KR102624794B1 - Black Photosensitive Resin Composition - Google Patents

Abstract

(Problem) Floating substances are unlikely to occur after development, and in particular, even when a patterned black film is formed on a surface made of a material containing a metal element, problems of adhesion of floating substances or residues to the substrate are unlikely to occur. Providing a black photosensitive composition and a method of forming a patterned black film using the black photosensitive composition.
(Solution) A black photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (S) a solvent, containing no more than a predetermined amount of carbon black, and A (C) colorant having a particle size distribution that satisfies the requirements and a (S) solvent containing a nitrogen-containing polar organic solvent are used.

Description

Black Photosensitive Resin Composition}

The present invention relates to a black photosensitive composition and a method of forming a patterned black film using the black photosensitive composition.

Display bodies such as liquid crystal displays have a structure in which a liquid crystal layer is sandwiched between two substrates on which paired electrodes are formed to face each other. And inside one of the substrates, a color filter having pixels of each color such as red (R), green (G), and blue (B) is formed. In this color filter, in order to prevent color mixing of different colors in each pixel or to hide the electrode pattern, a black matrix is usually arranged in a matrix form to partition the pixels of each color of R, G, and B. It is formed.

Generally, color filters are formed by lithographic methods. Specifically, first, a black photosensitive composition is applied to the substrate, exposed, and developed to form a black matrix. Thereafter, by repeating application, exposure, and development of the photosensitive composition of each color (R), green (G), and blue (B), a pattern of each color is formed at a predetermined position to form a color filter. do.

In addition, conventional photosensitive compositions for forming a black matrix sometimes contain organic pigments in addition to carbon black as auxiliary pigments in order to provide light-shielding properties (see Patent Document 1).

Japanese Patent Publication No. 6-289216

A patterned black film such as a black matrix may be formed on a surface made of a material containing a metal element such as a metal oxide or metal such as ITO. However, when using the conventional black photosensitive composition described in Patent Document 1, there is a problem that floating matter is likely to occur after development. A surface made of a material containing a metal element is prone to attaching such floating matter or development residue. In particular, when forming a patterned black film on a substrate that has a surface made of a material containing a metal element and has through holes or steps, floating matter or development residue may remain in the through holes or recesses on the substrate. .

In view of the above problems, the present invention prevents floating matter from occurring easily after development, and in particular, even when forming a patterned black film on a surface made of a material containing a metal element, adhesion of floating matter or residue to the substrate is provided. The object is to provide a black photosensitive composition that does not cause the problem and a method of forming a patterned black film using the black photosensitive composition.

The present inventors have proposed that a black photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (S) a solvent contains no more than a predetermined amount of carbon black, and It was found that the above problems were solved by using a colorant (C) having a particle size distribution that satisfies the requirements, and a solvent (S) containing a nitrogen-containing polar organic solvent, and the present invention was completed.

The first aspect of the present invention is a black photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (S) a solvent,

(C) The difference between the maximum particle diameter Dmax (μm) and the minimum particle diameter Dmin (μm) in the particle size distribution of the colorant, Dmax - Dmin, is 0.2500 μm or more,

(S) The solvent contains a nitrogen-containing polar organic solvent,

It is a black photosensitive composition in which the carbon black content relative to the mass of solid content of the black photosensitive composition is 3% by mass or less.

A second aspect of the present invention includes forming a coating film by applying the black photosensitive composition according to the first aspect,

Position-selective exposure of the coating film,

It is a method of forming a patterned black film including developing an exposed coating film with an alkaline developer.

According to the present invention, floating matter is less likely to occur after development, and in particular, even when a patterned black film is formed on a surface made of a material containing a metal element, the problem of adhesion of floating matter or residue to the substrate is likely to occur. It is possible to provide a black photosensitive composition that does not use the black photosensitive composition and a method of forming a patterned black film using the black photosensitive composition.

≪Black photosensitive composition≫

The black photosensitive composition (hereinafter also referred to as “black composition”) contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (S) a solvent. Hereinafter, the essential or optional materials contained in the black photosensitive composition and the preparation method of the black photosensitive composition will be described.

<(A) Photopolymerizable compound>

The black composition contains (A) a photopolymerizable compound (hereinafter also referred to as “(A) component”). (A) The component is not particularly limited, and conventionally known photopolymerizable compounds can be used. Among them, a resin having an ethylenically unsaturated group or a monomer having an ethylenically unsaturated group is preferable.

A resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group can be used in combination. When a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group are combined, the curability of the black composition is improved and pattern formation is easy.

[Resin having an ethylenically unsaturated group]

Resins having an ethylenically unsaturated group include (meth)acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, and ethylene. Glycol monoethyl ether (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth) ) Acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di( Oligomers made by polymerizing meth)acrylate, cardoepoxy diacrylate, etc.; Polyester (meth)acrylic obtained by reacting (meth)acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohols and monobasic acid or polybasic acid. Rate: Polyurethane (meth)acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting (meth)acrylic acid; Bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, phenol Or cresol novolak-type epoxy resin, resor-type epoxy resin, triphenolmethane-type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydride. and epoxy (meth)acrylate resin obtained by reacting epoxy resins such as hydroxybenzene type epoxy resin with (meth)acrylic acid. Additionally, a resin obtained by reacting an epoxy (meth)acrylate resin with a polybasic acid anhydride can be preferably used. In addition, in this specification, “(meth)acryl” means “acrylic or methacryl.”

Moreover, as the resin having an ethylenically unsaturated group, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride can be preferably used.

Among them, compounds represented by the following formula (a-1) are preferable. The compound represented by this formula (a-1) is preferable because it has high photocurability.

[Formula 1]

In the above formula (a-1), X ^a represents a group represented by the following formula (a-2).

[Formula 2]

In the formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a , a single bond, or a group represented by the following formula (a-3).

[Formula 3]

Moreover, in the above formula (a-1), Y ^a represents the residue excluding the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydrophthalic anhydride. Phthalic acid, glutaric anhydride, etc. can be mentioned.

Moreover, in the above formula (a-1), Z ^a represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

Moreover, in the above formula (a-1), m represents an integer of 0 to 20.

The acid value of the resin having an ethylenically unsaturated group is preferably 10 to 150 mgKOH/g, and more preferably 70 to 110 mgKOH/g, in terms of resin solid content. It is preferable that the acid value is 10 mgKOH/g or more because sufficient solubility in the developing solution is obtained. Also, setting the acid value to 150 mgKOH/g or less is preferable because sufficient curability can be obtained and surface properties can be improved.

Moreover, the mass average molecular weight of the resin having an ethylenically unsaturated group is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. It is preferable that the mass average molecular weight is 1000 or more because good heat resistance and film strength can be obtained. Moreover, it is preferable to set the mass average molecular weight to 40000 or less because good developability can be obtained.

[Monomer having an ethylenically unsaturated group]

Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and butoxymethyl. Toxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate Latex, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth) Acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) Acrylates, half (meth)acrylates of phthalic acid derivatives, etc. are mentioned. These monofunctional monomers may be used individually, or may be used in combination of two or more types.

Meanwhile, polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. (meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin Di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol Tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth) Acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene Glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycylate. Diylether poly(meth)acrylate, urethane(meth)acrylate (i.e. tolylene diisocyanate), trimethylhexamethylene diisocyanate and reactant of hexamethylene diisocyanate and 2-hydroxyethyl(meth)acrylate, methylene bis( Examples include polyfunctional monomers such as meth)acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth)acrylamide, and triacryl formals. These polyfunctional monomers may be used individually, or may be used in combination of two or more types.

The content of component (A) in the black composition is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, and particularly preferably 30 to 60% by mass, based on the mass of the solid content of the black composition.

＜(B) Photopolymerization initiator＞

The black composition contains (B) a photopolymerization initiator (hereinafter also referred to as “component (B)”). (B) As the photopolymerization initiator, various photopolymerization initiators conventionally blended in photosensitive compositions can be used as long as they do not impair the purpose of the present invention.

(B) Specific examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxy Toxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4 -Dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2 -Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1- one, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2- Ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime , o-benzoylmethylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2 -Chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4' -Bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. , Benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, Trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyaceto Phenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9 -acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6- Tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl] -4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2 -[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl) thenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4- Ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4- Methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloro and methyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine. These (B) photopolymerization initiators can be used individually or in combination of two or more types.

Among such photopolymerization initiators (B), oxime ester-based photopolymerization initiators are preferable.

Among oxime-based photopolymerization initiators, the oxime ester compound represented by the following formula (B1) is preferable.

[Formula 4]

In the above formula (B1), R ^B1 represents -NO ₂ or -COR ^B5 . Moreover, R ^B5 represents a heterocyclic group, a condensed cyclic aromatic group, or an aromatic group which may have a substituent. R ^B2 to R ^B4 each independently represent a monovalent organic group.

In order to obtain a black composition that is excellent in resolution when forming a fine pattern and easy to form a colored film with good adhesion to a substrate, among the compounds represented by formula (B1), R ^B1 is -NO ₂ or R A compound in which ^B5 is a group selected from a heterocyclic group and a condensed cyclic aromatic group is -COR ^B5 , and -NO ₂ or R ^B5 is a heterocyclic group. A compound in which -COR ^B5 is a heterocyclic group is more preferable.

Examples of the heterocyclic group represented by R ^B5 include a heterocyclic group of at least 5-membered rings containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom, preferably a 5-membered ring or a 6-membered ring. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl group, imidazolyl group, and pyrazolyl group; nitrogen-containing 6-membered ring groups such as pyridyl group, pyrazinyl group, pyrimidyl group, and pyridazinyl group. ; Nitrogen-containing sulfur-containing groups such as thiazolyl group and isothiazolyl group; Nitrogen-containing oxygen-containing groups such as oxazolyl group and isoxazolyl group; Sulfur-containing groups such as thienyl group and thiopyranyl group; Containing furyl group, pyranyl group, etc. Oxygen group; etc. are mentioned. Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of heterocyclic groups containing condensed rings include benzothienyl groups.

Examples of the condensed cyclic aromatic group represented by R ^B5 include naphthyl group, anthryl group, and phenanthryl group. Moreover, the aromatic group represented by R ^B1 includes a phenyl group.

The heterocyclic group, condensed cyclic aromatic group, or aromatic group may have a substituent. In particular, when R ^B5 is an aromatic group, it is preferable to have a substituent. Such substituents include -NO ₂ , -CN, -SO ₂ R ^B6 , -COR ^B6 , -NR ^B7 R ^B8 , -R ^B9 , -OR ^B9 , -OR ^B10 -OR ^B11 , etc.

R ^B6 each independently represents an alkyl group, which may be substituted with a halogen atom or may be interrupted by an ether bond, thioether bond, or ester bond. The alkyl group for R ^B6 preferably has 1 to 5 carbon atoms, and examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group.

R ^B7 and R ^B8 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom. Among these, the alkylene portion of the alkyl group and the alkoxy group is an ether bond, a thioether bond, or an ester bond. It may be interrupted by . Additionally, R ^B7 and R ^B8 may be combined to form a ring structure. The alkyl group or alkoxy group in R ^B7 and R ^B8 preferably has 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group. Period, propoxy group, etc. can be mentioned.

The ring structure that can be formed by combining R ^B7 and R ^B8 includes a heterocycle. Examples of this heterocycle include a heterocyclic ring containing at least a nitrogen atom and having at least 5 to 7 members, preferably having 5 to 7 members. This heterocyclic ring may contain a condensed ring. Examples of heterocycles include piperidine ring, morpholine ring, thiomorpholine ring, etc. Among these, a morpholine ring is preferable.

R ^B9 represents an alkyl group in which part or all of the hydrogen atoms may be substituted with halogen atoms. The alkyl group for R ^B9 preferably has 1 to 5 carbon atoms, and examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, and isobutyl group.

R ^B10 represents an alkylene group. R ^B11 represents an alkyl group, which may be substituted with a halogen atom or may be interrupted by an ether bond, thioether bond, or ester bond. The preferred number of carbon atoms and specific examples thereof are the same as those described for R ^B6 above.

Among these, preferred examples of R ^B5 include pyrrolyl group, pyridyl group, thienyl group, thiopyranyl group, benzothienyl group, naphthyl group, and phenyl group having a substituent.

In the formula (B1), R ^B2 represents a monovalent organic group. As this organic group, groups represented by -R ^B12 , -OR ^B12 , -COR ^B12 , -SR ^B12 , and -NR ^B12 R ^B13 are preferable. R ^B12 and R ^B13 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these may be substituted with a halogen atom, an alkyl group, or a heterocyclic group, and among these, the alkyl group and the aralkyl group are alkyl. The ren moiety may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Additionally, RB ¹² and RB ¹³ may be bonded to form a ring structure together with the nitrogen atom.

The alkyl groups represented by R ^B12 and R ^B13 preferably have 1 to 20 carbon atoms, and more preferably have 1 to 5 carbon atoms. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, and sec-pentyl group. , tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isode Straight-chain or branched-chain groups such as actual groups can be mentioned. Additionally, this alkyl group may have a substituent. Examples of those having a substituent include methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

The number of carbon atoms of the alkenyl groups represented by R ^B12 and R ^B13 is preferably 1 to 20, and more preferably 1 to 5. The alkenyl group may be linear or branched. Examples of alkenyl groups include vinyl group, allyl group, butenyl group, ethenyl group, and propynyl group. The alkenyl group may have a substituent. Examples of an alkenyl group having a substituent include 2-(benzooxazol-2-yl)ethenyl group.

The number of carbon atoms of the aryl group represented by R ^B12 and R ^1B12 is preferably 6 to 20, and more preferably 6 to 10. Examples of the aryl group include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, and phenanthryl group.

The number of carbon atoms of the aralkyl group represented by R ^B12 and R ^B13 is preferably 7 to 20, and more preferably 7 to 12. Examples of aralkyl groups include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group, and phenylethenyl group.

Examples of the heterocyclic group represented by R ^B12 and R ^B13 include a heterocyclic group having a 5-membered ring or more, preferably a 5-7 membered ring, containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. This heterocyclic group may contain a condensed ring. Examples of heterocyclic groups include pyrrolyl group, pyridyl group, pyrimidyl group, furyl group, and thienyl group.

Among these R ^B12 and R ^B13 , the alkylene portion of the alkyl group and aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.

Additionally, the ring structure that can be formed by combining R ^B12 and R ^B13 includes a heterocycle. Examples of this heterocycle include a heterocyclic ring containing at least a nitrogen atom and having at least 5 to 7 members, preferably having 5 to 7 members. This heterocyclic ring may contain a condensed ring. Examples of heterocycles include piperidine ring, morpholine ring, thiomorpholine ring, etc.

Among these, R ^B2 is most preferably a methyl group, ethyl group, propyl group, or phenyl group.

In the formula (B1), R ^B3 represents a monovalent organic group. This organic group is preferably an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (B2), or a heterocyclic group which may have a substituent. Examples of the substituent include the same groups as those for R ^B5 above. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, naphthyl group, anthryl group, and phenanthryl group.

[Formula 5]

In the above formula (B2), R ^B14 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Such alkylene groups include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, n-pentylene group, isopentylene group, sec-pentylene group, etc. Examples include straight-chain or branched-chain groups. Among these, it is most preferable that R ^B14 is an isopropylene group.

In the above formula (B2), R ^B15 represents a monovalent organic group represented by -NR ^B16 R ^B17 (R ^B16 and R ^B17 each independently represent a monovalent organic group). Among such organic groups, it is preferable that the structure of R ^B15 is represented by the following formula (B3) because the solubility of the oxime-based photopolymerization initiator can be improved.

[Formula 6]

In the formula (B3), R ^B18 and R ^B19 each independently represent an alkyl group having 1 to 5 carbon atoms. Such alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, and sec-phene. Tyl group, tert-pentyl group, etc. are mentioned. Among these, it is most preferable that R ^B18 and R ^B19 are methyl groups.

Examples of the heterocyclic group represented by R ^B3 include a heterocyclic group of at least 5-membered rings containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom, preferably a 5-membered ring or a 6-membered ring. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl group, imidazolyl group, and pyrazolyl group; nitrogen-containing 6-membered ring groups such as pyridyl group, pyrazinyl group, pyrimidyl group, and pyridazinyl group. ; Nitrogen-containing sulfur-containing groups such as thiazolyl group and isothiazolyl group; Nitrogen-containing oxygen-containing groups such as oxazolyl group and isoxazolyl group; Sulfur-containing groups such as thienyl group and thiopyranyl group; Containing furyl group, pyranyl group, etc. Oxygen group; etc. are mentioned. Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of heterocyclic groups containing condensed rings include benzothienyl groups.

Additionally, the heterocyclic group may have a substituent. Examples of the substituent include the same groups as those for R ^B5 above.

In the formula (B1), R ^B4 represents a monovalent organic group. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Such alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, and sec-phene. Tyl group, tert-pentyl group, etc. are mentioned. Among these, it is most preferable that R ^B4 is a methyl group.

The ratio of the amount of the compound represented by formula (B1) to the mass of component (B) is preferably 10 mass% or more, more preferably 30 mass% or more, and especially preferably 50 mass% or more. The upper limit is not particularly limited, but is, for example, 90% by mass or less, preferably 80% by mass or less.

In particular, the mass of component (B) is represented by formula ( ^B1 ), and R ^B1 is -NO ₂ or -COR ^B5 is a group selected from heterocyclic groups and fused cyclic aromatic groups. The upper limit of the compound content is preferably 90% by mass or less, and more preferably 80% by mass or less.

When the component (B) contains the compound represented by formula (B1) in an amount within this range, a black composition capable of forming a pattern with excellent resolution and excellent adhesion to the substrate can be easily obtained.

The content of component (B) in the black composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and particularly preferably 5 to 20% by mass, based on the mass of the solid content of the black composition.

＜(C) Colorant＞

The black composition contains (C) a colorant (hereinafter also referred to as “component (C)”).

(C) The difference between the maximum particle diameter Dmax (μm) and the minimum particle diameter Dmin (μm) in the particle size distribution of the colorant, Dmax - Dmin, is 0.2500 μm or more. (C) When the colorant contains a plurality of pigments and/or dyes, the particle size distribution of the (C) colorant is not the particle size distribution of individual pigments and/or dyes, but the particle size distribution as a mixture of pigments and/or dyes. .

In addition, (C) the particle size distribution of the colorant is measured by a laser diffraction type particle size distribution measuring device.

When the black composition contains the (C) colorant having a value of Dmax - Dmin of 0.2500 ㎛ or more, it is easy to suppress the generation of suspended matter after development, and as a result, development residue is less likely to be generated.

The value of Dmax - Dmin is preferably 0.2530 μm or more, and more preferably 0.2550 μm or more. Moreover, the upper limit of Dmax - Dmin is less than 1.0000 μm, preferably 0.8000 μm or less, more preferably 0.7000 μm or less, and still more preferably 0.3000 μm or less.

Since it is easy to form a pattern of a desirable black color using a black composition, the closer the value of Dmax - Dmin is to 0.2500, the more preferable it is.

(C) The method of adjusting the value of Dmax - Dmin of the colorant is not particularly limited. For example, by mixing multiple types of pigments or dyes with different particle size distributions to prepare the coloring agent (C), the value of Dmax or Dmin can be adjusted, and as a result, the value of Dmax - Dmin is adjusted.

(C) The dispersion of the colorant may be filtered through a filter with a desired pore diameter to remove coarse or fine particles and adjust the value of Dmax - Dmin.

(C) The value of Dmax - Dmin can also be adjusted by finely pulverizing the colorant. By fine pulverization, the particle size distribution of the coloring agent (C) widens, and the value of Dmax - Dmin increases.

(C) The colorant does not contain carbon black in an amount exceeding 3% by mass based on the mass of the solid content of the black composition. If carbon black is present in an amount exceeding 3% by mass relative to the mass of the solid content of the black composition, floating matter or development residue is likely to occur after development.

As described above, the content of carbon black relative to the mass of solid content of the black composition is 3% by mass or less. The content of carbon black relative to the mass of the solid content of the black composition is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0% by mass.

(C) The color of the pigment and dye contained in the colorant is not particularly limited. However, when pigments and/or dyes of colors other than black are blended into a black composition, a plurality of pigments and/or dyes are blended in combination so that the composition appears black.

Additionally, the colorant (C) may be a combination of multiple black colorants. In this case, as the black colorant, for example, perylene black, aniline black, and black azo compound can be used.

Since the color of black can be delicately adjusted and the value of Dmax - Dmin can be easily adjusted, it is preferable that the (C) colorant is a combination of multiple types of chromatic colorants rather than a colorant composed of a single type of colorant. .

(C) As the colorant, for example, it is preferable to combine two or more types selected from five organic pigments of blue, purple, yellow, red, and orange.

By combining two or more colors of organic pigments among the above five colors, a pseudo-blackened color can be displayed. Here, “pseudo black” is ideally a coloristic black, but any color acceptable for use as a black film formed using a black composition can be used.

The ratio (mass ratio) of the organic pigment of each color in the (C) colorant showing pseudo-black is preferably (blue organic pigment)/(yellow organic pigment + orange organic pigment)/(red organic pigment + purple organic pigment) Pigment) = (30 to 60 mass%)/(25 to 50 mass%)/(5 to 40 mass%).

As the organic pigments of the above five colors, known ones that have been used conventionally can be used.

Blue organic pigments include C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, and C.I. Pigment Blue 60.

Purple organic pigments include C.I. Pigment Violet 19 and C.I. Pigment Violet 23.

Yellow organic pigments include C. I. Pigment Yellow 83, C. I. Pigment Yellow 110, C. I. Pigment Yellow 128, C. I. Pigment Yellow 138, C. I. Pigment Yellow 139, C. I. Pigment Yellow 150, C. I. Pigment Yellow 151, and C. I. Pigment. C. I. Pigment Yellow 154, C. I. Pigment Yellow 155, C. I. Pigment Yellow 180, and C. I. Pigment Yellow 181.

Orange organic pigments include C. I. Pigment Orange 38, C. I. Pigment Orange 43, C. I. Pigment Orange 64, C. I. Pigment Orange 69, C. I. Pigment Orange 71, and C. I. Pigment Orange 73. Pigments belonging to red organic pigments include C. I. Pigment Red 122, C. I. Pigment Red 166, C. I. Pigment Red 177, C. I. Pigment Red 179, C. I. Pigment Red 242, C. I. Pigment Red 224, and C. I. Pigment Red. 254, C.I. Pigment Red 264, and C.I. Pigment Red 272.

Among them, the blue organic pigment is at least one selected from the group consisting of C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, and C.I. Pigment Blue 15:6, and the purple organic pigment is C.I. Pigment Violet. 23, the yellow organic pigment is C. I. Pigment Yellow 83 and/or C. I. Pigment Yellow 139, the orange organic pigment is C. I. Pigment Orange 43 and/or C. I. Pigment Orange 64, and the red organic pigment is C. I. Pigment Red 254. It is desirable to be

By using these organic pigments in combination, it is easy to form a black film with good black color and excellent optical density (OD value).

In order to obtain a pseudo-black (C) colorant, it is preferable to combine at least one selected from a blue organic pigment, a yellow organic pigment, and an orange organic pigment, and these organic pigments with a red organic pigment and a purple organic pigment. It is more preferable to further combine at least one type of organic pigment selected from pigments.

Combinations of pigments belonging to specific organic pigments of each color include, for example,

·C. A combination of I. Pigment Blue 15:4 and C. I. Pigment Yellow 139 and C. I. Pigment Red 254,

·C. A combination of I. Pigment Blue 15:6 and C. I. Pigment Orange 64 and C. I. Pigment Violet 23,

·C. A combination of I. Pigment Blue 15:4 or 15:3 and C. I. Pigment Yellow 83 and C. I. Pigment Violet 23 and C. I. Pigment Red 254,

etc. can be mentioned.

The content of component (C) in the black composition is not particularly limited as long as the film formed using the black composition exhibits black at the desired density. The content of component (C) in the black composition is preferably 20 to 80% by mass, more preferably 30 to 65% by mass, and particularly preferably 40 to 60% by mass, based on the mass of the solid content of the black composition.

＜(D) Silane coupling agent＞

(D) The silane coupling agent bonds or interacts with various components contained in the black composition via an alkoxy group and/or reactive group bonded to a silicon atom, or bonds with the surface of a support such as a substrate. For this reason, when the silane coupling agent (D) is added to the black composition, the exposed area is cured well, thereby easily suppressing the generation of floating matter or development residue after development, or forming a black film with excellent adhesion to the substrate.

The silane coupling agent is not particularly limited. Preferred examples of silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and n- Monoalkyltrialkoxysilanes such as butyltrimethoxysilane and n-butyltriethoxysilane; Dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; Phenyltrimethoxysilane, phenyltriethoxysilane, etc. Monophenyltrialkoxysilane; Diphenyldialkoxysilane such as diphenyldimethoxysilane and diphenyldiethoxysilane; Monovinyltrialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxysilane (meth)acryloxyalkyl monoalkyl dialkoxy such as propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Silane; (meth)acryloxyalkyltrialkoxysilane such as 3-acryloxypropyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- Trialkoxysilanes containing amino groups such as (1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Alkyl trialkoxysilanes containing non-alicyclic epoxy groups such as propyltriethoxysilane; Alkyl monoalkyl dialkoxysilanes containing non-alicyclic epoxy groups such as 3-glycidoxypropylmethyldiethoxysilane; 2-(3,4-epoxycyclohexyl) Alicyclic epoxy group-containing alkyltrialkoxysilanes such as ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, etc. Alicyclic epoxy group-containing alkylmonoalkyldialkoxysilane; [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltri Oxetanyl group-containing alkyltrialkoxysilanes such as ethoxysilane; Mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; Mercaptoalkylmonoalkyldialkoxys such as 3-mercaptopropylmethyldimethoxysilane Silane; Ureidoalkyl trialkoxysilane such as 3-ureidopropyltriethoxysilane; Isocyanate alkyltrialkoxysilane such as 3-isocyanatepropyltriethoxysilane; Acid anhydride group such as 3-trimethoxysilylpropylsuccinic anhydride Containing alkyltrialkoxysilanes; Alkyltrialkoxysilanes containing imide groups such as N-t-butyl-3-(3-trimethoxysilylpropyl)succinic acid imide; and the like. These silane coupling agents may be used individually, or may be used in combination of two or more types.

Moreover, a compound represented by the following formula (D1) is also preferably used as a silane coupling agent.

R ^D1 _d R ^D2 _(3-d) Si-R ^D3 -NH-C(O)-Y ^D -R ^D4 -X ^D … (D1)

(In formula (D1), R ^D1 is an alkoxy group, R ^D2 is an alkyl group, d is an integer of 1 to 3, R ^D3 is an alkylene group, Y ^D is -NH-, -O-, or -S ^{- ,} R ^D4 is a single bond or ^an alkylene group ^, and The ring is a nitrogen-containing 6-atom aromatic ring, and -Y ^D -R ^D5 - is bonded to a carbon atom in the nitrogen-containing 6-atom aromatic ring)

In formula (D1), R ^D1 is an alkoxy group. With respect to R ^D1 , the number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferred specific examples of R ^D1 include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and n-pentyloxy group. , and n-hexyloxy group. Among these alkoxy groups, methoxy group and ethoxy group are preferable.

As the silanol group produced by hydrolysis of the alkoxy group R ^D1 reacts with the surface of the substrate, the adhesion of the coating film formed using the energy-sensitive resin composition to the surface of the support such as the substrate tends to improve. For this reason, d is preferably 3 because it is easy to improve the adhesion of the coating film to the surface of a support such as a substrate.

In formula (D1), R ^D2 is an alkyl group. With respect to R ^D2 , the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferred specific examples of R ^D2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. , n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

In formula (D1), R ^D3 is an alkylene group. With respect to R ^D3 , the number of carbon atoms of the alkylene group is preferably 1 to 12, more preferably 1 to 6, and especially preferably 2 to 4. Preferred specific examples of R ^D3 include methylene group, 1,2-ethylene group, 1,1-ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1- Diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane- 2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, and hexane-1,6-diyl group, heptane-1,7- diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane 1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. I can hear it. Among these alkylene groups, 1,2-ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group are preferable.

Y ^D is -NH-, -O-, or -S-, and is preferably -NH-. Since the bond represented by -CO-NH- is less susceptible to hydrolysis than the bond represented by -CO-O- or -CO-S-, a compound where Y ^D is -NH- is contained as a silane coupling agent. When an energy-sensitive resin composition is used, a coating film with excellent adhesion to a support such as a substrate can be formed.

R ^D4 is a single bond or an alkylene group, and is preferably a single bond. A preferable example when R ^D4 is an alkylene group is the same as R ^D3 .

X ^D is a substituent, which can be a substituent, a single fluid or a fluid, and a ring that combines with -yd ^{-r d5} in x ^D is a 6 atomic direction of nitrogen, and ^-yd -R ^D5 - is bonded to a carbon atom in the nitrogen-containing 6-atom aromatic ring. Although the reason is unknown, when an energy-sensitive ^resin composition containing such a compound having

In the ^case where When X ^D is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 to 3. When X ^D is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen ^- containing 6-membered aromatic ring in .

^Substituents that may be included in alkenyloxy group, aliphatic acyl group having 2 to 6 carbon atoms, benzoyl group, nitro group, nitroso group, amino group, hydroxyl group, mercapto group, cyano group, sulfonic acid group, carboxyl group, and halogen atom. there is. The number of substituents that X ^D has is not particularly limited as long as it does not impair the purpose of the present invention. The number of substituents that X ^D has is preferably 5 or less, and more preferably 3 or less. When X ^D has a plurality of substituents, the plurality of substituents may be the same or different.

Preferred examples of X ^D include groups of the following formula.

[Formula 7]

Among the above groups, a group of the following formula is more preferable as X ^D.

[Formula 8]

Preferred specific examples of the compound represented by formula (D1) described above include the following compounds 1 to 8.

[Formula 9]

The content of the (D) silane coupling agent in the black composition is not particularly limited. (D) The content of the silane coupling agent is preferably 1,000 to 10,000 ppm by mass, more preferably 1,500 to 9,000 ppm by mass, and especially preferably 2,000 to 8,000 ppm by mass, relative to the mass of the entire black composition.

＜(S) Solvent＞

The black composition contains (S) solvent. (S) The solvent contains a nitrogen-containing polar organic solvent. When the black composition contains a (S) solvent containing a nitrogen-containing polar organic solvent, it is easy to form a fine pattern, and the adhesion of the formed pattern to the substrate is improved.

(S) The solvent may contain various nitrogen-containing polar organic solvents conventionally blended in photosensitive compositions. Preferred examples of nitrogen-containing polar organic solvents include amides such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide, and N,N-diethylformamide; 1, Heterocyclic polar organic solvents such as 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone, and γ-butyrolactone; and the following formula (S1):

[Formula 10]

(In formula (S1), R ^S1 and R ^S2 are each independently an alkyl group having 1 to 3 carbon atoms, and R ^S3 is represented by the following formula (S1-1) or the following formula (S1-2):

[Formula 11]

It is a group represented by . In formula (S1-1), R ^S4 is a hydrogen atom or a hydroxyl group, and R ^S5 and R ^S6 are each independently an alkyl group having 1 to 3 carbon atoms. In formula (S1-2), R ^S7 and R ^S8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

Compounds represented by can be mentioned. (S) The solvent may contain a combination of two or more nitrogen-containing polar organic solvents.

Among the above nitrogen-containing polar organic solvents, the compound represented by formula (S1) is preferable.

Among the compounds represented by formula (S1), specific examples where R ^S3 is a group represented by formula (S1-1) include N,N,2-trimethylpropionamide, N-ethyl, N,2-dimethylpropionamide, N,N-diethyl-2-methylpropionamide, N,N,2-trimethyl-2-hydroxypropionamide, N-ethyl-N,2-dimethyl-2-hydroxypropionamide, and N,N- Diethyl-2-hydroxy-2-methylpropionamide, etc. can be mentioned.

Among the compounds represented by formula (S1), specific examples where R ^S3 is a group represented by formula (S1-2) include N,N,N',N'-tetramethylurea, N,N,N',N '-tetraethyl urea, etc. can be mentioned.

Among the compounds represented by formula (S1), N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea are more preferable, and N,N,N',N'-tetramethyl Urea is particularly preferred.

(S) The solvent preferably contains a solvent other than the nitrogen-containing polar organic solvent along with the nitrogen-containing polar organic solvent.

Preferred examples of solvents other than nitrogen-containing polar organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol mono-n-propyl ether, Diethylene glycol mono-n-butyl ether, Triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, Propylene glycol monomethyl ether, Propylene glycol mono Ethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- (poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl (Poly)alkylene glycol monoalkyl ether acetates such as ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , other ethers such as diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, 2-hydroxy Alkyl lactic acid esters such as ethyl propionate; 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethoxy Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate , ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid. Other esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene, etc. I can hear it. These solvents can be used individually or in mixture of two or more types.

(S) The content of the nitrogen-containing polar organic solvent in the solvent is not particularly limited as long as it does not impair the purpose of the present invention. (S) The lower limit of the content of the nitrogen-containing polar organic solvent in the solvent is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, and most preferably 10% by mass or more. . (S) The upper limit of the content of the nitrogen-containing polar organic solvent in the solvent may be set appropriately. For example, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 30 mass% or less is particularly preferable. .

The content of the (S) solvent in the black composition is not particularly limited as long as it does not impair the purpose of the present invention, and is determined appropriately in consideration of the applicability of the black composition and the film thickness of the coating film. Typically, the (S) solvent is used so that the solid content concentration of the black composition is preferably 5 to 40 mass%, more preferably 10 to 35 mass%, and particularly preferably 15 to 30 mass%.

＜Other ingredients＞

The black composition may contain a thermal polymerization inhibitor, an antifoaming agent, a surfactant, etc. in addition to the components described above.

As a thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, etc. can be used. Silicone-based or fluorine-based compounds can be used as antifoaming agents. As the surfactant, various known thermal polymerization inhibitors such as anionic, cationic, nonionic, etc. can be used.

<Method for preparing black photosensitive composition>

The black photosensitive composition contains a predetermined amount of (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a colorant, and, if necessary, (D) a silane coupling agent and other components at a desired solid concentration. It is prepared by uniformly dispersing and dissolving in (S) a solvent as much as possible.

(C) A black composition may be prepared using a masterbatch in which the colorant is previously thickly dispersed in the (S) solvent.

The obtained black composition may be filtered using a filter having a desired opening diameter.

≪Method for forming patterned black film≫

Using the black composition described above, a patterned black film is formed.

The method of forming a patterned black film is,

Formation of a coating film by applying a black composition on a substrate,

Position-selective exposure of the coating film,

This includes development of the exposed coating film using an alkaline developer.

First, the black composition is applied to the substrate using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or a non-contact type coating device such as a spinner (rotary coating device), curtain flow coater, die coater, or slit coater. Thus, a coating film is formed.

The material of the substrate is not particularly limited. The patterned black film is preferably formed on a surface made of a material containing a metal element. In short, the substrate preferably has a surface made of a material containing a metal element. By using the black composition described above, even in the case of forming a patterned black film on a surface made of a material containing a metal element, it is difficult to cause floating matter or development residue generated after development to adhere to the substrate surface.

Materials containing metal elements include metal oxides such as ITO, IZO, ZnO, and IGZO, simple substances of various metals, and alloys such as APC (silver-palladium-copper alloy).

After applying the black composition, the coating film is usually dried to remove the solvent. The drying method is not particularly limited, and examples include (1) drying on a hot plate at a temperature of 80°C to 120°C, preferably 90°C to 100°C for 60 to 120 seconds, (2) several hours at room temperature. You may use any of the following methods: leaving it for a few days or (3) removing the solvent by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, the coating film is site-selectively exposed by irradiating active energy rays such as ultraviolet rays or excimer laser light through a negative mask. The energy dose to be irradiated varies depending on the composition of the black composition, but is preferably about 30 mJ/cm2 to 2000 mJ/cm2, for example.

Next, the film after exposure is developed with an alkaline developer and patterned into a desired shape. The development method is not particularly limited, and for example, an immersion method, a spray method, etc. can be used. Examples of alkaline developers include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium hydroxide.

For example, a surfactant is usually added to a developing solution such as an aqueous potassium hydroxide solution. For this reason, when using an aqueous solution of potassium hydroxide or the like as a developing solution, foaming may occur during development, making recovery and reuse of the developing solution difficult.

On the other hand, when an aqueous solution of quaternary ammonium hydroxide is used as a developer, no surfactant is usually added to the developer. For this reason, when an aqueous solution of quaternary ammonium hydroxide is used as a developer, foaming is unlikely to occur, making recovery and reuse of the developer easy. The risk of residue increases as no surfactant is added, but the black composition of the present invention makes it difficult to cause floating matter or development residue generated after development to adhere to the substrate surface.

Additionally, in the display panel manufacturing process, a positive-type photosensitive composition is often used when forming wiring. When forming a pattern using a positive photosensitive composition during wiring formation, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide is generally used.

For this reason, in the manufacturing process of the display panel, even when forming a patterned black film, the use of an aqueous solution of quaternary ammonium hydroxide is due to the low level of developer solution and the use of developer supply lines, etc. for forming wiring. It has a great advantage in that it can be shared with equipment.

The developed patterned black film is post-baked, for example, at a temperature of about 200° C., if necessary.

Since the patterned black film formed as described above is formed without adhesion of floating matter or development residue after development to the substrate, it can, for example, block light, such as a black matrix in various display device panels. It is preferably used as a material. In addition, because adhesion can be improved while suppressing the adhesion of floating substances or residues to the substrate, various types of display devices can be curved, bendable, or foldable. It is preferably used as a light-blocking material such as a black matrix in a panel having a curved display or flexible display in the form of ) or a rollable form that can be wound.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited to these examples.

[Preparation example 1]

First, in a 500 mL four-necked flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 mg of acrylic acid. g was injected and dissolved by heating at 90 to 100°C while blowing air at a rate of 25 mL/min. Next, the temperature was gradually raised while the solution was in a cloudy state, and it was heated to 120°C to completely dissolve. At this time, the solution gradually became transparent, but stirring was continued. In the meantime, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature, and bisphenol fluorene type epoxy acrylate represented by the following formula (a-4), which was colorless and transparent and was in a solid state, was obtained.

[Formula 12]

Next, 600 g of 3-methoxybutylacetate was added and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, the temperature was gradually raised, and the mixture was allowed to react at 110 to 115°C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and it was made to react at 90 degreeC for 6 hours, and resin A-1 was obtained. The disappearance of the acid anhydride group was confirmed by IR spectrum. In addition, this resin A-1 corresponds to the resin represented by the above formula (a-1).

[Examples 1 to 4, and Comparative Examples 1 to 5]

In the examples and comparative examples, (A) the following A1 and A2 were used as the photopolymerizable compounds.

A1: Resin A-1 obtained in Preparation Example 1 above

A2: Dipentaerythritol hexaacrylate

In the examples and comparative examples, B1, B2, and B3 having the following structures were used as photopolymerization initiators (B).

[Formula 13]

In the examples and comparative examples, the following C1, C2, and C3 were used as colorants (C). In addition, (C) the colorant dispersed with a dispersant (DisperBYK2001, manufactured by Big Chemistry) was used.

C1：C. A mixture of I. Pigment Blue 15:6, C. I. Pigment Orange 64, and C. I. Pigment Violet 23.

C2: mixture of pigment black containing perylene black

C3: Carbon black

In the examples and comparative examples, (D) N-phenyl-3-aminopropyltrimethoxysilane was used as the silane coupling agent.

In the examples and comparative examples, the following S1 to S4 were used as the (S) solvent.

S1: 3-methoxybutyl acetate

S2: Propylene glycol monomethyl ether acetate

S3: Cyclohexanone

S4: N,N,N',N'-Tetramethylurea

Component (A), component (B), and component (C) of the types and amounts shown in Table 1, and component (D) whose ratio to the mass of the entire black composition is shown in Table 1 are shown in Table 1. The solvent (S) of the composition described was mixed and dispersed so that the solid content concentration was 17% by mass, and the black compositions of each Example and Comparative Example were obtained. In addition, Example 4 used a pigment that was different from C1 used in Example 1 only in the value of Dmax - Dmin as C1.

Using the obtained black compositions of each Example and Comparative Example, the presence or absence of floating matter and development residue after development, resolution, and adhesion of the formed black film to the substrate were evaluated according to the following method.

<Evaluation of suspended matter and development residue>

The black compositions of Examples and Comparative Examples were applied onto a substrate having an ITO film on the surface, and then prebaked at 80°C for 120 seconds to form a coating film with a thickness of 2.5 μm. The formed coating film was exposed through a mask at an exposure dose of 48 mJ/cm2 (GAP 20 μm). After exposure, development was performed by an immersion method (25°C, 90 seconds) using an aqueous solution of tetramethylammonium hydroxide with a concentration of 3.58 mass% to obtain a patterned black film.

The obtained black film was observed using an optical microscope (manufactured by Olympus, brand name: MX50) to confirm the presence or absence of floating matter and development residue after development in the patterned black film.

The presence or absence of suspended matter and development residue after development is listed in Table 2.

Additionally, the OD value of the formed black film was measured. The measurement results of the OD value are listed in Table 2.

＜Resolution and Adhesion＞

By the same method as the evaluation of suspended matter and development residue, a line and space pattern was formed using a mask for forming a line and space pattern including line portions and space portions each having a width of 10 μm. The formed pattern was observed using a measurement SEM (scanning electron microscope, brand name: S-9380, manufactured by Hitachi Ltd.) to evaluate resolution. Cases where a line and space pattern with a predetermined dimension could be formed were judged as ○, and cases where a line and space pattern with a predetermined size could not be formed were judged as ×.

Additionally, the presence or absence of peeling was observed for the line and space pattern, and the adhesion of the formed pattern to the substrate was evaluated. Cases where peeling from the substrate at the line portion was observed were judged as ○, and cases where peeling from the substrate at the line portion was not observed were judged as ×.

The results of these evaluations are listed in Table 2.

Additionally, as a result of observing the surface conditions of the patterns formed using the black compositions of Examples 1 and 4, which were resolved, a good pattern with less surface roughness was obtained in Example 4.

From Examples 1 to 4, (S) a colorant (C) containing N,N,N',N'-tetramethylurea, a nitrogen-containing polar organic solvent, as the solvent, and having a Dmax - Dmin value of 0.2500 ㎛ or more. If the black composition contains and does not contain more than 5% by mass of carbon black relative to the mass of the solid content, even when forming a pattern on a surface made of ITO, suspended matter or development residue is unlikely to be generated after development. Able to know.

According to comparison between Example 1 and Example 2, the black composition contains, as component (B), a compound represented by the above-mentioned formula (B1), and also has -COR ^B5 as R ^B1 , where R ^B5 is a heterocyclic group. In this case, it can be seen that the black composition has excellent resolution and that it is easy to form a pattern with excellent adhesion to the substrate using the black composition.

According to the comparison between Example 1 and Example 3, the higher the content of component (D) in the black composition, the better the resolution of the black composition, and the easier it is to form a pattern with excellent adhesion to the substrate using the black composition. Able to know.

According to Comparative Examples 1 and 2, it can be seen that when the black composition does not contain a nitrogen-containing polar organic solvent as the (S) solvent, floating matter and development residue are likely to occur after development.

According to Comparative Examples 2 and 5, it can be seen that when the value of Dmax - Dmin of component (C) contained in the black composition is less than 0.2500 μm, floating matter and development residue are likely to occur after development.

According to Comparative Examples 2 to 4, it can be seen that when the amount of carbon black relative to the solid content of the black composition exceeds 3% by mass, floating matter and development residue are likely to occur after development.

In addition, the black compositions of Examples 1 to 4 were evaluated for suspended matter and development residue after development also on a substrate made of APC (silver-palladium-copper alloy). As a result, even when the black composition of any example was used, the generation of floating matter and development residue after development on a substrate made of APC was suppressed.

Claims (10)

A black photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (S) a solvent,
In the particle size distribution of the colorant (C), the difference between the maximum particle size Dmax (μm) and the minimum particle size Dmin (μm), Dmax - Dmin, is 0.2500 μm or more,
The (C) colorant contains an organic pigment,
The (S) solvent contains a nitrogen-containing polar organic solvent,
A black photosensitive composition wherein the carbon black content is 3% by mass or less based on the mass of solid content of the black photosensitive composition. According to claim 1,
The nitrogen-containing polar organic solvent has the following formula (S1):
[Formula 1]

(In formula (S1), R ^S1 and R ^S2 are each independently an alkyl group having 1 to 3 carbon atoms, and R ^S3 is represented by the following formula (S1-1) or the following formula (S1-2):
[Formula 2]

It is a group represented by . In formula (S1-1), R ^S4 is a hydrogen atom or a hydroxyl group, and R ^S5 and R ^S6 are each independently an alkyl group having 1 to 3 carbon atoms. In formula (S1-2), R ^S7 and R ^S8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
A black photosensitive composition containing the compound represented by . According to claim 1,
The photopolymerization initiator (B) has the following formula (B1):
[Formula 3]

(In formula (B1), R ^B1 represents -NO ₂ or -COR ^B5 , R ^B5 represents a heterocyclic group or fused cyclic aromatic group which may have a substituent, and R ^B2 to R ^B4 are each independently represents a monovalent organic group)
A black photosensitive composition containing the compound represented by . According to claim 1,
A black photosensitive composition further containing (D) a silane coupling agent. According to claim 1,
A black photosensitive composition wherein the colorant (C) is a mixture of a plurality of colorants. According to claim 1,
A black photosensitive composition used to form a patterned black film on a surface made of a material containing a metal element. Formation of a coating film by applying the black photosensitive composition according to claim 1 on a substrate,
Position-selective exposure of the coating film,
A method of forming a patterned black film comprising developing the exposed coating film with an alkaline developer. According to claim 7,
A method of forming a patterned black film, wherein the substrate has a surface made of a material containing a metal element, and the coating film is formed on the surface made of a material containing at least the metal element. According to claim 7,
A method of forming a patterned black film wherein the alkaline developer is an aqueous solution of quaternary ammonium hydroxide. According to claim 7,
A method of forming a patterned black film wherein the patterned black film is a black partition.