TW202311303A - Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, image display apparatus, and cured product forming method - Google Patents

Abstract

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

Description

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

The invention relates to a photosensitive resin composition. Also, the present invention relates to a cured product obtained by curing a photosensitive resin composition; a barrier rib made of the cured material; and an organic electroluminescent element, a color filter, and an image display device provided with the barrier rib. Also, the present invention relates to a method for forming a cured product. This application is based on Japanese Patent Application No. 2021-102054 filed in Japan on June 18, 2021, and its priority is claimed, and its content is incorporated into this specification.

In recent years, in order to achieve low power consumption and wide color gamut of displays, color filters using luminous nanocrystals such as quantum dots to form pixels have been studied. The photolithography method and the inkjet method are known as the manufacturing method of the color filter, and the latter method can reduce the loss of the ink material (for example, refer to Patent Document 1). In the case of manufacturing a color filter containing luminescent nanocrystal grains by an inkjet method, ink containing luminescent nanocrystal grains is jetted into a region (pixel portion) surrounded by pre-fabricated barrier ribs. to form pixels. Also, organic electroluminescence elements used in organic electroluminescence displays etc. are manufactured by forming barrier walls (banks) on a substrate, and laminating various functional layers in the area surrounded by the barrier walls. An inkjet method is known as a method for laminating a functional layer in a barrier rib. Regardless of whether it is a barrier rib for a color filter including luminescent nanocrystal grains or a barrier rib for an organic electroluminescent element, when ink is ejected by the inkjet method, it is necessary to prevent the mixing of inks between adjacent pixel parts, etc. Therefore, higher ink repellency (liquid repellency) is required. As a material for forming a liquid-repellent barrier rib by photolithography, according to Patent Document 2, by using two specific alkali-soluble resins in combination, a coloring photosensitive material with high liquid repellency and good linearity can be obtained. permanent resin composition. In the case of forming the above-mentioned barrier ribs by photolithography, the final pattern is usually formed by a thermal firing step at a temperature of 200°C or higher for 30 minutes or more after development. In the examples described in the aforementioned Patent Document 2, there is also a description of heating and hardening in an oven at 230° C. for 30 minutes. On the other hand, in recent years, from the viewpoint of reducing manufacturing costs or dealing with substrates with limited heat resistance such as plastic substrates, studies have been conducted on lowering the temperature or shortening the thermal firing step. A photosensitive resin composition that is reduced or shortened in duration and also has the same performance as before. For such performance requirements, there are known methods of using blocked isocyanate (eg, Patent Document 3), and methods of combining an epoxy group-containing material with a thermally active retarded fluorescent compound (eg, Patent Document 4). [Prior technical literature] [Patent literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2019-086745 [Patent Document 2] International Publication No. 2019/146685 [Patent Document 3] Japanese Patent No. 5708313 [Patent Document 4] Japanese Patent Laid-Open No. 2020-30290 bulletin

[Problem to be solved by the invention]

In the examples of Patent Document 3 and Patent Document 4, it is described that the desired performance can be obtained even if the thermal calcination step is set at 150° C., but there is no particular explanation on the liquid repellency. As such, the current state of the art is that the prior art related to a photosensitive resin composition that has high liquid repellency and can be cured at a lower temperature than before is not sufficient. The inventors of the present invention have found through research that using the colored photosensitive resin composition described in Patent Document 2 to form a barrier wall under the conditions of reducing the firing temperature to 90°C and shortening the firing time to 30 minutes, and spraying ink into the barrier wall, As a result, there is a problem that the ink bleeds into the barrier wall. When the ink seeps into the barrier wall, some components in the barrier wall move into the ink, which may contaminate the sprayed material, which is an existing problem. On the other hand, in Patent Documents 3 and 4, there is no relevant description of the liquid-repellent agent, and the liquid-repellent property when using the liquid-repellent agent is unknown.

Therefore, the object of the present invention is to provide a kind of photosensitive resin composition, it also has higher liquid repellency even under lower curing temperature, and the adverse situation such as ink bleed does not take place (hereinafter sometimes referred to as This property is called "bleed resistance"). Furthermore, the object of the present invention is to provide a cured product obtained by curing a photosensitive resin composition, a barrier rib made of the cured material, an organic electroluminescence element having a barrier rib, a color filter having a barrier rib, For an image display device with a barrier wall, the above-mentioned photosensitive resin composition has high liquid repellency even at a relatively low curing temperature, and does not cause problems such as ink bleeding. Also, the object of the present invention is to provide a method for producing a cured product using a photosensitive resin that has high liquid repellency even at a low curing temperature and does not cause problems such as ink bleeding. combination. [Technical means to solve problems]

As a result of earnest research, the present inventors found that the above-mentioned problems can be solved by using an alkali-soluble resin containing a specific resin in a photosensitive resin composition containing a liquid-repellent agent, and finally completed the present invention. That is, the gist of the present invention is as follows.

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

[chemical 1]

(In the formula (I), R ¹ to R ⁴ independently represent a hydrogen atom or a hydrocarbon group; n represents an integer of 0 to 2; * represents a bonding bond). [3] The photosensitive resin composition according to [1] or [2], wherein the above-mentioned copolymer resin (C1) has a repeating unit (II) containing a carboxyl group. [4] The photosensitive resin composition according to [3], wherein the repeating unit (II) containing a carboxyl group contains a repeating unit represented by the following general formula (II-1):

[Chem 2]

(In the formula (II-1), R ⁵ represents a hydrogen atom or an organic group; * represents a bonding bond). [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content ratio of the above-mentioned copolymer resin (C1) is 20% by mass based on the total solid content of the photosensitive resin composition above. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the above-mentioned (C) alkali-soluble resin further contains an alkali-soluble resin other than the above-mentioned copolymer resin (C1). [7] The photosensitive resin composition according to any one of [1] to [6], which further contains (E) a colorant. [8] The photosensitive resin composition according to any one of [1] to [7], which further contains a solvent. [9] The photosensitive resin composition according to any one of [1] to [8], which is used for thermal baking at a temperature of 140° C. or lower. [10] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [9]. [11] A barrier wall comprising the cured product described in [10]. [12] An organic electroluminescent device comprising the barrier rib according to [11]. [13] A color filter comprising the barrier rib according to [11], and further comprising luminescent nanocrystal grains. [14] An image display device comprising the barrier rib according to [11]. [15] A method for forming a cured product, which uses the photosensitive resin composition according to any one of [1] to [8], and at least includes the following steps (1) to (4), step (1) : the step of coating the above photosensitive resin composition on the substrate to form a coating film; step (2): the step of exposing at least a part of the coating film formed in the above step (1); step (3): applying the above The step of developing the exposed coating film in step (2); step (4): the step of baking the developed coating film in the above step (3). [16] The method for forming a cured product according to [15], wherein the firing temperature in the above step (4) is 140°C or lower. [17] The method for forming a cured product according to [15] or [16], wherein after the above step (3), there is a post-exposure step of exposing the coating film developed in the above step (3). [Effect of Invention]

According to the present invention, it is possible to provide a photosensitive resin composition that has high liquid repellency even at a relatively low curing temperature and that does not cause problems such as ink bleeding.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not limited to these examples in the range which does not exceed the summary. In the present invention, the following terms have the following meanings. The so-called "(meth)acrylic acid" means "either or both of acrylic acid and methacrylic acid". The so-called "total solid content" refers to the total amount of components other than the solvent in the photosensitive resin composition. Components other than solvents are included in the total amount of solids even if they are liquid at room temperature, and are not included in solvents. The numerical range indicated by "～" means the range including the numerical value recorded before and after "～" as the lower limit value and the upper limit value. The so-called "(co)polymer" means to include both homopolymer (homopolymer) and copolymer (copolymer). The so-called "(acid) anhydride" means both acid and its anhydride. The so-called "barrier wall material" refers to barrier wall material, wall material, and wall material. The so-called "blocking wall" refers to barriers, walls, walls. The "weight average molecular weight" means the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography). The so-called "acid value", unless otherwise specified, refers to the acid value converted from the effective solid content, which is calculated by the neutralization titration method.

In the present invention, the so-called barrier rib can be used, for example, to divide the functional layer (organic layer, light-emitting part) in the active-driven organic electroluminescent element, by spraying into the divided area (pixel area) as a functional layer The ink forming the material is dried and used to form, for example, pixels including functional layers and barrier ribs. In addition, it can also be used to divide pixel portions in a color filter including luminescent nanocrystal grains, and can be used to form pixels by ejecting ink into the divided regions and drying them.

[1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent as essential components . You may further contain other components as needed, for example, (E) coloring agent, (F) dispersing agent may be contained.

[1-1] Components and Composition of Photosensitive Resin Composition The components constituting the photosensitive resin composition of the present invention and their composition will be described.

[1-1-1] (A) Photopolymerizable compound The photosensitive resin composition of the present invention contains (A) a photopolymerizable compound. It is considered that the curability of the coating film is improved and the ink repellency is improved by containing the (A) photopolymerizable compound. As a photopolymerizable compound, it means a compound having one or more ethylenically unsaturated bonds in the molecule. For example, in terms of polymerizability, cross-linkability, and consequent enlargement of the difference in the solubility of the exposed part and the non-exposed part in the developing solution, it is preferable to have two or more ethylenic compounds in the molecule. Compounds with saturated bonds. The ethylenically unsaturated bond is preferably derived from a (meth)acryloxy group, and the photopolymerizable compound is more preferably a (meth)acrylate compound.

In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, and more preferably 15 or less, more preferably 10 or less, further preferably 8 or less, particularly preferably 7 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 2-15 are preferable, 2-10 are more preferable, 3-8 are still more preferable, and 5-7 are especially preferable. By making it more than the said lower limit, there exists a tendency for polymerizability to improve and ink repellency to become high. It exists in the tendency for developability to become more favorable by being below the said upper limit.

Specific examples of photopolymerizable compounds include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esters obtained by the esterification reaction of polyhydroxy compounds such as hydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.

Examples of esters of aliphatic polyols and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. ester, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerin acrylate and other aliphatic polyol acrylate; The methacrylate ester obtained by replacing the acrylate ester of these exemplary compounds with methacrylate; the itaconate ester obtained by replacing the acrylate ester of these exemplary compounds with itaconate ester; Crotonate esters obtained by substituting crotonate esters; maleate esters obtained by substituting maleate esters for acrylate esters of the exemplified compounds.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include: hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate Acrylate and methacrylate of aromatic polyhydroxy compounds such as acrylate and pyrogallol triacrylate.

As the ester obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids, it does not necessarily have to be a single substance. If representative specific examples are given, for example, List: 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, Acrylic acid, Hexadiene Condensate of acid, butanediol and glycerin.

In addition, as an example of a polyfunctional vinyl monomer, it is useful to react a polyisocyanate compound with a hydroxyl-containing (meth)acrylate, or to react a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate. Obtained urethane (meth)acrylates; epoxy acrylates such as addition reaction products of polyepoxides with hydroxy (meth)acrylates or with (meth)acrylic acid; Acrylamides such as bisacrylamide; Allyl esters such as diallyl phthalate; Vinyl-containing compounds such as divinyl phthalate.

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

From the viewpoint of the adhesion between the barrier rib and the substrate and the ink repellency, it is preferable to use an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, or a urethane ( Meth) acrylates, more preferably dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, 2-tri(meth)acryl Oxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dibasic anhydride adduct of dipentaerythritol penta(meth)acrylate, pentaerythritol tri(meth)acrylate Dibasic anhydride adducts of (meth)acrylates. (A) One type of photopolymerizable compound may be used alone, or two or more types may be used in combination.

(A) The molecular weight of the photopolymerizable compound is not particularly limited, but is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more, more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and more preferably 1000 or less, more preferably 700 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 100-1000, more preferably 150-1000, still more preferably 200-1000, still more preferably 300-700, still more preferably 400-700, especially preferably 500-700.

(A) The carbon number of the photopolymerizable compound is not particularly limited, but is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, and still more preferably 15 or more from the viewpoint of ink repellency and residue suppression. 20 or more, particularly preferably 25 or more, and preferably 50 or less, more preferably 40 or less, further preferably 35 or less, especially preferably 30 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 7-50 is preferable, 10-50 is more preferable, 15-40 is more preferable, 20-35 is still more preferable, 25-30 is especially preferable.

In terms of ink repellency and formation of high-definition barrier ribs with thinner line widths, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred. Base) acrylates; more preferably pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. Esters of (meth)acrylates, 2,2,2-tri(meth)acryloxymethylethyl phthalate, dibasic anhydrides of dipentaerythritol penta(meth)acrylate The adducts of acid anhydrides and trifunctional or higher ester (meth)acrylates.

From the viewpoint of improving the bleeding resistance of the barrier wall, it is preferable to use ester (meth)acrylates, epoxy (meth)acrylates, and urethanes having one or more hydroxyl groups in the molecule. ester (meth)acrylates, more preferably pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, glycidyl (meth)acrylate (addition number 1~3) Adducts with glycerin, adducts of glycidyl (meth)acrylate (addition number 1~4) and pentaerythritol, glycidyl (meth)acrylate (addition number 1~6) and di Adducts of pentaerythritol, adducts of glycidyl (meth)acrylate (addition number 1 to 6) and sorbitol, glycidyl acrylate (addition number 2) and 3-butene-1,2-di Alcohol adducts, reactants of diglycidylated bisphenols with (meth)acrylic acid and alkylene oxide modified products. Two or more of these may be used in combination.

(A) The hydroxyl equivalent of the photopolymerizable compound is preferably at most 1200 g/mol, more preferably at most 800 g/mol, still more preferably at most 400 g/mol, still more preferably at most 350 g/mol, especially preferably 300 g/mol or less, and preferably 100 g/mol or more, more preferably 150 g/mol or more, still more preferably 200 g/mol or more, especially preferably 225 g/mol or more. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, preferably 100-1200 g/mol, more preferably 150-600 g/mol, further preferably 200-400 g/mol, further preferably 225-350 g/mol, especially preferably 225-300 g /mol. There exists a tendency for the developability and the bleeding resistance of a barrier rib to improve by being below the said upper limit, and it exists in the tendency for ink repellency to improve by making it more than the said lower limit.

The content ratio of the (A) photopolymerizable compound in the photosensitive resin composition of the present invention is not particularly limited, but it is preferably at least 1% by mass, more 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, and more preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably Preferably it is 60 mass % or less, More preferably, it is 50 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-80 mass % is preferable, 5-80 mass % is more preferable, 10-70 mass % is more preferable, 15-60 mass % is still more preferable, 25-50 mass % is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, there exists a tendency for the formation of the high-definition barrier rib with a narrow line width to be possible.

The content ratio of (A) photopolymerizable compound with respect to 100 mass parts of (C) alkali-soluble resins is not specifically limited, Preferably it is 1 mass part or more, More preferably, it is 5 mass parts or more, More preferably, it is 10 mass parts or more , and more preferably more than 15 parts by mass, more preferably more than 20 parts by mass, more preferably more than 25 parts by mass, most preferably more than 30 parts by mass, and more preferably less than 200 parts by mass, more preferably 180 parts by mass Part or less, More preferably, 160 parts by mass or less, Even more preferably, 140 parts by mass or less, Most preferably, 120 parts by mass or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, preferably 1 to 200 parts by mass, more preferably 5 to 180 parts by mass, further preferably 10 to 160 parts by mass, further preferably 15 to 140 parts by mass, further preferably 20 to 125 parts by mass, especially Preferably, it is 30-125 mass parts, Most preferably, it is 50-105 mass parts. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, there exists a tendency for the formation of the high-definition barrier rib with a narrow line width to be possible.

[1-1-2] (B) Photopolymerization initiator The photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. (B) As long as the photopolymerization initiator is a compound that polymerizes the (A) photopolymerizable compound under the action of active light, for example, a compound that polymerizes the ethylenically unsaturated bond of the (A) photopolymerizable compound, No particular limitation.

The photosensitive resin composition of this invention can use the photoinitiator commonly used in this field as (B) photoinitiator. As such a photopolymerization initiator, for example, a metallocene compound containing a titanocene compound described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197; The hexaarylbiimidazole derivatives described in the publication No. 2000-56118; the halomethylated oxadiazole derivatives and the halomethyl symmetrical trioxazole derivatives described in the Japanese Patent Application Laid-Open No. 10-39503 , N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other free radical activators , α-Aminobenzophenone derivatives; oxime ester compounds described in Japanese Patent Application Laid-Open No. 2000-80068 and Japanese Patent Laid-Open No. 2006-36750.

Examples of metallocene compounds include dicyclopentadienyl titanium dichloride, diphenyl dicyclopentadienyl titanium, bis(2,3,4,5,6-pentafluorophenyl)dicyclopentadiene Dienyl titanium, bis(2,3,5,6-tetrafluorophenyl) dicyclopentadienyl titanium, bis(2,4,6-trifluorophenyl) dicyclopentadienyl titanium, di (2,6-difluorophenyl)dicyclopentadienyl titanium, bis(2,4-difluorophenyl)dicyclopentadienyl titanium, bis(2,3,4,5,6-penta Fluorophenyl)bis(methylcyclopentadienyl)titanium, bis(2,6-difluorophenyl)bis(methylcyclopentadienyl)titanium, [2,6-di-fluoro-3- (Pyrrol-1-yl)-phenyl] dicyclopentadienyl titanium.

Examples of biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis (3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

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

Examples of halomethyl symmetrical trioxetine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)symmetric trioxetine, 2-(4-methoxy Naphthyl)-4,6-bis(trichloromethyl)symmetric trisulfone, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)symmetric trisulfite, 2-(4 -Ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)symmetric trisulfone.

Examples of α-aminophenanone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl -2-Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4 -morpholinylphenyl)butan-1-one, 3,6-bis(2-methyl-2-morpholinylpropionyl)-9-octylcarbazole.

As a photopolymerization initiator, especially in terms of sensitivity or plate-making properties, oxime ester-based compounds are effective. For example, when using an alkali-soluble resin containing a phenolic hydroxyl group, it is disadvantageous in terms of sensitivity. Therefore, such Oxime ester compounds with excellent sensitivity are particularly useful. Due to the high quantum yield of the photoreaction and the high activity of the generated free radicals, the oxime ester compound has a high sensitivity even in a small amount and remains stable in the thermal reaction, and can obtain high-sensitivity photosensitivity with a small amount resin composition.

As an oxime ester compound, the compound represented by following general formula (IV) is mentioned, for example.

[Chem 3]

In 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. R ^21b represents any substituent including an aromatic ring. R ^22a represents an alkanoyl group which may have a substituent, or an arayl group which may have a substituent. n represents an integer of 0 or 1.

The carbon number of the alkyl group in R ^21a is not particularly limited, but it is preferably at least 1, more preferably at least 2, and more preferably at most 20, even more preferably from the viewpoint of solubility or sensitivity in a solvent. 15 or less, and more preferably 10 or less. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, and cyclohexylmethyl. Examples of substituents that the alkyl group may have include: aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, amido group, 4-(2-methoxy-1-methyl)ethoxy- 2-methylphenyl, N-acetyl-N-acetyloxyamine. From the viewpoint of easy synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group in R ^21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Moreover, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and more preferably 12 or less. For example, 5-30 are preferable, 5-20 are more preferable, and 5-12 are still more preferable.

As an aromatic ring group, a phenyl group, a naphthyl group, a pyridyl group, and a furyl group are mentioned, for example. From the viewpoint of developability, phenyl or naphthyl is preferred, and phenyl is more preferred. Examples of substituents that the aromatic ring group may have include: hydroxyl group, carboxyl group, halogen atom, amino group, amido group, alkyl group, alkoxy group, and groups formed by linking these substituents. From the standpoint, it is preferably an alkyl group, an alkoxy group, or a group formed by connecting these, more preferably a group formed by connecting an alkoxy group. From the viewpoint of sensitivity, R ^21a is preferably an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

基或可經取代之二苯硫醚基、可經取代之茀基或可經取代之吲哚基。就感度之觀點而言，更佳為可經取代之咔唑基。 R ^21b is preferably carbazolyl which may be substituted, or 9-oxothiol which may be substituted

or a substituted diphenylsulfide group, a substituted fenyl group or a substituted indolyl group. From the viewpoint of sensitivity, it is more preferably a carbazolyl group which may be substituted.

The carbon number of the alkyl group in R ^22a is not particularly limited, but it is preferably 2 or more, preferably 20 or less, more preferably 15 or less, from the viewpoint of solubility in a solvent or sensitivity. Preferably it is 10 or less, More preferably, it is 5 or less. For example, 2-20 is preferable, 2-15 is more preferable, 2-10 is still more preferable, 2-5 is still more preferable. As an alkyl group, an acetyl group, an ethanoyl group, a propionyl group, and a butyryl group are mentioned, for example. Examples of substituents 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 amido group. From the viewpoint of easy synthesis, it is preferably unsubstituted.

The carbon number of the aryl group in R ^22a is not particularly limited, but it is preferably 7 or more, preferably 20 or less, more preferably 15 or less, from the viewpoint of solubility or sensitivity in a solvent. Preferably it is 10 or less. For example, 7-20 are preferable, 7-15 are more preferable, and 7-10 are still more preferable. As an aryl group, a benzoyl group and a naphthyl group are mentioned, for example. Examples of the substituent that the aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, and an alkyl group. From the viewpoint of easy synthesis, it is preferably unsubstituted.

From the viewpoint of sensitivity, R ^22a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and more preferably an acetyl group.

For example, Japanese Patent No. 4454067, International Publication No. 2002/100903, International Publication No. 2012/45736, International Publication No. 2015/36910, International Publication No. 2006/18973, International Publication No. 2008/78678, Japanese Patent No. 4818458, International Publication No. 2005/80338, International Publication No. 2008/75564, International Publication No. 2009/131189, International Publication No. 2010/133077, International Publication No. 2010/102502, A photopolymerization initiator described in International Publication No. 2012/68879.

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

色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報中記載之包含雜環之香豆素色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報中記載之3-酮基香豆素化合物；日本專利特開平6-19240號公報中記載之吡咯甲川色素；日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本專利特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報中記載之具有二烷基胺基苯骨架之色素。In order to improve the sensitivity, if necessary, a sensitizing pigment and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be prepared in the photopolymerization initiator. As a sensitizing dye, for example, the pigments described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756 can be cited.

Pigment; Japanese Patent Laid-Open Publication No. 3-239703 and Japanese Patent Laid-Open Publication No. 5-289335, which contain heterocyclic coumarin pigments; The 3-ketocoumarin compound recorded in the Publication No. 2; the pyrromethene pigment described in the Japanese Patent Application Publication No. 6-19240; the Japanese Patent Application Publication No. 47-2528, and the Japanese Patent Application Publication No. 54-155292 Gazette, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-15503, Japanese Patent Laid-Open No. Publication No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Pigments having a dialkylaminobenzene skeleton described in JP-A-5-210240 and JP-A-4-288818.

The sensitizing dye is preferably an amino group-containing sensitizing dye, more preferably a compound containing an amino group and a phenyl group in the same molecule. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminodiphenyl Benzophenone-based compounds such as ketone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, etc., 2- (p-Dimethylaminophenyl)benzoxazole, 2-(p-Diethylaminophenyl)benzoxazole, 2-(p-Dimethylaminophenyl)benzo[4,5 ]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3, 4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzene and imidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethyl Aminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethyl Aminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine and other compounds containing p-dialkylaminophenyl groups; especially 4,4'-dialkylaminobenzophenone. One kind of sensitizing pigment can be used alone, or two or more kinds can be used in combination.

As a polymerization accelerator, for example, ethyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4- Aromatic amines such as dimethylaminoacetophenone and 4-dimethylaminopropiophenone, aliphatic amines such as n-butylamine, N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate . A polymerization accelerator may be used alone or in combination of two or more.

The content ratio of the photopolymerization initiator (B) in the photosensitive resin composition of the present invention is not particularly limited, but it is preferably 0.01% by mass or more, more preferably with respect to the total solid content of the photosensitive resin composition 0.1 mass % or more, more preferably 1 mass % or more, still more preferably 2 mass % or more, especially preferably 3 mass % or more, and more preferably 25 mass % or less, more preferably 20 mass % or less, Furthermore, it is more preferably 15 mass % or less, still more preferably 12 mass % or less, especially preferably 10 mass % or less, most preferably 8 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, still more preferably 0.1 to 15% by mass, still more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, especially Preferably, it is 3 to 7% by mass. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

The ratio of (B) photopolymerization initiator to (A) photopolymerizable compound in the photosensitive resin composition is preferably 1 part by mass or more with respect to 100 parts by mass of (A) photopolymerizable compound, More preferably at least 2 parts by mass, more preferably at least 4 parts by mass, even more preferably at least 6 parts by mass, especially preferably at least 10 parts by mass, and more preferably at most 200 parts by mass, more preferably at least 100 parts by mass or less, more preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-200 mass parts is preferable, 3-200 mass parts is more preferable, 5-100 mass parts is still more preferable, 8-50 mass parts is still more preferable, 10-20 mass parts is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

A chain transfer agent and a photopolymerization initiator can also be used together. Examples of the chain transfer agent include mercapto group-containing compounds and carbon tetrachloride. From the point of view that the chain transfer effect tends to be higher, it is more preferable to use a mercapto group-containing compound. The reason for this is considered to be that since the S-H bonding energy is small, bond breaking occurs easily, and a hydrogen abstraction reaction or a chain transfer reaction easily occurs. Use of a chain transfer agent is effective for improving sensitivity or surface hardening.

As a compound containing mercapto groups, there may be multiple mercapto groups in the molecule. Examples of mercapto-containing compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H)-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other mercapto-containing compounds with aromatic rings; hexanedithiol, decanedithiol, butanediol bis(3- mercaptopropionate), butanediol dimercaptopropionate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptopropionate, trimethylolpropane tris(3-mercaptopropionate) ), trimethylolpropane trimercaptoacetate, trihydroxyethyl trimercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis( 3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tri( 3-Mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione Such as aliphatic mercapto-containing compounds.

As the mercapto group-containing compound having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable. As an aliphatic mercapto group-containing compound, 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-mercaptobutoxy Ethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione.

In terms of sensitivity, it is preferably an aliphatic mercapto-containing compound, more preferably 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-tris-2,4,6(1H,3H,5H)-trione, more preferably pentaerythritol tetrakis(3-mercaptopropionic acid esters), pentaerythritol tetrakis(3-mercaptobutyrate). One type of aliphatic mercapto group-containing compound can be used alone, or two or more types can be used in combination.

From the point of view of increasing the cone angle, it is suitable to combine one or two or more kinds selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole with photopolymerization. Initiator combination, used as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.

From the viewpoint of sensitivity, it is preferable to use one or two or more selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate). From the viewpoint of sensitivity, it is further preferred to use one or more of the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole, and one or more selected from the group consisting of pentaerythritol One or more of the group consisting of tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are used in combination with a photopolymerization initiator.

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content ratio of the chain transfer agent is not particularly limited, but it is preferably 0.01% by mass or more with respect to the total solid content of the photosensitive resin composition. More preferably at least 0.1% by mass, more preferably at least 0.5% by mass, still more preferably at least 0.8% by mass, more preferably at most 5% by mass, more preferably at most 4% by mass, further preferably at most 3% by mass % or less, more preferably 2 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, further preferably 0.5 to 3% by mass, and particularly preferably 0.8 to 2% by mass. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, there exists a tendency for the formation of the high-definition barrier rib with a narrow line width to be possible.

As the content ratio of the chain transfer agent in the photosensitive resin composition relative to (B) photopolymerization initiator, it is preferably 5 mass parts or more with respect to (B) 100 mass parts of photopolymerization initiator, more preferably More than 10 parts by mass, more preferably more than 15 parts by mass, especially preferably more than 20 parts by mass, more preferably less than 500 parts by mass, more preferably less than 300 parts by mass, further preferably less than 100 parts by mass, especially Preferably, it is 50 mass parts or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 5-500 mass parts is preferable, 10-300 mass parts is more preferable, 15-100 mass parts is still more preferable, 20-50 mass parts is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, there exists a tendency for the formation of the high-definition barrier rib with a narrow line width to be possible.

[1-1-3] (C) Alkali-soluble resin The photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. (C) The alkali-soluble resin contains a copolymer resin (C1) having a repeating unit including an aliphatic polycyclic structure in the main chain (hereinafter sometimes abbreviated as "copolymer resin (C1)"). It is considered that by having a repeating unit with an aliphatic polycyclic structure in the main chain, there is a repeating unit with a structure that is not as rigid as an aromatic hydrocarbon ring structure, but has a large stereo volume. Therefore, using a certain degree of flexibility, photohardening and /or when the reaction points are close to each other during the thermosetting reaction, the progress of the hardening reaction will not be excessively inhibited, and then, after hardening, the large-volume structure can be used to show the function of effectively inhibiting the penetration of ink, etc. (hereinafter sometimes referred to as anti-bleeding) sex).

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

[chemical 4]

In formula (I), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group. n represents an integer of 0-2. ＊Indicates a bonding key.

<Repeating Unit (I)> In formula (I), R ¹ to R ⁴ are each independently a hydrogen atom or a hydrocarbon group. As a hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, an aromatic ring group, and an aralkyl group are mentioned, for example.

As the alkyl group, any of linear, branched and cyclic may be used. The carbon number of the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 3 or more, further preferably 6 or more, and is preferably 15 or less, more preferably 8 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-15 are preferable, 3-15 are more preferable, and 6-8 are still more preferable. There exists a tendency for ink bleed resistance to become favorable by making it more than the said lower limit. Developability tends to become favorable by making it below the said upper limit. Examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, pentyl, neopentyl, hexyl, heptyl base, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl, cyclooctyl.

The carbon number of the alkenyl group is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and is preferably 10 or less, more preferably 8 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 2-10 are preferable, and 3-8 are more preferable. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. Developability tends to become favorable by making it below the said upper limit. As an alkenyl group, a vinyl group, an allyl group, a butenyl group, and a pentenyl group are mentioned, for example.

The number of carbon atoms in the alkynyl group is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and is preferably 10 or less, more preferably 8 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 2-10 are preferable, and 3-8 are more preferable. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. Developability tends to become favorable by making it below the said upper limit. As an alkynyl group, an ethynyl group and a propargyl group are mentioned, for example.

As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned, for example. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, still more preferably 10 the following. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. Developability tends to become favorable by making it below the said upper limit. Examples of the aromatic ring group include phenyl, naphthyl, tolyl, and xylyl.

The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 5 or more, more preferably 6 or more, further preferably 7 or more, and is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. . The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 5-20 are preferable, 6-15 are more preferable, and 7-10 are still more preferable. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. Developability tends to become favorable by making it below the said upper limit. As an aralkyl group, the group which replaced one hydrogen atom of the said alkyl group by the said aromatic ring group is mentioned, for example. Examples thereof include benzyl and phenethyl.

R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, R ¹ and R ⁴ may be linked to form a ring structure, similarly, R ² and R ³ may be linked to form a ring structure. From the viewpoint of ease of synthesis, it is preferable that any of R ¹ to R ⁴ is a hydrogen atom, and it is more preferable that all of R ¹ to R ⁴ are hydrogen atoms.

n represents an integer of 0-2, and n is preferably 0 from the viewpoint of developability.

As the repeating unit (I), repeating units represented by the following general formulas (I-1) to (I-3) can be mentioned, and the following general formula (I-1) is more preferable from the viewpoint of bleeding resistance. ) represents the repeating unit.

[chemical 5]

＜Repeating unit (II)＞ The copolymer resin (C1) preferably has a repeating unit (II) containing a carboxyl group (hereinafter sometimes referred to as "repeating unit (II)"). The structure of the repeating unit (II) containing a carboxyl group is not particularly limited, and examples thereof include repeating units derived from unsaturated group-containing carboxylic acids or unsaturated group-containing carboxylic acid anhydrides. From the viewpoint of having both developability and anti-bleeding property, and the strength of these properties can be adjusted as needed, it is preferable to contain a repeating unit represented by the following general formula (II-1) (hereinafter sometimes referred to as "repeating unit") Unit (II-1)").

[chemical 6]

In formula (II-1), R ⁵ represents a hydrogen atom or an organic group. ＊Indicates a bonding key.

As an organic group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are mentioned. The carbon number of the alkyl group and aryl group is preferably 1-18.

When R ⁵ is an alkyl group, the carbon number is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, and is preferably 9 or less, more preferably 7 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-9 are preferable, 2-9 are more preferable, and 4-7 are still more preferable. Examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, pentyl, neopentyl, hexyl, heptyl base, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl, cyclooctyl.

When R ⁵ is an aryl group, the carbon number is not particularly limited, but is preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 6-20 are preferable, 6-15 are more preferable, and 6-10 are still more preferable. As an aryl group, a phenyl group, a naphthyl group, a tolyl group, and a xylyl group are mentioned, for example.

As a substituent which an alkyl group and an aryl group may have, a hydroxyl group and a (meth)acryl group are mentioned, for example.

From the viewpoint of bleeding resistance, R ⁵ is more preferably a unit having a structure represented by the following general formula (II-2).

[chemical 7]

In formula (II-2), R ⁶ represents a hydrogen atom or a methyl group. e represents an integer of 1-5. ＊Indicates a bonding key.

In formula (II-2), e is preferably 1-3, more preferably 1-2 from the viewpoint of bleeding resistance.

As the repeating unit (II-1), it is more preferably any of the repeating units represented by the following general formulas (II-3) to (II-6), especially preferably the following general formula (II-3) or the following A repeating unit represented by general formula (II-4).

[chemical 8]

In formulas (II-3) to (II-6), * represents a bond.

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

[chemical 9]

In formulas (III-1) to (III-4), R ⁵ has the same meaning as in formula (II-1), and R ⁷ represents a hydrogen atom or a methyl group. ＊Indicates a bonding key.

[chemical 10]

In formula (III-5), R ⁸ represents an alkyl group which may have a substituent. ＊Indicates a bonding key.

By having the repeating unit represented by the formula (III-5), there is a tendency for the heat resistance of the copolymer resin (C1) to be optimized.

Examples of the optionally substituted alkyl group in R ⁸ include methyl, ethyl, propyl, and benzyl.

In terms of surface smoothness and bleeding resistance, the copolymer resin (C1) preferably has repeating unit (I), repeating unit (II-1) and repeating unit (III-1), more preferably has repeating Unit (I), repeating unit (II-1), repeating unit (III-1) and repeating unit (III-4).

[Manufacturing method of copolymer resin (C1)] The method for producing the copolymer resin (C1) is not particularly limited, and a conventionally known method can be used. For example, it can be produced according to the following (step i) to (step iii). Furthermore, the ring-opened precursor polymer obtained in (step ii) can also be used as the copolymer resin (C1).

(Step i) A precursor polymer comprising the repeating unit represented by the formula (I) and the repeating unit represented by the above formula (III-4) is prepared.

(Step ii) Make the above-mentioned precursor polymer react with alcohols or water, so that the acid anhydride skeleton in the above-mentioned formula (III-4) is ring-opened, and a carboxyl group or its ester is generated in the precursor polymer to obtain a ring-opened precursor polymer.

As the alcohols used in (step ii), it is more preferable to use a compound represented by the following general formula (II-2-1) from the viewpoint of bleeding resistance.

[chemical 11]

In formula (II-2-1), R ⁶ and e have the same meaning as in formula (II-2).

(Step iii) optionally reacting the ring-opened precursor polymer obtained in (Step ii) with a compound having an epoxy group and an ethylenic double bond.

As a compound which has an epoxy group and an ethylenic double bond, glycidyl methacrylate is mentioned, for example.

The copolymer resin (C1) can also be produced according to the methods described in, for example, International Publication No. 2016/194619 or International Publication No. 2017/154439.

The content ratio of the repeating unit (I) in the copolymer resin (C1) is not particularly limited, but in the copolymer resin (C1), it is preferably at least 10% by mass, more preferably at least 20% by mass, still more preferably at least 25% by mass % or more, and preferably at most 50% by mass, more preferably at most 40% by mass, further preferably at most 30% by mass. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 10-50 mass % is preferable, 20-40 mass % is more preferable, and 25-30 mass % is still more preferable. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. Developability tends to become favorable by making it below the said upper limit.

The content ratio of the repeating unit (I) in the copolymer resin (C1) is not particularly limited, but it is preferably at least 20 mol%, more preferably at least 30 mol%, and still more preferably 40 mol% of all repeating units. mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, further preferably 60 mol% or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and still more preferably 40 to 60 mol%. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. Developability tends to become favorable by making it below the said upper limit.

When the copolymer resin (C1) has a repeating unit (II-1), its content rate is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, in all repeating units. Furthermore, it is more preferably at least 15 mol%, and more preferably at most 40 mol%, more preferably at most 30 mol%, and still more preferably at most 20 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and still more preferably 15 to 20 mol%. Developability tends to be favorable by setting it as more than the said lower limit. Bleeding resistance tends to be favorable by being below the said upper limit.

When the copolymer resin (C1) has a repeating unit (III-1), its content rate is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, in all repeating units, Furthermore, it is more preferably at least 15 mol%, and more preferably at most 40 mol%, more preferably at most 30 mol%, and still more preferably at most 20 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and still more preferably 15 to 20 mol%. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. Developability tends to become favorable by making it below the said upper limit.

When the copolymer resin (C1) has a repeating unit (III-4), its content rate is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, in all repeating units, Furthermore, it is more preferably at least 15 mol%, and more preferably at most 40 mol%, more preferably at most 30 mol%, and still more preferably at most 20 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and still more preferably 15 to 20 mol%. By making it more than the said lower limit, there exists a tendency for synthesis|combination to be easy. Bleeding resistance and developability tend to be favorable by being below the said upper limit.

When the copolymer resin (C1) has repeating unit (II-1), repeating unit (III-1) and repeating unit (III-4), relative to the repeating unit (II-1) in the copolymer resin (C1) . The total content ratio of the repeating unit (III-1) and the repeating unit (III-4), the content ratio of the repeating unit (II-1) is preferably at least 10 mol%, more preferably at least 20 mol%, Furthermore, it is more preferably at least 30 mol%, and more preferably at most 90 mol%, more preferably at most 70 mol%, and still more preferably at most 50 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 10 to 90 mol%, more preferably 20 to 70 mol%, and still more preferably 30 to 50 mol%. Developability tends to be favorable by setting it as more than the said lower limit. Bleeding resistance tends to be favorable by being below the said upper limit.

The acid value of the copolymer resin (C1) is not particularly limited, but is preferably at least 10 mgKOH/g, more preferably at least 30 mgKOH/g, further preferably at least 50 mgKOH/g, and more preferably at least 200 mgKOH/g Below, more preferably below 150 mgKOH/g, still more preferably below 100 mgKOH/g, especially preferably below 80 mgKOH/g. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 10-200 mgKOH/g, more preferably 10-150 mgKOH/g, still more preferably 30-100 mgKOH/g, especially preferably 50-80 mgKOH/g. There exists a tendency for developability to improve by making it more than the said lower limit. Image development adhesiveness tends to improve by making it below the said upper limit.

The weight average molecular weight (Mw) of the copolymer resin (C1) is not particularly limited, but is preferably at least 2000, more preferably at least 3000, further preferably at least 4000, still more preferably at least 5000, especially preferably at least 6000, and , preferably 35,000 or less, more preferably 20,000 or less, further preferably 15,000 or less, especially preferably 10,000 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 2000-35000, more preferably 3000-35000, still more preferably 4000-20000, still more preferably 5000-15000, especially preferably 6000-10000. Image development adhesiveness tends to improve by making it more than the said lower limit. Developability tends to become favorable by making it below the said upper limit.

The double bond equivalent of the copolymer resin (C1) is not particularly limited, but is preferably at least 200, more preferably at least 300, further preferably at least 400, especially preferably at least 500, and is preferably at most 800, more preferably at least 800. 700 or less, more preferably 600 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 200-800 is preferable, 300-800 is more preferable, 400-700 is further more preferable, 500-600 is especially preferable. Developability tends to be favorable by setting it as more than the said lower limit. Bleeding resistance tends to be favorable by being below the said upper limit.

The content ratio of the copolymer resin (C1) is not particularly limited, but is preferably at least 5% by mass, more preferably at least 10% by mass, and still more preferably 20% by mass, based on the total solid content of the photosensitive resin composition or more, more preferably at least 30% by mass, particularly preferably at least 40% by mass. Moreover, it is preferably 80 mass % or less, more preferably 60 mass % or less, and still more preferably 50 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 5-80 mass % is preferable, 10-80 mass % is more preferable, 20-60 mass % is more preferable, 30-60 mass % is still more preferable, 40-50 mass % is especially preferable. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. By setting it as below the said upper limit, it exists in the tendency for image development to become easy to become solution image development.

(C) The content ratio of the copolymer resin (C1) in the alkali-soluble resin is not particularly limited, but is preferably at least 20% by mass, more preferably at least 30% by mass, still more preferably at least 40% by mass, especially preferably at least 45% by mass. % by mass or more, and preferably not more than 100% by mass. For example, 20-100 mass % is preferable, 30-100 mass % is more preferable, 40-100 mass % is still more preferable, and 45-100 mass % is especially preferable. Bleeding resistance tends to be favorable by setting it as more than the said lower limit. By setting it as below the said upper limit, it exists in the tendency for image development to become easy to become solution image development.

The (C) alkali-soluble resin in the photosensitive resin composition of the present invention may further contain alkali-soluble resins other than the copolymer resin (C1) (hereinafter sometimes referred to as "other alkali-soluble resins"). By containing other alkali-soluble resins, not only the bleeding resistance described above is maintained, but also further characteristics including improvement of developability can be imparted, so it is preferable.

As another alkali-soluble resin, it is preferable to include epoxy (meth)acrylate resin (C2) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin) other than copolymer resin (C1) from the viewpoint of developing solubility. ) acrylate resin (C2)"), more preferably an epoxy (meth)acrylate resin (C2) having an aromatic ring in the main chain. From the viewpoint of ink repellency, it is preferable to include an acrylic copolymer resin (C3) having an ethylenically unsaturated group in a side chain (hereinafter sometimes referred to as "acrylic copolymer resin (C3)").

[Epoxy (meth)acrylate resin (C2)] Epoxy (meth)acrylate resin (C2) is an addition of ethylenically unsaturated monocarboxylic acid or ester compound to epoxy resin, optionally mixed with isocyanate The resin obtained by reacting the acid-based compound with polybasic acid or its anhydride. For example, the following are listed: Adding an ethylenically unsaturated group to an epoxy resin via an ester bond (-COO-) by ring-opening and adding a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin , and a carboxyl group of polybasic anhydride is added to the hydroxyl group formed at this time. When adding a polybasic acid anhydride, the thing which adds and adds a polyhydric alcohol simultaneously is also mentioned.

The above-mentioned epoxy (meth)acrylate resin (C2) also includes the resin obtained by further reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.

Examples of the epoxy resin include: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenol novolak epoxy resin Oxygen resin, Trisphenol epoxy resin, Polymerized epoxy resin of phenol and dicyclopentadiene, Dihydroxy fluorine type epoxy resin, Dihydroxy alkoxy fluorine type epoxy resin, 9,9-bis(4' Diglycidyl etherate of -hydroxyphenyl) terpene, diglycidyl etherate of 1,1-bis(4'-hydroxyphenyl)adamantane, epoxy resin with aromatic ring in the main chain can be preferably used .

As the epoxy resin, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and polymerized epoxy resin of phenol and dicyclopentadiene are preferable from the viewpoint of heat resistance , 9,9-bis(4'-hydroxyphenyl) diglycidyl etherate, and more preferably bisphenol A epoxy resin.

As the epoxy resin, for example, a bisphenol A type epoxy resin (for example, "jER (registered trademark, the same below) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, Japan "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Chemical Pharmaceutical Company, bisphenol F type resin (such as "jER807", "jER4004P", "jER4005P", "jER4007P" manufactured by Mitsubishi Chemical Corporation , "NER-7406" (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., bisphenol S-type epoxy resin, biphenyl glycidyl ether (such as "jERYX-4000" manufactured by Mitsubishi Chemical Corporation) "), phenol novolak type epoxy resin (such as "EPPN-201" manufactured by Nippon Kayaku Corporation, "jER152" and "jER154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company), (o-, m-, p-)cresol novolak type epoxy resins (such as "EOCN (registered trademark, the same below)-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), iso Triglycidyl cyanurate (such as "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenol methane-type epoxy resin (such as "EPPN (registered trademark, the same below)-501" manufactured by Nippon Kayaku Co., Ltd. EPPN-502", "EPPN-503"), alicyclic epoxy resin ("Celloxide (registered trademark, the same below) 2021P", "Celloxide EHPE" manufactured by DAICEL Co., Ltd.), which will be prepared by reacting dicyclopentadiene with phenol Epoxy resin obtained by glycidylating the obtained phenolic resin (such as "EXA-7200" manufactured by DIC Corporation, "NC-7300" and "XD-1000" manufactured by Nippon Kayaku Corporation), biphenyl type epoxy resin Resin (such as "NC-7000" manufactured by Nippon Kayaku Co., Ltd.), "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd.; more preferably "XD-1000" manufactured by Nippon Kayaku Co., Ltd. "NC-3000", "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. One type of epoxy resin can be used alone, or two or more types can be used in combination.

Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and pentaerythritol tri(meth)acrylic acid. Ester 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, reaction product of (meth)acrylic acid and ε-caprolactone, from the viewpoint of sensitivity , preferably (meth)acrylic acid. One type of ethylenically unsaturated monocarboxylic acid may be used alone, or two or more types may be used in combination.

Examples of the polybasic acid (acid anhydride) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methanoic acid, and Basetetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4- Methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, Phenylenetetracarboxylic acid and their anhydrides are preferably succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, six Hydrogen phthalic anhydride, more preferably succinic anhydride and tetrahydrophthalic anhydride. One kind of polybasic acid (anhydride) can be used alone, or two or more kinds can be used in combination.

By using polyhydric alcohol, there is a tendency to increase the molecular weight of the epoxy (meth)acrylate resin (C2), introduce branched chains into the molecule, and tend to balance the molecular weight and viscosity. Also, it tends to increase the rate of introduction of acid groups into the molecule, and tend to balance sensitivity and adhesiveness. As the polyhydric alcohol, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol are preferable. One type of polyol may be used alone, or two or more types may be used in combination.

Examples of the epoxy (meth)acrylate resin (C2) include resins described in Korean Laid-Open Patent No. 10-2013-0022955 in addition to the resins described above.

From the viewpoint of developing solubility, the epoxy (meth)acrylate resin (C2) preferably contains an epoxy (meth)acrylate resin ( Hereinafter sometimes referred to as "epoxy (meth)acrylate resin (C2-1)"), and epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii) (hereinafter sometimes At least one of the group consisting of "epoxy (meth)acrylate resin (C2-2)").

[chemical 12]

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

[chemical 13]

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

＜Epoxy (meth)acrylate resin (C2-1)＞

[chemical 14]

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

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

Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. Among them, a straight-chain aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic aliphatic group is preferable from the viewpoint of reducing penetration of the developing solution into the exposed portion. . The carbon number of the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, further preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, further preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 are preferable, 3-15 are more preferable, and 6-10 are still more preferable. There exists a tendency for film strength to improve by making it more than the said lower limit. There exists a tendency for ink repellency to improve by being below the said upper limit.

Examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, and n-heptyl. From the viewpoint of ink repellency or production cost, methylene is preferred. Examples of the divalent branched aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups having, for example, one or more divalent straight-chain aliphatic groups. , Second butyl, third butyl as the structure of the side chain.

The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, and 2-5 are more preferable. There exists a tendency for film strength to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit. Examples of divalent cyclic aliphatic groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, dicyclopentane rings, and northane rings having two free atomic valences. ring, iso-alkane ring, adamantane ring. From the viewpoint of film strength and developability, an adamantane ring and a dicyclopentane ring having two free atomic valences are preferable.

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

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number of the divalent aromatic ring group is preferably at least 4, more preferably at least 5, still more preferably at least 6, and is preferably at most 20, more preferably at most 15, even more preferably at most 10. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. There exists a tendency for film strength to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

環、聯三伸苯環、苊環、螢蒽環、茀環。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of divalent aromatic hydrocarbon ring groups include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring.

The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, and oxadiazole rings having two free atomic valences. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridine ring, pyrimidine ring, three sulfa ring, quinoline ring, isoquinoline ring, phenoline ring, quinoline ring Ozoline ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring. From the viewpoint of production cost, a benzene ring and a naphthalene ring having two free atomic valences are preferable, and a benzene ring having two free atomic valences is more preferable.

As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. From the viewpoint of curability, it is preferably unsubstituted.

Examples of groups in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include: one or more divalent aliphatic groups described above and one or more divalent aromatic ring groups described above. The base formed by linking ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, further preferably 3 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. There exists a tendency for developability to improve by making it more than the said lower limit. There exists a tendency for film strength to improve by making it below the said upper limit. The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, further preferably 3 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. There exists a tendency for film strength to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Specific examples of groups in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups represented by the following general formulas (i-A) to (i-F). From the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane, a group represented by the following general formula (i-A) is preferable.

[chemical 15]

The benzene ring in the formula (i) may be further substituted with an arbitrary substituent, and examples of the substituent include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. The number of substituents is not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.

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

[chemical 16]

In formula (i-1), R ^a , R ^b and k have the same meaning as R ^a , R ^b and k in formula (i). ^RY represents a hydrogen atom or a residue of a polybasic acid. The benzene ring in formula (i-1) may be further substituted with any substituent. *Indicates each bond key.

In ^RY in the formula (i-1), the polybasic acid residue means a valent or divalent group obtained by removing one or two OH groups from the polybasic acid. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, Benzophenone Tetracarboxylic Acid, Methyl Hexahydrophthalic Acid, Endomethylene Tetrahydrophthalic Acid, Chloride Acid, Methyl Tetrahydrophthalic Acid, Biphenyl Tetracarboxylic Acid. From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, meta Benzenetricarboxylic acid, biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid.

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

The repeating unit structure represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (C2-1) may be one kind, or two or more kinds.

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 still more preferably 3 or more, and preferably 10 or less, further preferably 8 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 2-10 are more preferable, and 3-8 are still more preferable. There exists a tendency for developability to improve by making it more than the said lower limit. There exists a tendency for ink repellency to improve by being below the said upper limit.

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, it is 3 or more, and it is more preferable that it is 10 or less, and it is still more preferable that it is 8 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 2-10 are more preferable, and 3-8 are still more preferable. There exists a tendency for developability to improve by making it more than the said lower limit. There exists a tendency for ink repellency to improve by being below the said upper limit.

Specific examples of epoxy (meth)acrylate resin (C2-1) are listed below.

[chemical 17]

[chemical 18]

[chemical 19]

[chemical 20]

[chem 21]

[chem 22]

＜Epoxy (meth)acrylate resin (C2-2)＞

[chem 23]

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

(R ^d ) In the formula (ii), R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit. The number of carbon atoms in the aliphatic ring group is preferably at least 4, more preferably at least 6, still more preferably at least 8, and preferably at most 40, more preferably at most 30, further preferably at most 20, especially preferably at most 15 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-40 is preferable, 4-30 is more preferable, 6-20 is still more preferable, 8-15 is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a northane ring, an isoheptane ring, and an adamantane ring. From the viewpoint of heat resistance, an adamantane ring is preferable.

The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and preferably 10 or less, more preferably 5 or less, and still more preferably Preferably 4 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 2-5 are more preferable, and 3-4 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is preferably at least 4, more preferably at least 6, further preferably at least 8, still more preferably at least 10, especially preferably at least 12, and is preferably at most 40, more preferably at least 40. 30 or less, more preferably 20 or less, particularly preferably 15 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-40 is preferable, 6-40 is more preferable, 8-30 is still more preferable, 10-20 is still more preferable, 12-15 is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

環、聯三伸苯環、苊環、螢蒽環、茀環。就耐熱性之觀點而言，較佳為茀環。As the aromatic ring in the aromatic ring group, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring. From the viewpoint of heat resistance, fennel ring is preferable.

Among the divalent hydrocarbon groups having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited, and examples thereof include: a divalent aliphatic group, a divalent aromatic ring group, one or more divalent aliphatic groups and one A group formed by linking the above divalent aromatic ring groups.

Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of improving developability, a straight-chain aliphatic group is preferred. From the viewpoint of heat resistance, a cycloaliphatic group is preferable. The carbon number of the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, further preferably 6 or more, and preferably 25 or less, more preferably 20 or less, further preferably 15 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-25 are preferable, 3-20 are more preferable, and 6-15 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, and n-heptyl. From the viewpoint of heat resistance, methylene is preferred. Examples of the divalent branched-chain aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl having, for example, one or more of the above-mentioned divalent straight-chain aliphatic groups. Group, second butyl, third butyl as the structure of the side chain.

The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably at least 1, more preferably at least 2, and is preferably at most 10, more preferably at most 5, and still more preferably at most 3. . The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Examples of divalent cyclic aliphatic groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, dicyclopentane rings, and northane rings having two free atomic valences. ring, iso-alkane ring, adamantane ring. From the viewpoint of heat resistance, an adamantane ring having two free valences is preferable.

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

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number of the divalent aromatic ring group is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and preferably 30 or less, more preferably 20 or less, further preferably 15 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

環、聯三伸苯環、苊環、螢蒽環、茀環。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of divalent aromatic hydrocarbon ring groups include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,

ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring.

The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, and oxadiazole rings having two free atomic valences. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridine ring, pyrimidine ring, three sulfa ring, quinoline ring, isoquinoline ring, phenoline ring, quinoline ring Ozoline ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring. From the viewpoint of production cost, a benzene ring and a naphthalene ring having two free atomic valences are preferable, and a benzene ring having two free atomic valences is more preferable.

As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. From the viewpoint of curability, it is preferably unsubstituted.

Examples of groups in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include: one or more divalent aliphatic groups described above and one or more divalent aromatic ring groups described above. The base formed by linking ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, further preferably 3 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for developability to improve by making it more than the said lower limit. There exists a tendency for heat resistance to improve by being below the said upper limit. The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, further preferably 3 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

As a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, for example, groups represented by formulas (i-A) to (i-F) are mentioned. From the viewpoint of film strength, the group represented by the formula (i-C) is preferable.

The form of the cyclic hydrocarbon as the side chain is not particularly limited based on the bonding form of the divalent hydrocarbon group, for example, a form in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted by a cyclic hydrocarbon group as a side chain, Or a form in which a cyclic hydrocarbon group as a side chain is constituted including one carbon atom of the aliphatic group.

(R ^e , R ^f ) In formula (ii), R ^e and R ^f each independently represent a divalent aliphatic group which may have a substituent.

Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of image development solubility, a straight-chain aliphatic group is preferable. From the viewpoint of heat resistance, a cycloaliphatic group is preferable.

The carbon number of the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, further preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, further preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 are preferable, 3-15 are more preferable, and 6-10 are still more preferable. There exists a tendency for the adhesiveness with a board|substrate and ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, it exists in the tendency for the deterioration of sensitivity and the film reduction at the time of image development to be suppressed easily, and resolution to improve.

Examples of the divalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl. From the viewpoint of the rigidity of the skeleton, methylene is preferred.

Examples of the divalent branched-chain aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl having, for example, one or more of the above-mentioned divalent straight-chain aliphatic groups. Group, second butyl, third butyl as the structure of the side chain.

The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 12 or less, more preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-12 are preferable, 1-10 are more preferable, and 2-10 are still more preferable. There exists a tendency for the adhesiveness with a board|substrate and ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, it exists in the tendency for the deterioration of sensitivity and the film reduction at the time of image development to be suppressed easily, and resolution to improve.

Examples of divalent cyclic aliphatic groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, noralkane rings, and isoalkane rings having two free atomic valences. , adamantane ring, dicyclopentadiene ring. From the viewpoint of heat resistance, a dicyclopentadiene ring and an adamantane ring having two free atomic valences are preferable.

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 and the like. From the viewpoint of easy synthesis, it is preferably unsubstituted.

(l, m) In formula (ii), l and m independently represent integers from 0 to 2. There exists a tendency for the adhesiveness with a board|substrate to improve by making it more than the said lower limit. Developability tends to become favorable by making it below the said upper limit. From the viewpoint of developability, l and m are preferably 0. From the viewpoint of the adhesiveness to the substrate, l and m are preferably 1 or more.

The partial structure represented by the formula (ii) is preferably a partial structure represented by the following general formula (ii-1) from the viewpoint of film strength and ink repellency.

[chem 24]

In formula (ii-1), R ^c , R ^e , R ^f , l and m have the same meanings as in formula (ii) above. R ^α represents a valent 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 any substituent. *Indicates each bond key.

(R ^α ) In the formula (ii-1), R ^α represents a valent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 4 or less, further preferably 3 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-6 are preferable, 1-4 are more preferable, 1-3 are still more preferable, 2-3 are especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit. The number of carbon atoms in the aliphatic ring group is preferably at least 4, more preferably at least 6, still more preferably at least 8, and preferably at most 40, more preferably at most 30, further preferably at most 20, especially preferably at most 15 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-40 is preferable, 4-30 is more preferable, 6-20 is still more preferable, 8-15 is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a northane ring, an isoheptane ring, and an adamantane ring. From the viewpoint of both ink repellency and developability, an adamantane ring is preferred.

The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 2-10 are more preferable, and 3-5 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and preferably 30 or less, more preferably 20 or less, further preferably 15 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of both ink repellency and developability, a ring is preferred.

Examples of substituents that the cyclic hydrocarbon group may have include: hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl, etc. Alkyl group with 1 to 5 carbons; alkoxy group with 1 to 5 carbons such as methoxy and ethoxy; nitro group; cyano group; carboxyl group. From the viewpoint of easy synthesis, it is preferably unsubstituted.

n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1-3 are preferable, and 2-3 are more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

From the viewpoint of both ink repellency and developability, R ^α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

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

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

[chem 25]

[chem 26]

[chem 27]

[chem 28]

[chem 29]

The partial structure represented by formula (ii) is preferably a partial structure represented by the following general formula (ii-2) from the viewpoint of image development adhesiveness.

[chem 30]

In formula (ii-2), R ^c , R ^e , R ^f , l and m have the same meanings as in formula (ii) above. R ^β represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with any substituent. *Indicates each bond key.

(R ^β ) In the formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent. As a cyclic hydrocarbon group, an aliphatic ring group or an aromatic ring group is mentioned.

The number of rings in the aliphatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, and 2-5 are more preferable. There exists a tendency for developability to improve by making it more than the said lower limit. There exists a tendency for ink repellency to improve by being below the said upper limit. The carbon number of the aliphatic ring group is preferably 4 or more, more preferably 6 or more, further preferably 8 or more, and preferably 40 or less, more preferably 35 or less, further preferably 30 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-40 are preferable, 6-35 are more preferable, and 8-30 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a northane ring, an isoheptane ring, and an adamantane ring. From the viewpoint of both ink repellency and developability, an adamantane ring is preferred.

The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and is preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 2-10 are more preferable, and 3-5 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is preferably at least 4, more preferably at least 6, further preferably at least 8, especially preferably at least 10, and is preferably at most 40, more preferably at most 30, and still more preferably at most Below 20, preferably below 15. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 4-40 is preferable, 6-30 is more preferable, 8-20 is still more preferable, 10-15 is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of ink repellency and developability, a ring is preferred.

Examples of substituents that the cyclic hydrocarbon group may have include: hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, pentyl, isopentyl Alkyl groups with 1 to 5 carbons; alkoxy groups with 1 to 5 carbons such as methoxy and ethoxy; nitro; cyano; carboxyl. From the viewpoint of easy synthesis, it is preferably unsubstituted.

From the viewpoint of both ink repellency, developability and heat resistance, R ^β is preferably a divalent aliphatic ring group, more preferably a divalent adamantane ring group. From the viewpoint of achieving both ink repellency, developability and heat resistance, R ^β is preferably a divalent aromatic ring group, more preferably a divalent fenene ring group.

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

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

[chem 31]

[chem 32]

[chem 33]

[chem 34]

From the viewpoint of developability, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following general formula (ii-3).

[chem 35]

In formula (ii-3), R ^c , R ^d , R ^e , R ^f , l and m have the same meanings as in formula (ii) above. R and ^Z each independently represent a hydrogen atom or a polybasic acid residue.

The so-called polybasic acid residues in R ^Z can be preferably those listed as R ^Y in formula (i-1).

The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (C2-2) may be one kind, or two or more kinds.

The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and more preferably Preferably it is 20 or less, more preferably 15 or less, still more preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 are preferable, 1-15 are more preferable, and 3-10 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

The number of partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , preferably 20 or less, more preferably 15 or less, further preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 are preferable, 1-15 are more preferable, and 3-10 are still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

The number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , preferably 20 or less, more preferably 15 or less, further preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 is preferable, 1-15 is more preferable, 1-10 is still more preferable, 3-10 is especially preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for developability to improve by being below the said upper limit.

The number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (C2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , preferably 20 or less, more preferably 15 or less, further preferably 10 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 is preferable, 1-15 is more preferable, 1-10 is still more preferable, 3-10 is especially preferable. There exists a tendency for developability to improve by making it more than the said lower limit. There exists a tendency for ink repellency to improve by being below the said upper limit.

The acid value of the epoxy (meth)acrylate resin (C2) is not particularly limited, but is preferably more than 10 mgKOH/g, more preferably more than 30 mgKOH/g, more preferably more than 50 mgKOH/g, and even more preferably Preferably at least 70 mgKOH/g, especially preferably at least 80 mgKOH/g, more preferably at most 200 mgKOH/g, more preferably at most 180 mgKOH/g, further preferably at most 150 mgKOH/g, and even more preferably It is 120 mgKOH/g or less, more preferably 110 mgKOH/g or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 10-200 mgKOH/g, more preferably 30-180 mgKOH/g, further preferably 50-150 mgKOH/g, further preferably 70-120 mgKOH/g, and most preferably 80-110 mgKOH /g. There exists a tendency for developability to improve by making it more than the said lower limit. There exists a tendency for ink repellency and film strength to improve by being below the said upper limit.

The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (C2) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, especially preferably 3500 or more, and , preferably 30,000 or less, more preferably 15,000 or less, further preferably 10,000 or less, still more preferably 8,000 or less, especially preferably 5,000 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1000-30000 is preferable, 1000-15000 is more preferable, 2000-10000 is more preferable, 3000-8000 is still more preferable, and 3500-5000 is especially preferable. There exists a tendency for ink repellency and film strength to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

[Acrylic Copolymer Resin (C3)] The acrylic copolymer resin (C3) has an ethylenically unsaturated group in the side chain. By setting it as having an ethylenically unsaturated group, it hardens|cures by the light by exposure, film reduction by an alkaline developing solution does not occur easily at the time of development, and surface smoothness becomes favorable. Moreover, there exists a tendency for the adhesiveness with a board|substrate to improve by having a soft main frame.

(repeating unit represented by the general formula (1)) The partial structure of the acrylic copolymer resin (C3) including a side chain having an ethylenically unsaturated group is not particularly limited. From the viewpoint of easy diffusibility and adhesiveness to the substrate, it is preferable to contain a repeating unit represented by the following general formula (1).

[chem 36]

In formula (1), R ^a1 and R ^a2 each independently represent a hydrogen atom or a methyl group. ＊Indicates a bonding key.

Among the repeating units represented by the formula (1), the repeating unit represented by the following general formula (1') is preferable from the viewpoint of sensitivity or alkali developability.

[chem 37]

In formula (1'), R ^a1 and R ^a2 each independently represent a hydrogen atom or a methyl group. R ^x represents a hydrogen atom or a residue of a polybasic acid.

The so-called polybasic acid residues can be preferably those listed as ^RY in formula (i-1).

When the acrylic copolymer resin (C3) contains a repeating unit represented by formula (1), the content ratio is not particularly limited, but it is preferably 10 mol% or more, more preferably 20 mol% relative to all repeating units More than 30 mol %, more preferably 40 mol % or more, especially 50 mol % or more, and preferably 90 mol % or less, more preferably 85 mol % or less , and more preferably 80 mol% or less, more preferably 75 mol% or less, especially preferably 70 mol% or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 10-90 mol %, more preferably 20-85 mol %, more preferably 30-80 mol %, further preferably 40-75 mol %, especially preferably 50-70 mol % Ear%. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

When the acrylic copolymer resin (C3) contains a repeating unit represented by the general formula (1'), the content ratio is not particularly limited, but it is preferably 10 mol% or more, more preferably 20 mol% of all repeating units mol% or more, and more preferably 25 mol% or more, and more preferably 30 mol% or more, especially preferably 35 mol% or more, and more preferably 80 mol% or less, more preferably 75 mol% % or less, more preferably less than 70 mol%, especially preferably less than 65 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 10-80 mol %, more preferably 20-80 mol %, further preferably 25-75 mol %, further preferably 30-70 mol %, especially preferably 35-65 mol % Ear%. There exists a tendency for ink repellency to improve by making it more than the said lower limit. There exists a tendency for it to be easy to ensure image development adhesiveness by making it below the said upper limit.

(Repeating unit represented by general formula (2)) When the acrylic copolymer resin (C3) contains a repeating unit represented by general formula (1), the other repeating units contained are not particularly limited, and are determined from the viewpoint of developing adhesiveness In other words, it is preferable to contain a repeating unit represented by the following general formula (2).

[chem 38]

In formula (2), R ^a3 represents a hydrogen atom or a methyl group. R ^a4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

(R ^a4 ) In formula (2), R ^a4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. Examples of the alkyl group in R ^a4 include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, especially preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and further preferably More preferably, it is 14 or less, especially preferably 12 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 is preferable, 1-18 is more preferable, 3-16 is still more preferable, 5-14 is still more preferable, 8-12 is especially preferable. By setting it as more than the said lower limit, there exists a tendency for film strength to become high and image development adhesiveness to improve. There exists a tendency for a residue to reduce by making it below the said upper limit.

As an alkyl group, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group are mentioned, for example. From the viewpoint of developability, dicyclopentyl or dodecyl is preferred, and dicyclopentyl is more preferred. Examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromine group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, phenyl group, carboxyl group , acryl group, methacryl group, from the viewpoint of developability, preferably a hydroxyl group and an oligoethylene glycol group.

環、聯三伸苯環、苊環、螢蒽環、茀環。  作為芳香族雜環基中之芳香族雜環基，可為單環，亦可為縮合環，例如可列舉：呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。就顯影性之觀點而言，較佳為苯環或萘環，更佳為苯環。 Examples of the aromatic ring group in R ^a4 include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups. The carbon number is preferably 6 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, particularly preferably 18 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 6-24 are preferable, 6-22 are more preferable, 6-20 are still more preferable, and 6-18 are especially preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit. As the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group, it can be a single ring or a condensed ring, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring , benzopyrene ring,

ring, terpene ring, acenaphthene ring, fluoranthracene ring, and fenene ring. The aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, for example, 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, furopyrrole ring, furan Furan ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridine ring, pyrimidine ring, three sulfa ring, quinoline ring, iso Quinoline ring, phenoline ring, quinoline ring, phenanthridine ring, phetidine ring, quinazoline ring, quinazolinone ring, azulene ring. From the viewpoint of developability, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.

Examples of substituents that the aromatic ring group may have include methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, Oligoethylene glycol groups, phenyl groups, and carboxyl groups are preferably hydroxyl groups and oligoethylene glycol groups from the viewpoint of developability.

Examples of the alkenyl group in R ^a4 include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably at least 2, preferably at most 22, more preferably at most 20, further preferably at most 18, even more preferably at most 16, particularly preferably at most 14. For example, 2-22 is preferable, 2-20 is more preferable, 2-18 is still more preferable, 2-16 is still more preferable, 2-14 is especially preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

Examples of substituents that an alkenyl group may have include: methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligoglycol, phenyl, carboxyl , from the viewpoint of developability, preferably a hydroxyl group and an oligoethylene glycol group.

Among them, R ^a4 is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group, from the viewpoint of developability and film strength.

When the acrylic copolymer resin (C3) contains a repeating unit represented by formula (2), its content ratio is not particularly limited, but it is preferably 1 mol% or more, more preferably 5 mol% of all repeating units More than 10 mol%, more preferably 10 mol% or more, more preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, and more preferably 50 mol% or less , preferably less than 40 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 1-70 mol%, more preferably 5-60 mol%, still more preferably 10-50 mol%, especially preferably 20-40 mol%. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

(Repeating unit represented by general formula (3)) When the acrylic copolymer resin (C3) contains a repeating unit represented by formula (1), it is preferable to contain the following general formula from the viewpoint of heat resistance and film strength The repeating unit represented by (3) is used as the other repeating unit included.

[chem 39]

In the above formula (3), R ^a5 represents a hydrogen atom or a methyl group. R ^a6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted Alkylthio group of the substituent. t represents an integer of 0-5.

(R ^a6 ) In formula (3), R ^a6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, or an optionally substituted alkyl group. An oxy group, a thiol group, or an optionally substituted alkylthio group. Examples of the alkyl group in R ^a6 include linear, branched or cyclic alkyl groups. The carbon number is preferably at least 1, more preferably at least 3, more preferably at least 5, and preferably at most 20, more preferably at most 18, further preferably at most 16, and even more preferably at most 14, Preferably under 12. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-20 is preferable, 1-18 is more preferable, 3-16 is still more preferable, 3-14 is still more preferable, 5-12 is especially preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

As an alkyl group, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group are mentioned, for example. From the viewpoint of developability and film strength, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred. Examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromine group, fluorine group, hydroxyl group, amino group, epoxy group, oligoglycol group, phenyl group, carboxyl group , acryl group, methacryl group, from the viewpoint of developability, preferably a hydroxyl group and an oligoethylene glycol group.

Examples of the alkenyl group in R ^a6 include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably at least 2, preferably at most 22, more preferably at most 20, further preferably at most 18, even more preferably at most 16, particularly preferably at most 14. For example, 2-22 is preferable, 2-20 is more preferable, 2-18 is still more preferable, 2-16 is still more preferable, 2-14 is especially preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

Examples of substituents that an alkenyl group may have include: methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligoglycol, phenyl, carboxyl , from the viewpoint of developability, preferably a hydroxyl group and an oligoethylene glycol group.

Examples of the alkynyl group in R ^a6 include linear, branched or cyclic alkynyl groups. The number of carbon atoms is preferably at least 2, preferably at most 22, more preferably at most 20, further preferably at most 18, even more preferably at most 16, particularly preferably at most 14. For example, 2-22 is preferable, 2-20 is more preferable, 2-18 is still more preferable, 2-16 is still more preferable, 2-14 is especially preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

Examples of substituents that an alkynyl group may have include: methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligomer Ethylene glycol group, phenyl group, and carboxyl group are preferably hydroxyl group and oligoethylene glycol group from the viewpoint of developability.

Examples of the halogen atom in R ^a6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred from the viewpoint of developability.

Examples of the alkoxy group in R ^a6 include linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably at least 1, preferably at most 20, more preferably at most 18, further preferably at most 16, even more preferably at most 14, particularly preferably at most 12. For example, 1-20 is preferable, 1-18 is more preferable, 1-16 is still more preferable, 1-14 is still more preferable, 1-12 is especially preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

Examples of substituents that an alkoxy group may have include: methoxy, ethoxy, chlorine, bromine, fluorine, hydroxyl, amino, epoxy, oligoethylene glycol, phenyl, A carboxyl group, an acryl group, and a methacryl group are preferably a hydroxyl group and an oligoglycol group from the viewpoint of developability.

Examples of the alkylthio group in R ^a6 include linear, branched or cyclic alkylthio groups. The number of carbon atoms is preferably at least 1, preferably at most 20, more preferably at most 18, further preferably at most 16, even more preferably at most 14, particularly preferably at most 12. For example, 1-20 is preferable, 1-18 is more preferable, 1-16 is still more preferable, 1-14 is still more preferable, 1-12 is especially preferable. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

Examples of substituents that the alkyl group in the alkylthio group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amine, epoxy, oligoethylene glycol A phenyl group, a carboxyl group, an acryl group, a methacryl group, and a hydroxyl group and an oligoglycol group are preferable from the viewpoint of developability.

Among them, R ^a6 is preferably a hydroxyl group or a carboxyl group, more preferably a carboxyl group, from the viewpoint of developability.

In formula (3), t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of manufacture.

When the acrylic copolymer resin (C3) contains a repeating unit represented by formula (3), its content ratio is not particularly limited, but it is preferably 0.5 mol% or more, more preferably 1 mol% of all repeating units More than above, more preferably at least 2 mol%, especially preferably at least 5 mol%. Also, it is preferably at most 50 mol%, more preferably at most 40 mol%, further preferably at most 30 mol%, even more preferably at most 20 mol%, and especially preferably at most 15 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 0.5-50 mol %, more preferably 0.5-40 mol %, further preferably 1-30 mol %, further preferably 2-20 mol %, especially preferably 5-15 mol % Ear%. Image development adhesiveness tends to improve by making it more than the said lower limit. There exists a tendency for a residue to reduce by making it below the said upper limit.

(Repeating unit represented by general formula (4)) When the acrylic copolymer resin (C3) contains a repeating unit represented by formula (1), it is preferable to contain the following general formula (4) from the viewpoint of developability Repeat units indicated are included as other repeat units.

[chemical 40]

In the above formula (4), R ^a7 represents a hydrogen atom or a methyl group.

When the acrylic copolymer resin (C3) contains a repeating unit represented by formula (4), the content ratio is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% of all repeating units Above, more preferably at least 20 mol%, and more preferably at most 80 mol%, more preferably at most 70 mol%, still more preferably at most 60 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 20 to 60 mol%. There exists a tendency for developability to improve by making it more than the said lower limit. Image development adhesiveness tends to improve by making it below the said upper limit.

The acid value of the acrylic copolymer resin (C3) is not particularly limited, but is preferably at least 30 mgKOH/g, more preferably at least 40 mgKOH/g, still more preferably at least 50 mgKOH/g, still more preferably at least 60 mgKOH/g The above, but also, preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, still more preferably 130 mgKOH/g or less, still more preferably 120 mgKOH/g or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 30-150 mgKOH/g, more preferably 40-140 mgKOH/g, still more preferably 50-130 mgKOH/g, especially preferably 60-120 mgKOH/g. There exists a tendency for developability to improve by making it more than the said lower limit. Image development adhesiveness tends to improve by making it below the said upper limit.

The weight average molecular weight (Mw) of the acrylic copolymer resin (C3) is not particularly limited, but is preferably at least 1000, more preferably at least 2000, further preferably at least 4000, still more preferably at least 6000, especially preferably at least 7000, More preferably, it is 8,000 or more, and it is more preferably 30,000 or less, more preferably 20,000 or less, further preferably 15,000 or less, and particularly preferably 10,000 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 1000-30000, more preferably 2000-30000, still more preferably 4000-20000, still more preferably 6000-20000, still more preferably 7000-15000, especially preferably 8000-10000. Image development adhesiveness tends to improve by making it more than the said lower limit. Developability tends to become favorable by making it below the said upper limit.

Examples of the acrylic copolymer resin (C3) include resins described in JP-A-8-297366 or JP-A-2001-89533.

The (C) alkali-soluble resin in this invention may further contain the alkali-soluble resin other than epoxy (meth)acrylate resin (C2) and acrylic copolymer resin (C3) as another alkali-soluble resin.

(C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably at least 30 mgKOH/g, more preferably at least 50 mgKOH/g, more preferably at least 60 mgKOH/g, and more preferably at least 300 mgKOH/g Below, more preferably below 200 mgKOH/g, more preferably below 100 mgKOH/g, especially preferably below 80 mgKOH/g. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 30-300 mgKOH/g, more preferably 30-200 mgKOH/g, still more preferably 50-100 mgKOH/g, especially preferably 60-80 mgKOH/g. There exists a tendency for developability to improve by making it more than the said lower limit. Image development adhesiveness tends to improve by making it below the said upper limit. In the case of (C) the mixture of two or more alkali-soluble resins, the acid value means the weighted average value corresponding to their content ratio.

The content ratio of the (C) alkali-soluble resin in the photosensitive resin composition of the present invention is not particularly limited, but is preferably at least 5% by mass, more preferably 10% by mass, based on the total solid content of the photosensitive resin composition. % or more, preferably more than 15% by mass, more preferably more than 20% by mass, particularly preferably more than 25% by mass, particularly preferably more than 30% by mass, especially preferably more than 40% by mass, and more preferably Preferably, it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 70 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, still more preferably 15 to 90% by mass, still more preferably 20 to 80% by mass, still more preferably 30 to 80% by mass, especially More preferably, it is 35-70 mass %, Most preferably, it is 40-60 mass %. There exists a tendency for a residue to reduce by setting it as more than the said lower limit. There exists a tendency for ink repellency to improve by being below the said upper limit.

The sum of the content ratio of (A) photopolymerizable compound and the content ratio of (C) alkali-soluble resin in the total solid content of the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more , more preferably at least 30% by mass, more preferably at least 60% by mass, especially preferably at least 80% by mass, and more preferably at most 95% by mass, more preferably at most 92% by mass, and even more preferably at least 90% by mass %the following. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 10-95 mass % is preferable, 30-95 mass % is more preferable, 60-92 mass % is still more preferable, 80-90 mass % is especially preferable. There exists a tendency for the adhesiveness of a barrier rib on a board|substrate to improve by making it more than the said lower limit. There exists a tendency for light-shielding property or ink repellency to improve by being below the said upper limit.

[1-1-4] (D) Liquid-repellent agent The photosensitive resin composition of the present invention contains (D) liquid-repellent agent, and the (D) liquid-repellent agent contains a crosslinking group, contains fluorine atoms and/or Or a compound (D1) with a siloxane chain. By containing the liquid repellant, ink repellency can be imparted to the upper surface of the obtained barrier rib, so that the obtained barrier rib can prevent color mixing of pixels. The following, as compound (D1), preferably include Compound (D1-1): a resin containing fluorine atoms having a crosslinking group, and/or Compound (D1-2): a resin containing a crosslinking group and a siloxane chain resin.

<Compound (D1-1)> Examples of crosslinking groups include epoxy groups, ethylenically unsaturated groups, and active groups that generate free radicals by irradiating active energy rays. Examples of active radicals that generate free radicals by irradiation with active energy rays include benzophenone groups, acetophenone groups, α-hydroxyketone groups, α-aminoketone groups, α-diketone groups, and α-diketone groups. - diketone dialkyl acetal groups. Among them, an α-hydroxyketone group is preferred from the viewpoint of overlap between the wavelength distribution of the light source used for exposure and the absorbance spectrum of the active group. The crosslinking group is preferably an ethylenically unsaturated group from the viewpoint of inhibiting the liquid-repellent agent from flowing out into the developer. It is considered that by using a liquid-repelling agent with a cross-linking group, the cross-linking reaction on the surface of the formed coating film can be accelerated when it is exposed, and the liquid-repelling agent is not easy to flow out during the development process. As a result, the obtained barrier can be improved. The wall shows a high ink repellency.

The compound (D1-1) which is a fluorine atom-containing resin is aligned on the surface of the barrier rib, and tends to exhibit the function of preventing ink bleeding or color mixing. More specifically, the base containing fluorine atoms repels the ink, and tends to function to prevent ink bleeding or color mixing caused by the ink crossing the barrier wall and entering the adjacent region.

The fluorine atom-containing resin having a crosslinking group preferably has any one or two or more of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group. It is preferably a perfluoro or fluoroalkyl group, a perfluoro or fluoroalkylene group, a perfluoro or fluoroalkylene ether chain, a perfluoro or fluoroaromatic group, and in terms of liquid repellency, it is more preferred to contain a perfluorinated or fluoroalkylene group. Fluoroalkyl, perfluoroalkylene, perfluoroalkylene ether chain, perfluoroaromatic. By having any one or more of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group, the resin containing fluorine atoms is more likely to align the surface of the barrier wall, and exhibits more High ink repellency, to further prevent the tendency of ink bleeding or color mixing.

Examples of perfluoro or fluoroalkyl groups include perfluoro or fluoromethyl, perfluoro or fluoroethyl, perfluoro or fluoropropyl, perfluoro or fluorobutyl, perfluoro or fluorohexyl. Examples of perfluoro or fluoroalkylene chains include: perfluoro or fluoromethylene chains, perfluoro or fluoroethylene chains, perfluoro or fluoropropyl chains, perfluoro or fluorobutylene chains, perfluoro Or fluorohexyl chain. Examples of perfluoroalkylene ether chains include -CF ₂ -O-, -(CF ₂ ) ₂ -O-, -(CF ₂ ) ₃ -O-, -CF ₂ -C(CF ₃ )O -, -C(CF ₃ )-CF ₂ -O-, and divalent groups having these repeating units, as the fluoroalkylene ether chain, include: not all parts of the perfluoroalkylene ether chain F Fluoroalkylene ether chains substituted by H. Examples of perfluoro or fluoroaromatic groups include perfluoro or fluorophenyl, perfluoro or fluoronaphthyl, and perfluoro or fluoroanthracenyl.

As resins containing fluorine atoms with crosslinking groups, for example, esters include: acrylic copolymer resins with epoxy groups and perfluoroalkyl groups, acrylic copolymer resins with epoxy groups and perfluoroalkylene ether chains, vinyl resins with ethylene Acrylic copolymer resin with permanent unsaturated group and perfluoroalkyl group, acrylic copolymer resin with ethylenically unsaturated group and perfluoroalkylene ether chain, epoxy (meth)acrylic acid with epoxy group and perfluoroalkyl group Ester resin, epoxy (meth)acrylate resin with epoxy group and perfluoroalkylene ether chain, epoxy (meth)acrylate resin with ethylenically unsaturated group and perfluoroalkyl group, epoxy (meth)acrylate resin with vinyl Epoxy (meth)acrylate resin with permanent unsaturated groups and perfluoroalkylene ether chains. From the viewpoint of ink repellency, it is preferably an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, and more preferably It is an acrylic copolymer resin with ethylenically unsaturated groups and perfluoroalkylene ether chains.

As a commercial product of a fluorine-containing resin having a crosslinking group, for example, a fluorine-containing organic compound marketed under the following trade names can be used: "MEGAFAC (registered trademark, the same below) F116" manufactured by DIC Corporation, "MEGAFAC F120 ", "MEGAFAC F142D", "MEGAFAC F144D", "MEGAFAC F150", "MEGAFAC F160", "MEGAFAC F171", "MEGAFAC F172", "MEGAFAC F173", "MEGAFAC F177", "MEGAFAC F178A", "MEGAFAC F178K ", "MEGAFAC F179", "MEGAFAC F183", "MEGAFAC F184", "MEGAFAC F191", "MEGAFAC F812", "MEGAFAC F815", "MEGAFAC F824", "MEGAFAC F833", "MEGAFAC RS101", "MEGAFAC RS102 "MEGAFAC RS105", "MEGAFAC RS201", "MEGAFAC RS202", "MEGAFAC RS301", "MEGAFAC RS303", "MEGAFAC RS304", "MEGAFAC RS401", "MEGAFAC RS402", "MEGAFAC RS501", "MEGAFAC RS502", "MEGAFAC RS-72-K", "MEGAFAC RS-78", "MEGAFAC RS-90", "DEFENSA (registered trademark, the same below) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", "Fluorad FC430", "Fluorad FC431", "FC-4430", and "FC4432" manufactured by 3M Japan, "AsahiGuard (registered trademark) AG710" and "Surflon (registered trademark, the same below) S-382 manufactured by AGC Corporation ", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106". As acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene groups, "MEGAFAC RS-72-K", "MEGAFAC RS-78", and "MEGAFAC RS-90" can be preferably used.

The content ratio of fluorine atoms in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but in the fluorine atom-containing resin having a crosslinking group, it is preferably at least 5% by mass, more preferably at least 10% by mass, Furthermore, it is more preferable that it is 15 mass % or more, and it is still more preferable that it is 20 mass % or more. Also, it is preferably at most 50% by mass, more preferably at most 35% by mass. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 5-50 mass % is preferable, 10-50 mass % is more preferable, 15-35 mass % is still more preferable, and 20-35 mass % is especially preferable. By setting it as more than the said lower limit, it exists in the tendency which the outflow to a pixel part can be suppressed. There exists a tendency for a high contact angle to be shown by making it below the said upper limit.

The molecular weight of the fluorine-containing resin having a crosslinking group is not particularly limited, and may be a low-molecular-weight compound or a high-molecular-weight compound. A high molecular weight body is more preferable because it can suppress bleeding during development or fluidity caused by post-baking, and can suppress outflow from barrier ribs. In the case of a fluorine atom-containing resin having a crosslinking group, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 or more, more preferably 500 or more, and still more preferably 1000 or more . Also, it is preferably at most 150,000, more preferably at most 130,000, more preferably at most 100,000. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 100 to 150,000, more preferably 500 to 130,000, and still more preferably 1,000 to 100,000.

Also, the weight average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably at least 1,000, more preferably at least 5,000, and still more preferably at least 10,000. Also, it is preferably at most 150,000, more preferably at most 130,000. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 1,000 to 150,000, more preferably 5,000 to 130,000, and still more preferably 10,000 to 130,000.

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

Specifically, the siloxane chain contained in the compound (D1-2) is preferably polysiloxane represented by the following general formula (d1-2). R ⁶¹ R ⁶² R ⁶³ Si-O-(SiR ⁶⁴ R ⁶⁵ -O)n-SiR ⁶⁶ R ⁶⁷ R ⁶⁸ (d1-2) In formula (d1-2), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , and R ⁶⁸ each independently represent a monovalent organic group or a hydrogen atom.

The monovalent organic group is preferably a hydrocarbon group with 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and other alkyl groups; vinyl, allyl , butenyl, pentenyl, hexenyl and other alkenyl groups; phenyl, tolyl, xylyl and other aryl groups; benzyl, phenethyl and other aralkyl groups; chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, nonafluorobutylethyl and other substituted alkyl groups, and these organic groups may also have an ester bond.

n is an integer of 0 or more, preferably 5 or more, more preferably 10 or more, and is preferably 2000 or less, more preferably 1500 or less, further preferably 1000 or less, still more preferably 500 or less, especially preferably Below 300. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 5-2000 is preferable, 5-1500 is more preferable, 5-1000 is more preferable, 10-500 is still more preferable, 10-300 is especially preferable. There exists a tendency for ink repellency to become high by making it more than the said lower limit. There exists a tendency for the uniformity of a coating film to become high by making it below the said upper limit.

As a commercially available resin containing a crosslinking group and a siloxane chain, for example, "BYK-UV3500 series" manufactured by BYK-Chemie, and "8SS" series manufactured by Taisei Fine Chemical are commercially available. compound.

Examples of the compound having a crosslinking group and containing a fluorine atom and a siloxane chain include those commercially available under the trade names of "8FS" series manufactured by Taisei Fine Chemical Co., Ltd. and "KP series" manufactured by Shin-Etsu Chemical Co., Ltd. .

The compound (D1) may contain both fluorine atoms and siloxane chains in one molecule, or a plurality of compounds (D1) may be used in combination.

The content ratio of (D) liquid-repelling agent in the photosensitive resin composition of the present invention is not particularly limited, but it is preferably 0.01% by mass or more, more preferably 0.05% with respect to the total solid content of the photosensitive resin composition Mass % or more, More preferably, it is 0.1 mass % or more, Moreover, Preferably it is 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 0.01-5 mass % is preferable, 0.05-3 mass % is more preferable, and 0.1-2 mass % is still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, it exists in the tendency which becomes easy to obtain a uniform coating film when ink is apply|coated to a pixel part after barrier rib formation.

The content ratio of the compound (D1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably at least 0.01% by mass, more preferably 0.05% by mass, based on the total solid content of the photosensitive resin composition Above, more preferably at least 0.1% by mass, and more preferably at most 5% by mass, more preferably at most 3% by mass, further preferably at most 2% by mass. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 0.01-5 mass % is preferable, 0.05-3 mass % is more preferable, and 0.1-2 mass % is still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, it exists in the tendency which becomes easy to obtain a uniform coating film when ink is apply|coated to a pixel part after barrier rib formation.

When the photosensitive resin composition of the present invention contains the compound (D1-1), the content ratio of the compound (D1-1) is not particularly limited, but relative to the total solid content of the photosensitive resin composition, preferably It is 0.01 mass % or more, more preferably 0.05 mass % or more, still more preferably 0.1 mass % or more, and is preferably 5 mass % or less, more preferably 3 mass % or less, still more preferably 2 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 0.01-5 mass % is preferable, 0.05-3 mass % is more preferable, and 0.1-2 mass % is still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, it exists in the tendency which becomes easy to obtain a uniform coating film when ink is apply|coated to a pixel part after barrier rib formation.

When the photosensitive resin composition of the present invention contains the compound (D1-2), the content ratio of the compound (D1-2) is not particularly limited, but relative to the total solid content of the photosensitive resin composition, preferably It is at least 0.1 mass %, more preferably at least 0.2 mass %, still more preferably at least 0.5 mass %, and is preferably at most 5 mass %, more preferably at most 3 mass %, further preferably at most 2 mass %. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 0.1-5 mass % is preferable, 0.2-3 mass % is more preferable, and 0.5-2 mass % is still more preferable. There exists a tendency for ink repellency to improve by making it more than the said lower limit. By making it below the said upper limit, it exists in the tendency which becomes easy to obtain a uniform coating film when ink is apply|coated to a pixel part after barrier rib formation.

In the photosensitive resin composition of the present invention, a surfactant may also be used together with (D) the liquid repellent. For example, in order to improve the applicability of the photosensitive resin composition as a coating liquid and the developability of the coating film, a surfactant can be used, for example: a fluorine-based surfactant without a crosslinking group, polysiloxane Department of surfactants. In particular, it has the function of removing the residue of the photosensitive resin composition from the unexposed part during development, and also has the function of exhibiting wettability. It is preferably a polysiloxane-based surfactant, and more preferably Polyether modified polysiloxane surfactant.

The fluorine-based surfactant not containing a crosslinking group is preferably a compound having a fluoroalkyl group or a fluoroalkylene group in at least any of the terminal, main chain, and side chain. Examples of commercially available fluorine-based surfactants that do not contain a crosslinking group include "BM-1000" and "BM-1100" manufactured by BMChemie, and "MEGAFAC F142D" and "MEGAFAC F172" manufactured by DIC Corporation. , "MEGAFAC F173", "MEGAFAC F183", "MEGAFAC F470", "MEGAFAC F475", "MEGAFAC F554", "MEGAFAC F559", "FC430" manufactured by 3M Japan, "DFX-18" manufactured by NEOS Corporation.

Examples of commercially available polysiloxane-based surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", and "8032 Additive" manufactured by Dow Corning Toray Co., Ltd. , "SH8400", "BYK (registered trademark, hereinafter the same) 323" and "BYK330" manufactured by BYK-Chemie.

Surfactants other than fluorine-based surfactants and silicone-based surfactants may also be included as the surfactant. Examples of the surfactant include nonionic, anionic, cationic, and amphoteric surfactants.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl ethers, Oxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan Sugar alcohol fatty acid esters, polyoxyethylene sorbitol fatty acid esters. Examples of such commercially available products include polyoxyethylene-based surfactants such as "Emulgen (registered trademark, the same hereinafter) 104P" and "Emulgen A60" manufactured by Kao Corporation.

Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, and alkyl sulfates. , Alkyl sulfates, Higher alcohol sulfates, Aliphatic alcohol sulfates, Polyoxyethylene alkyl ether sulfates, Polyoxyethylene alkyl phenyl ether sulfates, Alkyl phosphates Classes, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants. Among them, a special polymer-based surfactant is preferred, and a special polycarboxylic acid-type polymer-based surfactant is further preferred. Such commercially available products include, for example, "Emal (registered trademark, the same hereinafter) 10" manufactured by Kao Corporation as alkyl sulfate ester salts, and "Pelex ( Registered trademark) NB-L", special polymer surfactant, for example, "Homogenol (registered trademark, the same hereinafter) L-18" and "Homogenol L-100" manufactured by Kao Corporation are mentioned.

Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Among these, quaternary ammonium salts are preferred, and stearyl trimethylammonium salts are further preferred. As such commercially available products, examples of alkylamine salts include "Acetamin (registered trademark) 24" manufactured by Kao Corporation, and examples of quaternary ammonium salts include "Quartamin (registered trademark, the same applies hereinafter)" manufactured by Kao Corporation. 24P", "Quartamin 86W". Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, and amino acids.

Surfactants may be used alone or in combination of two or more. Examples include: the combination of polysiloxane-based surfactants and fluorine-based surfactants, the combination of polysiloxane-based surfactants and special polymer-based surfactants, the combination of fluorine-based surfactants and special polymer-based surfactants The combination of surfactants is preferably a combination of polysiloxane-based surfactants and fluorine-based surfactants.

Examples of combinations of silicone-based surfactants and fluorine-based surfactants include "DFX-18" manufactured by NEOS, "BYK-300" or "BYK-330" manufactured by BYK-Chemie, and AGC Combination of "S-393" manufactured by Seimi Chemical Co., Ltd.; combination of "KP340" manufactured by Shin-Etsu Silicones Co., Ltd. and "F-554" or "F-559" manufactured by DIC Corporation; "SH7PA" manufactured by Dow Corning Toray Co., Ltd. A combination of "DS-401" manufactured by Daikin Corporation; a combination of "L-77" manufactured by NUC Corporation and "FC4430" manufactured by 3M Japan Corporation.

[1-1-5] (E) Colorant The photosensitive resin composition of the present invention may further contain (E) colorant. By containing the (E) colorant, moderate light absorption can be obtained, and moderate light-shielding property can be obtained especially when it is used for the use which forms the light-shielding member containing a colored barrier rib. Moreover, when it is used for the purpose of light-scattering, good light-scattering property can be acquired by using a white coloring agent.

The kind of (E) coloring agent used in this invention is not specifically limited, A pigment or a dye can be used. From the viewpoint of durability, it is preferable to use a pigment.

(E) The pigment contained in the colorant may be one kind, or two or more kinds. In particular, two or more are preferable from the viewpoint of uniformly shielding light in the visible light range. The types of pigments that can be used as (E) colorants are not particularly limited, for example, organic pigments or inorganic pigments can be mentioned. When aiming at light-shielding property, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the photosensitive resin composition and efficiently curing it. Examples of organic pigments include organic colored pigments and organic black pigments. Here, the organic colored pigment means an organic pigment that exhibits a color other than black, and examples thereof include red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

Among organic pigments, it is preferable to use organic coloring pigments from the viewpoint of ultraviolet absorbing properties. One type of organic coloring pigment can be used alone, or two or more types can be used in combination. When used for a light-shielding application, it is more preferable to use a combination of organic coloring pigments of different colors, and it is more preferable to use a combination of organic coloring pigments showing a color close to black.

The chemical structure of these organic pigments is not particularly limited, examples include: azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, biphae-based, indan Shilin Department, Perylene Department. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers. The term "C.I. Pigment Red 2" listed below refers to the Color Index (C.I.).

Examples of red pigments include: C.I. 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 . From the viewpoint of shading and dispersibility, C.I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 is preferred, and more preferably C.I. Pigment Red 177, 209, 224, 254. In terms of dispersibility or light-shielding properties, C.I. Pigment Red 177, 254, and 272 are preferred. When curing the photosensitive resin composition with ultraviolet rays, it is preferable to use one with a low ultraviolet absorption rate as a red pigment, and from this point of view, C.I. Pigment Red 254 and 272 are preferable.

Examples of orange pigments include: C.I. 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, 79. From the viewpoint of dispersibility or light-shielding properties, C.I. Pigment Orange 13, 43, 64, and 72 are preferred, and C.I. Pigment Orange 43, 64, and 72 are more preferred. When curing the photosensitive resin composition with ultraviolet rays, it is preferable to use one with a low ultraviolet absorption rate as an orange pigment, and C.I. Pigment Orange 64 and 72 are preferable from this viewpoint.

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

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

Examples of usable organic coloring pigments other than red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.

Examples of green pigments include: C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 , preferably C.I. Pigment Green 7,36.

Examples of yellow pigments include: C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 , 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81 ,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133 ,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169 ,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198 , 199,200,202,203,204,205,206,207,208, more preferably C.I. Pigment Yellow 83,117,129,138,139,150,154,155,180,185, and more preferably C.I. Pigment Yellow 83, 138, 139, 150, 180.

It is preferable to use at least 1 sort(s) selected from the group which consists of a red pigment, an orange pigment, a blue pigment, and a purple pigment from a viewpoint of light-shielding property or ink repellency.

From the viewpoint of light-shielding properties or ink-repelling properties, it is preferable to include at least one or more of the following pigments. Red Pigment: C.I. Pigment Red 177, 254, 272 Orange Pigment: C.I. Pigment Orange 64, 72 Blue Pigment: C.I. Pigment Blue 15: 6, 16, 60 Purple Pigment: C.I. Pigment Violet 23, 29

When two or more organic coloring pigments are used in combination, the combination of organic coloring pigments is not particularly limited. From the viewpoint of light-shielding properties, the colorant (E) preferably contains a colorant selected from red pigments and orange pigments. At least one of the group consisting of and at least one selected from the group consisting of blue pigments and purple pigments. The combination of colors is not particularly limited. From the viewpoint of light-shielding properties, for example, combinations of red pigments and blue pigments, combinations of blue pigments and orange pigments, combinations of blue pigments, orange pigments, and purple pigments are listed.

It is preferable to contain a purple pigment as (E) colorant from a viewpoint of the light-shielding property of blue light.

It is preferable to use an organic black pigment as (E) coloring agent from a light-shielding viewpoint. In particular, from the viewpoint of suppressing the absorption of ultraviolet rays and having good ink repellency, it is preferable to use a compound (hereinafter also referred to as "compound (A)"), a compound (A ) geometric isomer, compound (A) salt, and compound (A) geometric isomer salt of at least one organic black pigment (hereinafter sometimes referred to as "general formula (A) ) represented by organic black pigment").

[chem 41]

In formula (A), R ¹¹ and ^{R 16} independently represent a hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ¹² , R ¹³ , R 14 , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ independently represent hydrogen atom, halogen atom, R ²¹ , 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 ; selected from R ¹² and R ¹³ , R ¹³ and R ¹⁴ , At least one combination of R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be directly bonded to each other, or may be bonded to each other via an oxygen atom, sulfur atom, NH Or NR ²¹ bridge bonded to each other; R ²¹ and R ²² are independently an alkyl group with 1 to 12 carbons, a cycloalkyl group with 3 to 12 carbons, an alkenyl group with 2 to 12 carbons, or an alkenyl group with 3 to 12 carbons Cycloalkenyl or alkynyl with 2 to 12 carbons.

Compound (A) and geometric isomers of compound (A) have the following core structures (wherein, the substituents in the structural formula are omitted), and the most stable one may be the trans-trans isomer.

[chem 42]

When the compound (A) is anionic, it is preferably a salt obtained by compensating its charge through any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically, an alkali metal, alkaline earth Metals, transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complexes. Moreover, when the geometric isomer of compound (A) is anionic, it is preferable that it is the same salt.

Among the substituents of the general formula (A) and the definitions thereof, the following are preferable from the point of view that the shielding ratio tends to be high. The reason for this is considered to be that the following substituents have no absorption and do not affect the hue of the pigment. R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom. R ¹³ and R ¹⁸ are independently preferably 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, SO ₃ H or SO ₃ ^- , further preferably a hydrogen atom or SO ₃ H, especially preferably a hydrogen atom .

R ¹¹ and R ¹⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom. Preferably, two of at least one group selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ are the same, More preferably, R ¹¹ is the same as R ¹⁶ , R ¹² is the same as R ¹⁷ , R ¹³ is the same as R ¹⁸ , R ¹⁴ is the same as R ¹⁹ , and R ¹⁵ is the same as R ²⁰ .

Alkyl groups with 1 to 12 carbons are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, third-butyl, 2-methylbutyl, n-butyl Pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2- Ethylhexyl, Nonyl, Decyl, Undecyl, Dodecyl.

Cycloalkyl groups with 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, arborvityl, and northyl .

Alkenyl groups with 2 to 12 carbon atoms are, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene -2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl , 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl, dodecenyl.

Cycloalkenyl groups with 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl , 2,4-cyclohexadien-1-yl, 1-p-en-8-yl, 4(10)-thujen-10-yl, 2-nor-en-1-yl, 2,5 -norcardien-1-yl, 7,7-dimethyl-2,4-norcardien-3-yl, camphenyl.

Alkynyl groups with 2 to 12 carbon atoms are, 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-yne -1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nononyl Alkyn-9-yl, 1-decyn-10-yl, 1-dodecyn-12-yl.

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

The organic black pigment represented by the general formula (A) is preferably selected from compounds represented by the following general formula (B) (hereinafter also referred to as "compound (B)"), and geometric isomers of the compound (B) At least one organic black pigment of the group consisting of.

[chem 43]

As such an organic black pigment, it shows by a brand name, Irgaphor (registered trademark) Black S 0100 CF (made by BASF Corporation) is mentioned. The organic black pigment is preferably used after being dispersed by the following dispersant, solvent, and method. At the time of dispersion, if there is a sulfonic acid derivative of the compound (A), especially a sulfonic acid derivative of the compound (B), the dispersibility or storage stability may be improved. Therefore, the organic black pigment preferably contains these Sulfonic acid derivatives.

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

As a coloring agent other than these organic pigments, an inorganic black pigment is mentioned. Moreover, you may further use an inorganic black pigment together with an organic pigment.

Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, titanium black, and the like. Among them, carbon black can be preferably used from the viewpoint of light-shielding properties. As an example of carbon black, the following carbon black is mentioned.

Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B Manufactured by Degussa: Printex (registered trademark, the same below) 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, manufactured by Cabot Corporation: Monarch (registered trademark, same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100 . , VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark)-8 Manufactured by Birla: RAVEN (registered trademark, hereinafter the same) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN20, 10RA 119 , RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000

Carbon black coated with resin can also be used. If resin-coated carbon black is used, there is an effect of improving the adhesion with the glass substrate or the volume resistance value. As the resin-coated carbon black, for example, carbon black described in JP-A-09-71733 can be preferably used. In terms of volume resistance or dielectric constant, resin-coated carbon black is preferably used.

These organic pigments and inorganic pigments are preferably used after being dispersed such that the average particle diameter is generally 1 μm or less, preferably 0.5 μm or less, further preferably 0.25 μm or less. Here, the basis of the average particle diameter is the number of pigment particles. The average particle size of the pigment is the value obtained from the particle size of the pigment measured by the dynamic light scattering method (DLS). For the fully diluted photosensitive resin composition (usually the pigment concentration is adjusted to about 0.005-0.2% by mass. However, it depends on the measuring machine, if there is a recommended concentration, it should be based on the concentration), at 25°C. Determination.

In addition to organic pigments and inorganic black pigments, dyes can also be used. Examples of dyes that can be used as colorants include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine Department of dyes, etc.

Examples of azo-based dyes include: C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, C.I. Mordant Black 7.

Examples of anthraquinone dyes include C.I. Vat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, and C.I. Disperse Blue 60. Examples of phthalocyanine dyes include C.I. Vat Blue 5. Examples of quinone imine dyes include C.I. Basic Blue 3 and C.I. Basic Blue 9. Examples of quinoline dyes include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, and C.I. Disperse Yellow 64. Examples of nitro-based dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42.

When the photosensitive resin composition of the present invention contains the (E) colorant, the content ratio of the (E) colorant is not particularly limited, but it is preferably 1 to the total solid content of the photosensitive resin composition. % by mass or more, more preferably at least 2 mass %, still more preferably at least 3 mass %, especially preferably at least 4 mass %, and more preferably at most 50 mass %, more preferably at most 30 mass %, still more preferably It is 20 mass % or less, more preferably 15 mass % or less, especially preferably 12 mass % or less, most preferably 10 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, further preferably 2 to 20% by mass, further preferably 2 to 15% by mass, still more preferably 3 to 12% by mass, especially Preferably, it is 4 to 10% by mass. There exists a tendency for light-shielding property to be securable by setting it as more than the said lower limit. Since alkali-soluble resin and a photopolymerizable compound increase relatively by making it below the said upper limit, there exists a tendency for the curability of a coating film and ink repellency to improve.

When aiming at light-scattering property, the white pigment (E2) can be used partly or entirely in (E) coloring agent. Examples of the white pigment (E2) include metal oxides such as titanium oxide, zirconium oxide, hafnium oxide, and barium titanate, and inorganic fillers such as calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate. White pigment (E2) can be used alone or in combination of two or more.

From the viewpoint of refractive index and light scattering properties, metal oxides are preferably used, more preferably titanium oxide, zirconium oxide, and hafnium oxide, and still more preferably titanium oxide.

When the photosensitive resin composition of the present invention contains the white pigment (E2), it is preferably at least 1% by mass, more preferably at least 2% by mass, based on the total solid content of the photosensitive resin composition, and further Preferably at least 3% by mass, particularly preferably at least 4% by mass, and preferably at most 50% by mass, more preferably at most 30% by mass, further preferably at most 20% by mass, and still more preferably at most 15% by mass or less, preferably 10% by mass or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-50 mass % is preferable, 1-30 mass % is more preferable, 2-20 mass % is more preferable, 3-15 mass % is still more preferable, 4-10 mass % is especially preferable. By setting it as more than the said lower limit, there exists a tendency for a high refractive index and light-scattering property to be optimized. By setting it below the said upper limit, the transmittance in an ultraviolet region can be made high, and the curability of a coating film and ink repellency tend to improve.

[1-1-6] (F) Dispersant When the photosensitive resin composition of the present invention contains the (E) colorant, in order to finely disperse the (E) colorant and keep the dispersed state stable, (F) A dispersant may also be included. As the (F) dispersant, it is preferably a polymer dispersant with a functional group. In terms of dispersion stability, it is more preferably a carboxyl group, a phosphoric acid group, a sulfonic acid group or a salt group thereof; , secondary or tertiary amine groups; quaternary ammonium bases; polymer dispersants derived from nitrogen-containing heterocyclic rings such as pyridine, pyrimidine, and pyrimidine. From the point of view that the pigment can be dispersed with a small amount of dispersant, it is especially preferred to have a primary, secondary or tertiary amine group; a quaternary ammonium base; derived from pyridine, pyrimidine, pyridine, etc. Polymer dispersant for basic functional groups such as heterocyclic groups.

Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, monomers containing amino groups and macromolecular dispersants. Monomer dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan aliphatic ester dispersant, fat Family modified polyester dispersant.

Examples of such dispersants include trade names such as EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Corporation), Disparlon (registered trademark, manufactured by Kusumoto Chemical 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.). One polymer dispersant can be used alone, or two or more can be used in combination.

The weight average molecular weight (Mw) of the polymer dispersant is preferably at least 700, more preferably at least 1,000, and is preferably at most 100,000, more preferably at most 50,000. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 700 to 100,000, more preferably 1,000 to 50,000.

From the viewpoint of the dispersibility of the pigment, the (F) dispersant preferably contains either or both of a functional group-containing urethane-based polymer dispersant and an acrylic-based polymer dispersant, especially preferably Contains acrylic polymer dispersant. In terms of dispersibility and preservation, polymer dispersants with basic functional groups and either or both of polyester bonds and polyether bonds are preferred.

Examples of urethane-based and acrylic polymer dispersants include: DISPERBYK-160-167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic) (all manufactured by BYK-Chemie). Urethane-based polymer dispersants include, for example, polyisocyanate compounds, compounds with a number average molecular weight of 300 to 10,000 containing one or two hydroxyl groups in the same molecule, and reactive polyisocyanate compounds in the same molecule. A dispersed resin with a weight average molecular weight of 1,000-200,000 obtained by reacting hydrogen with a tertiary amino compound. These are treated with a quaternization agent such as benzyl chloride, whereby all or part of the tertiary amine groups can be converted into quaternary ammonium groups.

Examples of the polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as benzylidine diisocyanate; fatty acids such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate Cycloaliphatic diisocyanates such as isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω,ω'-diisocyanatodimethylcyclohexane, etc.; benzene Dimethyl diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate and other aliphatic diisocyanates with aromatic rings; lysine triisocyanate, 1,6,11-undecyl alkane triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tri(isocyanate phenylmethane), tris(isocyanatophenyl)phosphorothioate and other triisocyanates; their trimers, their water adducts, and their polyol adducts. The polyisocyanate is preferably a trimer of organic diisocyanate, particularly preferably a trimer of toluene diisocyanate or a trimer of isophorone diisocyanate. One type of polyisocyanate compound may be used alone, or two or more types may be used in combination.

As a method for producing a trimer of isocyanate, the following method can be cited: using a suitable trimerization catalyst, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, polyisocyanate Partial trimerization of similar isocyanate groups. After the trimerization is stopped by adding catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation, and the target polyisocyanurate group is obtained. isocyanate.

Examples of compounds containing one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include: polyether diol, polyester diol, polycarbonate diol, polyolefin diol, etc., and the use of carbon number An alkyl group of 1 to 25 is obtained by alkoxylation of one of the terminal hydroxyl groups of these compounds, and a mixture of two or more of these compounds. Examples of the polyether diol include: polyether diol, polyether ester diol, and mixtures of two or more of these. Examples of polyether diols include polyether diols obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, Polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and mixtures of two or more thereof.

Examples of polyether ester diols include reacting ether group-containing diols or mixtures with other diols with dicarboxylic acids or their anhydrides, or reacting polyester diols with alkylene oxides. The resulting polyether ester diol is, for example, poly(polyoxytetramethylene) adipate. The polyether diol is preferably polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound obtained by alkoxylation of one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbons.

Examples of polyester diols include: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or the like Anhydrides and diols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol Alcohol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1 ,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-Trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8 -Aliphatic diols such as octamethylene glycol, 2-methyl-1,8-octamethylene glycol, and 1,9-nonanediol, and alicyclic diols such as bishydroxymethylcyclohexane , aromatic diols such as benzenedimethanol and bishydroxyethoxybenzene, and N-alkyldialkanolamines such as N-methyldiethanolamine), polyester diols obtained by polycondensation, such as polyethylene adipate ester, polybutylene adipate, polyhexamethylene adipate, polyethylene adipate/propylene glycol; or use the above-mentioned diols or monohydric alcohols with 1 to 25 carbons as the starting The polylactone diol or polylactone monoalcohol obtained by using an agent, such as polycaprolactone diol, polymethylvalerolactone, and a mixture of two or more thereof. As the polyester diol, polycaprolactone diol and polycaprolactone obtained by using an alcohol having 1 to 25 carbon atoms as a starter are particularly preferable.

Examples of polycarbonate diols include: poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, etc.; examples of polyolefin diols include : Polybutadiene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol.

A compound having a number average molecular weight of 300 to 10,000 containing one or two hydroxyl groups in the same molecule may be used alone or in combination of two or more.

The number average molecular weight of the compound containing one or two hydroxyl groups in the same molecule is preferably from 300 to 10,000, more preferably from 500 to 6,000, and still more preferably from 1,000 to 4,000.

In the compound containing active hydrogen and tertiary amine group in the same molecule, as active hydrogen, that is, hydrogen atom directly bonded to oxygen atom, nitrogen atom or sulfur atom, examples include: hydroxyl group, amino group, thiol group The hydrogen atom in the functional group, among them, preferably the hydrogen atom of the amine group, especially the primary amine group.

The tertiary amino group is not particularly limited, and examples thereof include an amino group containing an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, and examples of the heterocyclic structure include an imidazole ring and a triazole ring.

Examples of compounds containing active hydrogen and tertiary amine groups in the same molecule include: N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine , N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethyl ethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butylenediamine, N,N-diethyl -1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine.

Examples of the nitrogen-containing heterocycle in the case where the tertiary amino group is a nitrogen-containing heterocycle structure include: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring , benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring and other nitrogen-containing 5-membered rings, pyridine ring, pyridine ring, pyrimidine ring, three-ring , quinoline ring, acridine ring, isoquinoline ring and other nitrogen-containing 6-membered rings, preferably imidazole ring and triazole ring.

Examples of compounds containing an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole. Examples of compounds containing 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, 3-amino-1-benzyl-1H-2,4-triazole. Preferred are N,N-dimethyl-1,3-propylenediamine, N,N-diethyl-1,3-propylenediamine, 1-(3-aminopropyl)imidazole, 3-amine base-1,2,4-triazole. The compound containing imidazole ring or triazole ring and amine group can be used alone or in combination of two or more.

As a preferred blending ratio of raw materials for the production of urethane-based polymer dispersants, relative to 100 parts by mass of polyisocyanate compounds, the compound with a number average molecular weight of 300-10000 containing one or two hydroxyl groups in the molecule is 10-10 200 parts by mass, preferably 20-190 parts by mass, more preferably 30-180 parts by mass, 0.2-25 parts by mass, preferably 0.3-24 parts by mass of compounds containing active hydrogen and tertiary amine groups in the same molecule share.

The urethane-based polymer dispersant can be produced in accordance with known methods for producing polyurethane resins. As solvents during production, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; ethyl acetate, butyl acetate, acetic acid soluble Esters such as fiber agent; Hydrocarbons such as benzene, toluene, xylene, hexane, etc.; Some alcohols such as diacetone alcohol, isopropanol, second butanol, third butanol, etc.; Chlorides such as dichloromethane, chloroform, etc.; Ethers such as tetrahydrofuran and diethyl ether; aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide. One kind of solvent can be used alone, or two or more kinds can be used in combination.

When producing a urethane-based polymer dispersant, for example, a urethane-forming reaction catalyst is used. Examples of the urethanization reaction catalyst include tin-based products such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate, iron acetylacetonate, and iron chloride. Such as iron series, triethylamine, triethylenediamine and other tertiary amine series. Urethane reaction catalysts can be used alone or in combination of two or more.

The introduction amount of compounds containing active hydrogen and tertiary amine groups in the same molecule is preferably based on the amine value after the reaction, and the amine value is preferably controlled at 1-100 mgKOH/g, more preferably 5-95 mgKOH/g range of g. The amine value is the value corresponding to the acid value expressed in mg of KOH by using an acid to neutralize the basic amine group. By setting it as more than the said lower limit, there exists a tendency for a dispersibility to optimize. There exists a tendency for developability to be optimized by making it below the said upper limit.

When the isocyanate group remains in the polymer dispersant, it is preferable to deactivate the isocyanate group with an alcohol or an amine compound because the stability of the product over time is improved.

The weight-average molecular weight (Mw) of the urethane-based polymer dispersant is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, and still more preferably from 3,000 to 50,000. There exists a tendency for dispersibility and dispersion stability to be optimized by making it more than the said lower limit. By making it below the said upper limit, there exists a tendency for solubility to improve and dispersibility to optimize.

As an acrylic polymer dispersant, it is preferable to use unsaturated group-containing monomers with functional groups (the functional groups mentioned here refer to the above-mentioned functional groups contained in polymer dispersants) and monomers without functional groups. Random copolymers, graft copolymers, and block copolymers of monomers containing unsaturated groups. These copolymers can be produced by known methods.

Examples of unsaturated group-containing monomers having functional groups include (meth)acrylic acid, 2-(meth)acryloxyethylsuccinic acid, 2-(meth)acryloxyethyl Unsaturated monomers with carboxyl groups such as phthalic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, dimerized acrylic acid, dimethylaminoethyl (meth)acrylate, (methyl ) unsaturated monomers with tertiary amine groups and quaternary ammonium groups such as diethylaminoethyl acrylate and their quaternary ammonium compounds. One type of unsaturated group-containing monomer having a functional group may be used alone, or two or more types may be used in combination.

Examples of unsaturated group-containing monomers that do not have a functional 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, ring (meth)acrylate Hexyl ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, iso(meth)acrylate, tricyclodecane (Meth)acrylates, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide , N-phenylmaleimide, N-benzylmaleimide and other N-substituted maleimides, acrylonitrile, vinyl acetate, and poly(meth)acrylic acid Methyl ester macromer, polystyrene macromer, poly(2-hydroxyethyl meth)acrylate macromer, polyethylene glycol macromer, polypropylene glycol macromer, polycaprolactone macromer, etc. giant monomer. One kind of unsaturated group-containing monomers without functional groups can be used alone, or two or more kinds can be used in combination.

The acrylic polymer dispersant is preferably an A-B or B-A-B block copolymer comprising an A segment with a functional group and a B segment without a functional group. In addition to the partial structure of unsaturated group-containing monomers, partial structures derived from the above-mentioned unsaturated group-containing monomers that do not have functional groups may be included, and these may be included in the A segment in any form of random copolymerization or block copolymerization . The content of the partial structure without functional groups in segment A is preferably 80% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less.

Block B contains a partial structure derived from the above-mentioned unsaturated group-containing monomers without functional groups, but one block B may contain partial structures derived from two or more monomers, which can be randomly copolymerized or block Any form of copolymerization is included in section B.

A-B or B-A-B block copolymers are prepared, for example, by the living polymerization method shown below. Living polymerization methods include anionic living polymerization, cationic living polymerization, and free radical living polymerization.

When synthesizing the acrylic polymer dispersant, for example, Japanese Patent Laying-Open No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B.C. Anderson, G.D. Andrews et al. al, Macromolecules, 14, 1601(1981), K. Hatada, K. Ute, et al, Polym.J. 17, 977(1985), Polym.J. 18, 1037(1986), Koichi Right, Koichi Hatada, Polymer Processing, 36, 366(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189(1989), M. Kuroki, T. Aida, J. Am.Chem. Soc, 109, 4737( 1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300(1985), D. Y. Sogoh, W.R. Hertler et al, Macromolecules, 20, 1473(1987).

The acrylic polymer dispersant that can be used among the present invention can be A-B block copolymer, also can be B-A-B block copolymer, and the A segment/B segment that constitutes this copolymer is preferably 1/99～80/20 ( mass ratio), especially preferably 5/95 to 60/40 (mass ratio). By setting it as the said range, there exists a tendency for the balance of dispersibility and storage stability to be securable. The amount of the quaternary ammonium base in 1 g of the A-B block copolymer and B-A-B block copolymer that can be used in the present invention is preferably 0.1-10 mmol. There exists a tendency for favorable dispersibility to be securable by setting it as the said range.

When the block copolymer contains amine groups generated during the production process, the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, it is preferably 10 mgKOH/g or more, more preferably It is 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, further preferably 75 mgKOH/g or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 1-100 mgKOH/g, more preferably 10-90 mgKOH/g, still more preferably 30-80 mgKOH/g, especially preferably 50-75 mgKOH/g. The amine value of dispersants such as block copolymers is represented by the mass of KOH corresponding to the amount of alkali per 1 g of the solid content in the dispersant sample except the solvent, and is measured by the following method. Accurately weigh 0.5-1.5 g of dispersant sample, place it in a 100 mL beaker, and dissolve it in 50 mL of acetic acid. Use an automatic titration device equipped with a pH electrode to neutralize and titrate the solution with 0.1 mol/L HClO ₄ acetic acid solution. The inflection point of the titration pH curve was used as the titration end point, and the amine value was obtained according to the following formula.

Amine value [mgKOH/g]=(561×V)/(W×S) [Wherein, W represents the weighted amount of the dispersant sample [g], V represents the titration at the end point of the titration [mL], S represents the dispersion Concentration of solid content of agent sample [mass%]]

The acid value of the block copolymer depends on the presence or absence and type of the acidic group as the source of the acid value, and the acid value should be relatively low, preferably below 10 mgKOH/g. The weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. There exists a tendency for favorable dispersibility to be securable by setting it as the said range.

In the case of having a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferred to have a repeating unit represented by the following general formula (r-i) ( Hereinafter, it may be referred to as "repeating unit (r-i)").

[chem 44]

In formula (ri), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent; among R ³¹ to R ³³ Two or more can also be bonded to each other to form a ring structure; R ³⁴ is a hydrogen atom or a methyl group; X is a divalent linking group; Y ^- is a counter anion.

The carbon number of the optionally substituted alkyl group in R ³¹ to R ³³ of formula (ri) is not particularly limited, but is preferably 1 or more, and is preferably 10 or less, more preferably 6 or less. For example, 1-10 are preferable, and 1-6 are more preferable. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl. , more preferably methyl, ethyl, propyl, butyl. The alkyl group may be either linear or branched. Moreover, for example, it may contain a ring structure like a cyclohexyl group and a cyclohexylmethyl group.

The carbon number of the aryl group which may have a substituent in R ³¹ to R ³³ of formula (ri) is not particularly limited, but is preferably 6 or more, and is preferably 16 or less, more preferably 12 or less. For example, 6-16 is preferable, and 6-12 is more preferable. Examples of the aryl group include: phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, preferably phenyl, methylphenyl, Ethylphenyl, dimethylphenyl, diethylphenyl, more preferably phenyl, methylphenyl, ethylphenyl.

The carbon number of the aralkyl group which may have a substituent in R ³¹ to R ³³ of formula (ri) is not particularly limited, but is preferably 7 or more, and is preferably 16 or less, more preferably 12 or less. For example, 7-16 is preferable, and 7-12 is more preferable. Examples of the aralkyl group include: phenylmethyl (benzyl), phenylethyl (phenethyl), phenylpropyl, phenylbutyl, phenylisopropyl, preferably phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, more preferably phenylmethyl group, phenylethyl group.

From the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ are each independently an alkyl or aralkyl group, more preferably R ³¹ and R ³³ are each independently a methyl or ethyl group, and R ³² is a phenylmethyl group. or phenylethyl, more preferably ^R31 and ^R33 are methyl, and ^R32 is phenylmethyl.

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

[chem 45]

In formula (r-ii), R ³⁵ and R ³⁶ independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent; R ³⁵ and R ³⁶ They can also bond with each other to form a ring structure; R ³⁷ is a hydrogen atom or a methyl group; Z is a divalent linking group.

As the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of formula (r-ii), those exemplified as R ³¹ to R ³³ of formula (ri) can be preferably used. As the aryl group which may have a substituent in R ³⁵ and R ³⁶ of formula (r-ii), those exemplified as R ³¹ to R ³³ of formula (ri) can be preferably used. As the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of formula (r-ii), those exemplified as R ³¹ to R ³³ of formula (ri) can be preferably used.

R ³⁵ and R ³⁶ are each independently preferably an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group.

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

In the formula (ri) and formula (r-ii), as the divalent linking groups X and Z, for example, an alkylene group having 1 to 10 carbons, an arylylene group having 6 to 12 carbons, -CONH-R ⁴³ -yl, -COOR ⁴⁴ -yl (where R ⁴³ and R ⁴⁴ are single bonds, alkylene groups with 1 to 10 carbons, or ether groups (alkoxyalkyl) with 2 to 10 carbons), and Preferably it is -COO-R ⁴⁴ -group. In formula (ri), Y ^- as the counter anion includes, for example, Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , and PF ₆ ^- .

The content ratio of the repeating unit represented by the formula (r-i) is not particularly limited. From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (r-i) and the content of the repeating unit represented by the formula (r-ii) The total ratio is preferably at most 60 mol %, more preferably at most 50 mol %, further preferably at most 40 mol %, especially preferably at most 35 mol %, and more preferably at most 5 mol % Above, more preferably at least 10 mol%, further preferably at least 20 mol%, especially preferably at least 30 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 5-60 mol%, more preferably 10-50 mol%, still more preferably 20-40 mol%, especially preferably 30-35 mol%.

The content ratio of the repeating unit represented by the formula (r-i) in all the repeating units of the polymer dispersant is not particularly limited. From the perspective of dispersibility, it is preferably 1 mol % or more, more preferably 5 mol % Mole % or more, and more preferably 10 mole % or more, and, preferably less than 50 mole %, more preferably less than 30 mole %, further preferably less than 20 mole %, especially preferably 15 mole % %the following. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 1-50 mol%, more preferably 1-30 mol%, still more preferably 5-20 mol%, especially preferably 10-15 mol%.

The content ratio of the repeating unit represented by the above formula (r-ii) in all the repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mole % or more, more preferably It is more than 10 mol %, more preferably 15 mol % or more, especially preferably 20 mol % or more, and more preferably 60 mol % or less, more preferably 40 mol % or less, and more preferably Less than 30 mol%, preferably less than 25 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 5-60 mol%, more preferably 10-40 mol%, still more preferably 15-30 mol%, especially preferably 20-25 mol%.

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

[chem 46]

In formula (r-iii), R ⁴⁰ is an ethylidene group or a propylidene group; R ⁴¹ is an alkyl group that may have a substituent; R ⁴² is a hydrogen atom or a methyl group; n is an integer of 1-20.

The carbon number of the alkyl group that may have a substituent in R ⁴¹ of the formula (r-iii) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 6 the following. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, and 2-6 are more preferable. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, preferably methyl, ethyl, propyl, butyl, pentyl, or Hexyl, more preferably methyl, ethyl, propyl, or butyl. The alkyl group may be either linear or branched. Moreover, for example, it may contain a ring structure like a cyclohexyl group and a cyclohexylmethyl group.

From the viewpoint of compatibility and dispersibility with solvents or binder components, n in formula (r-iii) is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable.

The content ratio of the repeating unit represented by formula (r-iii) in all the repeating units of the polymer dispersant is not particularly limited, preferably more than 1 mole%, more preferably more than 2 mole%, and more preferably It is preferably at least 4 mol%, and more preferably at most 30 mol%, more preferably at most 20 mol%, further preferably at most 10 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 4 to 10 mol%. In the case of being within the above-mentioned range, there exists a tendency for compatibility with the compatibility with a solvent or a binder component, and dispersion stability.

From the viewpoint of increasing the compatibility between the dispersant and the solvent or binder components and improving the dispersion stability, the polymer dispersant is preferably a repeating unit represented by the following general formula (r-iv) (hereinafter sometimes referred to as "repeating unit (r-iv)").

[chem 47]

In formula (r-iv), R ³⁸ is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent; R ³⁹ is a hydrogen atom or a methyl group.

The carbon number of the alkyl group which may have a substituent in ^R38 of the formula (r-iv) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, more preferably 4 or more, and preferably 10 Below, more preferably below 8. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 1-10 are preferable, 2-8 are more preferable, and 4-8 are still more preferable. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl. , more preferably methyl, ethyl, propyl, butyl. The alkyl group may be either linear or branched. Moreover, for example, it may contain a ring structure like a cyclohexyl group and a cyclohexylmethyl group.

The carbon number of the aryl group that may have a substituent in R ³⁸ of the formula (r-iv) is not particularly limited, but is preferably 6 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less. For example, 6-16 are preferable, 6-12 are more preferable, and 6-8 are still more preferable. Examples of the aryl group include: phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, preferably phenyl, methylphenyl, Ethylphenyl, dimethylphenyl, diethylphenyl, more preferably phenyl, methylphenyl, ethylphenyl.

The carbon number of the aralkyl group that may have a substituent in R ³⁸ of the formula (r-iv) is not particularly limited, and is preferably 7 or more, and preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. For example, 7-16 are preferable, 7-12 are more preferable, and 7-10 are still more preferable. Examples of the aralkyl group include: phenylmethyl (benzyl), phenylethyl (phenethyl), phenylpropyl, phenylbutyl, phenylisopropyl, preferably phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, more preferably phenylmethyl group, phenylethyl group.

From the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group, or a phenylmethyl group.

Examples of substituents that the alkyl group in R ³⁸ may have include halogen atoms and alkoxy groups. Examples of substituents that the aryl or aralkyl group in R ³⁸ may have include chain alkyl groups, halogen atoms, and alkoxy groups. The chained alkyl group represented by ^R38 includes any of linear and branched chains.

From the perspective of dispersibility, the content ratio of the repeating unit represented by the above formula (r-iv) in all the repeating units of the polymer dispersant is preferably 30 mole % or more, more preferably 40 mole % More than above, more preferably at least 50 mol%, and more preferably at most 80 mol%, more preferably at most 70 mol%. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and still more preferably 50 to 70 mol%.

The polymer dispersant may have repeating units other than repeating unit (r-i), repeating unit (r-ii), repeating unit (r-iii) and repeating unit (r-iv). As an example of such a repeating unit, for example: derived from styrene-based monomers such as styrene and α-methylstyrene, (meth)acrylic acid salt-based monomers such as (meth)acryl chloride, (meth)acrylate (meth)acrylamide-based monomers such as acrylamide, N-methylolacrylamide, vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, N-methyl Repeating unit of acrylmorpholine.

From the point of view of further improving the dispersibility, the polymer dispersant preferably comprises a segment A with repeating unit (r-i) and repeating unit (r-ii) and segment A without repeating unit (r-i) and repeating unit (r-ii). ) The block copolymer of the B segment. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing not only a quaternary ammonium group but also a tertiary amine group in the A stage, the dispersing ability of the dispersant tends to be significantly improved. Block B preferably has a repeating unit (r-iii), more preferably further has a repeating unit (r-iv).

Repeating unit (r-i) and repeating unit (r-ii) can be contained in any form of random copolymerization or block copolymerization in segment A. The repeating unit (r-i) and repeating unit (r-ii) contained in one segment A may be one or two or more. In this case, each repeating unit may be contained in any form of random copolymerization or block copolymerization in section A.

Repeating units other than repeating unit (r-i) and repeating unit (r-ii) may be contained in segment A. Examples of such repeating units include: repeating units derived from the above-mentioned (meth)acrylate monomers . The content of repeating units other than repeating unit (r-i) and repeating unit (r-ii) in section A is preferably 0-50 mol%, more preferably 0-20 mol%, especially preferably 0 mol% .

Repeating units other than repeating units (r-iii) and (r-iv) may be contained in the B segment. Examples of such repeating units include: (meth)acrylamide monomers, (meth)acrylamide monomers such as (meth)acryl chloride, (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide, vinyl acetate Repeating unit of ester, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, N-methacryl morpholine. The content of repeating units other than repeating unit (r-iii) and repeating unit (r-iv) in segment B is preferably 0-50 mol%, more preferably 0-20 mol%, especially preferably 0 mol% Ear%.

When the photosensitive resin composition of the present invention contains (F) a dispersant, its content ratio is not particularly limited, but it is preferably 0.1% by mass or more, more preferably It is preferably at least 0.5% by mass, more preferably at most 8% by mass, more preferably at most 5% by mass, further preferably at most 3% by mass, particularly preferably at most 2% by mass. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 0.1-8 mass % is preferable, 0.1-5 mass % is more preferable, 0.5-3 mass % is still more preferable, and 0.5-2 mass % is especially preferable. By setting it as more than the said lower limit, it exists in the tendency which can suppress generation|occurrence|production of residue by an aggregate. There exists a tendency for ink repellency or developability to improve by being below the said upper limit.

[1-1-7] Ultraviolet absorber The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The purpose of adding the ultraviolet absorber is to control the photohardening distribution by absorbing the specific wavelength of the light source used for exposure with the ultraviolet absorber. By adding an ultraviolet absorber, it is possible to obtain, for example, the effect of forming a high-definition barrier rib with a thinner line width and removing the residue remaining in the non-exposed portion after development. As the ultraviolet absorber, from the viewpoint of suppressing the light absorption of the (B) photopolymerization initiator, for example, a compound having an absorption maximum value at a wavelength of 250 nm to 400 nm can be used.

As the ultraviolet absorber, it is preferable to contain any one or both of benzotriazole-based compounds and trioxane-based compounds. It is considered that by including either or both of the benzotriazole-based compound and the triazole-based compound, the light absorption rate of the initiator at the bottom of the film is reduced, and the line width of the lower part of the coating film is reduced. High-definition barrier ribs with thinner line width.

Examples of benzotriazole-based compounds include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H- Benzotriazole, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-th Tributyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethylhexyl propionate, 2-[2-hydroxy-3,5-bis(α ,α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary 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, 3-[3-tert-butyl-5-(5-chloro-2H -Ester compounds of benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid and C7-9 linear and branched chain alkyl alcohols.

Examples of commercially available benzotriazole-based compounds include: SUMISORB (registered trademark, hereinafter the same) 200, SUMISORB250, SUMISORB300, SUMISORB340, SUMISORB350 (manufactured by Sumitomo Chemical); Industrial manufacturing); TINUVIN (registered trademark, the same below) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF); EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Yongguang Chemical Industry); Tomissorb (registered trademark, hereinafter the same) 100, Tomissorb600 (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.).

Examples of trioxane-based compounds include: 2-[4,6-bis(2,4-xylyl)-1,3,5-trizil-2-yl]-5-octyloxyphenol, 2 -[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri-2-yl]-5-[3-(dodecyloxy)-2-hydroxyl Propoxy]phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethanone and 2-ethylhexyl The reaction product of glycidyl ether, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-tributoxyphenyl, From the viewpoint of ink repellency and formation of high-definition barrier ribs with thinner line widths, hydroxyphenyl trisulfone compounds are preferred.

Examples of commercially available trioxane-based compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

Examples of other ultraviolet absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and derivatives thereof, binaphthyl compounds, phenanthroline compounds, and dyes. For example, SUMISORB130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongguang Chemical Industry), Tomissorb800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107 (SEESORB107, SEESORB107) Kasei) and other benzophenone compounds; SUMISORB400 (Sumitomo Chemical), benzoate compounds such as phenyl salicylate; 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate , Isopropyl Methoxycinnamate, Isoamyl Methoxycinnamate and other cinnamic acid derivatives; 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 Hydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other naphthalene derivatives; anthracene, 9,10-dihydroxyanthracene and other anthracene and its derivatives; azo series Dyes, benzophenone-based dyes, aminoketone-based dyes, quinoline-based dyes, anthraquinone-based dyes, diphenylcyanoacrylate-based dyes, trisanthin-based dyes, p-aminobenzoic acid-based dyes, and other dyes. From the viewpoint of ink repellency, cinnamic acid derivatives and naphthalene derivatives are preferred, and cinnamic acid derivatives are particularly preferred.

From the viewpoint of inclined shape, any one or both of a benzotriazole-based compound and a hydroxyphenyltriazole-based compound is preferable, and a benzotriazole-based compound is particularly preferable.

One kind of ultraviolet absorber may be used alone, or two or more kinds may be used in combination.

When the photosensitive resin composition of the present invention contains an ultraviolet absorber, its content ratio is not particularly limited, but it is preferably 0.01% by mass or more, more preferably 0.05 mass % or more, more preferably 0.1 mass % or more, still more preferably 0.5 mass % or more, especially preferably 1 mass % or more, and more preferably 15 mass % or less, more preferably 10 mass % or less, and further preferably Preferably it is 5 mass % or less, Especially preferably, it is 3 mass % or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 0.01 to 15% by mass, more preferably 0.05 to 15% by mass, still more preferably 0.1 to 10% by mass, still more preferably 0.5 to 5% by mass, and particularly preferably 1 to 3% by mass. By setting it as more than the said lower limit, it exists in the tendency for the formation of the high-definition barrier rib with a narrow line width to be possible. There exists a tendency for ink repellency to become high by making it below the said upper limit.

When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the compounding ratio of the ultraviolet absorber to (B) photopolymerization initiator is 100 parts by mass relative to (B) photopolymerization initiator The blending amount is preferably at least 1 part by mass, more preferably at least 10 parts by mass, more preferably at least 30 parts by mass, even more preferably at least 50 parts by mass, especially preferably at least 80 parts by mass, and more preferably It is 500 mass parts or less, More preferably, it is 300 mass parts or less, More preferably, it is 200 mass parts or less, Most preferably, it is 100 mass parts or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, preferably 1-500 mass parts, more preferably 10-500 mass parts, still more preferably 30-300 mass parts, still more preferably 50-200 mass parts, especially preferably 80-100 mass parts. By setting it as more than the said lower limit, it exists in the tendency for the formation of the high-definition barrier rib with a narrow line width to be possible. There exists a tendency for ink repellency to become high by making it below the said upper limit.

[1-1-8] Polymerization inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, since radical polymerization is suppressed, it exists in the tendency for the inclination angle of the obtained barrier rib to be enlarged. Examples of polymerization inhibitors include: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT ). From the viewpoint of polymerization inhibiting ability, hydroquinone, methoxyphenol, and methylhydroquinone are preferable, and methylhydroquinone is more preferable. One kind of polymerization inhibitor may be used alone, or two or more kinds may be used in combination.

Depending on the production method of (C) alkali-soluble resin, the produced alkali-soluble resin may contain a polymerization inhibitor. In this case, the alkali-soluble resin may be used as it is in the state where the polymerization inhibitor is contained, or in addition to the polymerization inhibitor contained in the resin, the same or different substances may be added when producing the photosensitive resin composition. Polymerization inhibitor.

When the photosensitive resin composition contains a polymerization inhibitor, the content ratio is not particularly limited, but it is preferably 0.0005% by mass or more, more preferably 0.001% by mass relative to the total solid content of the photosensitive resin composition Above, more preferably at least 0.01% by mass, and more preferably at most 0.1% by mass, more preferably at most 0.08% by mass, still more preferably at most 0.05% by mass. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 0.0005 to 0.1 mass %, more preferably 0.001 to 0.08 mass %, and still more preferably 0.01 to 0.05 mass %. By setting it as more than the said lower limit, it exists in the tendency which can increase an inclination angle. There exists a tendency for ink repellency to become high by making it below the said upper limit.

[1-1-9] Thermal polymerization initiator The photosensitive resin composition of the present invention may also contain a thermal polymerization initiator. There exists a tendency for the degree of crosslinking of a film to be increased by containing a thermal-polymerization initiator. As such a thermal polymerization initiator, an azo compound, an organic peroxide, and hydrogen peroxide are mentioned, for example. One of these can be used alone, or two or more can be used in combination.

When using a thermal polymerization initiator in combination with a photopolymerization initiator in order to improve the ink repellency or increase the crosslinking density of the film, it is preferable to make the total content ratio of these in the photosensitive resin composition described above. The content ratio of the photopolymerization initiator, and the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator, from the viewpoint of ink repellency, it is preferable to make the thermal polymerization initiator relative to the photopolymerization initiator. 100 parts by mass of the starter is 5 to 300 parts by mass.

[1-1-10] Amino compound The photosensitive resin composition of the present invention may also contain an amine compound in order to accelerate thermosetting. When the photosensitive resin composition of the present invention contains an amino compound, the content ratio of the amino compound is preferably 40% by mass or less, more preferably 30% by mass or less, and preferably at least 0.5% by mass, more preferably at least 1% by mass. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 0.5-40 mass % is preferable, and 1-30 mass % is more preferable. There exists a tendency for storage stability to be maintained by making it below the said upper limit. There exists a tendency for sufficient thermosetting property to be securable by setting it as more than the said lower limit.

As the amino compound, for example, an amino compound having at least two functional groups among a methylol group and an alkoxymethyl group obtained by condensation-modifying the methylol group with an alcohol having 1 to 8 carbon atoms is exemplified. Specifically, for example, melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; Urea resin formed by polycondensation of urea and formaldehyde; resin formed by co-condensing two or more of melamine, benzoguanamine, glycoluril or urea with formaldehyde; modified by alcohol condensation of the methylol groups of the above resins The modified resin; preferably melamine resin and its modified resin, the modified resin is more preferably a modified resin with a methylol modification ratio of 70% or more, and more preferably a modified resin with a methylol modification ratio of 80% or more. One kind of amino compound can be used alone, or two or more kinds can be used in combination.

Examples of melamine resins and modified resins thereof include "Cymel" (registered trademark, hereinafter the same) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701 manufactured by Cytec Corporation. , 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "NIKALAC" (registered trademark, the same below) manufactured by Sanwa Chemical Co., Ltd. MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302. Examples of benzoguanamine resins and modified resins thereof include "Cymel" 1123, 1125, and 1128 manufactured by Cytec Corporation. Examples of glycoluril resins and modified resins thereof include "Cymel" 1170, 1171, 1174, and 1172 manufactured by Cytec Corporation, and "NIKALAC" MX-270 manufactured by Sanwa Chemical Co., Ltd. Examples of urea resins and modified resins thereof include "UFR" (registered trademark) 65 and 300 manufactured by Cytec Corporation, and "NIKALAC" MX-290 manufactured by Sanwa Chemical Co., Ltd.

[1-1-11] Silane coupling agent In order to improve the adhesion with the substrate, the photosensitive resin composition of the present invention may also contain a silane coupling agent. As the silane coupling agent, for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are preferred. . When the photosensitive resin composition of the present invention contains a silane coupling agent, its content is preferably 20% by mass or less with respect to the total solid content of the photosensitive resin composition from the viewpoint of adhesion, more preferably Preferably, it is 15% by mass or less.

[1-1-12] Inorganic filler In order to improve the strength of the cured product, and to realize the excellent verticality of the coating film and increase the inclination angle by utilizing the appropriate interaction with the alkali-soluble resin (formation of a matrix structure), etc., The photosensitive resin composition of the present invention may also contain an inorganic filler. Examples of inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those obtained by surface-treating them with various silane coupling agents. In particular, silica sol and silica sol-modified products tend to have both excellent dispersion stability and the effect of increasing the inclination angle, so they are preferable.

The average particle diameter of the inorganic filler is preferably from 0.005 to 2 μm, more preferably from 0.01 to 1 μm. The average particle diameter is a value measured by a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter Co., Ltd. or the like.

When the photosensitive resin composition of the present invention contains an inorganic filler, its content is preferably 5% by mass relative to the total solid content of the photosensitive resin composition from the viewpoint of ink repellency. The above, more preferably at least 10% by mass, and more preferably at most 80% by mass, more preferably at most 70% by mass. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, 5-80 mass % is preferable, and 10-70 mass % is more preferable.

[1-1-13] Adhesion improving agent The photosensitive resin composition of the present invention may contain an adhesion improving agent in order to impart adhesion to the substrate. As an adhesive improvement agent, the vinylic monomer of phosphoric acid system is mentioned, for example. As the ethylenic monomer of phosphoric acid system, it is preferably phosphoric acid esters containing (meth)acryloyloxy group, preferably the (methyl) ) Phosphate esters of acryloxy.

[chem 48]

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

Phosphate-based vinyl monomers may be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains a phosphoric acid-based vinyl monomer as an adhesion improving agent, its content ratio is preferably 0.02% by mass or more with respect to the total solid content of the photosensitive resin composition. More preferably at least 0.05% by mass, more preferably at least 0.1% by mass, especially preferably at least 0.2% by mass, more preferably at most 4% by mass, more preferably at most 3% by mass, further preferably at most 2% by mass or less, preferably 1% by mass or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 0.02 to 4% by mass, more preferably 0.05 to 3% by mass, further preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass. There exists a tendency for the improvement effect of the adhesiveness with a board|substrate to be enough by making it more than the said lower limit. By setting it as below the said upper limit, it exists in the tendency which becomes easy to suppress the adhesiveness deterioration with a board|substrate.

[1-1-14] Solvent The photosensitive resin composition of the present invention usually contains a solvent, and is used in a state where each component contained in the photosensitive resin composition is dissolved or dispersed in the solvent. It does not specifically limit as this solvent, For example, the organic solvent described below is mentioned.

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 tertiary butyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methyl Oxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether and other glycol monoalkyl ethers; ethylene glycol dimethyl ether, ethylene glycol di 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 ether, etc. Glycol dialkyl ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, 3-methoxy-1-butyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether Acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol Glycol alkyl ether acetates such as monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethylene glycol diacetate, propylene glycol diacetate, 1,3 -Diol diacetates such as butanediol diacetate, 1,4-butanediol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate Classes; Ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl Ketones such as butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; Methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol , butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol and other monohydric or polyhydric alcohols; n-pentane, n-octane, diisobutylene, Aliphatic hydrocarbons such as n-hexane, hexene, isoprene, dipentene, and dodecane; lipids such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl Cyclic hydrocarbons; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, isobutyric acid Methyl propionate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, ethyl benzoate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, gamma - Chain or cyclic esters such as butyrolactone; Alkoxy carboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated compounds such as chlorobutane and chloropentane Hydrocarbons; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile; Tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

As a commercially available solvent, for example, mineral spirits, Varsol#2, Apco#18 solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso#150, Shell TS28 solvent, carbitol, ethyl alcohol, Base carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl acetate cellosolve, methyl acetate cellosolve, diethylene glycol dimethyl ether (all trade names) .

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

One kind of solvent may be used alone, or two or more kinds may be used in combination. The solvent is preferably such that the content ratio of the total solids in the solution of the photosensitive resin composition is preferably at least 10% by mass, more preferably at least 15% by mass, further preferably at least 20% by mass, and most preferably at least 20% by mass. 25% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, particularly preferably 35% by mass or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferable that the content ratio of the total solids in the photosensitive resin composition solution is preferably 10 to 90% by mass, more preferably 15 to 50% by mass, still more preferably 20 to 40% by mass, More preferably, it is used in the form of 25 to 35% by mass. By setting it as more than the said lower limit, it exists in the tendency which can suppress generation|occurrence|production of coating unevenness. There exists a tendency for generation|occurrence|production of a foreign material, shrinkage, etc. to be suppressed by making it below the said upper limit.

[1-2] Preparation method of photosensitive resin composition The photosensitive resin composition of the present invention is prepared by mixing the components contained in the photosensitive resin composition with a mixer. For example, when the (E) colorant contains a component that does not require a solvent such as a pigment, it is preferable to use a paint conditioner, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, etc. in advance. Distributed processing. Since the (E) colorant is micronized by the dispersion treatment, the coating properties of the photosensitive resin composition are improved.

Dispersion treatment is generally preferably carried out in a system in which (E) a colorant, a solvent, and (F) a dispersant are used in combination, or in a system in which any or all of (C) an alkali-soluble resin is used in combination (hereinafter, sometimes referred to as The mixture used for dispersion treatment and the composition obtained after dispersion treatment are called "ink" or "pigment dispersion liquid"). In particular, when a polymer dispersant is used as the (F) dispersant, the obtained ink and photosensitive resin composition are excellent in dispersion stability and suppress thickening over time, which is preferable. Thus, in the step of producing the photosensitive resin composition, it is preferable to produce a pigment dispersion containing at least (E) a colorant, a solvent and (F) a dispersant. As the (E) colorant, organic solvent, and (F) dispersant that can be used in the pigment dispersion liquid, it is preferable to use the (E) colorant, organic solvent, and (F) dispersant that can be used in the photosensitive resin composition. The agent is recorded. As the content rate of each coloring agent of (E) coloring agent in a pigment dispersion liquid, what was described as the content rate in a photosensitive resin composition can be used preferably.

When dispersing the (E) colorant using a sand mill, it is preferable to use glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm. The temperature for dispersion treatment is preferably in the range of 0°C to 100°C, more 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 should be adjusted appropriately. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50-300.

The dispersed particle size of the pigment dispersed in the ink is preferably 0.03-0.3 μm, as measured by a dynamic light scattering method. Next, mix the ink obtained through the dispersion treatment with other components contained in the photosensitive resin composition to make a uniform solution or dispersion. In the production process of the photosensitive resin composition, since fine dirt may be mixed in the liquid, it is preferable to filter the obtained photosensitive resin composition with a filter or the like.

[2] Barrier rib and method for forming same The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention can be used to form a barrier wall, for example, it can be preferably used to form a barrier wall used to divide the organic layer of an organic electroluminescent element, or to divide a color containing luminescent nanocrystal grains. The barrier wall of the pixel part in the filter. The barrier wall of the present invention is composed of the cured product of the present invention. The method of forming barrier ribs using the photosensitive resin composition of the present invention is not particularly limited, and previously known methods can be used. When forming a cured product using the photosensitive resin composition of the present invention, it is preferable to include at least the following steps (1) to (4). Step (1): The step of coating the photosensitive resin composition of the present invention on the substrate to form a coating film. Step (2): a step of exposing at least a part of the coating film formed in step (1). Step (3): a step of developing the exposed coating film in step (2). Step (4): The step of firing the developed coating film in step (3).

<Step (1): Step of coating a photosensitive resin composition on a substrate to form a coating film> As a supply method of supplying a photosensitive resin composition to a board|substrate, an inkjet method and a photolithography method are mentioned, for example.

In the case of the inkjet method, use a photosensitive resin composition whose viscosity is adjusted by solvent dilution etc. The photosensitive resin composition is coated on the substrate to form a pattern of unhardened barrier ribs. Then, the pattern of the unhardened barrier ribs is exposed to form cured barrier ribs on the substrate. The exposure of the pattern of the uncured barrier ribs was performed in the same manner as the exposure step in the photolithography method described later, except that a mask was not used.

In the case of photolithography, the photosensitive resin composition is coated on the entire region of the substrate where barrier ribs are to be formed to form a photosensitive resin composition layer. Corresponding to the specific pattern of barrier ribs, after exposing the formed photosensitive resin composition layer, the exposed photosensitive resin composition layer is developed to form barrier ribs on the substrate.

In the coating step of coating the photosensitive resin composition on the substrate in the photolithography method, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater is used or Non-contact coating devices such as spin coater (spin coating device) and curtain-type flat coater coat the photosensitive resin composition on the substrate to be formed with barrier walls. After supplying the photosensitive resin composition on the substrate, it is preferable to dry it to form a coating film. Drying is preferably a drying method using a heating plate, an IR oven, or a convection oven. It can also be combined with drying in a decompression chamber to avoid the decompression drying method where the temperature is too high. Drying conditions can be appropriately selected according to the type of solvent components, the performance of the dryer used, and the like. Drying time depends on the type of solvent components, the performance of the dryer used, etc., usually at a temperature of 40°C to 100°C within the range of 15 seconds to 5 minutes, preferably at a temperature of 50°C to 80°C Choose from the range of 30 seconds to 3 minutes. Moreover, it is preferable to carry out within the range which does not exceed the calcination temperature mentioned later.

<Step (2): Step of exposing at least a part of the coating film formed in step (1)> In the exposing step, the photosensitive resin composition is irradiated with an active substance such as ultraviolet rays or excimer laser light using a negative mask. The energy ray corresponds to the pattern of the barrier ribs and partially exposes the photosensitive resin composition layer. Light sources emitting ultraviolet rays, such as high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, and carbon arc lamps, can be used for exposure. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to 400 mJ/cm ² , for example.

<Step (3): The step of developing the exposed coating film in step (2) > In the developing step, the exposed photosensitive resin composition layer corresponding to the pattern of the barrier ribs is developed with a developer, Thereby, a barrier wall is formed. The image development method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of developing solutions include organic systems such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. . Moreover, you may add an antifoaming agent or surfactant to a developer.

After the development step, an exposure step (post-exposure step) is further carried out as necessary. The developed barrier ribs are exposed to active energy rays such as ultraviolet rays and excimer laser light. At this time, partial exposure using a mask can also be used. Light sources emitting ultraviolet rays such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, and UV-FL (ultraviolet fluorescent lamps) can be used for exposure. The exposure amount varies depending on the composition of the photosensitive resin composition, and is preferably at least 10 mJ/cm ² , more preferably at least 100 mJ/cm ² , further preferably at least 500 mJ/cm ² , especially preferably at least 800 mJ/cm 2 cm ² or more, and preferably 10000 mJ/cm ² or less, more preferably 5000 mJ/cm ² or less, further preferably 2000 mJ/cm ² or less. For example, it is preferably 10-10000 mJ/cm ² , more preferably 100-10000 mJ/cm ² , further preferably 500-5000 mJ/cm ² , especially preferably 800-2000 mJ/cm ² . Bleeding resistance tends to improve by setting it as more than the said lower limit. By setting it as below the said upper limit, it is preferable at the point which can simultaneously achieve acquisition of anti-bleeding property, and avoid too long irradiation time and ensure productivity.

<Step (4): Step of baking the developed coating film in step (3)> Baking (post-baking) the barrier ribs after development or subsequent exposure after development, that is, heat hardening treatment . The conditions for firing (post-baking) are preferably at least 80°C, more preferably at least 90°C, preferably at most 250°C, more preferably at most 200°C, further preferably at most 180°C, and still more preferably at most 250°C. Preferably it is below 140°C, especially preferably below 120°C, most preferably below 100°C. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 80-250°C, more preferably 80-200°C, further preferably 80-180°C, further preferably 80-140°C, further preferably 80-120°C, and still more preferably 80-120°C. 100°C, preferably 90-100°C. Bleeding resistance or heat resistance tend to be favorable by setting it as more than a lower limit. By making it below the upper limit, there exists a tendency for manufacturing cost reduction and the influence on the board|substrate of limited heat resistance, such as a plastic board|substrate, and a device to reduce. The roasting time is preferably 5 to 120 minutes.

The substrate used for forming the barrier ribs is not particularly limited, and is appropriately selected according to the type of organic electroluminescence element or color filter manufactured using the substrate on which the barrier ribs are formed. Examples of suitable substrate materials include glass and various resin materials. Examples of the resin material include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonates; poly(meth)acrylic resins; polyethylene; In terms of excellent heat resistance, glass and polyimide are preferable. Depending on the type of organic electroluminescent element or color filter to be produced, a transparent electrode layer such as ITO or ZnO may also be provided in advance on the surface of the substrate for forming barrier ribs. Moreover, the barrier rib for color filters can also be formed on the board|substrate which has an element. In order to improve the surface physical properties such as adhesion, the substrate can also be subjected to various resin film forming treatments such as corona discharge treatment, ozone treatment, silane coupling agent or urethane resin as needed.

The film thickness of the barrier rib of the present invention is preferably at least 0.1 μm, more preferably at least 1 μm, further preferably at least 5 μm, especially preferably at least 10 μm, and more preferably at most 1 mm, more preferably at least 100 μm. μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, especially preferably 20 μm or less. The above-mentioned upper limit and lower limit may be combined arbitrarily. For example, it is preferably 0.1 μm to 1 mm, more preferably 0.1 to 100 μm, further preferably 1 to 50 μm, still more preferably 5 to 30 μm, and especially preferably 10 to 20 μm. There exists a tendency for light-shielding property to improve by making it more than the said lower limit. Adhesiveness tends to improve by making it below the said upper limit. The film thickness of the barrier wall is measured using a step difference, surface roughness, and micro shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectrometer, and an electron microscope.

[3] Organic electroluminescence element The organic electroluminescence element of the present invention has the barrier rib of the present invention. Various organic electroluminescence elements were produced using the substrate having the barrier rib pattern produced by the method described above. The method of forming the organic electroluminescent element is not particularly limited, preferably, after forming the pattern of the barrier ribs on the substrate by the above method, injecting ink into the area surrounded by the barrier walls on the substrate to form organic layers such as pixels , thereby fabricating organic electroluminescent elements.

As a type of organic electroluminescence element, a bottom emission type or a top emission type is mentioned, for example. Bottom emission type, for example, is produced by forming a barrier wall on a glass substrate laminated with a transparent electrode, and laminating a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer in an opening surrounded by the barrier wall. The top emission type is manufactured by, for example, forming a barrier wall on a glass substrate laminated with a metal electrode layer, and laminating an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the barrier wall.

When the barrier ribs are skirt-shaped, the bottom of the barrier ribs repels the ink for forming an organic layer, and therefore, the region surrounded by the barrier ribs may not be sufficiently covered with the ink for forming an organic layer. On the other hand, by forming a favorable shape without a skirt, it is possible to sufficiently cover the region surrounded by the barrier ribs with the ink for forming an organic layer. Thereby, for example, the problem of halation in an organic EL display element can be solved.

As the solvent used when preparing the ink for forming an organic layer, water, an organic solvent, and a mixed solvent of these can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after the ink is injected. Examples of organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, and ethanol , isopropanol, ethyl acetate, butyl acetate, 3-phenoxytoluene. Surfactants, antioxidants, viscosity modifiers, UV absorbers, etc. can be added to the ink.

As a method of injecting ink into the region surrounded by the barrier ribs, an inkjet method is preferable in that a small amount of ink can be easily injected into a specific portion. The ink used for forming the organic layer is appropriately selected according to the kind of organic electroluminescent element to be produced. In the case of injecting ink by the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected from the inkjet head well, but it is preferably 4 to 20 mPa·s, more preferably 5 to 10 mPa・s. The viscosity of the ink can be adjusted by adjusting the solid content of the ink, changing the solvent, adding a viscosity modifier, etc.

Examples of the light-emitting layer include organic electroluminescent layers described in Japanese Patent Application Laid-Open No. 2009-146691 or Japanese Patent No. 5734681 . Quantum dots as described in Japanese Patent No. 5653387 or Japanese Patent No. 5653101 may also be used.

[4] Color filter containing luminescent nanocrystal grains The color filter comprising luminescent nanocrystal grains of the present invention is not particularly limited as long as it has the barrier wall of the present invention, and can be listed in the categories classified by barrier walls. Regions form pixels.

FIG. 1 is a schematic cross-sectional view of an example of a color filter provided with a barrier rib of the present invention. As shown in FIG. 1 , the color filter 100 includes a substrate 10 , barrier ribs 20 provided on the substrate, red pixels 30 , green pixels 40 , and blue pixels 50 . The red pixels 30 , the green pixels 40 and the blue pixels 50 are sequentially and repeatedly arranged in a grid pattern. The barrier wall 20 is disposed between the adjacent pixels. In other words, the adjacent pixels are separated from each other by barrier ribs 20 .

The red pixel 30 comprises red luminescent nanocrystals 2 and the green pixel 40 comprises green luminescent nanocrystals 1 . The blue pixel 50 is a pixel that transmits blue light from a light source.

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

Luminescent nanocrystals can emit light of a different wavelength (fluorescence or phosphorescence) from the absorbed light by absorbing light of a specific wavelength. For example, red luminescent nanocrystals 2 emit in the range of 605-665 nm Light with a luminous peak wavelength (red light), and the green luminescent nanocrystal grain 1 emits light with a luminous peak wavelength in the range of 500-560 nm (green light).

According to the solution of the Schrödinger wave equation of the well-type potential model, the wavelength (luminous color) of the light emitted by the luminescent nanocrystals depends on the size (such as particle size) of the luminescent nanocrystals, and also depends on the size of the luminescent nanocrystals. The energy gap of the crystal grains. Therefore, the luminescent color can be selected by changing the constituent material and size of the luminescent nanocrystal grains used. Examples of the luminescent nanocrystalline particles include quantum dots and the like.

The method of manufacturing a color filter including luminescent nanocrystal grains is not particularly limited, and the following methods are exemplified: preparing a substrate having barrier ribs formed of the cured product of the present invention, and forming a luminescent filter containing luminescent nanocrystals in regions divided by the barrier ribs. layer of nanocrystals. The method of forming the layer containing the luminescent nanocrystal grains is not particularly limited. For example, it can be produced by the method of selectively attaching the ink composition containing the luminescent nanocrystal grains by using an inkjet method, and irradiating active energy rays. Or heat to harden the ink composition.

[5] Image display device The image display device of the present invention includes the barrier rib of the present invention. As the image display device of the present invention, for example, an image display device including the organic electroluminescent element of the present invention can be cited. The type or structure of the image display device is not particularly limited as long as it includes an organic electroluminescent element. For example, an active-driven organic electroluminescent element can be used and assembled according to a conventional method. For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Ohmsha, Ltd., published on August 20, 2004, by Shizushi, Adachi Chihaya, and Murata Hideyuki at the time). . For example, an organic electroluminescent element that emits white light and a color filter can be combined to display an image, and an organic electroluminescent element that emits different colors such as RGB can be combined to display an image.

As the image display device of the present invention, for example, an image display device provided with the color filter including the luminescent nanocrystal particles of the present invention can be cited. Examples of types of image display devices include liquid crystal display devices, image display devices including organic electroluminescent elements, and the like. A liquid crystal display device includes a light source including a blue LED, and a liquid crystal layer including an electrode for controlling blue light emitted from the light source for each pixel unit. On the other hand, regarding an image display device including an organic electroluminescent element, an organic electroluminescent element that emits blue light is arranged at a position corresponding to each pixel portion of the above-mentioned color filter. Specifically, the method described in Unexamined-Japanese-Patent No. 2019-87746 is mentioned. [Example]

Hereinafter, specific examples are given to illustrate the photosensitive resin composition of the present invention. The present invention is not limited to the following examples unless the gist is exceeded.

＜Alkali-soluble resin-1＞ (Synthesis of Precursor Resin) Weigh 2-northene (75% by mass toluene solution, manufactured by Maruzen Petrochemical Co., Ltd., 125.5 g, 1.00 mol) and dimethyl 2,2'-azobis(2-methylpropionate) (V-601 , manufactured by Wako Pure Chemical Industries, Ltd., 9.2 g, 40 mmol) was placed in a reaction vessel of appropriate size equipped with a stirrer and a condenser, and dissolved with methyl ethyl ketone (MEK, 196.1 g). After bubbling nitrogen into this solution for 10 minutes to remove oxygen, it heated to 80 degreeC, stirring. While keeping the solution at 80°C, a solution prepared in advance by dissolving maleic anhydride (manufactured by Nippon Shokubai Co., Ltd., 98.1 g, 1.00 mol) in 119.9 g of MEK was added dropwise over 1.5 hours. and then reacted for 8 hours. This reaction mixture was added dropwise to a large amount of methanol to precipitate a polymer. After filtering with a Nutsche filter, the solid was further washed with methanol, and vacuum-dried at 70°C. The weight average molecular weight Mw of the obtained precursor resin was 6900.

(Synthesis of Alkali Soluble Resin-1) The above precursor resin (50.0 g) was weighed and placed in a reaction vessel of appropriate size equipped with a stirrer and a condenser, and dissolved with MEK (90 g). Furthermore, 2-hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd., 21.2 g, 163 mmol) and triethylamine (5.0 g) were added, and it heated at 70 degreeC for 6 hours. Glycidyl methacrylate (11.1 g, 78 mmol) was added to this reaction liquid, and it stirred at 70 degreeC for 4 hours further. After adding formic acid to the reaction liquid for acid treatment, it was added dropwise to a large amount of pure water to deposit a polymer. The solid obtained by filtration was dried at 40° C. for 16 hours using a vacuum dryer to obtain alkali-soluble resin-1. The weight average molecular weight Mw was 7800. Also, the double bond equivalent is 540 g/mol. Alkali-soluble resin-1 corresponds to copolymer resin (C1).

＜Alkali-soluble resin-2＞ For the copolymer resin with dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.02/0.045/0.935) as the constituent monomers, equal amounts of acrylic acid and glycidyl methacrylate Alkali-soluble acrylic copolymer resin obtained by adding tetrahydrophthalic anhydride to 1 mole of the above-mentioned copolymer resin so that the molar ratio is 0.096. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 8900, and the solid content acid value was 27 mgKOH/g. Alkali-soluble resin-2 corresponds to alkali-soluble resin (acrylic copolymer resin (C3)) other than copolymer resin (C1).

＜Alkali-soluble resin-3＞ For a copolymer resin using tricyclodecane methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) as a constituent monomer, acrylic acid and glycidyl methacrylate Alkali-soluble acrylic copolymer resin obtained by adding tetrahydrophthalic anhydride to 1 mole of the above-mentioned copolymer resin in a molar ratio of 0.39. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 9000, and the solid content acid value was 80 mgKOH/g. Alkali-soluble resin-3 corresponds to alkali-soluble resin (acrylic copolymer resin (C3)) other than copolymer resin (C1).

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

＜Photopolymerizable compound＞ In Examples 1-9 and Comparative Example 1, one of the following was selected and prepared. Selection and formulation of photopolymerizable compounds (photopolymerizable monomers) are shown in Table 2 below.

＜Photopolymerizable Monomer-1＞ ・DPHA: Made by Nippon Kayaku Co., Ltd. A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. ＜Photopolymerizable monomer-2＞ ・A-9570W: Product made in Shin-Nakamura Chemical Industry Co., Ltd. A mixture of dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. ＜Photopolymerizable monomer-3＞ ・A mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and succinic acid half ester of dipentaerythritol pentaacrylate. (Molar ratio is 50/25/25%) ＜Photopolymerizable monomer-4＞ ・LIGHT-ACRYLATE PE-4A: Made by Kyoeisha Chemical Co., Ltd. pentaerythritol tetraacrylate ＜Photopolymerizable Monomer-5＞ ・M-933: Made by Toagosei Co., Ltd. Mixture of pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate

＜Dispersant＞ Polymer acrylic A-B block copolymer comprising segment A with quaternary ammonium base and tertiary amine group in the side chain, and segment B without quaternary ammonium base and tertiary amine group. The amine value was 70 mgKOH/g. The acid value is 1 mgKOH/g or less. The repeating units of the following formulas (1a) and (2a) are included in the segment A of the dispersant, and the repeating units of the following formula (3a) are included in the segment B. The content ratios of the repeating units of the following formulas (1a), (2a) and (3a) in the total repeating units of the dispersant were 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[chem 49]

<Solvent-1> PGMEA: Propylene Glycol Monomethyl Ether Acetate <Solvent-2> MB: 3-methoxybutanol <Solvent-3> PGME: Propylene Glycol Monomethyl Ether

＜Photopolymerization Initiator＞ Compounds having the following chemical structures were used. The following compounds can be produced by the synthesis method described in International Publication No. 2009/131189.

[chemical 50]

＜Liquid repellant＞ An acrylic copolymer resin comprising a constituent unit having a perfluoroalkyl group, a constituent unit having an ethylenic double bond, and a constituent unit having a carboxyl group. Mw90000, the content rate of fluorine atoms is 20% by mass. The liquid-repelling agent corresponds to compound (D1).

＜Surfactant＞ F-559 (nonionic surfactant, oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups) manufactured by DIC Corporation. Since this surfactant does not have a crosslinking group, it does not correspond to compound (D1).

＜Additive-1＞ Karenz MT PE1 (pentaerythritol tetrakis(3-mercaptobutyrate)) manufactured by Showa Denko Co., Ltd. ＜Additive-2＞ KAYAMER PM-21 (Phosphate Ester Containing Methacrylyl) manufactured by Nippon Kayaku Co., Ltd. ＜Additive-3＞ XIAMETER OFS-6040 Silane (glycidyloxypropyltrimethoxysilane) manufactured by Dow Toray

＜Preparation of pigment dispersion＞ The pigments, dispersants, alkali-soluble resins, and solvents listed in Table 1 were mixed according to the mass ratios listed in Table 1. Using a paint shaker, the solution was dispersed at 25 to 45° C. for 3 hours. As beads, use 0.5 mmϕ zirconia beads, and add 2.5 times the mass of the dispersion. After the dispersion is completed, the beads and the dispersion are separated by a filter to prepare a pigment dispersion.

[Table 1] Pigment dispersion Blending ratio (parts by mass) Pigment (solid content conversion) CI Pigment Violet 29 49 CI Pigment Blue 60 50 CI Pigment Orange 64 1 Dispersant (solid content conversion) Dispersant 20 Alkali soluble resin Alkali soluble resin-2 33 solvent Solvent-1 367 Solvent-2 92

[Examples 1 to 10 and Comparative Examples 1 and 2] Using the pigment dispersion prepared above, each component was added so that the content ratio of the solid content of each component to the total solid content became the value recorded in Table 2, and then the PGME content in the entire solvent The content rate was 20 mass %, PGMEA was added so that the content rate of the solid content total amount might become 31 mass %, it stirred and melt|dissolved, and the photosensitive resin composition was prepared. Using the obtained photosensitive resin composition, it evaluated by the method mentioned later.

[Table 2] Example comparative example 1 2 3 4 5 6 7 8 9 10 1 2 Mixing ratio of photosensitive resin composition (with solid content as 100 parts by weight) Pigment dispersion pigment 4.30 4.30 4.30 4.30 4.30 4.30 4.30 4.30 4.30 4.30 4.30 4.32 Dispersant 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 Alkali soluble resin 1.43 1.43 1.43 1.43 1.43 1.43 1.43 1.43 1.43 1.43 1.43 1.44 Alkali soluble resin-1 41.74 41.74 41.74 41.74 41.74 20.87 20.87 20.87 20.87 20.87 41.92 Alkali soluble resin-3 20.87 20.87 20.87 33.39 Alkali soluble resin-4 20.87 20.87 8.35 photopolymerizable compound Photopolymerizable monomer-1 43.17 43.17 43.17 43.36 Photopolymerizable monomer-2 43.17 43.17 43.17 Photopolymerizable monomer-3 43.17 43.17 43.17 Photopolymerizable monomer-4 43.17 Photopolymerizable monomer-5 43.17 Photopolymerization initiator 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 Liquid repellant 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Surfactant 0.10 Additive-1 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Additive-2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Additive-3 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Ink Bleeding Evaluation Results Just after coating A A A A A A A A A A A A after 1 hour A A A A A A A A A A C B after 2 hours A A B A A B A B B B C C after 3 hours A A B A A B B B B B C C PGMEA contact angle 59.7 59.4 57.2 60.8 58.6 61.6 61.6 61.6 61.5 61.6 61.5 30.6

Hereinafter, the method of performance evaluation is demonstrated.

<Preparation of the barrier rib for evaluation> Using the spin coater, the photosensitive resin composition was apply|coated on the glass substrate so that the thickness after heat hardening might become 10.0 micrometers. Thereafter, a drying process was performed for 60 seconds using a vacuum dryer. Then, it heat-dried for 120 second on the hot plate heated up to 90 degreeC. The obtained coating film was exposed using a photomask. Using a mirror projection type exposure machine (MPA-600FA) manufactured by CANON, exposure was performed for 25 seconds so that the exposure amount would be 100 mJ/cm ² . The illuminance was 500 mW/cm ² , and the slit width was 1.6 mm. A mask with a 10 mm square opening and a grid-shaped opening is used for the mask (with a covering part of 100 μm x 300 μm, and an exposure part separated by 100 μm in the long-axis direction has the above-mentioned covering part, in the uniaxial direction The exposed portion with an interval of 10 μm has the above-mentioned covering portion, and the above-mentioned covering portion is plural). Next, using 0.033% KOH aqueous solution, spraying at a pressure of 0.05 MPa was performed for a development time of 70 seconds, followed by washing with pure water for 10 seconds. Afterwards, using a proximity exposure machine (MA-1100 ⁾ manufactured by Dainippon Kaken Co., Ltd., using an ND60 filter (60% light reduction filter), 1000 mJ/ cm ² after exposure. Finally, the substrate was heat-treated in an oven at 90°C for 30 minutes to obtain a substrate having a coating film for measuring the contact angle corresponding to the 10 mm square opening of the photomask and a barrier wall for evaluating ink bleeding. .

＜Measurement of contact angle＞ ＜Measurement of liquid samples＞ PGMEA: Propylene Glycol Monomethyl Ether Acetate ＜Device used＞ DMo-502 manufactured by Kyowa Interface Science ＜Measurement＞ Using the droplet method, the liquid volume was set to 0.7 μL, and the contact angle was calculated by the θ/2 method.

＜Ink Bleeding Evaluation＞ ＜Using Ink＞ YED216D (1,6-hexanediol diglycidyl ether) manufactured by Mitsubishi Chemical Corporation ＜Device used＞ DMP-2831 manufactured by FUJIFILM For spraying nozzles, use one corresponding to 10pL. ＜Coating of ink＞ Using the above-mentioned DMP-2831, 24 drops of the above-mentioned ink were applied to the openings of 100 μm x 300 μm in 5 rows x 3 columns in the barrier ribs for evaluation, that is, a total of 15 openings.

＜Observation and Evaluation of Bleeding＞ With respect to the barrier ribs around the openings in 3 rows x 2 columns located in the central part among the 15 openings coated with ink, ink bleeding was observed with an optical microscope. When ink bleeding occurs, abnormal forms such as discoloration of the barrier ribs or occurrence of mottled patterns are observed. Immediately after coating, after 1 hour, 2 hours, and 3 hours, the conditions were observed. In addition, if no abnormality was observed, it was rated as A, if a part of the barrier wall was stained, it was rated as B, if the barrier wall as a whole was stained, it was rated as C, and the ratings A and B were acceptable levels. Fig. 2A and Fig. 2B show schematic diagrams and evaluation results of ink bleeding observation results.

From Examples 1 to 5, it was found that when the copolymer resin (C1) is used, it has bleeding resistance when combined with various photopolymerizable compounds. It is considered that the used copolymer resin (C1) has repeating units including an aliphatic polycyclic structure in the main chain. Specifically, as a structure represented by formula (I), it has a large volume but is not as rigid as aromatic hydrocarbons. The alkane skeleton shows a certain degree of flexibility. Therefore, during the photohardening and/or thermosetting reaction of the photosensitive resin composition, the reaction points of the photopolymerizable compound are close to each other, and the hardening reaction will not be excessively inhibited. Furthermore, after hardening, the large-volume structure is used to effectively inhibit the penetration of ink.

From Examples 6 to 10, it can be seen that, in addition to the copolymer resin (C1), when other alkali-soluble resins are used in combination, it also has bleeding resistance. Importantly, in addition to the performance of Examples 1 to 5, when it is desired to impart properties other than anti-bleeding properties such as liquid repellency, adhesion, and resolution to the photosensitive resin composition, even if such Alkali-soluble resin with special characteristics, and will not lose anti-bleeding property.

According to the comparison between Examples and Comparative Example 1, it can be seen that if the copolymer resin (C1) is not used, the anti-bleeding property will not be exhibited. Furthermore, it can be understood from Examples 6 to 8 that by using a photopolymerizable compound containing more hydroxyl groups such as dipentaerythritol tetraacrylate as the photopolymerizable compound, compared with using a photopolymerizable compound that does not , showing high resistance to bleeding. According to research, because the copolymer resin (C1) itself has strong anti-bleeding property, there is no such difference in Examples 1-5 in which the same photopolymerizable compound is added. The improvement in bleeding resistance by using a photopolymerizable compound containing more hydroxyl groups is believed to be due to the fact that the copolymer resin (C1) contains more In the case of the highly polar substituents shown (carboxyl and hydroxyl groups in this embodiment), these substituents form a non-covalent network structure such as hydrogen bonds with the hydroxyl groups of the photopolymerizable compound, thereby, Can suppress ink bleeding more efficiently.

According to the comparison of Examples and Comparative Example 2, if no compound (D1) having a cross-linking group and containing fluorine atoms and/or siloxane chains is used, the contact angle of PGMEA is significantly reduced compared with other examples. Exhibited liquid repellency and impaired bleed resistance. Moreover, by comparing with the comparative example 1 at the same time, it turns out that even if compound (D1) is used, unless it uses together with copolymer resin (C1), it turns out that anti-bleeding property cannot be acquired. The liquid repellant exhibits liquid repellency by segregating to the surface. It is speculated that if it is used together with a resin such as copolymer resin (C1) that has a repeating unit containing an aliphatic polycyclic structure in the main chain and makes it difficult for ink to penetrate, then the ink-repelling function of the liquid repellant itself can be used to enhance anti-bleeding. However, if it is combined with a resin that does not have a repeating unit of an aliphatic polycyclic structure in the main chain like the copolymer resin (C1), although the ink is repelled macroscopically (that is, the contact angle becomes larger), it cannot be expressed at the molecular level. Penetration inhibition effect of ink.

1:Green Luminescent Nanocrystal Grain 2:Red Luminescent Nanocrystal Grain 10:Substrate 20:Barrier Wall 30:Red Pixel 40:Green Pixel 50:Blue Pixel 100:Color Filter

FIG. 1 is a schematic cross-sectional view of an example of a color filter provided with a barrier rib of the present invention. Figure 2A is a schematic diagram of the ink bleeding evaluation results in the present invention. Figure 2B is a schematic diagram of the ink bleeding evaluation results in the present invention.

Claims (17)

A photosensitive resin composition, characterized in that: it contains (A) photopolymerizable compound, (B) photopolymerization initiator, (C) alkali-soluble resin and (D) liquid repellant, The above-mentioned (C) alkali-soluble resin contains a copolymer resin (C1) having repeating units including an aliphatic polycyclic structure in the main chain, The liquid repellent (D) above contains a compound (D1) having a crosslinking group and containing a fluorine atom and/or a siloxane chain. The photosensitive resin composition according to claim 1, wherein the above-mentioned copolymer resin (C1) has a repeating unit (I) represented by the following general formula (I): [Chemical 1]

(In the formula (I), R ¹ to R ⁴ independently represent a hydrogen atom or a hydrocarbon group; n represents an integer of 0 to 2; * represents a bonding bond). The photosensitive resin composition according to claim 1 or 2, wherein the above-mentioned copolymer resin (C1) has a repeating unit (II) containing a carboxyl group. The photosensitive resin composition as claimed in item 3, wherein the above-mentioned repeating unit (II) containing a carboxyl group contains a repeating unit represented by the following general formula (II-1): [Chemical 2]

(In the formula (II-1), R ⁵ represents a hydrogen atom or an organic group; * represents a bonding bond). The photosensitive resin composition according to any one of claims 1 to 4, wherein the content ratio of the copolymer resin (C1) is 20% by mass or more relative to the total solid content of the photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 5, wherein the above-mentioned (C) alkali-soluble resin further contains an alkali-soluble resin other than the above-mentioned copolymer resin (C1). The photosensitive resin composition according to any one of claims 1 to 6, further comprising (E) a colorant. The photosensitive resin composition according to any one of Claims 1 to 7, which further contains a solvent. The photosensitive resin composition according to any one of Claims 1 to 8, which is used for thermal baking at a temperature below 140°C. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 9. A barrier wall made of the hardened material according to claim 10. An organic electroluminescent element, which is provided with the barrier wall as claimed in claim 11. A color filter, which is provided with the barrier wall as claimed in claim 11, and further includes luminescent nanocrystal grains. An image display device provided with the barrier wall according to claim 11. A method for forming a cured product, which uses the photosensitive resin composition according to any one of claims 1 to 8, and at least includes the following steps (1) to (4), Step (1): a step of coating the above photosensitive resin composition on the substrate to form a coating film; Step (2): a step of exposing at least a part of the coating film formed in the above step (1); Step (3): a step of developing the exposed coating film in the above step (2); Step (4): The step of firing the developed coating film in the above step (3). The method for forming a hardened product according to claim 15, wherein the firing temperature in the above-mentioned step (4) is below 140°C. The method for forming a cured product according to claim 15 or 16, wherein after the above step (3), there is a post-exposure step of exposing the coating film developed in the above step (3).

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