TW201809884A - Photosensitive resin composition for forming black column spacer, black column spacer and image display device - Google Patents

Abstract

The present invention is a photosensitive resin composition for forming a black column spacer, which is characterized by containing: (A) a resin that has a constituent unit (a) having a carboxyl group and at least one constituent unit selected from the group consisting of constituent units (b-1) having a (meth)acryloyloxy group and constituent units (b-2) having a functional group reactive with a carboxyl group; (B) a solvent; (C) a photopolymerization initiator; and (D) a coloring agent. It is preferable that the resin (A) additionally has a constituent unit (c) having an aromatic ring skeleton.

Description

Photosensitive resin composition for forming black columnar spacer, black columnar spacer, and image display device

The present invention relates to a photosensitive resin composition for forming a black columnar spacer, a black columnar spacer, and an image display device.

An image display device such as a liquid crystal display device or an organic EL display device uses a spacer in order to maintain a constant distance (liquid crystal layer gap) between two substrates. In recent years, various methods have been proposed for forming a spacer from a photosensitive resin composition. In this method, a photosensitive resin composition is coated on a substrate to form a resin layer. After exposing the resin layer through a specific mask, the resin layer is developed to form a columnar spacer or the like. This method can form a spacer only in a specific portion other than the pixel representation portion. In addition, it is also proposed to form a black columnar spacer having a light-shielding property by using a photosensitive resin composition to which a light-shielding agent such as an organic black pigment is added (see the patent) References 1 and 2).

In particular, black columnar spacers require high dimensional accuracy for height. Furthermore, in image display devices such as liquid crystal display devices, a substrate such as a TFT substrate in which an element is formed on a substrate is often used. When such a substrate is used, a black columnar spacer may be required to be formed on an element formed on the substrate or an element facing the substrate on which the element is paired with the substrate. In this case, considering the height of the element, the height of the black columnar spacer must be changed where the element is formed and elsewhere. By exposing through a half-tone mask and changing the exposure amount according to where the black columnar spacers are formed, black columnar spacers of different heights can be formed at one time.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-191234

[Patent Document 2] Japanese Patent Laid-Open No. 2014-146029

[Summary of Invention]

However, since the photosensitive resin composition for forming a black columnar spacer has a high optical density (OD), light cannot reach the lower portion of the resin layer at the exposure stage, and hardening is difficult to proceed. Therefore, in the conventional technology, exposure and development are performed to form black columnar spaces. After the step of the spacer, heat curing is performed in the post-baking stage to form a pattern. At this time, the step difference of the black columnar spacer becomes a margin, which becomes very narrow, and there is a problem that the height of each step cannot be maintained uniformly over the entire substrate (the excellent development margin is obtained). In addition, since the lower part of the resin layer is hardened mainly by thermosetting, there is a problem that the required chemical resistance cannot be sufficiently obtained. In addition, in the case of using an organic black pigment as a light-shielding agent, compared with the case of using an inorganic black pigment such as carbon black, the solvent used in the manufacturing process includes metal ions and organic compounds contained in the spacer pattern. Black pigments are prone to problems with solvent resistance due to dissolution. Therefore, there is a problem that the reliability of the black columnar spacer which is in contact with the liquid crystal becomes low.

The present invention has been made to solve the problems described above, and an object of the present invention is to provide a photosensitive resin composition for forming a black columnar spacer having excellent colorant dispersibility, development margin, solvent resistance, and elastic recovery.

That is, the present invention is shown in the following [1] to [12].

[1] A photosensitive resin composition for forming a black columnar spacer, which contains a structural unit (b-1) selected from the group consisting of a structural unit (a) having a carboxyl group and a (meth) acryloxy group. And a resin (A), a solvent (B), a photopolymerization initiator (C), and a coloring agent (D) having at least one constituent unit grouped by the constituent unit (b-2) having a functional group that reacts with a carboxyl group ).

[2] Composition of photosensitive resin for forming black columnar spacers as in [1] The resin (A) is a structural unit (c) further having an aromatic ring skeleton.

[3] The photosensitive resin composition for forming a black columnar spacer according to [1] or [2], wherein the resin (A) is a structural unit further including a bridge alicyclic hydrocarbon group having 7 to 20 carbon atoms (d).

[4] The photosensitive resin composition for forming a black columnar spacer according to [2], wherein the aromatic ring skeleton is at least one selected from the group consisting of a biphenyl skeleton, a naphthalene skeleton, and an anthracene skeleton.

[5] The photosensitive resin composition for forming a black columnar spacer according to any one of [1] to [4], wherein the functional group that reacts with a carboxyl group is oxetanyl group, epoxy group, or isopropyl group A functional group of at least one kind of cyano group.

[6] The photosensitive resin composition for forming a black columnar spacer according to any one of [1] to [5], wherein the carboxyl group is a carboxyl group derived from an unsaturated carboxylic acid, a carboxyl group derived from a polyacid, or a polyacid anhydride The carboxyl group.

[7] The photosensitive resin composition for forming a black columnar spacer according to any one of [1] to [6], wherein the unsaturated group equivalent of the resin (A) is 200 to 2000 g / mole.

[8] The photosensitive resin composition for forming a black columnar spacer according to any one of [1] to [7], wherein the colorant (D) contains an inorganic black pigment and an organic black pigment.

[9] The photosensitive resin composition for forming a black columnar spacer according to any one of [1] to [8], wherein the resin (A) contains 1 to 20% by mass and the solvent (B) contains 50 to 94 mass%, the photopolymerization initiator (C) contains 0.01 to 5 mass%, and the colorant (D) contains 3 to 30 mass%.

[10] The photosensitive resin composition for forming a black columnar spacer according to [9], further containing a reactive diluent (E) in an amount of 1 to 20% by mass.

[11] A black columnar spacer characterized in that the photosensitive resin composition for forming a black columnar spacer according to any one of [1] to [10] is hardened.

[12] An image display device including a black columnar spacer as described in [11].

According to the present invention, a photosensitive resin composition for forming a black columnar spacer having excellent colorant dispersibility, development margin, solvent resistance, and elastic recovery can be provided. The black columnar spacer-based colorant hardened by the photosensitive resin composition for forming a black columnar spacer of the present invention has dispersibility, solvent resistance, and elastic recovery.

[Form of Implementing Invention] <Photosensitive resin composition for forming black columnar spacers>

Hereinafter, the photosensitive resin composition for forming a black columnar spacer of the present invention will be described in detail.

The photosensitive resin composition for forming a black columnar spacer according to the present invention contains a constituent unit (b-1) selected from the constituent units (a) having a carboxyl group, The functional unit constituting the carboxyl group (b-2) Resin (A), solvent (B), photopolymerization initiator (C) and coloring agent (D).

In the present specification, "(meth) acryloxy" means at least one selected from the group consisting of acryloxy and methacryloxy, and "(meth) acrylic" refers to acrylic and methyl. At least one kind of methacrylic acid and "(meth) acrylate" means at least one kind selected from acrylate and methacrylate.

<Resin (A)>

The resin (A) used in the present invention has a constitutional unit (a) selected from a constitutional unit (a) having a carboxyl group, a constitutional unit (b-1) having a (meth) acryloxy group, and a functional group having a functional group that reacts with a carboxyl group ( b-2) At least one constituent unit of the group. In the present specification, the "constituting unit" means a monomer unit that forms the main chain of the resin (A). In addition, in the case where a monomer unit forming the main chain of the resin (A) is added with another monomer to form a side chain, the monomer unit forming the main chain and the monomer unit forming the side chain are added together as a "constituting unit" . Therefore, the resin (A) used in the present invention also includes one having a carboxyl group and a (meth) acryloxy group in one constituent unit. In addition, in this specification, when there is a carboxyl group and a (meth) acryl fluorenyloxy group in one structural unit, it may be expressed as a structural unit (a, b-1).

The constituent unit (a) has a carboxyl group. A carboxyl group may be contained in an acid anhydride form. The constituent unit (a) can be generally introduced into the resin (A) by the following two methods.

The first method is used when the resin (A) is produced by copolymerization. The polymerizable monomer used is a method of introducing (from a polymerizable monomer containing a carboxyl group) by using a polymerizable monomer containing a carboxyl group. Examples of the polymerizable monomer containing a carboxyl group include (meth) acrylic acid, 2- (meth) acryloxyethyl succinic acid, and 2- (meth) acryloxyethyl hexahydrophthalic acid. , Α-bromo (meth) acrylic acid, β-furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, maleate Unsaturated carboxylic acids such as monoethyl acid, monoisopropyl maleate, monomethyl fumarate, monoethyl econate, and the like. These polymerizable monomers containing a carboxyl group may be used alone or in combination of two or more kinds. Among these, (meth) acrylic acid is preferable from the viewpoints of ease of acquisition and reactivity.

The second method is to use a (meth) acrylic acid ester containing an epoxy group as a polymerizable monomer used in the production of the precursor of the resin (A) by copolymerization. Addition reaction, a method in which an epoxy group is ring-opened, and a polybasic acid or polybasic acid anhydride is added to a hydroxyl group generated at this time, thereby introducing a carboxyl group. Examples of the epoxy-containing (meth) acrylate include glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, and epoxy-containing (meth) acrylate. 3,4-epoxycyclohexylmethyl (meth) acrylate, lactone adducts thereof (e.g., Cyclomer (registered trademark) A200, M100, manufactured by DAICEL Chemical Industries, Ltd.), 3,4-epoxy Mono (meth) acrylate, cyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth) acrylate, dicyclopentene Oxyethyl (meth) acrylate, etc. (Meth) propylene containing epoxy groups The acid ester may be used alone or in combination of two or more. Among these, from the viewpoints of ease of acquisition and reactivity, epoxypropyl (meth) acrylate is preferred. Also, a carboxyl group-containing monomer. The unsaturated carboxylic acids listed in the first method described above can be used. Among these, (meth) acrylic acid is preferred from the viewpoint of reactivity. Examples of the polybasic acid include tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, and succinic acid. Examples of the polybasic acid anhydride include the above-mentioned polybasic acid anhydrides. These polybasic acids and polybasic anhydrides can be used alone or in combination of two or more kinds. Among these, from the viewpoint of improving developability, tetrahydrophthalic anhydride is preferred. In the second method, a constituent unit (a, b-1) having a carboxyl group and a (meth) acryloxy group may be introduced into the resin (A).

The constituent unit (b-1) can be generally introduced into the resin (A) by the following two methods.

The first method is to use a (meth) acrylate containing an epoxy group as a polymerizable monomer used in the production of a precursor of the resin (A) by copolymerization, and add a (meth) acrylate containing a carboxyl group. This epoxy group is used to introduce the method. As the (meth) acrylate containing an epoxy group, the above can be used. Examples of the (meth) acrylate containing a carboxyl group include (meth) acrylic acid, 2- (meth) acryloxyethyl succinic acid, and 2- (meth) acryloxyethyl hexahydroo-benzene Dicarboxylic acid, α-bromo (meth) acrylic acid, β-furyl (meth) acrylic acid, and the like.

The second method is to use a monomer containing a carboxyl group as the polymerizable monomer used in the production of the precursor of the resin (A) by copolymerization, and to use a (meth) acrylate containing an epoxy group or an isocyanate-containing monomer. (Meth) acrylic A method of introducing an acrylate into the carboxyl group to thereby introduce it. As the carboxyl group-containing monomer, the unsaturated carboxylic acid listed as the carboxyl group-containing polymerizable monomer can be used. As the (meth) acrylate containing an epoxy group, the above can be used. Examples of the (meth) acrylate containing an isocyanate group include 2-isocyanate ethyl (meth) acrylate and the like.

The functional group that reacts with a carboxyl group in the structural unit (b-2) is not particularly limited, and usually includes an epoxy group, an oxetanyl group, an isocyanate group, and the like, and an epoxy group is particularly preferred. The constituent unit (b-2) is introduced as a polymerizable monomer used in the production of the resin (A) by copolymerization using a polymerizable monomer containing a functional group that reacts with a carboxyl group (derived from a polymer containing a reaction with a carboxyl group). Functional polymerizable monomer). Examples of the polymerizable monomer containing a functional group that reacts with a carboxyl group include oxetanyl (meth) acrylate and (meth) acrylic acid (3) -Methyloxetane-3-yl) methyl ester, (3-ethyloxetane-3-yl) methyl (meth) acrylate, (3-methyloxy) (meth) acrylic acid Hexane-3-yl) ethyl ester, (3-ethyloxetan-3-yl) ethyl (meth) acrylate, (3-chloromethyloxetan) (meth) acrylate Alkyl-3-yl) methyl ester, (oxetane-2-yl) methyl (meth) acrylate, (2-methyloxetane-2-yl) methyl (meth) acrylate (2-ethyloxetan-2-yl) methyl (meth) acrylate, (1-methyl-1-oxetan-2-phenyl) -3- (methyl ) Acrylate, (1-methyl-1-oxetanyl) -2-trifluoromethyl-3- (meth) acrylate, (1-methyl-1-oxetanyl) ) -4-trifluoromethyl-2- (meth) acrylate, etc. (Meth) acrylate; isocyanate-containing (meth) acrylate and the like such as 2-isocyanatoethyl (meth) acrylate and the like.

The structural unit (a) having a carboxyl group, the structural unit (b-1) having a (meth) acryloxy group, and the structural unit (b-2) having a functional group reactive with a carboxyl group are introduced into the resin (A). The method can be introduced by combining the methods of the above-mentioned constituent unit (a), constituent unit (b-1), and constituent unit (b-2) as appropriate. A preferred method is to use a polymerizable monomer containing a carboxyl group and a polymerizable monomer containing a functional group that reacts with a carboxyl group as a polymerizable monomer used in the production of the precursor of the resin (A) by copolymerization. An oxy (meth) acrylate or an isocyanate-containing (meth) acrylate may be added to a part of a carboxyl group derived from a carboxyl-containing polymerizable monomer. Another method is to use a (meth) acrylate containing an epoxy group as a polymerizable monomer used in the production of a precursor of the resin (A) by copolymerization, and add a (meth) acrylate containing a carboxyl group. Formed in a part of the epoxy group, thereby performing ring opening of the epoxy group, and adding the polybasic acid anhydride to a part of the hydroxyl group that occurs at this time. That is, in the latter example, the constituent unit introduced into the resin (A) includes a constituent unit (b-2) having a functional group that reacts with a carboxyl group, and a constituent unit having a (meth) acryloxy group ( b-1) and a structural unit (a, b-1) having a carboxyl group and a (meth) acryloxy group.

The resin (A) used in the present invention, if necessary, further contains a constituent unit (c) having an aromatic ring skeleton, so that a resin (A) having more excellent colorant dispersibility can be obtained. The constituent unit (c) is a polymerizable monomer used in the production of the resin (A) by copolymerization, and contains an aromatic ring Polymerizable monomer (from a polymerizable monomer containing an aromatic ring). Examples of the polymerizable monomer containing an aromatic ring include styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, o-chlorostyrene, and m-chlorobenzene. Ethylene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetamidine Aromatic vinyl compounds such as amino styrene; benzyl (meth) acrylate, rosin (meth) acrylate, phenyl (meth) acrylate, cumyl (meth) acrylate, phenoxy Ethyl (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate (trade name: Light Acrylate P-200A, manufactured by Kyoei Chemical Co., Ltd.), nonylphenoxy polyethylene glycol Mono (meth) acrylate, o-phenoxybenzyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, biphenoxyethyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, naphthalene (meth) acrylate , Anthracene (meth) acrylate and the like. Among these, from the viewpoint of the elastic recovery rate, it is preferable to introduce a constituent unit having a skeleton containing a plurality of aromatic rings into the resin (A) used in the present invention, and more preferably to introduce a resin selected from a biphenyl skeleton, a naphthalene skeleton, and At least one kind of constituent unit grouped by an anthracene skeleton.

The resin (A) used in the present invention can further obtain a resin (A) having an excellent elastic recovery rate by further having a constituent unit (d) having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms. The constituent unit (d) is a polymerizable monomer used in the production of the resin (A) by copolymerization, and a polymerizable monomer having a bridge alicyclic hydrocarbon group having 7 to 20 carbon atoms is used to improve Introduced (from a polymerizable monomer having a bridge alicyclic hydrocarbon group having 7 to 20 carbon atoms). Bridging alicyclic hydrocarbons are those having a structure represented by the following formula (1) or (2) represented by adamantane and norbornane. Bridging alicyclic hydrocarbon group refers to a group equivalent to removing the remainder of the hydrogen atom in a part of these structures.

(In formula (1), A ¹ and B ¹ each independently represent a linear or branched alkylene group (may contain a ring), and R ⁴ represents a hydrogen atom or a methyl group. A ¹ and B ¹ may also be A ¹ and B The branches of ¹ are connected to each other to form a ring.)

(In formula (2), A ² , B ² and L each independently represent a linear or branched alkylene group (may contain a ring), and R ⁵ represents a hydrogen atom or a methyl group. A ² , B ² and L may also be The branches of A ² , B ² and L are connected to each other to form a ring.)

Among the monomers having the above structure, a (meth) acrylate having an alicyclic hydrocarbon group having 7 to 20 carbon atoms is preferred, an adamantyl (meth) acrylate having the following formula is more preferred (3) Structure of representation (Meth) acrylate.

(In the formula (3), R ⁶ to R ⁸ each independently represent a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are hydrogen atoms or methyl groups, or may be connected to each other to form a saturated or unsaturated ring (preferably 5 members) Ring or 6-membered ring). In formula (3), * represents a bonding bond to a (meth) acrylic fluorenyloxy group.)

Examples of the polymerizable monomer having a bridging alicyclic hydrocarbon group having 7 to 20 carbon atoms include dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate, isofluorenyl (methyl Group) acrylate, adamantyl (meth) acrylate, and the like. Among these, dicyclopentyl methacrylate is preferable from the viewpoints of thermal decomposition resistance and thermal discoloration resistance. These polymerizable monomers can be used alone or in combination of two or more.

The norbornene-based monomer represented by the following formula (4) can also be used as a preferable polymerizable monomer for introducing the constituent unit (d).

(In the formula (4), X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a carboxyl group, or 1 to 20 carbon atoms. Hydrocarbon group (which may have a substituent). R ¹ and R ² may be bonded to each other to form a cyclic structure.)

Specific examples of the linear or branched hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl. . Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-pentyl, and deca Linear or branched alkyl groups such as octyl, lauryl, 2-ethylhexyl, etc .; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecane Cycloaliphatic groups such as methyl, isofluorenyl, adamantyl, 2-methyl-2-adamantyl and the like. Specific examples of the substituent include alkoxy groups such as methoxy and ethoxy, and aryl groups such as phenyl.

Specific examples of norbornene-based monomers include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] Hept-2-ene, tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-methyltetracyclo [4.4.0.12,5.17,10] dodec-3-ene , 8-ethyltetracyclo [4.4.0.12,5.17,10] dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.02,6] dec-8-ene, tricyclo [5.2.1.02 , 6] dec-3-ene, tricyclic [4.4.0.12,5] undec-3-ene, tricyclic [6.2.1.01,8] undec-9-ene, tricyclic [6.2.1.01,8] Undec-4-ene, tetracyclo [4.4.0.12,5.17,10.01,6] dodec-3-ene, 8-methyltetracyclo [4.4.0.12,5.17,10.01,6] dodec-3-ene , 8-ethylene tetracyclo [4.4.0.12,5.17,12] dodec-3-ene, 8-ethylene tetracyclo [4.4.0.12,5.17,10.01,6] dodec-3-ene, five Ring [6.5.1.13, 6.02, 7.09, 13] penta-4-ene, pentacyclic [7.4.0.12, 5.19, 12.08, 13] penta-3-ene and the like. Among these, from heat resistance From the viewpoints of decomposability and heat discoloration resistance, norbornene and dicyclopentadiene are preferred. These norbornene-based monomers may be used alone or in combination of two or more.

The resin (A) used in the present invention may contain, if necessary, a constituent unit derived from a radical polymerizable monomer having an ethylenic carbon-carbon double bond in addition to the aforementioned constituent units. A constituent unit derived from a radical polymerizable monomer having an ethylenic carbon-carbon double bond. As a polymerizable monomer used in the production of the resin (A) by copolymerization, radical polymerization having an ethylenic carbon-carbon double bond is used. Sex monomers, thereby introducing. Examples of the radically polymerizable monomer having an ethylenic carbon-carbon double bond include, for example, diene compounds such as butadiene, isoprene, and chloroprene; meth (meth) acrylate, ethyl ( (Meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate Ester, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (methyl) ) Acrylate, 5-ethyl norbornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (Meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, 3- (N, N-dimethylamino) propyl ( (Meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acryloyloxy (acryloylo xy) ethyl isocyanate (i.e. 2-isocyanatoethyl (meth) acrylate) and ε-caprolactam (Meth) acrylate compounds such as reaction products of amines, reaction products of (meth) acryloxyethyl isocyanate and propylene glycol monomethyl ether; ammonium (meth) acrylate, (meth) acrylic acid N , N-dimethylamidamine, N, N-diethylamidine (meth) acrylate, N, N-dipropylamidine (meth) acrylate, N, N-di- (meth) acrylate (Meth) acrylamide (e.g. isopropylammonium amine, anthrylamine (meth) acrylate); aniline (meth) acrylic acid, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride Vinyl compounds such as ethylene, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene, etc .; diethyl citraconic acid, diethyl maleate, fumaric acid Unsaturated dicarboxylic acid diester compounds such as diethyl, diethyl itaconic acid, etc .; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide , N- (4-hydroxyphenyl) maleimide and other monomaleimide compounds.

The reaction conditions for obtaining a copolymerization reaction for the resin (A) used in the present invention or for obtaining a copolymerization reaction for the resin (A) precursor before the addition reaction are performed according to a conventional method and may be appropriately set. In the copolymerization reaction, for example, the polymerizable monomer for copolymerization and the polymerization initiator are dropped in a solvent, preferably at 50 to 150 ° C, and more preferably at 60 to 140 ° C for 1 to 12 hours. Just fine. The addition reaction of the resin (A) precursor is to add the resin (A) precursor and the monomer for the addition reaction to the solvent, and then add the addition reaction catalyst, preferably 50 to 150 ° C, more preferably The reaction may be performed at 80 to 130 ° C for 3 to 12 hours. In addition, there is no problem even if this addition reaction includes a solvent for a copolymerization reaction for obtaining a resin (A) precursor. Therefore, the copolymerization reaction for obtaining the resin (A) precursor is completed. After that, it is not necessary to remove the solvent, and then the addition reaction may be performed.

Preferred ratios of constituent units of the resin (A) used in the present invention are as follows (I) to (IV).

(I) The resin (A) containing the structural unit (a) having a carboxyl group and the structural unit (b-1) having a (meth) acrylic fluorenyloxy group, preferably having a structural unit of 10 to 70 mol% ( a) and the constituent unit (b-1) of 10 to 80 mole%, more preferably the constituent unit (a) of 20 to 60 mole% and the constituent unit (b-1) of 15 to 70 mole%.

(II) The resin (A) containing the structural unit (a) having a carboxyl group and the structural unit (b-2) having a functional group that reacts with a carboxyl group, preferably a structural unit (a) having 10 to 80 mole% And a constituent unit (b-2) of 10 to 70 mole%, more preferably a constituent unit (a) of 20 to 70 mole% and a constituent unit (b-2) of 15 to 60 mole%.

(III) Resin (A) containing a structural unit (a) having a carboxyl group, a structural unit (b-1) having a (meth) acryloxy group, and a structural unit (b-2) having a functional group reactive with a carboxyl group ), Preferably having a constituent unit (a) of 10 to 70 mole% and a constituent unit (b-1) of 10 to 70 mole% and a constituent unit (b-2) of 10 to 50 mole%, more Preferably, it has a constituent unit (a) of 20 to 60 mole% and a constituent unit (b-1) of 20 to 60 mole% and a constituent unit (b-2) of 20 to 40 mole%.

(IV) Contains a structural unit (a, b-1) having a carboxyl group and a (meth) acryloxy group and a structural unit (b-1) having a (meth) acryloxy group and a function having a reaction with a carboxyl group The resin (A) of the constituent unit (b-2) of the base is preferably a constituent unit (a, b-1) having 10 to 80 mol% and 10 ~ 80 mol% constituent units (b-1) and 1 ~ 10 mol% constituent units (b-2), more preferably 20 ~ 70 mol% constituent units (a, b-1) And 15 ~ 70 mol% of constituent units (b-1) and 1 ~ 5 mol% of constituent units (b-2).

When the structural unit (a) having a carboxyl group is 10 mol% or more, the developability is good, so it is preferable. On the other hand, when the ratio of the structural unit (a) having a carboxyl group is equal to or lower than the aforementioned upper limit value, it is preferable to prevent a reduction in the residual film rate during development.

When the structural unit (b-1) having a (meth) acrylic fluorenyloxy group is 10 mol% or more, the solvent resistance and the developability are good, so it is preferable. On the other hand, when the ratio of the constituent unit (b-1) having (meth) acrylic fluorenyloxy group is below the aforementioned upper limit value, it is preferable to suppress the occurrence of residues during development.

When the structural unit (b-2) having a functional group that reacts with a carboxyl group is 10 mol% or more, the solvent resistance becomes good, which is preferable. Moreover, when the ratio of the structural unit (b-2) which has a functional group which reacts with a carboxyl group is below the said upper limit, storage stability becomes favorable, and it is preferable.

In the resin (A) of (I), (II), (III), and (IV), if necessary, a structural unit (c) having an aromatic ring skeleton and a bridge alicyclic system having 7 to 20 carbon atoms can be introduced. The structural unit (d) of a hydrocarbon group or a structural unit other than these.

When the constituent unit (c) having an aromatic ring skeleton is introduced, the constituent unit of the resin (A) preferably exceeds 0 mol% to 50 mol%, and more preferably exceeds 0 mol% to 40 mol%.

Introduction of structural units with bridging alicyclic hydrocarbon groups having 7 to 20 carbon atoms In the case of (d), the constituent unit of the resin (A) is more than 0 mol% to 40 mol%, and more preferably 0 mol% to 30 mol%.

In the case of introducing constituent units other than these, it is preferable that the constituent unit of the resin (A) exceeds 0 mol% to 60 mol%, and more preferably 0 mol% to 50 mol%.

The solvent usable in the copolymerization reaction is not particularly limited, and a known one can be suitably used. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol. Mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate (Poly) alkylene glycol monoalkyl ether acetates such as esters, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethyl ether Glycol diethyl ether, tetrahydrofuran and other ether compounds; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketone compounds; methyl 2-hydroxypropionate, 2-hydroxypropionic acid Ethyl ester, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -Methyl ethoxypropionate, 3-ethoxypropionate Ester, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, acetic acid i- Amyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvate n- Ester compounds such as propyl ester, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate; aromatic hydrocarbon compounds such as toluene and xylene; N-methylpyrrolidone, N, N-di Carboxamide compounds such as methylformamide and N, N-dimethylacetamide and the like. These solvents may be used alone or in combination of two or more.

Among these, (poly) alkylene glycol monomethyl ether such as propylene glycol monomethyl ether and (poly) alkylene glycol monomethyl ether acetate such as propylene glycol monomethyl ether acetate, that is, that is, , Glycol ether solvent.

The amount of the solvent used for the copolymerization reaction is not particularly limited. When the total amount of the monomers is 100 parts by mass, it is generally 30 to 1,000 parts by mass, and preferably 50 to 800 parts by mass. When the amount of the solvent used is 1,000 parts by mass or less, the decrease in the molecular weight of the resin (A) due to the chain transfer effect can be effectively suppressed, and the viscosity of the resin (A) can be controlled within a suitable range, so it is preferable . Moreover, when the usage-amount of a solvent is 30 mass parts or more, since an abnormality of a copolymerization reaction can be prevented and a copolymerization reaction can be performed stably, it is preferable. It is also possible to prevent the coloring or gelation of the resin (A).

The polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and a known one can be suitably used. Specific examples of the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzamidine peroxide, and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator is not particularly limited. When the total input amount is 100 parts by mass, it is generally 0.5 to 20 parts by mass, preferably 0.7 to 15 parts by mass, and more preferably 1 to 10 parts by mass.

For the resin (A) precursor, the type of the addition reaction catalyst used for the addition reaction of the monomer is not particularly limited, and may be selected if necessary. Examples of the addition reaction catalyst include tertiary amines of triethylamine, quaternary ammonium salts of triethylbenzyl ammonium chloride, phosphorus compounds of triphenylphosphine, chelate compounds of chromium, and the like. . These addition reaction catalysts may be used alone or in combination of two or more kinds. The amount of the addition reaction catalyst is not particularly limited. When the amount of the resin (A) precursor is 100 parts by mass, it is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2. ~ 1 part by mass.

In the case of the resin (A) precursor, when a monomer addition reaction is performed, it is preferable to add a polymerization inhibitor in order to prevent gelation. The type of the polymerization inhibitor is not particularly limited, and may be selected if necessary. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor used is not particularly limited. When the amount of the resin (A) precursor is 100 parts by mass, it is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 Parts by mass.

The resin (A) used in the present invention is a weight average molecular weight obtained by polystyrene conversion of gel permeation chromatography (GPC), preferably 1,000 to 50,000, and more preferably 3,000 to 40,000. When the weight average molecular weight is 1,000 or more, it is preferable that pattern defects do not occur after alkali development. When the weight-average molecular weight is 50,000 or less, the development time becomes moderate. It is more practical to use, so it is better. From the viewpoint of elastic recovery, the weight average molecular weight of the resin (A) is preferably 3,000 to 30,000.

The acid value (JIS K6901 5.3) of the resin (A) used in the present invention is not limited as long as the desired effect of the present invention can be exhibited, and it is usually 20 to 300 KOHmg / g, preferably 30 to 200 KOHmg / g. When the acid value is 20 KOHmg / g or more, the developability becomes good, so it is preferable. In addition, when the acid value is 300 KOHmg / g or less, it is preferable that the exposed portion (light-cured portion) does not easily dissolve in the alkali developing solution. From the viewpoint of elastic recovery, the acid value of the resin (A) is preferably from 30 to 200 KOHmg / g.

The unsaturated group equivalent of the resin (A) used in the present invention is not limited as long as the desired effect of the present invention can be exerted, and is usually 100 to 4000 g / mole, preferably 200 to 2000 g / mole, more It is preferably 300 ~ 500g / mole. When the unsaturated group equivalent is 100 g / mol or more, it is preferable because the coating film physical properties and alkali developability can be effectively improved. In addition, when the unsaturated group equivalent is 4000 g / mole or less, the sensitivity can be improved more effectively, so it is preferable. From the viewpoint of elastic recovery, the unsaturated group equivalent of the resin (A) is preferably 200 to 2000 g / mole. The unsaturated group equivalent refers to the mass of the resin (A) having 1 mol of unsaturated bond (ethylene-carbon-carbon double bond) in the resin (A). The unsaturated group equivalent can be obtained by dividing the mass of the resin (A) by the number of unsaturated groups in the resin (A) (g / mole). In addition, in this specification, an unsaturated group equivalent is a theoretical value calculated from the input amount of the raw material used for introducing an unsaturated group.

The epoxy equivalent of the resin (A) used in the present invention When the desired effect of the present invention is exerted, that is, without limitation, it is usually 100 to 4000 g / mole, preferably 200 to 2000 g / mole, and more preferably 300 to 500 g / mole. When the epoxy equivalent is 100 g / mol or more, it is effective because it can effectively improve the coating film physical properties and storage stability. Conversely, when the epoxy equivalent is 4000 g / mole or less, the solvent resistance can be effectively improved. The epoxy equivalent refers to the mass of the polymer having 1 mol of epoxy group. This value can be obtained by dividing the mass of the polymer by the amount of epoxy group of the polymer (g / mole). In this specification, "epoxy equivalent" is a theoretical value calculated from the input amount of the raw material used for introducing an epoxy group.

<Solvent (B)>

The solvent (B) used in the present invention is not particularly limited as long as it is an inert solvent that dissolves the resin (A) and does not react with the resin (A), and can be arbitrarily selected. The solvent (B) is preferably compatible with a reactive diluent described later. As the solvent (B), the same solvents as those used in the production of the resin (A) can be used. The solvent (B) is preferably a (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and a (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.

The solvent (B) may be used to isolate the intended resin (A) from the solution of the resin (A) after the copolymerization reaction is completed, and is suitably added to the resin (A) after being separated. However, it is not necessary to separate the intended resin (A) from the resin solution. The solvent contained at the end of the copolymerization reaction is not separated from the resin (A) solution, and the solvent may be used as the solvent (B) directly. If necessary, other solvents can be added to the resin (A) in solution. Moreover, the solvent contained in other components used when preparing the photosensitive resin composition for black columnar spacer formation can also be used as a solvent (B) as it is.

<Photopolymerization initiator (C)>

The photopolymerization initiator (C) used in the present invention is not particularly limited, and examples thereof include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenone , 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy) -1-methylethyl) Acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-propane-1one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone-1 and other acetophenone compounds; 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc. Anthraquinone compounds; xanthone, xanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, xanthone compounds such as 2-chlorothioxanthone; phenethyl Ketal dimethyl acetal, benzyl dimethyl acetal and other acetal compounds; benzophenone, 4- (1-t-butylperoxy-1-methylethyl) benzophenone, 3 , 3 ', 4,4'-(t-butylperoxycarbonyl) benzophenone and other benzophenone compounds; fluorenyl phosphorus oxide compounds and the like. These photopolymerization initiators may be used alone or in combination of two or more.

<Colorant (D)>

The coloring agent (D) used in the present invention is not particularly limited when it is soluble or dispersible in the solvent (B), and examples thereof include dyes and pigments. Dyes and pigments can be used alone or in combination of two or more, or a combination of dyes and pigments use. In the case where the black columnar spacer of the present invention is formed, the photosensitive resin composition for forming the black columnar spacer is formed from the solubility of the solvent (B) and the alkali developer, the interaction with other components, and the light-shielding property. From a viewpoint, it is preferable to contain a black pigment as a colorant (D).

Examples of the black pigment include inorganic black pigments and organic black pigments. Specific examples include aniline black, perylene black, titanium black, flower blue black, lignin black, lactam organic black, RGB black, and carbon black. These black pigments may be used alone or in combination of two or more. From the viewpoint of optical density, it is preferable to use an inorganic black pigment and an organic black pigment together, and it is more preferable to use a carbon black and a lactam organic black together.

When a pigment is used as the colorant (D), a conventional dispersant can be blended into the photosensitive resin composition for forming a black columnar spacer from the viewpoint of improving the dispersibility of the pigment. Since a dispersant is excellent in dispersion stability over time, a polymer dispersant is preferably used. The polymer dispersant can be arbitrarily selected, and examples thereof include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, and sorbitan. Sugar alcohol anhydride aliphatic ester-based dispersant, aliphatic modified ester-based dispersant, and the like. Such polymer dispersants can also be used with EFKA (registered trademark, manufactured by BASF JAPAN), Disperbyk (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (registered trademark) , Made by Zeneca), and others. The compounding amount of the dispersant may be appropriately set according to the type of the pigment to be used.

Photosensitive resin for forming black columnar spacer of the present invention The preferable blending amounts of the resin (A), the solvent (B), the photopolymerization initiator (C), and the coloring agent (D) in the composition are as follows.

The blending amount of the resin (A) is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass based on the entire photosensitive resin composition. When the blending amount of the resin (A) is 1% by mass or more, it is preferable because it has good photocurability. In addition, when the blending amount of the resin (A) is 20% by mass or less, it is preferable because it has good coatability.

The blending amount of the solvent (B) is preferably 50 to 94% by mass, and more preferably 60 to 90% by mass based on the entire photosensitive resin composition. When the blending amount of the solvent (B) is 50% by mass or more, it is preferable because it has good coatability. Moreover, when the compounding quantity of a solvent (B) is 94 mass% or less, since a coating film can have sufficient film thickness, it is preferable.

The blending amount of the photopolymerization initiator (C) is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the entire photosensitive resin composition. When the blending amount of the photopolymerization initiator (C) is 0.01% by mass or more, the resist may have a hardening property, so it is preferable. In addition, when the blending amount of the photopolymerization initiator (C) is 5% by mass or less, residues are less likely to be generated after development, so it is preferable.

The blending amount of the colorant (D) is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass relative to the entire photosensitive resin composition. When the blending amount of the colorant (D) is 3% by mass or more, it is preferable because it has light-shielding properties. In addition, when the blending amount of the colorant (D) is 30% by mass or less, residues are less likely to be generated after development, so it is preferable.

The photosensitive resin composition for forming a black columnar spacer of the present invention may further contain a viewpoint of viscosity adjustment and sensitivity adjustment. Reactive diluent (E).

<Reactive Diluent (E)>

The reactive diluent (E) is a compound having at least one ethylenically unsaturated group in the molecule. Among them, a compound having a plurality of ethylenically unsaturated groups is preferred. The reactive diluent (E) is not an essential component of the photosensitive resin composition for forming a black columnar spacer. However, by using the reactive diluent (E) in combination with the resin (A), the film strength of the coating film formed from the photosensitive resin composition for forming a black columnar spacer and the adhesion to the substrate can be improved.

Examples of the monofunctional monomer used as the reactive diluent (E) include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, Ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (meth) acrylate , Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl Acrylate), 4-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl Phthalic acid ester, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, epoxypropyl (meth) acrylate, 2,2,2-trifluoroethyl (Meth) acrylate compounds such as (meth) acrylates, 2,2,3,3-tetrafluoropropyl (meth) acrylates, (meth) acrylic acid half esters of phthalic acid derivatives, etc .; benzene Aromatic vinyl compounds such as ethylene, α-methylstyrene, α-chloromethylstyrene, vinyl toluene, etc .; carboxylic acid esters such as vinyl acetate, vinyl propionate, and the like. These monofunctional monomers can be used alone or in combination of two or more.

Examples of the polyfunctional monomer that can be used as the reactive diluent (E) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and tetraethylene glycol di (methyl) ) Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) propenyloxydiethoxyphenyl) propane, 2, 2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, ethylene glycol di Glycidyl ether di (meth) acrylate, Diethylene glycol diglycidyl ether di (meth) acrylate, Diglycidyl phthalate di (meth) acrylate, Glycerol Triacrylate, glycerol polypropylene oxide Ether poly (meth) acrylate, urethane (meth) acrylate (i.e., methylenephenyl diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. and 2 -Reactants of hydroxyethyl (meth) acrylate, (meth) acrylate compounds such as tris (meth) acrylate of ginsyl (hydroxyethyl) trimeric isocyanate; divinylbenzene, diallyl Aromatics such as phthalates, diallyl phenylphosphonates, etc. Vinyl compounds; Dicarboxylate compounds such as divinyl adipate; triallyl cyanurate, methylene bis (meth) acrylamide, (meth) acrylamine methylene ether 2. Polycondensates of N-hydroxymethyl (meth) acrylamide. These polyfunctional monomers can be used alone or in combination of two or more.

When the reactive diluent (E) is blended, the blending amount is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass relative to the entire photosensitive resin composition. When the blending amount of the reactive diluent (E) is 1% by mass or more, it is preferable because it has good hardenability. In addition, when the amount of the reactive diluent (E) to be formulated is 20% by mass or less, residues are less likely to be generated after development, so it is preferable.

The photosensitive resin composition for forming a black columnar spacer of the present invention may contain conventional additives such as a coupling agent, a flattening agent, and a thermal polymerization inhibitor, as long as the effects of the present invention are not impaired. The blending amount of these additives is not particularly limited as long as the range of the effects of the present invention is not impaired.

The photosensitive resin composition for forming a black columnar spacer of the present invention can be produced by mixing the above components using a conventional mixing device. If desired, a composition containing a resin (A) and a solvent (B) may be prepared in advance, and a photopolymerization initiator (C), a colorant (D), and a reactive diluent (E ), Manufactured by mixing.

<Black columnar spacer>

Next, the black columnar spacer of the present invention will be described in detail.

The black columnar spacer of the present invention is one obtained by curing the above-mentioned photosensitive resin composition for forming a black columnar spacer. Specifically, first, a photosensitive resin composition for forming a black columnar spacer is coated on a substrate to form a resin layer (coating film). Then, by exposing the resin layer through a half-tone mask of a predetermined pattern, the exposed portion is light-cured. Then, the unexposed portion and the half-exposed portion were developed with an alkali developing solution to form a black columnar spacer. Then, if necessary, the black columnar spacer is post-baked.

The material of the substrate is not particularly limited, and examples thereof include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyimide substrate, a polyimide substrate, a polyimide substrate, an aluminum substrate, and printed wiring. Substrate, Array Substrate, etc.

The coating method of the black columnar spacer-forming photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method. . After coating the photosensitive resin composition for forming the black columnar spacer, if necessary, the resin layer may be heated by heating means such as a circulating oven, an infrared heater, or a heating plate to contain the resin layer. The solvent (B) is volatile. The heating conditions are not particularly limited, and the composition of the photosensitive resin composition for forming a black columnar spacer used in combination can be appropriately set. In general, it is better to heat for 30 seconds to 30 minutes at a temperature of 50 ° C to 120 ° C.

The method for exposing the resin layer is not particularly limited, and examples thereof include irradiation with active energy rays such as ultraviolet rays and excimer laser light. The amount of the energy ray to be irradiated is set in accordance with the composition of the photosensitive resin composition for forming a black columnar spacer, and can be appropriately set. For example, 30 to 2000 mJ / cm ^{2 is} preferable, but it is not limited to this range. The light source used for the exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be arbitrarily selected for use.

The alkali developing solution used for development is not particularly limited, and examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; ethylamine, diethylamine, and dimethylethanolamine. Aqueous solution of amine compounds; tetramethylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyl Ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N -β-methoxyethylaniline and an aqueous solution of a p-phenylenediamine-based compound such as sulfate, hydrochloride or p-toluenesulfonate. In addition, these alkali developing solutions may be added with a defoaming agent, a surfactant, etc., if necessary. In addition, after development with an alkali developing solution, washing with water and drying are preferred.

The black columnar spacer formed by alkali development is post-baked to further harden the resin. The conditions for the post-baking are not particularly limited and can be arbitrarily selected. The composition of the photosensitive resin composition for forming a black columnar spacer may be selected, and heat treatment may be performed by selecting preferable conditions. For example, at a temperature of 130 ° C to 250 ° C, heating is preferably performed for 10 minutes to 4 hours, and more preferably heating is performed for 20 minutes to 2 hours.

The thus produced black columnar spacer-based colorant is excellent in dispersibility, solvent resistance, and elastic recovery.

<Image display device>

The image display device of the present invention is an image display device including the black columnar spacer. Specific examples of the image display device include a liquid crystal display device and an organic EL display device. When the image display device is manufactured, there are no restrictions other than the formation of the black columnar spacers described above, and it can be manufactured by a conventional method.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

<Synthesis example 1>

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 139 g of propylene glycol monomethyl ether acetate was added as a solvent, and the inside of the flask was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C.

Next, a single unit consisting of 22.0 g (0.1 mole) of tricyclodecyl methacrylate, 70.0 g (0.4 mole) of benzyl methacrylate, and 43.0 g (0.5 mole) of methacrylic acid was separately prepared. To the mixture, 6.6 g of t-butylperoxy-2-ethylhexanoate (a polymerization initiator, manufactured by Nippon Oil Corporation, Perbutyl (registered trademark) O) was added. The mixture of the monomer and the polymerization initiator was dropped into the flask from the dropping funnel over 2 hours. After completion of the dropping, the mixture was further stirred at 120 ° C for 2 hours to perform a copolymerization reaction to synthesize a precursor of the resin (A). Then, the inside of the flask was replaced with air, and propylene oxide was 21.3 g (0.15 mol) of methacrylic acid ester, 0.5 g of triphenylphosphine (catalyst), and 0.5 g of butylhydroxytoluene (polymerization inhibitor) were put into the resin (A) precursor solution. Then, the reaction was continued at 110 ° C for 10 hours to obtain a solution of the resin (A). This resin is referred to as "resin (A-1)". The resin (A-1) contained in this resin solution had an acid value of 126 KOHmg / g, a weight average molecular weight of 10,000, and an unsaturated group equivalent of 1100.

To this resin solution, propylene glycol monomethyl ether acetate was further added to prepare a resin (A-1) solution (solid content concentration: 40% by mass) in Synthesis Example 1. The solid content refers to the residual heating content after heating the resin solution at 130 ° C. for 2 hours, and contains the resin (A-1) and a polymerization initiator as main components.

<Synthesis example 2>

To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 140 g of propylene glycol monomethyl ether acetate was added as a solvent, and the inside of the flask was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C.

Next, it was prepared separately from 66.0 g (0.3 mol) of tricyclodecyl methacrylate, 31.2 g (0.3 mol) of styrene, and 56.8 g (0.4 mol) of epoxypropyl methacrylate. To the monomer mixture, 7.3 g of t-butylperoxy-2-ethylhexanoate (a polymerization initiator, manufactured by Nippon Oil Corporation, Perbutyl (registered trademark) O) was added. The mixture of the monomer and the polymerization initiator was dropped into the flask from the dropping funnel over 2 hours. After the dropping was completed, the mixture was stirred at 120 ° C for another 2 hours, and a copolymerization reaction was performed to produce Precursor of resin (A). Then, the inside of the flask was replaced with air, and 28.8 g of acrylic acid (0.4 mole), 0.6 g of triphenylphosphine (catalyst), and 0.6 g of butylhydroxytoluene (polymerization inhibitor) were charged into the resin (A) precursor. In solution. Then, the reaction was continued at 110 ° C for 10 hours. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the flask, and the reaction was continued at 110 ° C. for 3 hours to obtain a solution of the resin (A). This resin is referred to as "resin (A-2)". The resin (A-2) contained in this resin solution had an acid value of 65 KOHmg / g, a weight average molecular weight of 9400, and an unsaturated group equivalent of 600. In the same manner as in Synthesis Example 1, propylene glycol monomethyl ether acetate was added to prepare a resin (A-2) solution (solid content concentration: 40% by mass) in Synthesis Example 2.

<Synthesis example 3>

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 191 g of propylene glycol monomethyl ether acetate was added as a solvent, and the inside of the flask was stirred while being replaced with nitrogen, and the temperature was raised to 100 ° C.

Next, 22.0 g (0.1 mole) of tricyclodecyl methacrylate, 50.0 g (0.5 mole) of methmethacrylate, 21.5 g (0.25 mole) of methacrylic acid, and propylene oxide were separately prepared. 12.6 g of azobisisobutyronitrile was added to a monomer mixture of 21.3 g (0.15 mol) of methacrylic acid ester. The mixture of the monomer and the polymerization initiator was dropped into the flask from the dropping funnel over 2 hours. After completion of the dropping, the mixture was stirred at 100 ° C. for another 2 hours to perform a copolymerization reaction to obtain a solution of the resin (A). This resin As "resin (A-3)". The resin (A-3) contained in this resin solution had an acid value of 100 KOHmg / g and a weight average molecular weight of 8,400. As in Synthesis Example 1, propylene glycol monomethyl ether acetate was added to prepare a resin (A-3) solution (solid content concentration: 40% by mass) in Synthesis Example 3.

<Synthesis example 4>

To a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 226 g of propylene glycol monomethyl ether acetate was added as a solvent, and the inside of the flask was stirred while being replaced with nitrogen, and the temperature was raised to 70 ° C.

Next, 22.0 g (0.1 mole) of tricyclodecyl methacrylate, 50.0 g (0.5 mole) of methmethacrylate, 21.5 g (0.25 mole) of methacrylic acid, and 2-isopropyl To a monomer mixture of 40.2 g (0.15 mole) of the reaction product of cyanoethyl methacrylate and ε-caprolactam, 2,2'-azobis (2,4-di Methylvaleronitrile) (polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd., V-65) 13.0 g. The mixture of the monomer and the polymerization initiator was dropped into the flask from the dropping funnel over 2 hours. After completion of the dropping, the mixture was stirred at 70 ° C. for another 2 hours to perform a copolymerization reaction to obtain a solution of the resin (A). This resin is referred to as "resin (A-4)". The resin (A-4) contained in this resin solution had an acid value of 85 KOHmg / g and a weight average molecular weight of 8,800. As in Synthesis Example 1, propylene glycol monomethyl ether acetate was added to prepare a resin (A-4) solution (solid content concentration: 40% by mass) in Synthesis Example 4.

<Synthesis example 5>

As a mixture of a monomer and a polymerization initiator, 41.8 g (0.19 mole) of tricyclodecyl methacrylate, 24.6 g (0.14 mole) of benzyl methacrylate, and 57.6 g (0.67 of methacrylic acid) were used. Mol) and t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Corporation, Perbutyl (registered trademark) O) 12.4 g A solution of the resin (A) was obtained in the same manner as in Synthesis Example 1 except that the addition amount of the acrylate was changed to 42.6 g (0.3 mol). This resin is referred to as "resin (A-5)". The resin (A-5) contained in this resin solution had an acid value of 124 KOHmg / g, a weight average molecular weight of 10,000, and an unsaturated group equivalent of 600. In the same manner as in Synthesis Example 1, propylene glycol monomethyl ether acetate was added to prepare a resin (A-5) solution (solid content concentration: 40% by mass) in Synthesis Example 5.

<Synthesis example 6>

As a mixture of a monomer and a polymerization initiator, 52.8 g (0.24 mole) of tricyclodecyl methacrylate, 53.6 g (0.2 mole) of ethoxylated o-phenylphenol acrylate, and methyl A mixture of 48.2 g of acrylic acid (0.56 mole) and 5.7 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Corporation, Perbutyl (registered trademark) O), A solution of the resin (A) was obtained in the same manner as in Synthesis Example 1 except that the amount of the glycidyl methacrylate was changed to 24.1 g (0.17 mol). This resin is referred to as "resin (A-6)". The resin (A-6) contained in this resin solution had an acid value of 125 KOHmg / g, a weight average molecular weight of 9200, and an unsaturated group equivalent weight of 1100. In the same manner as in Synthesis Example 1, propylene glycol monomethyl ether acetate was added to prepare a resin (A-6) solution (solid content concentration: 40% by mass) in Synthesis Example 6.

<Synthesis example 7>

The resin was obtained in the same manner as in Synthesis Example 2 except that the amount of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Corporation, Perbutyl (registered trademark) O) was changed to 4.7 g. (A). This resin is referred to as "resin (A-7)". The resin (A-7) contained in this resin solution had an acid value of 65 KOHmg / g, a weight average molecular weight of 15,000, and an unsaturated group equivalent of 600.

<Synthesis example 8>

The resin was obtained in the same manner as in Synthesis Example 2 except that the amount of t-butylperoxy-2-ethylhexanoate (a polymerization initiator, manufactured by Nippon Oil Corporation, Perbutyl (registered trademark) O) was changed to 2.3 g. (A). This resin is referred to as "resin (A-8)". The resin (A-8) contained in this resin solution had an acid value of 65 KOHmg / g, a weight average molecular weight of 30,000, and an unsaturated group equivalent of 600.

<Synthesis example 9>

As a mixture of a monomer and a polymerization initiator, 39.6 g (0.18 mole) of tricyclodecyl methacrylate, 57.0 g (0.57 mole) of methmethacrylate, and 7.7 g (0.09 of methacrylic acid) were used. A resin (A) solution was obtained in the same manner as in Synthesis Example 3, except that a mixture of 22.7 g (0.16 mol) of epoxypropylmethacrylate and 14.0 g of azobisisobutyronitrile was used. This resin is referred to as "resin (A-9)". Resin contained in this resin solution (A-9) had an acid value of 30 KOHmg / g and a weight average molecular weight of 8,500.

<Synthesis example 10>

As a mixture of a monomer and a polymerization initiator, 22.0 g (0.1 mol) of tricyclodecyl methacrylate, 42.0 g (0.42 mol) of methmethacrylate, and 2-ethylhexyl acrylate were used. In addition to a mixture of 11.0 g (0.06 mole), 22.4 g (0.26 mole) of methacrylic acid, 22.7 g (0.16 mole) of epoxypropylmethacrylate, and 13.2 g of azobisisobutyronitrile, Synthesis Example 3 also obtained a solution of resin (A). This resin is referred to as "resin (A-10)". The resin (A-10) contained in this resin solution had an acid value of 100 KOHmg / g and a weight average molecular weight of 8,700.

<Comparative Synthesis Example 1> (1) Preparation of copolymer

A monomer mixture of 64.1 g of N-phenylmaleimide imine, 18.8 g of methacrylic acid, 10.3 g of epoxypropylmethacrylate, and 6.8 g of styrene, and propylene glycol monomethyl ether acetic acid as a solvent 300 g of the ester and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator were placed in a 500 mL round bottom flask equipped with a reflux cooler and a stirrer. The temperature was raised to 70 ° C, and the mixture was stirred for 5 hours in order to form a copolymer for polymerization. The acid value of the copolymer thus produced was 80 KOHmg / g, and the weight average molecular weight was 11,000.

(2) Compounds with a xanthene skeleton structure

125.4 g of spiro [茀 -9,9'-xanthene] -3 ', 6'-diol and 0.1386 g of t-butylammonium bromide were placed in a 3000 mL round bottom flask and mixed. 78.6 g of epichlorohydrin was further added, and the mixture was heated to 90 ° C. for reaction. After confirming the complete consumption of spiron [螺 -9,9'-xanthene] -3 ', 6'-diol by liquid chromatography analysis, the reaction was cooled to 30 ° C and a 50% NaOH aqueous solution was slowly added. (3 equivalents). After confirming the complete consumption of epichlorohydrin by liquid chromatography analysis, the reaction was extracted with dichloromethane and washed three times. The organic layer was dried using magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The solvent of a mixture of dichloromethane and methanol (50:50, v / v) was used to crystallize the crude product.

With respect to 1 equivalent of the epoxy-based compound thus obtained, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid were added. Then, 8.29 g of propylene glycol monomethyl ether acetate was further added and mixed. In the solution thus prepared, air was blown in at 25 mL / minute, and the solution was heated to 90 to 100 ° C to dissolve the reaction body. When the solution was white and cloudy, the temperature was raised to 120 ° C. in order to completely dissolve the reactant. When the solution becomes transparent and the viscosity increases, the acid value of the solution is measured, and the solution is stirred until the acid value becomes less than 1.0 KOHmg / g. Until the acid value reached the target value (0.8 KOHmg / g), stirring was continued for 11 hours. After the reaction, the temperature of the reactor was reduced to room temperature, and a colorless transparent solid was obtained.

43 g of the solid product thus obtained, 33.6 g of acrylic acid, 0.04 g of 2,6-di-t-butyl-p-cresol, 0.21 g of tetrabutylammonium acetate, and 18 g of propylene glycol monomethyl ether acetate were placed in the reaction. In the flask, the mixture was stirred at 120 ° C for 13 hours. Then, the reaction body was cooled to room temperature, 24 g of propylene glycol monomethyl ether acetate and 10 g of succinic anhydride were added, and then the mixture was stirred at 100 ° C. Stir for 3 hours. 8 g of bisphenol Z glycidyl ether was added to the mixture, and the mixture was stirred at 120 ° C. for 4 hours, 90 ° C. for 3 hours, 60 ° C. for 2 hours, and then 40 ° C. for 5 hours. Reprecipitation is performed in water and alcohol to obtain the final resin in powder form. Next, propylene glycol monomethyl ether acetate was added so that solid content concentration might be 48 mass%. The acid value of the resin thus obtained was 105 KOHmg / g, and the weight average molecular weight was 5,500.

The copolymer obtained in (1) and the compound having a xanthene skeleton structure obtained in (2) were mixed at a solid content ratio of 6: 4 to prepare a resin solution of Comparative Synthesis Example 1.

<Measurement method of physical property value>

The acid values, unsaturated group equivalents, and weight average molecular weights described in the Synthesis Examples are values obtained by the methods described below.

(1) Acid value: The acid value of resin (A) measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K6901 5.3.2. The number of mg of potassium hydroxide required for neutralizing the acidic component contained in 1 g of the resin (A).

(2) Unsaturated group equivalent: The mass of the polymer per mole of polymerizable unsaturated bonds, a calculated value based on the amount of monomer used.

(3) Weight average molecular weight (Mw): The weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions.

Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Corporation)

Column temperature: 40 ℃

Sample: 0.2% tetrahydrofuran solution of copolymer

Development solvent: tetrahydrofuran

Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Corporation)

Flow rate: 1mL / min

<Examples 1 to 10 and Comparative Examples 1 to 2>

Using the resin solutions of Synthesis Examples 1 to 10, Comparative Synthesis Example 1, and commercially available resin solutions, the formulations (mass% basis) of Tables 1 and 2 below were used to prepare Examples 1 to 10 and Comparative Examples 1 to 2 A photosensitive resin composition for forming a black columnar spacer. Comparative Example 1 corresponds to an example of Patent Document 2. In the following formulation, the amount of the resin (A) does not include the solvent used in the preparation. The amount of the solvent contained in the solution of the resin (A) is added to the solvent (B) as a preparation component. In Tables 1 and 2, V259ME is a propylene-type epoxy-based acrylate / anhydride polymerization adduct propylene glycol monomethyl ether acetate solution (56.5 mass% of resin content, etc.), Nippon Steel Chemical Co., Ltd. V259ME, PGMEA Propylene glycol monomethyl ether acetate, Oxe 01 is 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzidine oxime)], IRGACURE OXE 01 manufactured by BASF, Color paste (mill base) 1 is a color paste containing organic amine based organic black (manufactured by BASF), and the pigment concentration is 18% by mass. Color paste 2 is a color paste containing carbon black, and the pigment concentration is 25% by mass. DPHA series 2 Pentaerythritol hexaacrylate, A-DPH manufactured by Shin Nakamura Industrial Co., Ltd., KBM-403 3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone KBM-403.

<Evaluation of colorant dispersibility>

The colorant dispersibility was evaluated by the method shown below.

First, the photosensitive resin composition for forming a black columnar spacer in Examples 1 to 10 and Comparative Examples 1 to 2 was spin-coated on an IZO substrate of 10 cm × 10 cm so that the thickness of the coating film was 1.5 μm. Then, it heated at 90 degreeC for 3 minutes, and evaporated the solvent. Next, the entire coating film was exposed using a multi-light ML-251D / B manufactured by Oxtail Electric Co., Ltd. and an irradiation optical unit PM25C-100 (exposure amount: 50 mJ / cm ² ) to harden the light. Then, using a 0.2% by mass potassium hydroxide aqueous solution, development was performed for 120 seconds, and then baking was performed at 230 ° C. for 30 minutes to obtain a desired hardened coating film. The optical density (Optical Density: OD) of the hardened coating film having a thickness of 1 μm was measured by using a transmission densitometer (361T, X-lite). The results are shown in Table 2. The higher the optical density, the better the dispersibility of the colorant.

<Evaluation of development margin>

Using the same method as the optical density, a 2.5 μm coating film was produced on a substrate, and a stylus type step difference meter T4000M manufactured by Kosaka Laboratory was used to measure the reduction rate of the coating film thickness between 100 seconds and 150 seconds of auto-development time. The results are shown in Table 2. The larger the reduction rate of the coating film thickness, the better the development margin.

<Evaluation of Solvent Resistance>

The black columnar spacer sample used for the evaluation of optical density was peeled from the substrate, cut into a size of 1 cm × 1 cm, placed in a glass bottle containing 5 mL of N-methylpyrrolidone, and left in an oven at 100 ° C. for 15 minutes Then, the presence or absence of decoloration was evaluated based on the following criteria. The results are shown in Table 2.

○: No discoloration when observed with the naked eye

×: Very much discolored when viewed with the naked eye

<Evaluation of Elastic Response Rate>

The black columnar spacer produced by the evaluation of the development margin was measured for compression displacement and elastic recovery rate at 25 ° C by using an elasticity measuring device (DUH-W201S, Shimadzu Corporation) and the following measurement conditions.

The method of unloading a load uses a flat pressing body having a diameter of 50 μm as a pressing body of a pressing pattern. In order to obtain a recognizable result between the comparison groups, the elastic recovery rate was measured by a test with a load of 300 mN. Maintain a load speed of 3gf / s and a hold time of 3s. Regarding the elastic recovery rate, a constant load is applied to a flat pressing body for 3 seconds. Secondly, a three-dimensional thickness measuring device is used to measure the actual elastic recovery rate of the pattern before and after the load. The elastic recovery rate is the ratio of the compressed distance (compression displacement) to the compressed distance (compression displacement) when a certain force is applied after the recovery time of 10 minutes has elapsed.

Elastic recovery rate (%) = [(Restoration distance / Compression displacement) × 100]

The results are shown in Tables 3 and 4.

From the above results, it is understood that the photosensitive resin composition-based colorant for forming the black columnar spacers of Examples 1 to 10 is excellent in dispersibility, development margin, solvent resistance, and elastic recovery. On the other hand, in the photosensitive resin composition for forming a black columnar spacer of Comparative Example 1, in the elastic recovery rate test, when a load was applied, the spacer was broken, and the physical properties of the spacer were poor. In addition, the photosensitive resin composition for forming a black columnar spacer in Comparative Example 2 had a large decolorization result in the evaluation of the solvent resistance.

Claims (12)

A photosensitive resin composition for forming a black columnar spacer, comprising: a photosensitive resin composition selected from the group consisting of a structural unit (a) having a carboxyl group, a structural unit (b-1) having a (meth) acrylic acid group, and A resin (A), a solvent (B), a photopolymerization initiator (C), and a coloring agent (D) of at least one constituent unit grouped by the constituent unit (b-2) of the functional group of the carboxyl reaction. The photosensitive resin composition for forming a black columnar spacer according to claim 1, wherein the resin (A) is a structural unit (c) further including an aromatic ring skeleton. The photosensitive resin composition for forming a black columnar spacer according to claim 1 or 2, wherein the resin (A) is a structural unit (d) further including a bridge alicyclic hydrocarbon group having 7 to 20 carbon atoms. The photosensitive resin composition for forming a black columnar spacer according to claim 2, wherein the aromatic ring skeleton is at least one selected from the group consisting of a biphenyl skeleton, a naphthalene skeleton, and an anthracene skeleton. The photosensitive resin composition for forming a black columnar spacer according to any one of claims 1 to 4, wherein the functional group that reacts with a carboxyl group is at least at least an oxetanyl group, an epoxy group, or an isocyanate group. One type of functional group. The photosensitive resin composition for forming a black columnar spacer according to any one of claims 1 to 5, wherein the carboxyl group is a carboxyl group derived from an unsaturated carboxylic acid, a carboxyl group derived from a polybasic acid, or a carboxyl group derived from a polybasic acid anhydride. The photosensitive resin composition for forming a black columnar spacer according to any one of claims 1 to 6, wherein the unsaturated group equivalent of the resin (A) is 200 to 2000 g / mole. The photosensitive resin composition for forming a black columnar spacer according to any one of claims 1 to 7, wherein the colorant (D) contains an inorganic black pigment and an organic black pigment. The photosensitive resin composition for forming a black columnar spacer according to any one of claims 1 to 8, wherein the resin (A) contains 1 to 20% by mass, the solvent (B) contains 50 to 94% by mass, and the foregoing The photopolymerization initiator (C) contains 0.01 to 5% by mass and the colorant (D) contains 3 to 30% by mass. The photosensitive resin composition for forming a black columnar spacer according to claim 9, further comprising a reactive diluent (E) in an amount of 1 to 20% by mass. A black columnar spacer characterized by hardening a photosensitive resin composition for forming a black columnar spacer according to any one of claims 1 to 10. An image display device includes a black columnar spacer as claimed in claim 11.