represented by the following general formula (Z2), or a group represented by the following general formula (Z3), and R 3e represents a hydrogen atom or a halogen atom.

[0681] [Chemical formula 59]

[0682]

[0683] In the above formula (Z2), R 4e represents an alkylene group optionally having a substituent, R 5e It represents an alkyl group which may have a substituent.

[0684] [Chemical formula 60]

[0685]

[0686] In the above formula (Z3), R 6e represents an alkylene group optionally having a substituent, R 7e represents a hydrogen atom or a methyl group.

[0687] (R 1e and R 2e )

[0688] In the above formula (Z1), R 1e and R 2e Each independently represents a hydrogen atom, an alkyl group which may have a substituent, a group represented by the general formula (Z2), or a group represented by the general formula (Z3).

[0689] Examples of the alkyl group include linear, branched or cyclic alkyl groups, and the number of carbon atoms is preferably 1 or more, more preferably 2 or more, and further preferably 4 or more, and is preferably 10 or less, more preferably 6 or less, and further preferably 4 or less.

[0690] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, etc. Among these alkyl groups, a tert-butyl group is preferred.

[0691] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0692] (R 3e )

[0693] In the above formula (Z1), R 3e represents a hydrogen atom or a halogen atom.

[0694] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0695] Among these, R is preferred from the viewpoint of ease of synthesis. 3e A hydrogen atom.

[0696] (R 4e )

[0697] In the above formula (Z2), R 4e It represents an alkylene group which may have a substituent.

[0698] Examples of the alkylene group include linear, branched or cyclic alkylene groups, and the number of carbon atoms thereof is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.

[0699] Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, etc. Among these, an ethylene group is preferred.

[0700] Examples of the substituent which the alkylene group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0701] Among these, R 4e For ethylene.

[0702] (R 5e )

[0703] In the above formula (Z2), represents an alkyl group which may have a substituent.

[0704] Examples of the alkyl group include linear, branched or cyclic alkyl groups, and the number of carbon atoms is preferably 4 or more, more preferably 5 or more, and further preferably 7 or more, and is preferably 15 or less, more preferably 10 or less, and further preferably 9 or less.

[0705] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group.

[0706] Examples of the substituent which the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0707] Among these, R 5e It is heptyl, octyl and nonyl.

[0708] (R 6e )

[0709] Examples of the alkylene group include linear, branched or cyclic alkylene groups, and the number of carbon atoms thereof is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.

[0710] Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, etc. Among these, an ethylene group is preferred.

[0711] Examples of the substituent which the alkylene group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group, an acryloyl group, and a methacryloyl group.

[0712] Among these, R 1e is tert-butyl, R 2e is a group represented by the general formula (Z2) (wherein R 4e is ethylene, R 5e is an alkyl group having 7 to 9 carbon atoms), R 3e A compound in which R 1e is a hydrogen atom, R 2e is a group represented by the general formula (Z3) (wherein R 6e is ethylene, R 7e is methyl), R 3e A compound in which R 1e is tert-butyl, R 2e is a group represented by the general formula (Z2) (wherein R 4e is ethylene, R 5e is an alkyl group having 7 to 9 carbon atoms), R 3e A compound containing hydrogen atoms.

[0713] Specific examples of other benzotriazole compounds include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, a mixture of octyl-3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy-3,5-bis(α,α-dimethyl 2-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole), 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

[0714] Examples of commercially available benzotriazole compounds include SUMISORB (registered trademark, the same hereinafter) 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, the same hereinafter) PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 326, TINUVIN 900, "TINUVIN 928", TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81, Tomisorb (registered trademark, hereinafter the same) 100, Tomisorb 600 (manufactured by API Corporation), SEESORB (registered trademark, hereinafter the same) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by SHIPRO KASEI), RUVA-93 (Otsuka Chemical Co., Ltd.), etc.

[0715] Examples of the triazine compounds include 2-[4,6-di(2,4-dimethylphenyl)-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, a reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and glycidic acid (2-ethylhexyl) ester, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. Among these, hydroxyphenyl triazine compounds are preferred from the viewpoint of cone angle and exposure sensitivity.

[0716] Examples of commercially available triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (manufactured by BASF).

[0717] Examples of other ultraviolet absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.

[0718] More specifically, benzophenone compounds include SUMISORB 130 (manufactured by Sumitomo Chemical), EVERSORB 10, EVERSORB 11, EVERSORB 12, Tomisorb 800 (manufactured by API Corporation), SEESORB 100, SEESORB 101, SEESORB 101S, SEESORB 102, SEESORB 103, SEESORB 105, SEESORB 106, SEESORB 107, and SEESORB 151 (manufactured by SHIPROKASEI); SUMISORB 400 (manufactured by Sumitomo Chemical), benzoate compounds such as phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; naphthalene derivatives such as α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; anthracene and its derivatives such as anthracene and 9,10-dihydroxyanthracene; dyes such as azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, and p-aminobenzoic acid dyes; and the like. Among these, from the viewpoint of exposure sensitivity, cinnamic acid derivatives and naphthalene derivatives are preferably used, and cinnamic acid derivatives are particularly preferably used.

[0719] Among these, from the viewpoint of the taper angle shape, benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are particularly preferred.

[0720] As the ultraviolet absorber, one compound may be used alone, or two or more compounds may be used in combination.

[0721] When the colored photosensitive resin composition of the present invention contains an ultraviolet absorber, its content ratio is not particularly limited, and is generally 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and generally 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less. By setting it to above the lower limit, there is a tendency for the cone angle to become larger, and by setting it to below the upper limit, there is a tendency to become highly sensitive. When the colored photosensitive resin composition contains an ultraviolet absorber, the content ratio of the ultraviolet absorber in the total solid content of the colored photosensitive resin composition is, for example, 0.01~15% by mass, preferably 0.05~10% by mass, more preferably 0.1~5% by mass, more preferably 0.5~3% by mass, and more preferably 1~3% by mass.

[0722] In addition, when the colored photosensitive resin composition of the present invention contains an ultraviolet absorber, as a blending ratio relative to the (B) photopolymerization initiator, the amount of the ultraviolet absorber relative to 100 parts by mass of the (B) photopolymerization initiator is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 80 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and more preferably 100 parts by mass or less. By setting it to more than the above lower limit, there is a tendency for the cone angle to become larger, and by setting it to less than the above upper limit, there is a tendency to become highly sensitive. As the amount of the ultraviolet absorber relative to 100 parts by mass of the (B) photopolymerization initiator, for example, 1 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, more preferably 50 to 100 parts by mass, and even more preferably 80 to 100 parts by mass.

[0723] [1-1-8] Polymerization inhibitor

[0724] The colored photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. By containing a polymerization inhibitor, since it inhibits radical polymerization, there is a tendency to increase the taper angle of the partition wall obtained.

[0725] Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol (BHT). Among these polymerization inhibitors, hydroquinone, methylhydroquinone, or methoxyphenol is preferred, and methylhydroquinone is more preferred, from the viewpoint of polymerization inhibition ability.

[0726] The polymerization inhibitor preferably contains one or more. Usually, when manufacturing (C) the alkali-soluble resin, the resin sometimes contains a polymerization inhibitor, which can be used as the polymerization inhibitor of the present invention. In addition to the polymerization inhibitor in the resin, the same or different polymerization inhibitor can also be added when manufacturing the colored photosensitive resin composition.

[0727] When the colored photosensitive resin composition contains a polymerization inhibitor, its content ratio is not particularly limited, and is generally 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and generally 0.1% by mass or less, preferably 0.08% by mass or less, and more preferably 0.05% by mass or less in the total solid content of the colored photosensitive resin composition. By setting it to above the above lower limit, there is a tendency to increase the cone angle, and by setting it to below the above upper limit, there is a tendency to maintain high sensitivity. When the colored photosensitive resin composition contains a polymerization inhibitor, the content ratio of the polymerization inhibitor in the total solid content of the colored photosensitive resin composition is, for example, 0.0005~0.1% by mass, preferably 0.001~0.08% by mass, and more preferably 0.01~0.05% by mass.

[0728] [1-1-9] Thermal polymerization initiator

[0729] Furthermore, the colored photosensitive resin composition of the present invention may also contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there is a tendency to increase the degree of crosslinking of the film. Specific examples of such thermal polymerization initiators include, for example, azo compounds, organic peroxides, and hydrogen peroxide. These thermal polymerization initiators may be used alone or in combination of two or more.

[0730] It should be noted that, when a thermal polymerization initiator is used in combination with a photopolymerization initiator in order to increase the sensitivity and the crosslinking density of the film, it is preferred that the total of their content ratios reach the content ratio of the photopolymerization initiator in the total solid content of the colored photosensitive resin composition. In addition, as the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator, from the viewpoint of sensitivity, it is preferred that the thermal polymerization initiator is 5 to 300 parts by mass relative to 100 parts by mass of the photopolymerization initiator.

[0731] [1-1-10] Amino compounds

[0732] In the colored photosensitive resin composition of the present invention, an amino compound may also be included to promote thermosetting. In this case, the content of the amino compound in the colored photosensitive resin composition is generally 40% by mass or less, preferably 30% by mass or less, relative to the total solid content of the colored photosensitive resin composition, and is generally 0.5% by mass or more, preferably 1% by mass or more. By setting it to below the above upper limit, there is a tendency to maintain storage stability, and by setting it to above the above lower limit, there is a tendency to ensure sufficient thermosetting. When the colored photosensitive resin composition contains an amino compound, the content ratio of the amino compound in the total solid content of the colored photosensitive resin composition is, for example, 0.5~40% by mass, preferably 1~30% by mass.

[0733] As the amino compound, for example, there can be mentioned: an amino compound having at least two of methylol groups and alkoxymethyl groups modified by condensation of methylol groups with alcohol having 1 to 8 carbon atoms as functional groups. Specifically, for example, there can be mentioned: a melamine resin formed by condensation of melamine and formaldehyde; a benzoguanamine resin formed by condensation of benzoguanamine and formaldehyde; a glycoluril resin formed by condensation of glycoluril and formaldehyde; a urea resin formed by condensation of urea and formaldehyde; a resin formed by co-condensation of two or more of melamine, benzoguanamine, glycoluril or urea with formaldehyde; a modified resin formed by condensation of the methylol groups of the above resins with alcohol, etc. These amino compounds can be used alone or in combination of two or more. As the amino compound, melamine resin and its modified resin are preferred, and a modified resin having a modification ratio of methylol groups of 70% or more is further preferred, and a modified resin having a modification ratio of 80% or more is particularly preferred.

[0734] Specific examples of the amino compounds include melamine resins and modified resins thereof, such as Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158 manufactured by SaiTech, and Nicorac (registered trademark) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302 manufactured by Sanwa Chemical. In addition, benzoguanamine resins and modified resins thereof include Cymel (registered trademark) 1123, 1125, 1128 manufactured by SaiTech. Examples of the glycoluril resin and its modified resin include Cymel (registered trademark) 1170, 1171, 1174, and 1172 manufactured by SaiTech, and Nicarac (registered trademark) MX-270 manufactured by Sanwa Chemical. Examples of the urea resin and its modified resin include UFR (registered trademark) 65 and 300 manufactured by SaiTech, and Nicarac (registered trademark) MX-290 manufactured by Sanwa Chemical.

[0735] [1-1-11] Coating improvers, development improvers

[0736] In the colored photosensitive resin composition of the present invention, in order to improve the coating property and the development solubility, a coating property enhancer and a development improver may also be included. As a coating property enhancer or a development improver, for example, known cationic, anionic, nonionic, fluorine-based, and silicone-based surfactants may be used. In addition, as a development improver, known development improvers such as organic carboxylic acids or their anhydrides may also be used. In addition, from the viewpoint of sensitivity, the content ratio is generally 20% by mass or less, preferably 10% by mass or less relative to the total solid content of the colored photosensitive resin composition.

[0737] [1-1-12] Silane coupling agent

[0738] In order to improve the adhesion with the substrate, it is also preferred to add a silane coupling agent to the colored photosensitive resin composition of the present invention. As the type of silane coupling agent, various silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used. From the viewpoint of improving adhesion, epoxy and imidazole silane coupling agents are particularly preferred. From the viewpoint of adhesion, the content ratio is usually 20% by mass or less, preferably 15% by mass or less relative to the total solid content of the colored photosensitive resin composition.

[0739] [1-1-13] Inorganic fillers

[0740] In addition, in order to improve the strength of the cured product and to improve the excellent flatness and taper angle of the coating film based on the appropriate interaction with the alkali-soluble resin (formation of a matrix structure), the colored photosensitive resin composition of the present invention may further contain an inorganic filler. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, or those obtained by surface-treating them with various silane coupling agents.

[0741] The average particle size of these inorganic fillers is usually 0.005~20μm, preferably 0.01~10μm. Among them, the average particle size in this embodiment refers to the value measured by a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter. Among these inorganic fillers, silica sol and silica sol modification are particularly preferred because they have excellent dispersion stability and excellent cone angle improvement effects. When the colored photosensitive resin composition of the present invention contains these inorganic fillers, as its content, from the viewpoint of sensitivity, relative to the total solid content, it is usually 5% by mass or more, preferably 10% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less.

[0742] [1-1-14] Adhesion improving agent

[0743] The colored photosensitive resin composition of the present invention may contain a phosphoric acid olefin monomer for the purpose of imparting adhesion to the substrate. The phosphoric acid olefin monomer is preferably a phosphoric acid ester containing a (meth)acryloyloxy group, and preferably a phosphoric acid olefin monomer represented by the following general formula (g1), (g2), or (g3).

[0744] [Chemical formula 61]

[0745]

[0746] In the above general formulas (g1), (g2) and (g3), R 51represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.

[0747] These phosphoric acid olefinic monomers can be used alone or in combination of two or more. For the proportion of these phosphoric acid olefinic monomers, it is usually preferably 0.02% by mass or more, more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more in the total solid content of the colored photosensitive resin composition, in addition, preferably 4% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, particularly preferably 1% by mass or less. By setting it to more than the above lower limit, there is a tendency that the improvement effect of the adhesion with the substrate becomes sufficient, and by setting it to less than the above upper limit, there is a tendency that the adhesion with the substrate is easily suppressed. When the colored photosensitive resin composition contains phosphoric acid olefinic monomers, the proportion of phosphoric acid olefinic monomers in the total solid content of the colored photosensitive resin composition is, for example, 0.02~4% by mass, preferably 0.05~3% by mass, more preferably 0.1~2% by mass, and more preferably 0.2~1% by mass.

[0748] [1-1-15] Solvent

[0749] The colored photosensitive resin composition of the present invention usually contains a solvent, and can be used in a state where the above-mentioned components are dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the organic solvents described below.

[0750] 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 tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ethers; glycol dialkyl 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, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; glycol alkyl ether acetates such as ethylene glycol diacetate, 1,3-butanediol diol diacetates such as 1,6-hexanediol diacetate and the like; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone and methoxymethyl amyl ketone; monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl amyl alcohol, glycerol and benzyl alcohol; n-pentane, n-octane aliphatic hydrocarbons such as cyclohexane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone;Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentyl ketone; nitriles such as acetonitrile and benzonitrile; tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran and dimethoxytetrahydrofuran, etc.;

[0751] Examples of commercially available solvents corresponding to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TSsolvent 28, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and Diglyme (all trade names).

[0752] The above-mentioned solvent is a solvent capable of dissolving or dispersing each component in the colored photosensitive resin composition, and can be selected according to the method of using the colored photosensitive resin composition of the present invention, but from the viewpoint of coating properties, it is preferred to select a solvent having a boiling point in the range of 60 to 280° C. at atmospheric pressure (1013.25 hPa). More preferably, a solvent having a boiling point of 70 to 260° C. is preferably propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.

[0753] These solvents can be used alone or in combination of two or more. In addition, these solvents are preferably used in a manner such that the content ratio of all solid components in the colored photosensitive resin composition reaches usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less. By setting it to more than the above lower limit, there is a tendency to suppress the generation of uneven coating, and by setting it to less than the above upper limit, there is a tendency to suppress the generation of foreign matter, difficulty in brushing, etc. For example, the solvent can be used in a manner such that the content ratio of all solid components in the colored photosensitive resin composition is 10 to 90% by mass, preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and further preferably 20 to 35% by mass.

[0754] [1-2] Method for preparing colored photosensitive resin composition

[0755] The colored photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components with a stirrer.

[0756] For example, when a component that does not require a solvent such as a pigment as the (E) colorant is included, it is preferably dispersed in advance using a paint shaker, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, etc. The (E) colorant is micronized by the dispersion treatment, thereby improving the coating properties of the colored photosensitive resin composition.

[0757] The dispersion treatment is usually preferably performed in a system using a combination of (E) a colorant, a solvent, and (F) a dispersant, and in a system using a part or all of the (C) alkali-soluble resin in combination with the above components as needed (hereinafter, the mixture subjected to the dispersion treatment and the composition obtained in the treatment may be referred to as "ink" or "pigment dispersion"). In particular, it is preferred to use a polymer dispersant as the (F) dispersant because the viscosity increase over time of the obtained ink and colored photosensitive resin composition can be suppressed (excellent dispersion stability).

[0758] Therefore, in the step of producing the colored photosensitive resin composition, it is preferred to produce a pigment dispersion containing at least (E) a colorant, a solvent, and (F) a dispersant.

[0759] As the (E) colorant, organic solvent and (F) dispersant that can be used in the pigment dispersion, those described as being usable in the colored photosensitive resin composition can be preferably used. In addition, as the content ratio of each colorant in the (E) colorant in the pigment dispersion, those ratios described as the content ratio in the colored photosensitive resin composition can be preferably used.

[0760] When the colorant (E) is dispersed by a sand mill, glass beads or zirconium oxide beads with a particle size of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually 0°C to 100°C, preferably in the range of room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid and the size of the dispersion treatment device, so it can be adjusted appropriately. The general standard for dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the colored photosensitive resin composition reaches the range of 50 to 300.

[0761] The dispersed particle size of the pigment dispersed in the ink is generally 0.03 to 0.3 μm, which can be measured by a dynamic light scattering method or the like.

[0762] Next, the ink obtained by the above dispersion treatment is mixed with the above other components contained in the colored photosensitive resin composition to prepare a uniform solution. In the production process of the colored photosensitive resin composition, fine dust may be mixed into the liquid, so the obtained colored photosensitive resin composition is preferably filtered through a filter or the like.

[0763] [2] Partition wall and method for forming the same

[0764] The colored photosensitive resin composition of the present invention can be used to form partition walls, particularly partition walls for partitioning an organic layer of an organic electroluminescent element. The partition walls of the present invention are composed of the colored photosensitive resin composition of the present invention.

[0765] The method for forming the partition wall using the colored photosensitive resin composition described above is not particularly limited, and a conventionally known method can be used. As a method for forming the partition wall, for example, a method including a coating step of coating the colored photosensitive resin composition on a substrate to form a photosensitive resin composition layer and an exposure step of exposing the photosensitive resin composition layer can be cited. As a specific example of such a method for forming the partition wall, an inkjet method and a photolithography method can be cited.

[0766] In the inkjet method, a colored photosensitive resin composition having a viscosity adjusted by dilution with a solvent is used as ink, and ink droplets are ejected onto a substrate along a given pattern of partition walls by an inkjet method ink, thereby applying the colored photosensitive resin composition to the substrate to form a pattern of uncured partition walls. Then, the pattern of the uncured partition walls is exposed to form cured partition walls on the substrate. The exposure of the pattern of the uncured partition walls is performed in the same manner as the exposure process in the photolithography described later, except that a mask is not used.

[0767] In the photolithography method, a colored photosensitive resin composition is applied to the entire surface of a region of a substrate where partition walls are to be formed to form a colored photosensitive resin composition layer. After the formed colored photosensitive resin composition layer is exposed in accordance with a predetermined pattern of partition walls, the exposed colored photosensitive resin composition layer is developed to form partition walls on the substrate.

[0768] In the coating step of coating a colored photosensitive resin composition on a substrate in the photolithography method, the photosensitive resin composition is coated on the substrate on which partition walls are to be formed using a contact transfer coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact coating device such as a spin coater (rotary coating device) or a curtain coating flow coater, and the solvent is removed by drying as needed to form a colored photosensitive resin composition layer.

[0769] Next, in the exposure step, the colored photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays or excimer lasers using a negative mask, so that the colored photosensitive resin composition layer is partially exposed corresponding to the pattern of the partition wall. For exposure, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure amount also varies depending on the composition of the colored photosensitive resin composition, but is preferably 10 to 400 mJ / cm 2about.

[0770] Next, in the development step, the colored photosensitive resin composition layer exposed to the pattern corresponding to the partition wall is developed in a developer to form the partition wall. The development method is not particularly limited, and an immersion method, a spray method, etc. can be used. Specific examples of the developer include organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. In addition, a defoamer or a surfactant can be added to the developer.

[0771] Thereafter, the developed partition walls are post-baked and heat-cured. The post-baking is preferably performed at 150 to 250° C. for 15 to 60 minutes.

[0772] The substrate used to form the partition wall is not particularly limited and can be appropriately selected according to the type of organic electroluminescent element manufactured using the substrate with the partition wall formed thereon. Preferred substrate materials include glass and various resin materials. Specific examples of resin materials include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resins; polysulfone; polyimide. Among these substrate materials, glass and polyimide are preferred because of their excellent heat resistance. In addition, a transparent electrode layer such as ITO and ZnO can be pre-set on the surface of the substrate on which the partition wall is to be formed, depending on the type of organic electroluminescent element to be manufactured.

[0773] The shape of the partition wall is not particularly limited. When an ink containing a component with low solvent solubility is used to form a functional layer of a given film thickness, it is preferably formed into a thick film. The film thickness of the partition wall at this time is preferably 5 μm or more, more preferably 7 μm or more, further preferably 8 μm or more, particularly preferably 10 μm or more, and usually 20 μm or less. The film thickness of the partition wall is, for example, 5 to 20 μm, preferably 7 to 20 μm, more preferably 8 to 20 μm, and further preferably 10 to 20 μm.

[0774] [3] Organic electroluminescent elements

[0775] The organic electroluminescent element of the present invention comprises the partition walls of the present invention.

[0776] Various organic electroluminescent elements can be manufactured using a substrate having a partition wall pattern manufactured by the method described above. The method for forming the organic electroluminescent element is not particularly limited, but it is preferred to form an organic layer such as a pixel by injecting ink into the area surrounded by the partition walls on the substrate after forming a partition wall pattern on the substrate by the method described above.

[0777] Examples of the type of organic electroluminescent element include a bottom emission type and a top emission type.

[0778] In the bottom emission type, for example, a partition wall is formed on a glass substrate laminated with a transparent electrode, 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 wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate laminated with a metal electrode layer, 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 wall.

[0779] When the partition wall is in a hem shape, the ink for forming the organic layer will be repelled at the hem portion of the partition wall, so the area surrounded by the partition wall may not be fully covered by the ink for forming the organic layer. In contrast, by forming a good shape without hem, the area surrounded by the partition wall can be fully covered by the ink for forming the organic layer. Thus, the problem of halo in the organic EL display element can be eliminated.

[0780] As the solvent used when forming the ink for forming the organic layer, water, an organic solvent, and a mixed solvent thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the formed film after the ink is injected. Specific examples of the organic solvent include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, 3-phenoxytoluene, etc. In addition, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber, etc. can be added to the ink.

[0781] As a method for injecting ink into the area surrounded by the partition wall, the inkjet method is preferred because a small amount of ink can be easily injected into a given position. The ink used to form the organic layer can be appropriately selected according to the type of organic electroluminescent element to be manufactured. In the case of injecting ink using the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected well from the inkjet head, but is preferably 4 to 20 mPa·s, more preferably 5 to 10 mPa·s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, etc.

[0782] As the light-emitting layer, there can be mentioned organic electroluminescent layers as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. In addition, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 can also be used.

[0783] [4] Image display device

[0784] The image display device of the present invention includes the organic electroluminescent element of the present invention. As long as the organic electroluminescent element of the present invention is included, there is no particular limitation on the type and structure of the image display device. For example, an actively driven organic electroluminescent element can be used for assembly according to a conventional method. For example, the image display device of the present invention can be formed by a method described in "Organic EL Display" (OHM Co., Ltd., published on August 20, 2001, written by Shizuo Tokito, Chiba Ya Andachi, and Hideyuki Murata). For example, an organic electroluminescent element emitting white light can be combined with a color filter to display an image, or organic electroluminescent elements with different luminous colors such as RGB can be combined to display an image.

[0785] [5] Lighting

[0786] The lighting of the present invention comprises the organic electroluminescent element of the present invention. There is no particular limitation on its type and structure, and the organic electroluminescent element of the present invention can be assembled according to conventional methods. The organic electroluminescent element can be driven by a simple matrix or an active matrix.

[0787] In order to make the lighting of the present invention emit white light, an organic electroluminescent element emitting white light may also be used. In addition, the lighting of the present invention may be configured in a manner that organic electroluminescent elements of different luminous colors are combined so that each color is mixed to form white, or in a manner that the color mixing ratio can be adjusted to give a color adjustment function.

[0788] Example

[0789] Hereinafter, the colored photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples within the scope of the gist thereof.

[0790] <Alkali-soluble resin-I>

[0791] An alkali-soluble acrylic copolymer resin obtained by addition reaction of acrylic acid with a copolymer resin having dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6) as constituent monomers in an equal amount relative to glycidyl methacrylate, and further addition reaction of tetrahydrophthalic anhydride in an amount of 0.39 moles relative to 1 mole of the copolymer resin. The polystyrene-converted weight average molecular weight (Mw) measured by GPC is 9000, and the solid content acid value is 80 mgKOH / g. Equivalent to (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain.

[0792] <Alkali-soluble resin-II>

[0793] “ZCR-1642H” (Mw 6500, acid value 98 mgKOH / g) manufactured by Nippon Kayaku Co., Ltd. corresponds to (c2) epoxy (meth)acrylate resin.

[0794] <Alkali-soluble resin-III>

[0795] [Chemical formula 62]

[0796]

[0797] 50 g of the epoxy compound (epoxy equivalent 264) of the above structure, 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of p-methoxyphenol were added to a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted at 90° C. while stirring until the acid value reached 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

[0798] 25 parts by mass of the above epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 3.95 parts by mass of biphenyltetracarboxylic anhydride (BPDA), and 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) were added to a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105°C while stirring to react to obtain an alkali-soluble resin-III. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 4100, and the solid content acid value was 112 mgKOH / g. Equivalent to (c2) epoxy (meth) acrylate resin.

[0799] <Alkali-soluble resin-IV>

[0800] Acrylic acid was subjected to addition reaction with a copolymer resin having dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio: 2 / 5 / 93) as a constituent monomer in an amount equal to glycidyl methacrylate, and further subjected to addition reaction with tetrahydrophthalic anhydride in an amount of 0.1 mole relative to 1 mole of the copolymer resin to obtain an alkali-soluble resin-IV. The polystyrene-converted weight average molecular weight (Mw) measured by GPC was 7700, and the solid content acid value was 28.5 mgKOH / g. Equivalent to (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain.

[0801] <Alkali soluble resin-V>

[0802] The alkali-soluble acrylic copolymer resin having cyclohexyl methacrylate / methacrylic acid (molar ratio: 85 / 15) as monomers had a polystyrene-equivalent weight average molecular weight (Mw) of 12,300 as measured by GPC and a solid content acid value of 94 mgKOH / g.

[0803] <Alkali-soluble resin-VI>

[0804] The alkali-soluble acrylic copolymer resin having methyl methacrylate / methacrylic acid (molar ratio: 82 / 18) as monomers had a polystyrene-equivalent weight average molecular weight (Mw) of 11,400 as measured by GPC and a solid content acid value of 97 mgKOH / g.

[0805] <Organic black pigment>

[0806] "Irgaphor (registered trademark) Black S 0100 CF" manufactured by BASF Corporation (having a chemical structure represented by the following formula (1-1))

[0807] [Chemical formula 63]

[0808]

[0809] <Dispersant-I>

[0810] BYK-LPN21116 manufactured by BYK-Chemie (an acrylic AB block copolymer consisting of an A block having a quaternary ammonium salt group and a tertiary amino group in the side chain and a B block having no quaternary ammonium salt group and a tertiary amino group, with an amine value of 70 mgKOH / g and an acid value of 1 mgKOH / g or less.)

[0811] The A block of the dispersant-I contains repeating units of the following formulae (1a) and (2a), and the B block contains repeating units of the following formulae (3a). The content ratios of the repeating units of the following formulae (1a), (2a), and (3a) in the total repeating units of the dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[0812] [Chemical formula 64]

[0813]

[0814] <Pigment derivatives>

[0815] Lubrizol's Solsperse 12000

[0816] <Solvent-I>

[0817] PGMEA: Propylene glycol monomethyl ether acetate

[0818] <Solvent-II>

[0819] MB: 3-methoxy-1-butanol

[0820] <Photopolymerizable monomer>

[0821] DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

[0822] <Photopolymerization initiator>

[0823] The compounds having the following chemical structures were used.

[0824] [Chemical formula 65]

[0825]

[0826] <Liquid repellent>

[0827] DIC Megaface RS-72-K (fluorinated, oligomer with olefinic double bonds)

[0828] <Additives-I>

[0829] Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate) manufactured by Showa Denko K.K.

[0830] <Additives-II>

[0831] Nippon Kayaku Co., Ltd. KAYAMER PM-21 (methacryloyl-containing phosphate ester)

[0832] <Preparation of Pigment Dispersions I to III>

[0833] The pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent listed in Table 1 were mixed in the mass ratio listed in Table 1. The mixed solution was dispersed for 3 hours at 25 to 45°C using a paint shaker. Zirconia beads of 0.5 mm φ were used as beads, and 2.5 times the mass of the mixed solution was added. After the dispersion was completed, the beads were separated from the dispersion using a filter to prepare pigment dispersions I to III.

[0834] It should be noted that the mixing ratios of the dispersant and the alkali-soluble resin in Table 1 are values ​​calculated based on solid content, and the mixing ratio of the solvent also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[0835]

[0836] [Examples 1 to 9, and Comparative Examples 1 to 3]

[0837] Using the pigment dispersion prepared above, the components were mixed and stirred to dissolve in the proportions shown in Tables 2 and 3 to prepare colored photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3. The obtained colored photosensitive resin compositions were used to perform performance evaluation according to the method described below.

[0838] It should be noted that the mixing ratio of the alkali-soluble resin and the liquid repellent in Table 2 and Table 3 is a solid content conversion value, and the mixing ratio of the solvent also includes the amount of the solvent from the alkali-soluble resin and the liquid repellent. On the other hand, the mixing ratio of the pigment dispersion is not a solid content conversion value, but includes the total amount of the solvent.

[0839]

[0840]

[0841] Next, the method of performance evaluation is described.

[0842] <Fabrication of measurement substrate>

[0843] Each of the colored photosensitive resin compositions was applied to a glass substrate using a spin coater to a thickness of 10.0 μm after heat curing. Then, the coated substrate was dried at 100° C. on a hot plate for 90 seconds. The substrate was not exposed to light, but spray developed at 24° C. using an aqueous solution containing 0.04% by mass of KOH and 0.07% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation) as a developer, and the time when the coating was completely developed and removed was read as the break time.

[0844] Next, the same procedure was followed to obtain a coated substrate, and an exposure dose of 50 mJ / cm was used without using an exposure mask. 2 The intensity at a wavelength of 365 nm was 45 mW / cm 2 The substrate was spray developed at 24°C using the developer for a development time 1.2 times the image development time, and then washed with pure water for 10 seconds. The substrate was heat-cured in an oven at 230°C for 30 minutes to obtain a measurement substrate.

[0845] <Measurement of optical density (OD)>

[0846] The optical density (OD) of the above-mentioned substrate for measurement was measured using a transmission densitometer (Gretag Macbeth "D200-II"). Furthermore, the film thickness of the measurement site was measured using the non-contact surface / layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka Systems Co., Ltd., and the optical density per unit film thickness (1 μm) (unit OD, OD / μm) was calculated from the optical density (OD) and the film thickness. The results are shown in Tables 2 and 3.

[0847] <Measurement of PGMEA contact angle>

[0848] 0.7 μL of PGMEA (propylene glycol monomethyl ether acetate) was dropped onto the measurement substrate at 23° C. and 50% humidity, and the contact angle was measured 1 second later using a Drop Master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Tables 2 and 3. A larger contact angle indicates higher ink repellency.

[0849] <Production of partition walls>

[0850] Each of the above colored photosensitive resin compositions was applied to a glass substrate using a spin coater to a thickness of 10.0 μm after heat curing. Then, the coating was dried on a hot plate at 100° C. for 90 seconds. The resulting coating was exposed to ultraviolet light using a photomask. The exposure dose was 50 mJ / cm 2 , the exposure gap is set to 16μm. At this time, the intensity at a wavelength of 365nm is 45mW / cm 2 As a photomask, a mask with a grid-shaped opening (a mask with multiple 80μm×280μm covering parts at 40μm intervals) was used. Next, under the same conditions as the above-mentioned <Preparation of the Substrate for Measurement>, development was performed for a development time 1.2 times the image development time, and then washed with pure water for 10 seconds. The substrate was heated and cured in an oven at 230°C for 30 minutes to obtain a substrate with a grid-shaped partition wall.

[0851] <Evaluation of linearity of edge portion of partition wall pattern>

[0852] The surface of the partition wall of the substrate with the lattice partition wall was observed by SEM at 6000 times, and the linearity of the edge of the partition wall was evaluated. The edge of the partition wall was straight and had no residue, which was evaluated as "A", and the edge of the partition wall had an irregular hem and was not straight or the residue was seen, which was evaluated as "B". The results are shown in Tables 2 and 3.

[0853] <Evaluation of substrate surface condition>

[0854] The surface state of the above-mentioned substrate for measurement was observed with the naked eye to evaluate the presence or absence of surface roughness. If the surface was sufficiently glossy, it was evaluated as "A", and if it was not glossy, it was evaluated as "B". The results are shown in Tables 2 and 3.

[0855] The case of having gloss is a state close to mirror reflection, that is, a uniform surface state with low roughness, while the case of having no gloss is a state of diffuse reflection, that is, a state of high roughness and rough surface.

[0856] As shown in Table 2, in the colored photosensitive resin compositions of Examples 1 and 2, the content ratio of the colorant is less than 20% by mass in the total solid content, and contains (c1) an acrylic resin having an ethylenically unsaturated group in the side chain, and (c2) an epoxy (meth) acrylate resin, and the light-shielding property is good, the PGMEA contact angle is high, and the ink repellency is good, and the linearity of the edge of the partition wall is good. In addition, it can be seen that the substrate surface state is also good, has gloss, and has no surface roughness.

[0857] On the other hand, in the colored photosensitive resin composition of Comparative Example 2, the content of the colorant exceeds 20% by mass in the total solid content, that is, the colorant is excessively contained, therefore, despite the absence of (c1) acrylic resin having an ethylenically unsaturated group in the side chain, the PGMEA contact angle is high, showing good ink repellency, and the linearity of the edge of the partition wall is good. It can be seen from this that when the colorant is excessively contained, there is no problem of ink repellency and linearity, but it should be noted that the substrate surface is not glossy and a rough surface is produced.

[0858] In contrast, the colored photosensitive resin composition of Comparative Example 1 is an example in which the content ratio of the colorant is changed to less than 20% by mass in Comparative Example 2. It is known that although the linearity of the edge portion of the partition wall is good, the contact angle of PGMEA is low and the ink repellency is poor. As can be seen from the comparison of Comparative Example 2 and Comparative Example 1, by making the content ratio of the colorant less than 20% by mass in the total solid content, the problem of reduced contact angle of PGMEA and poor ink repellency will occur. It is believed that this is due to the fact that by reducing the content ratio of the colorant, the orientation of the liquid repellent to the surface increases, and most of the liquid repellent that is not fully bonded to the film surface flows out during development.

[0859] Comparative Example 1 does not contain (c1) an acrylic resin having an ethylenically unsaturated group in the side chain but contains (c2) an epoxy (meth) acrylate resin. On the other hand, when (c1) an acrylic resin having an ethylenically unsaturated group in the side chain but does not contain (c2) an epoxy (meth) acrylate resin as in Comparative Example 3, it can be seen that PGMEA has a high contact angle and good ink repellency, but the linearity of the edge portion of the partition wall becomes poor.

[0860] It is believed that this is because, by containing (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain, due to its soft skeleton, the free radicals generated during exposure have a high degree of freedom in the film, and the free radical deactivation caused by oxygen on the film surface can be suppressed, and the curability of the film surface is high. In addition, by having an ethylenically unsaturated group in the side chain, the liquid repellent oriented on the film surface can be fully captured, and it will not flow out and remain on the film surface during development. As a result, the PGMEA contact angle is high and the ink repellency becomes good. However, it is believed that since it does not contain (c2) epoxy (meth) acrylate resin, and (c2) epoxy (meth) acrylate resin has a tendency to not make the adhesion to the substrate too high by having a rigid skeleton, the adhesion to the substrate becomes too high, and the linearity of the edge of the partition wall is insufficient.

[0861] In contrast, for the colored photosensitive resin composition of Example 1 and Example 2, it can be considered that although the content ratio of its colorant is less than 20% by mass in the total solid content, by containing (c1) acrylic resin with ethylenically unsaturated groups in the side chain, due to its soft skeleton, the free radicals generated during exposure have a high degree of freedom in the film, and the free radical deactivation caused by oxygen on the film surface can be suppressed, and the curability of the film surface becomes high. In addition, by having ethylenically unsaturated groups in the side chain, the liquid repellent having orientation on the film surface can be fully captured, and it will not flow out and remain on the film surface during development, and the PGMEA contact angle is high and the ink repellency becomes good. It can also be considered that by containing (c2) epoxy (meth) acrylate resin, the bonding force of the hydroxyl group and the silanol group on the substrate is weakened due to the rigid skeletons such as its aromatic rings, and the unexposed portion is easily developed, and the linearity of the edge of the partition wall becomes good. In addition, by making the content ratio of the colorant less than 20 mass % in the total solid content, the difference in curability between the film surface and the inside is reduced, so the difference in shrinkage between the film surface and the inside during heat curing is also reduced, the surface state of the substrate becomes good, and surface roughness is suppressed.

[0862] In addition, embodiment 3~6 uses the acrylic resin containing (c1) side chain with ethylenically unsaturated group as the pigment dispersion of dispersing resin, and its PGMEA contact angle is high, ink repellency is good, and the linearity of the edge of the partition wall is also good, and the substrate surface state is also good, and surface roughness is suppressed.As can be seen from the comparison of embodiment 3 and embodiment 4, the ratio of (c1) acrylic copolymer resin is high, and there is a tendency that the contact angle of PGMEA increases.In addition, as can be seen from the comparison of embodiment 3,5 and 6, as long as the containing ratio of colorant is less than 20 mass % in all sol...

Claims

1. A colored photosensitive resin composition comprising: (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent, and (E) a colorant, in, The content ratio of the (E) colorant in the total solid content of the colored photosensitive resin composition is 20 mass % or less, The (C) alkali-soluble resin contains (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain, and (c2) an epoxy (meth)acrylate resin. The content ratio of the epoxy (meth)acrylate resin (c2) is 10% by mass or more and 70% by mass or less relative to the total amount of the alkali-soluble resin (C), The (D) liquid repellent has a cross-linking group.

2. The colored photosensitive resin composition according to claim 1, in, The acrylic copolymer resin (c1) having an ethylenically unsaturated group in the side chain has a partial structure represented by the following general formula (I): ， In formula (I), R 1 and R 2 Each independently represents a hydrogen atom or a methyl group, and * represents a bonding position.

3. The colored photosensitive resin composition according to claim 1 or 2, in, The (c2) epoxy (meth) acrylate resin 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), an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (ii), and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii). ， In formula (i), R a represents a hydrogen atom or a methyl group, R b represents a divalent hydrocarbon group which may have a substituent, the benzene ring in formula (i) may be further substituted with an arbitrary substituent, * represents a bonding position, ， In formula (ii), R c Each independently represents a hydrogen atom or a methyl group, R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, * represents a bonding position, ， In formula (iii), R e represents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent, the benzene ring in formula (iii) may be further substituted with an arbitrary substituent, and * represents a bonding position.

4. The colored photosensitive resin composition according to claim 1 or 2, in, The (E) colorant contains an organic pigment.

5. The colored photosensitive resin composition according to claim 1 or 2, in, The (E) colorant includes at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment. The colored photosensitive resin composition according to claim 1 or 2, further comprising a chain transfer agent. 7 . A partition wall composed of the colored photosensitive resin composition according to claim 1 .

8. An organic electroluminescent element comprising the partition wall according to claim 7.

9. An image display device comprising the organic electroluminescent element according to claim 8.

10. A lighting device comprising the organic electroluminescent element according to claim 8.

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