JP2024000587A - Photosensitive coloring composition, and film, color filter, solid state image sensor, and image display device each including the same - Google Patents

Abstract

To provide a photosensitive coloring composition that can form a cured film with superior adhesion, pattern shape, and surface smoothness, and retains superior developability even after storage.SOLUTION: A photosensitive coloring composition includes a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the general formula (1). In the general formula (1), R's independently represent an alkyl group, L represents a bivalent linking group, and n represents an integer of 2-10.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive coloring composition.

Color filters are produced by, for example, applying a photosensitive coloring composition to a transparent substrate such as glass, and removing the solvent from the photosensitive coloring composition layer (hereinafter referred to as a coating film) by drying (hereinafter referred to as a pre-baking process), and this coating film. A step of curing the coating film by irradiating it with ultraviolet rays or the like (hereinafter referred to as "exposure") through a photomask having a desired pattern, then a step of cleaning and removing the unexposed portions of this coating film (hereinafter referred to as "developing"), Thereafter, a first color pattern is obtained through a step of heat treatment (hereinafter referred to as post-baking) to sufficiently cure the cured film. Then, by performing the same operation as this, patterns of other colors are formed and manufactured.

In recent years, the area per pixel has tended to become smaller due to the miniaturization and increase in the number of pixels of image display devices and solid-state image sensors. There is a demand for higher definition patterns. However, when the colorant is highly concentrated, the ultraviolet rays do not reach the inside of the coating film, resulting in poor adhesion such as pattern chipping after development due to insufficient photocuring or pattern peeling off from the substrate, and internal defects during post-baking in the next process. There was a problem that there was a difference in thermal curing shrinkage of the surface and wrinkles on the surface. Furthermore, when the amount of photopolymerization initiator is increased in order to increase the degree of curing, there are problems such as deterioration of the shape of the pattern. Furthermore, when the photosensitive coloring composition is stored, there is a problem that the developability changes, such as a slow development time.

For example, as an effort to improve pattern forming properties when containing a high concentration of colorant, Patent Document 1 discloses a colored photosensitive resin composition containing a polyfunctional thiol compound and an acetophenone compound. As an effort to improve wrinkles on the surface of a film, Patent Document 2 discloses a colored resin composition containing a photopolymerizable monomer having a double bond equivalent of 400 g/mol or less and having a bisphenol skeleton. . Further, Patent Document 3 discloses that the total solid content contains 25% by mass or more of an organic pigment, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and the photopolymerization initiator has an absorbance at a wavelength of 400 nm. An oxime ester photopolymerization initiator whose absorbance at a maximum absorption wavelength of 300 to 400 nm is 30% or more, and an absorbance at a wavelength of 400 nm is 10% to the absorbance at a maximum absorption wavelength of 300 to 400 nm. A photosensitive colored resin composition containing an oxime ester photopolymerization initiator having the following specific structure is disclosed.

Japanese Patent Application Publication No. 2004-83857 JP 2019-183053 Publication JP2020-148990A

However, none of the compositions of Patent Documents 1 to 3 were satisfactory in terms of adhesion, pattern shape, surface smoothness, and developability after storage.

The present invention aims to provide a photosensitive coloring composition that can form a cured film with excellent adhesion, pattern shape, and surface smoothness, and has excellent developability even after storage.

The present invention provides a photosensitive material containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the following general formula (1). This invention relates to a coloring composition.
General formula (1)

In general formula (1), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer of 2 to 10.

According to the present invention, a cured film having excellent adhesion, pattern shape, and surface smoothness can be formed, and a photosensitive coloring composition having excellent developability even after storage can be provided. Further, the present invention can provide a film, a color filter, a solid-state image sensor, and an image display device.

Below, the form for carrying out the photosensitive coloring composition of this invention is demonstrated in detail. Note that the present invention is not limited to the following embodiments, and can be modified and implemented within the scope that can solve the problem.

In this specification, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" means, unless otherwise specified, respectively mean "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide" do. Further, "C.I." means Color Index (C.I.; published by The Society of Dyers and Colorists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.
In addition, regarding the molecular weight of the compound in the present invention, for low-molecular compounds whose molecular weight can be specified, the molecular weight is the value calculated by calculation or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the molecular weight distribution is The weight average molecular weight of the compound in terms of polystyrene is measured by gel permeation chromatography using tetrahydrofuran as a solvent.
Monomers are compounds that form resins upon polymerization. The monomers are in an unreacted state, and the monomer units are in a state where the monomers form a resin after polymerization.

<Photosensitive coloring composition>
The photosensitive coloring composition of the present invention comprises a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound represented by the following general formula (1) ( E).
General formula (1)

In general formula (1), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer of 2 to 10.

Although the mechanism by which the photosensitive coloring composition having the above structure can solve the problems of the present invention is not clear, it is speculated as follows.

Since the compound (E) represented by the general formula (1) has six -OR groups (hereinafter referred to as alkoxy groups), the alkoxy group is hydrolyzed, and the compound (E) represented by the general formula (1) They tend to react with each other and other components, base materials, etc. contained in the photosensitive coloring composition. Then, a part of (-S-)n (hereinafter referred to as polysulfide bond) is cleaved and reacts with the polymerizable unsaturated groups of the alkali-soluble resin (B) and the polymerizable compound (C), thereby creating a sufficient crosslinked structure. A cured film having the following properties is obtained. Therefore, it is presumed that the adhesion is improved, the difference in thermal curing shrinkage between the inside and the surface during post-baking is reduced, and the occurrence of wrinkles is suppressed. Furthermore, since sulfide bonds and polysulfide bonds have excellent flexibility, it is assumed that they relieve stress and suppress the occurrence of wrinkles. Furthermore, since the polysulfide bond has lower reactivity than the thiol group, it is assumed that there is less reaction during storage of the photosensitive coloring composition, and that excellent developability can be obtained even after storage.

[Colorant (A)]
The photosensitive coloring composition of the present invention contains a colorant (A).

The colorant (A) is not particularly limited, and may be either a pigment or a dye, and can be used in combination. Pigments include organic pigments and inorganic pigments, and pigments are preferred for color filter applications in terms of light resistance, heat resistance, and solvent resistance.

(pigment)
The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the Color Index.

The red pigment is, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81: 3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281,282,283,284,285,286,287,291,295,296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like.

The orange pigment is, for example, C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Yellow pigments include, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments described in JP 2012-226110A.

The yellow pigment may include at least one anion selected from the group consisting of mono, di, tri, and tetra anions of an azo compound represented by the following general formula (2) and an azo compound having a tautomeric structure thereof. , Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (3). .

General formula (2)

In general formula (2), the two R ₁ 's each independently represent -OH, -NH ₂ , -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and the two R ₂ 's each independently represent a represents -OH or _-NH2 .

General formula (3)

In general formula (3), three R ₃ 's each independently represent a hydrogen atom or an alkyl group.

The green pigment is, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 etc. are mentioned.

The blue pigment is, for example, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, Examples include 35, 36, 56, 56:1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like.

The purple pigment is, for example, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

The black pigment is, for example, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like.

Among these pigments, C. I. Pigment Green 7, 36, 58, 59, 62, 63, C. I. It is preferable that the pigment contains at least one selected from the group consisting of Pigment Blue 15:2, 15:3, 15:4, and 15:6.

In addition, silica, talc, titanium oxide, zinc oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green. , amber, synthetic iron black, and other inorganic pigments.

It is preferable to use the pigment in a finely divided form. The refinement method is not particularly limited, and, for example, any of wet milling, dry milling, and dissolution precipitation methods can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. Note that from the viewpoint of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

A resin may be added to the salt milling treatment if necessary. By adding a resin, the pigment is coated with the resin, and stability, light resistance, etc. are improved. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferably solid at room temperature, insoluble in water, and partially soluble in organic solvents. The amount of resin added is preferably 2 to 200 parts by weight per 100 parts by weight of the pigment.

(dye)
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Further, as the dye, derivatives thereof or lake pigments obtained by turning the dye into a lake can also be used.

It is preferable that the acidic dye has an acidic group such as sulfonic acid or carboxylic acid. Direct dyes can form salt-forming compounds with inorganic salts of acidic dyes, or acidic dyes with nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds. preferable. Also preferred are salt-forming compounds that are salts of resin components having these functional groups and acidic dyes. Further, by sulfonamidating the salt-forming compound and modifying it into a sulfonic acid amide compound, it is easy to obtain a photosensitive coloring composition with excellent resistance (light resistance, solvent resistance).
Further, a salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent resistance (light resistance, solvent resistance). Note that the compound having an onium base is preferably a resin having a cationic group.

Although the basic dye can be used as it is, it is preferably a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion components that act as counter ions in the salt-forming compounds of basic dyes include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and carbonized halides. Preferred are salt forming compounds obtained by forming salts with an anionic compound having a conjugate base of an organic acid having a hydrogen group and an acidic dye. Note that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples include pigment structures derived from dyes selected from dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof, but in particular these but not limited to.

Among these pigment structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium It is preferable to have a pigment structure derived from a dye selected from dyes such as quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes, such as xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes. A dye structure derived from a dye selected from dyes is more preferable.

The colorant (A) can be used alone or in combination of two or more.

The content of the colorant (A) is preferably 5 to 70% by weight, more preferably 10 to 60% by weight based on 100% by weight of the nonvolatile content of the photosensitive coloring composition.

[Alkali-soluble resin (B)]
The photosensitive coloring composition of the present invention contains an alkali-soluble resin (B).

The alkali-soluble resin (B) is not particularly limited, and known resins can be used. Examples include (meth)acrylic resin, styrene resin, styrene/(meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, and cyclic olefin resin.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 3,000 to 50,000, more preferably 4,000 to 40,000.

The acid value of the alkali-soluble resin (B) is preferably 30 to 200 mgKOH/g, more preferably 40 to 180 mgKOH/g.

The alkali-soluble resin (B) can be used alone or in combination of two or more types.

The alkali-soluble resin (B) is preferably 1 to 95% by weight, more preferably 5 to 80% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition.

(Alkali-soluble resin (B1) having hydroxyl group-containing monomer unit (b1))
From the viewpoint of adhesion, pattern shape, and surface smoothness, the alkali-soluble resin (B) is an alkali-soluble resin (B1) having a hydroxyl group-containing monomer unit (b1) (hereinafter also simply referred to as an alkali-soluble resin (B1)). ) is preferably included. The reaction between the hydroxyl group in the alkali-soluble resin (B1) and the compound (E) represented by the general formula (1) improves adhesion, pattern shape, and surface smoothness.

The alkali-soluble resin (B1) having a hydroxyl group-containing monomer unit (b1) is not particularly limited as long as it is an alkali-soluble resin having a hydroxyl group, and can be produced by a known method. For example, it can be produced by methods (i) to (iii) shown below.

<Method (i)>
There is a method (i) in which a hydroxyl group-containing monomer forming the hydroxyl group-containing monomer unit (b1) and a monomer optionally copolymerizable with the hydroxyl group-containing monomer are copolymerized.

[Hydroxyl group-containing monomer unit (b1)]
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2- Examples include hydroxyethylphthalic acid.

The copolymerizable monomer is not particularly limited, and known compounds can be used. For example, the following acidic group-containing monomers, epoxy group-containing monomers, alicyclic hydrocarbon-containing monomers, aromatic ring-containing monomers, isocyanate group-containing monomers (isocyanate groups are protected with blocking agents) ), and other monomers.

<Method (ii)>
There is a method (ii) in which a hydroxyl group is introduced by adding a carboxyl group-containing compound (modified compound) to an epoxy group contained in a resin (precursor).

<Method (iii)>
There is a method (iii) in which a hydroxyl group is introduced by adding a compound having an epoxy group (modified compound) to a carboxyl group contained in a resin (precursor).

The content of the hydroxyl group-containing monomer unit (b1) is 1 to 60 mol in all the constituent units of the alkali-soluble resin (B1) from the viewpoint of adhesion, pattern shape, surface smoothness, and developability after storage. % is preferable, and 5 to 40 mol% is more preferable.

In addition to the hydroxyl group-containing monomer unit (b1), the alkali-soluble resin (B1) also contains an acidic group-containing monomer unit (b2), an epoxy group-containing monomer unit (b3), and an alicyclic hydrocarbon-containing monomer. body unit (b4), aromatic ring-containing monomer unit (b5), isocyanate group-containing monomer unit (b6), polymerizable unsaturated group-containing monomer unit (b7), other monomer unit (b8) It may have.

[Acidic group-containing monomer unit (b2)]
It is preferable that the alkali-soluble resin (B1) has an acidic group-containing monomer unit (b2) from the viewpoint of pattern shape and developability.
Examples of acidic group-containing monomers include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, and anhydrous Maleic acid, fumaric acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamide-2- Examples include methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[Epoxy group-containing monomer unit (b3)]
The alkali-soluble resin (B1) can have an epoxy group-containing monomer unit (b3).
Examples of the epoxy group-containing monomer include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, and 2-oxiranylethyl (meth)acrylate. , 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, Examples include 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, and the like.

[Alicyclic hydrocarbon-containing monomer unit (b4)]
It is preferable that the alkali-soluble resin (B1) has an alicyclic hydrocarbon-containing monomer unit (b4) from the viewpoint of adhesiveness and pattern shape.
Alicyclic hydrocarbon-containing monomers include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, ) acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, and the like. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[Aromatic ring-containing monomer unit (b5)]
It is preferable that the alkali-soluble resin (B1) has an aromatic ring-containing monomer unit (b5) from the viewpoint of adhesiveness and pattern shape.
Aromatic ring-containing monomers include, for example, styrene, α-methylstyrene, vinylnaphthalene, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, paracumylphenolethylene oxide (EO), or propylene oxide. (PO) modified (meth)acrylate, phenol EO or PO modified (meth)acrylate, nonylphenol EO or PO modified (meth)acrylate, N-phenylmaleimide, N-benzylmaleimide and the like. Among these, styrene, benzyl (meth)acrylate, paracumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate is preferred.

[Isocyanate group-containing monomer unit (b6)]
The alkali-soluble resin (B1) can have an isocyanate group-containing monomer unit (b6). In the isocyanate group-containing monomer unit (b6), from the viewpoint of developability after storage, it is preferable that the isocyanate group is protected with a compound (blocking agent) that is removed by heat.

Isocyanate group-containing monomers include, for example, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, and 2-isocyanato-1-methylethyl (meth)acrylate. ) acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, and the like. Equimolar reaction products of 2-hydroxyalkyl (meth)acrylates and diisocyanate compounds can also be used.

Examples of blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds. .

Examples of oxime compounds include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, and the like. Among these, methyl ethyl ketoxime is preferred.
Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam.
Phenol compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, Examples include p-nitrophenol. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred.
Examples of alcohol compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol.
Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, carbazole, and the like.
Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred.
Examples of the pyrazole compound include pyrazole, methylpyrazole, 3,5-dimethylpyrazole, and the like, with 3,5-dimethylpyrazole being preferred.
Examples of mercaptan compounds include butyl mercaptan, thiophenol, tert-dodecyl mercaptan, and the like.
Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and the like.
Examples of the imide compound include succinimide, maleimide, maleimide, phthalimide, and the like.
Examples of the urea compound include urea, thiourea, and ethylene urea.
Examples of the imine compound include ethyleneimine and polyethyleneimine.
Examples of the bisulfite compound include sodium bisulfite, potassium bisulfite, and the like.

Blocking agents can be used alone or in combination of two or more types.

The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds; From the viewpoint of deprotection reaction, one or more compounds selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds are more preferable.

Examples of the blocked isocyanate group-containing monomer include the following compounds. Note that the present invention is not limited to these.

Commercially available monomers containing blocked isocyanate groups include Karenz MOI-DEM (blocking agent desorption temperature: 85-95°C), MOI-BP (blocking agent desorption temperature: 105-115°C) manufactured by Showa Denko. ℃), MOI-BM (blocking agent desorption temperature: 125-135°C), etc.

[Polymerizable unsaturated group-containing monomer unit (b7)]
The alkali-soluble resin (B1) preferably has a polymerizable unsaturated group-containing monomer unit (b7) from the viewpoints of adhesion, pattern shape, and surface smoothness.
The method for introducing the polymerizable unsaturated group-containing monomer unit (b7) is not particularly limited, and any known method can be used. For example, there are methods (iv) to (vi) shown below.

<Method (iv)>
There is a method (iv) in which the acidic group of the above-mentioned acidic group-containing monomer (modified compound) is added to the epoxy group contained in the resin (precursor).

<Method (v)>
There is a method (v) in which the epoxy group of the above-mentioned epoxy group-containing monomer (modified compound) is added to the acidic group contained in the resin (precursor).

Furthermore, the hydroxyl groups produced by the reactions in methods (iv) and (v) can be further reacted with an acid anhydride (modified compound) to contain acidic groups.

Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

<Method (vi)>
There is a method (vi) in which the isocyanate group of the above-mentioned isocyanate group-containing monomer (modified compound) is reacted with the hydroxyl group contained in the resin (precursor).

[Other monomer units (b8)]
The alkali-soluble resin (B1) can have other monomer units (b8).
Other monomers include, for example, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, Acrylic acid esters such as pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate;
(Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine. ;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
N-substituted maleimides such as methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin ;
Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'- [oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene) )] bis-2-propenoate and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin (B1) is preferably 3,000 to 50,000, more preferably 4,000 to 40,000.

The acid value of the alkali-soluble resin (B1) is preferably 30 to 200 mgKOH/g, more preferably 40 to 180 mgKOH/g.

The alkali-soluble resin (B1) can be used alone or in combination of two or more types.

The content of the alkali-soluble resin (B1) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass based on 100% by mass of the alkali-soluble resin (B).

[Polymerizable compound (C)]
The photosensitive coloring composition of the present invention contains a polymerizable compound (C).

Examples of the polymerizable compound (C) include monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. The polymerizable compound (C) is, for example, a polymerizable compound (C1) having a hydroxyl group, a polymerizable compound (C2) having an acidic group, a polymerizable compound (C3) having a urethane bond, a lactone-modified polymerizable compound ( C4), a polymerizable compound (C5) having a tertiary amine structure, a polymerizable compound (C6) having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds (C7).

(Polymerizable compound (C1) having a hydroxyl group)
The photosensitive coloring composition of the present invention preferably contains a polymerizable compound (C1) having a hydroxyl group as the polymerizable compound (C) from the viewpoints of adhesion, pattern shape, and surface smoothness. The reaction between the hydroxyl group in the polymerizable compound (C1) having a hydroxyl group and the compound (E) represented by the general formula (1) improves adhesion, pattern shape, and surface smoothness.

The polymerizable compound (C1) having a hydroxyl group is, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4 -Hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2 -Hydroxy-3-phenoxypropyl acrylate, isocyanuric acid EO or PO modified (meth)acrylate, isocyanuric acid EO or PO modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, poly Acrylic esters such as pentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, epoxy group of epoxy compound and carboxyl of (meth)acrylic acid Examples include epoxy (meth)acrylate with reacted groups. Among these, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred.

Commercially available products of the polymerizable compound (C1) having a hydroxyl group include, for example, KAYARAD R-128H, R-167 manufactured by Nippon Kayaku Co., Ltd., Aronix M-5700, M-920, M-930 manufactured by Toagosei Co., Ltd. NK ester 701A manufactured by Nakamura Chemical Co., Ltd., light ester HOP (N), HOA (N), HOP-A (N), HOB (N), G-201P, epoxy ester M-600A, 40EM manufactured by Kyoeisha Chemical Co., Ltd. Examples include 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), 3000A, OGSOL GA-5060P, GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

The content of the polymerizable compound (C1) having a hydroxyl group is preferably 10 to 80% by mass, more preferably 20 to 70% by mass based on 100% by mass of the polymerizable compound (C).

(Polymerizable compound (C2) having an acidic group)
The polymerizable compound (C2) having an acidic group is, for example, an esterified product of a free hydroxyl group-containing poly(meth)acrylate containing a polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid; Examples include esterified products with hydroxyalkyl (meth)acrylates. Note that the polymerizable compound (C2) having an acidic group is a compound having no urethane bond.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

Examples of the polyhydric carboxylic acids include trimellitic acid and pyromellitic acid.
Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and pentaerythritol. Examples include triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like.

Commercial products of the polymerizable compound (C2) having an acidic group include Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-510, M-520, M-521 manufactured by Toagosei Co., Ltd. , β-CEA manufactured by Daicel Allnex Co., Ltd., and the like.

(Polymerizable compound (C3) having a urethane bond)
From the viewpoint of surface smoothness, the photosensitive coloring composition of the present invention particularly preferably contains a polymerizable compound (C3) having a urethane bond as the polymerizable compound (C). The physical crosslinked structure formed by intermolecular hydrogen bonds in the urethane bond has appropriate flexibility, so it relieves stress and suppresses the occurrence of wrinkles.

The polymerizable compound (C3) having a urethane bond is, for example, a urethane (meth)acrylate obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, or a urethane (meth)acrylate obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate, and further reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate. Examples include urethane (meth)acrylates obtained by reacting containing (meth)acrylates.

Examples of the hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO) modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO) modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy(meth)acrylate, Examples include hydroxyl group-containing polyol polyacrylate.

Examples of the polyfunctional isocyanates include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanate such as isophorone diisocyanate. , their burette bodies, isocyanate nurate bodies, trimethylolpropane adducts, and the like.

The number of polymerizable unsaturated groups in the urethane bond-containing polymerizable compound (C3) is preferably 5 to 12 from the viewpoint of pattern shape and surface smoothness.

The molecular weight of the polymerizable compound (C3) having a urethane bond is preferably from 500 to 5,000, more preferably from 500 to 3,000, from the viewpoint of pattern shape and surface smoothness, and more preferably from 500 to 3,000. Particularly preferred is 2,000.

It is preferable that the polymerizable compound (C3) having a urethane bond further has an acidic group from the viewpoint of developability and pattern shape. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among these, a carboxyl group is preferred.

As a method for introducing an acidic group into the polymerizable compound (C3) having a urethane bond, for example, first, the hydroxyl group-containing (meth)acrylate and the polyfunctional isocyanate are reacted. Next, it can be synthesized by adding a mercapto compound having a carboxyl group to the product.

Examples of the above-mentioned mercapto compounds having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

Commercial products of the polymerizable compound (C3) having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., and Shin Nakamura Chemical Co., Ltd. Examples include UA-1100H, U-6LPA, UA-33H, U-10HA, U-15HA manufactured by Daicel Corporation, and EBECRYL1290 and KRM8452 manufactured by Daicel Allnex.

The content of the polymerizable compound (C3) having a urethane bond is preferably 10 to 80% by mass, more preferably 20 to 70% by mass based on 100% by mass of the polymerizable compound (C).

(Lactone-modified polymerizable compound (C4))
The lactone-modified polymerizable compound (C4) is a compound having a lactone-modified structure in its molecule. The lactone-modified polymerizable compound (C4) is a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimerolmelamine. It can be obtained by esterifying (meth)acrylic acid and ε-caprolactone or other lactone compounds.

Examples of commercially available lactone-modified polymerizable compounds (C4) include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

(Polymerizable compound (C5) having a tertiary amine structure)
The polymerizable compound (C5) having a tertiary amine structure is, for example, tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, or (methacryloyloxyethyl)amine. ) A Michael addition reaction product between an acrylate compound (X) and an amine compound (Y), and the like.

The (meth)acrylate compound (X) is, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ) acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra (meth)acrylate, trimethylolpropane alkylene oxide modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide modified tri and tetra(meth)acrylate, pentaerythritol alkylene oxide modified tri and tetra(meth)acrylate, diglycerin alkylene oxide modified tri and tetra(meth)acrylate, dipeneerythritol alkylene oxide modified tetra, penta and hexa(meth)acrylate, and the like.
Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide.
Further, examples of the (meth)acrylate compound (X) include (meth)acrylate compounds having an acidic group.

The (meth)acrylate compound (X) can be used alone or in combination of two or more types.

Amine compounds (Y) include, for example, n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m- Primary amines such as aminophenol and p-aminophenol;
Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, 4 - Secondary amines such as aniline phenol, etc.

The amine compound (Y) can be used alone or in combination of two or more types.

The method for producing the Michael addition reaction product between the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and any known method can be used. For example, methods described in International Publication No. 2006/075754, Japanese Translated Patent Publication No. 2008-545859, Japanese Patent Application Laid-Open No. 2017-066347, etc. can be mentioned.

The polymerizable compound (C5) having a tertiary amine structure may have an acidic group and/or a hydroxyl group. The method of introducing an acidic group and/or a hydroxyl group is, for example, a method of using a compound having an acidic group or/and a hydroxyl group in a (meth)acrylate compound (X) or an amine compound (Y), or a method of introducing a compound having an acidic group and/or a hydroxyl group after a Michael addition reaction. Examples include a method of adding an acid anhydride.

Commercially available products of the polymerizable compound (C5) having a tertiary amine structure include, for example, Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd.

(Polymerizable compound (C6) having dendrimer structure or hyperbranched structure)
A polymerizable compound having a dendrimer structure has a chemical structure in which branches are regularly repeated outward from a chemical structure constituting the core (hereinafter also referred to as the core part), and a polymerizable unsaturated group is bonded to the end of the chemical structure. It has a spherical, highly controlled chemical structure and molecular weight. Hyperbranched structures have chemical structures similar to dendrimer structures.

Commercial products of the polymerizable compound (C6) having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., and Miramer SP- manufactured by Miwon Specialty Chemical Company. 1106 (dendrimer structure, average number of acryloyl groups 18), SP-1108 (dendrimer structure, average number of acryloyl groups 13), CN2301 manufactured by SARTOMER (hyperbranched structure, average number of acryloyl groups 9), CN2302 (hyperbranched structure, average number of acryloyl groups 16) ), CN2303 (hyperbranched structure, average number of acryloyl groups 6), CN2304 (hyperbranched structure, average number of acryloyl groups 18), Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups 8) manufactured by Eternal Materials (hyperbranched structure, average number of acryloyl groups 8), 6362-100 (hyperbranched structure, average number of acryloyl groups 8), Branched structure, average number of acryloyl groups 12), 6363 (hyperbranched structure, average number of acryloyl groups 16), DR-E522 (hyperbranched structure, average number of acryloyl groups 15), etc.

(Other polymerizable compounds (C7))
Other polymerizable compounds (C7) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, Ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol(meth)acrylate, phenoxyhexaethylene glycol(meth)acrylate, trimethylolpropane modified with EO or PO Tri(meth)acrylate, isocyanuric acid EO or PO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO or PO Modified hexa(meth)acrylate, dipentaerythritol caprolactone modified hexa(meth)acrylate, tricyclodecanyl(meth)acrylate, (meth)acrylic ester such as methylolated melamine (meth)acrylic ester, styrene, vinyl acetate , ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

Other commercially available polymerizable compounds (C7) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R manufactured by Nippon Kayaku Co., Ltd. -684, GPOD-303, TMPTA, T-1420 (T), RP-1040, DPEA-12, D-310, Toagosei Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, M-211B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M- 360, M-408, M-460, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310 manufactured by Osaka Organic Chemical Industry Co., Ltd. , #700HV, #295, OGSOL EA-0200, EA-0300 manufactured by Osaka Gas Chemical Co., Ltd., Miwon Specialty Chemical Co. , Ltd. Miramer HR6060, 6100, 6200, Shin Nakamura Chemical Industry Co., Ltd. NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP , ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, AD-TMP etc.

The polymerizable compound (C) can be used alone or in combination of two or more types.

The content of the polymerizable compound (C) is preferably 5 to 70% by weight, more preferably 10 to 60% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition.

[Polymerization initiator (D)]
The photosensitive coloring composition of the present invention contains a polymerization initiator (D).

The polymerization initiator (D) is not particularly limited, and known compounds can be used. Examples include compounds that generate radicals by the action of light or heat to initiate or accelerate radical polymerization reactions.
The polymerization initiator that generates radicals when exposed to light (hereinafter also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals when exposed to light in the visible range from ultraviolet rays.
The polymerization initiator that generates radicals by heat (hereinafter also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl] -2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Acetophenone compounds;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s -triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-triazine methyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4 , 6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine. system compound;
1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole Oxime compounds such as 3-yl]-,1-(O-acetyloxime);
Acyl phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone; borate compounds; carbazole compounds, and the like.

Commercially available products include Omnirad 907, 369E, 379EG, 127, 184, 1173, 2959 manufactured by IGM Resins as an acetophenone compound, Omnirad 819, TPO manufactured by IGM Resins as an acylphosphine compound, and Omnirad 819, TPO manufactured by IGM Resins as an oxime compound. IRGACURE OXE-01, 02, 03, 04 manufactured by ADEKA, NCI-730, NCI-831E, NCI-930 manufactured by ADEKA, TRONLY TR-PBG-301 manufactured by Changzhou Strong New Materials , 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057, Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06 manufactured by Samyang Corporation. , 07, DFI-020, 306, EOX-01 manufactured by Daito Chemix Co., Ltd., and the like. In addition, JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-215575, JP 2011-020998, International Publication No. 2015/036910, Also included are compounds described in PCT Publication No. 2019-507108, PCT Publication No. 2019-528331, International Publication No. 2021/175855, etc. Among these, oxime compounds are preferred from the viewpoints of adhesion, pattern shape, and surface smoothness.

Specific examples of oxime compounds are shown below. Note that the present invention is not limited to these.

Among these, oxime compounds (D-1) to (D-4) are preferred.

Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, and 1,2-dimethoxy-1,1,2,2-tetraphenylethane. -diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2, 2-tetra(4-methoxyphenyl)ethane, 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsiloxy)-1,1,2,2 -tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane , 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, and other pinacol-based compounds ;
2,2'-azobis(4-methoxy2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate) ), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropion amide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2 -Azo compounds such as methylpropionamide);
Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, Examples include organic peroxides such as 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide. Among these, pinacol compounds are preferred.

The polymerization initiator (D) can be used alone or in combination of two or more types.

The content of the polymerization initiator (D) is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition.

(Compound (E) represented by general formula (1))
The photosensitive coloring composition of the present invention contains a compound (E) represented by the following general formula (1).

General formula (1)

In general formula (1), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer of 2 to 10.

In general formula (1), each R independently represents an alkyl group. The alkyl group may be linear or branched, preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Among these, from the viewpoint of pattern shape and surface smoothness, methyl group or ethyl group is preferable, and from the viewpoint of developability after storage, ethyl group is more preferable.

In general formula (1), L represents a divalent linking group. Examples of the divalent linking group include those consisting of an alkylene group, an arylene group, or a combination of these groups. The alkylene group may be linear or branched, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms is preferred. The arylene group is preferably a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.

In general formula (1), n represents an integer of 2 to 10. From the viewpoints of adhesion, pattern shape, surface smoothness, and developability after storage, n is preferably 2 to 6, more preferably 2 to 4.

The method for producing the compound (E) represented by the general formula (1) is not particularly limited, and known methods can be used. Examples include methods described in JP-A-8-198883, JP-A-10-175981, JP-A-11-100388, and the like.

Specific examples of the compound (E) represented by the general formula (1) are shown below. Note that the present invention is not limited to these.

The content of the compound (E) represented by the general formula (1) is determined from the viewpoints of adhesion, pattern shape, surface smoothness, and developability after storage. ) is preferably 0.5 to 15 parts by weight, more preferably 1.5 to 12 parts by weight.

It is preferable to use at least two kinds of compounds (E) represented by the general formula (1) in combination from the viewpoints of adhesion, pattern shape, and surface smoothness.

The compound (E) represented by the general formula (1) preferably includes a compound where n=2 from the viewpoint of adhesion, pattern shape, and surface smoothness.

The content of the compound where n = 2 is preferably 30% by mass or more based on 100% by mass of the compound (E) represented by the general formula (1) from the viewpoint of adhesion, pattern shape, and surface smoothness. , more preferably 40 to 95% by mass.

[Dye derivative (F)]
The photosensitive coloring composition of the present invention can contain a dye derivative (F).

The dye derivative (F) is not particularly limited, and includes dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (F) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, or an amine salt thereof, or a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimido alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzene pigments. Examples include indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo. .

Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520 A, WO 2009/081930, WO 2011/052617, WO 2012/102399, JP 2017 -156397, as phthalocyanine dye derivatives, JP 2007-226161, WO 2016/163351, JP 2017-165820, and Japanese Patent No. 5753266, as anthraquinone dye derivatives, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, International Publication No. 2009/025325, Quinacridone series Examples of dye derivatives include JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; examples of dioxazine-based dye derivatives include JP-A-2011-162662; thiazine indigo dyes; Derivatives include JP 2007-314785, triazine dye derivatives include JP 61-246261, JP 11-199796, JP 2003-165922, and JP 2003-168208. Publications, JP 2004-217842, JP 2007-314681, benzisoindole dye derivatives, JP 2009-57478, quinophthalone dye derivatives, JP 2003-167112, JP 2006-291194, JP 2008-31281, JP 2012-226110, naphthol dye derivatives include JP 2012-208329, JP 2014-5439, and azo dyes. The derivatives are described in JP-A-2001-172520 and JP-A-2012-172092, the acidic substituent is in JP-A-2004-307854, and the basic substituent is in JP-A-2002-201377 and JP-A-2002-201377. Examples include known dye derivatives described in JP-A No. 2003-171594, JP-A No. 2005-181383, JP-A No. 2005-213404, and the like. In addition, in these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. A compound having a substituent such as a neutral group has the same meaning as a dye derivative.

The dye derivative (F) can be used alone or in combination of two or more types.

The content of the dye derivative (F) is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the colorant (A).

[Dispersion resin (G)]
The photosensitive coloring composition of the present invention can contain a dispersion resin (G).

The dispersion resin (G) is not particularly limited as long as it has dispersion ability, and any known resin can be used. Among these, it is preferable that the adsorption group has a high affinity for the colorant (A), and it is more preferable that the adsorption group has at least one kind of a basic group and an acidic group.

Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen atom-containing group such as a nitrogen-containing heterocycle.

Examples of acidic groups include carboxyl groups, phosphoric acid groups, and sulfonic acid groups. Among these, carboxyl groups and phosphoric acid groups are preferred from the viewpoint of adsorption to pigments and developability.

The resin species of the dispersion resin (G) include, for example, urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acids. Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups. Water-soluble products such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples include water-soluble resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, and the like.

Examples of the structure of the dispersed resin (G) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, block structures, graft structures, and comb structures are preferred from the viewpoint of dispersion stability.

Commercially available products of the dispersion resin (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, manufactured by BYK Chemie Japan Co., Ltd. 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650 manufactured by Lubrizol Japan. ,13940 ,16000,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,38500,41000,41 090,53095,55000,56000,76500 etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Techno, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, etc. Mention may be made of the resins described.

The dispersion resin (G) can be used alone or in combination of two or more types.

The content of the dispersion resin (G) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the colorant (A).

[Sensitizer (H)]
The photosensitive coloring composition of the present invention can contain a sensitizer (H).

Examples of the sensitizer (H) include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone. Derivatives, polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaryloporphyrin derivatives Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-alpha Siloxy ester, acyl oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'- Examples include tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Among the sensitizers (H), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specific compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like are preferred.

The sensitizer (H) can be used alone or in combination of two or more.

The content of the sensitizer (H) is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymerization initiator (D).

[Thermosetting compound (I)]
The photosensitive coloring composition of the present invention can contain a thermosetting compound (I).

The thermosetting compound (I) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (I) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(epoxy compound)
Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted Polycondensates of dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenol Polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol) , biphenyl dimethanol, α, α, α', α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins made by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins , glycidyl ester-based epoxy resins, and the like.

Commercially available epoxy compounds include, for example, Epicote 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, and EPPN-201, 501H manufactured by Nippon Kayaku Co., Ltd. , 502H, EOCN-102S, 103S, 104S, 1020 Epicote 1004, 1256 manufactured by Japan Epoxy Resin Co., Ltd., JER1032H60, 157S65, 157S70, 152, 154, Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., EHPE-3150, Nagase ChemteX Co., Ltd. Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nissan Chemical Industries, Ltd., TEPIC-L, H manufactured by Nissan Chemical Industries, Ltd. , S, DIC EPICLON 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP- 4770, HP-5000, HP-6000, HP-9500, etc.

The content of the epoxy compound is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition.

(Oxetane compound)
An oxetane compound is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or more functional oxetane compounds.

Monofunctional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxy) silyl)propoxy]methyl}oxetane, and the like.

Bifunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3 -Ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)- 5-Oxanonan, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3 -ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3- ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like.

Trifunctional or higher functional oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, oxetane group-containing resin ( For example, oxetane-modified phenol novolak resin described in Japanese Patent No. 3783462, etc.) can be mentioned.

Examples of commercially available oxetane compounds include OXBP and OXTP manufactured by Ube Industries, OXE-10, 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101, 212 manufactured by Toagosei Co., Ltd.

The content of the oxetane compound is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight based on 100% by weight of the nonvolatile content of the photosensitive coloring composition.

A melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol type or ether type compound, and more preferably a melamine compound having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. Having an appropriate number of methylol groups or ether groups makes it easy to obtain just the right amount of heat resistance.

Commercially available melamine compounds include, for example, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS manufactured by Sanwa Chemical Co., Ltd. -11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43 , MX-417, MX-410, and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries.

Among these, Nicarac MW-30HM, MW-390, MW-100LM, MX manufactured by Sanwa Chemical Co., Ltd. has an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. -750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45, Cymel 232, 235, 236, 238, 300, 301 manufactured by Nihon Cytec Industries, 303, 350, etc. are preferable in that they can increase the crosslinking density.

The thermosetting compound (I) can be used alone or in combination of two or more types.

[Curing agent (curing accelerator)]
The photosensitive coloring composition of the present invention can contain a curing agent (curing accelerator) in order to assist in curing of the thermosetting compound (I).

Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, -Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.).

The curing agents can be used alone or in combination of two or more types.

The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of thermosetting compound (I).

[Thiol chain transfer agent (J)]
The photosensitive coloring composition of the present invention can contain a thiol chain transfer agent (J).

When the thiol-based chain transfer agent (J) is used in combination with the polymerization initiator (D), thiyl radicals, which are less susceptible to polymerization inhibition by oxygen, are generated during radical polymerization after light irradiation, improving the photosensitivity of the photosensitive coloring composition. do.

The thiol-based chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). In addition, it is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, it becomes easier to photocure from the surface of the film to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercapto Tris(2-hydroxyethyl)propionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- Examples include s-triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent (J) can be used alone or in combination of two or more types.

The content of the thiol-based chain transfer agent (J) is preferably 1 to 10% by weight, more preferably 2 to 8% by weight based on 100% by weight of the nonvolatile content of the photosensitive coloring composition.

[Polymerization inhibitor (K)]
The photosensitive coloring composition of the present invention can contain a polymerization inhibitor (K).

Examples of the polymerization inhibitor (K) include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, and 4-ethylcatechol. , 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol , 4-t-butylcatechol, alkylcatechol compounds such as 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 - Alkylresorcinol compounds such as propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine phosphine compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucin, and the like.

The content of the polymerization inhibitor (K) is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[Ultraviolet absorber (L)]
The photosensitive coloring composition of the present invention can contain an ultraviolet absorber (L).

The ultraviolet absorber (L) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. Examples include compounds.

Examples of benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1- dimethylethyl)-4-hydroxy, a mixture of C7-9 side-chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H -benzotriazol2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol2-yl)-4-(1,1,3, 3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H- benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl) -2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy- 5-(5-chloro-2H-benzotriazol2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol2-yl) ) phenyl] propionate.

Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, and ADEKA STAB LA-29, LA-31RG, LA manufactured by ADEKA. -32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by ChemiPro Kasei Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis(2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- Examples include tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, KEMISORB102 manufactured by ChemiPro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, ADEKA STAB LA-46, LA-F70, and CYASORB UV- manufactured by Sun Chemical Company. 1164 etc. are mentioned.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3, 2-hydroxy-4-n-oct xybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxy Examples include benzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Commercially available products include, for example, KEMISORB10, 11, 11S, 12,111 manufactured by Chemipro Kasei Co., Ltd., SEESORB101, 107 manufactured by Shipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., and UV-12 manufactured by Sun Chemical Co., Ltd., and the like.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate.

The content of the ultraviolet absorber (L) is preferably 5 to 70% by mass out of the total 100% by mass of the polymerization initiator (D) and the ultraviolet absorber (L).

[Antioxidant (M)]
The photosensitive coloring composition of the present invention can contain an antioxidant (M).

Examples of the antioxidant (M) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

The hindered phenolic antioxidant is, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2- t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8 , 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3 ,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2' -Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis (dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[ 3-(3-Methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl) - Examples include phenol.

Commercially available products include, for example, Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, and KEMINOX101, 179, 76, 9425 manufactured by Chemipro. , IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, Syanox CY-1790, CY-2777 manufactured by Sun Chemical, etc. Can be mentioned.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) ) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3, Ester of 5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy) decanedioate) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bis(1, 1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4 -diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2, 2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6- Hexamethylene diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. Can be mentioned.

Commercially available products include, for example, ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87. , LA-402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by ChemiPro Kasei Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan, Siasorb UV-3346, UV manufactured by Sun Chemical Co., Ltd. -3529, UV-3853, etc.

Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2'-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4' -Isopropylidene diphenyl diphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropylidene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethylbis(2,4-phosphite) -di-t-butyl-6-methylphenyl) and the like.

Commercially available products include, for example, ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. - EPQ etc.

Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'- Ditridecyl thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o- Examples include cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, and the like.

Examples of commercially available products include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by ChemiPro Kasei.

The antioxidant (M) can be used alone or in combination of two or more.

The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[Leveling agent (N)]
The photosensitive coloring composition of the present invention can contain a leveling agent (N).

Examples of the leveling agent (N) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, manufactured by BYK Chemie. 378, 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning, X-22-4952, X-22-4272, X-22 manufactured by Shin-Etsu Chemical Co., Ltd. -6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Examples of the fluorosurfactant include a surfactant or a leveling agent having a fluorocarbon chain.

Commercially available products include, for example, Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical, and Megafac F-253, 477, 551, 552, 555, 558, 560, 570 manufactured by DIC. , 575, 576, R-40-LM, R-41, RS-72-K, DS-21, FC-4430, 4432 manufactured by Sumitomo 3M, EF-PP31N09, EF-PP33G1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. , EF-PP32C1, and Futergent 602A manufactured by Neos.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristele ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan triolate, sorbitan sesquiolate, polyoxyethylene sorbitan monolaurate , polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol Monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline etc.

Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 manufactured by Kao Corporation. , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemur PD-420, PD-430, PD-430S, PD-450, Rheodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amito 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44,61,62,64,71,72,101,121, TR-701,702,704,913R, (meth)acrylic acid-based (co)polymer Polyflo-No. manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 etc. are mentioned.

Examples of the cationic surfactant include alkyl amine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Conc manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyl ether disulfonates, and lauryl sulfate monoethanol. Examples include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Commercially available products include, for example, Ftergent 100 and 150 manufactured by Neos, ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E, and EC-8600 manufactured by ADEKA.

Examples of the amphoteric surfactant include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkyl amine oxides such as lauryl dimethylamine oxide.

Commercially available products include Amhitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

The leveling agent (N) can be used alone or in combination of two or more types.

The content of the leveling agent (N) is preferably 0.001 to 2.0% by weight, more preferably 0.005 to 1.0% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition.

[Storage stabilizer (O)]
The photosensitive coloring composition of the present invention can contain a storage stabilizer (O).

Storage stabilizers (O) include, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl. Examples include organic phosphines and phosphites.

The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the colorant (A).

[Adhesion improver (P)]
The photosensitive coloring composition of the present invention can contain an adhesion improver (P).

Examples of the adhesion improver (P) include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxy. Silane, 3-methacryloxypropyltriethoxysilane, (meth)acrylic silanes such as 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxysilanes such as dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1, Aminosilanes such as hydrochloride of 3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3- Mercapto compounds such as mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryl compounds such as p-styryltrimethoxysilane, ureido compounds such as 3-ureidopropyltriethoxysilane, and 3-isocyanatepropyltriethoxysilane. Examples include isocyanates.

The adhesion improver (P) can be used alone or in combination of two or more types.

The content of the adhesion improver (P) is preferably 0.1 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[Organic solvent (Q)]
The photosensitive composition of the present invention can contain an organic solvent (Q).

The organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol. Diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone , ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxy Butyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N -Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether Propyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether , diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol mono Propyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, acetic acid Examples include propyl and dibasic acid esters.

From an environmental point of view, the photosensitive coloring composition of the present invention preferably does not substantially contain organic solvents such as aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). "Substantially not containing" means 50 mass ppm or less in the photosensitive coloring composition, preferably 30 mass ppm or less, and more preferably 10 mass ppm or less.

The organic solvent (Q) can be used alone or in combination of two or more.

The content of the organic solvent (Q) is preferably such that the nonvolatile content of the photosensitive coloring composition is 5 to 70% by mass.

[Water content]
From the viewpoint of storage stability, the photosensitive coloring composition of the present invention preferably has a water content of 2.0% by mass or less.

The content of water contained in the photosensitive coloring composition is more preferably 1.5% by mass or less, particularly preferably 1.0% by mass or less. Moreover, there is no particular restriction on the lower limit of the water content.

The method for controlling the water content is not particularly limited, and any known method can be used. For example, each of the above-mentioned components may be sufficiently dried to reduce the amount of water contained in the components. Other methods include a method of producing a photosensitive coloring composition while blowing dry air, an inert gas, or a mixed gas thereof, and a method of adding molecular sieve to dehydrate the composition after production.

The water content can be measured by a known method such as the Karl Fischer method.

[Method for producing photosensitive coloring composition]
The photosensitive coloring composition of the present invention can be prepared by mixing the above-mentioned components. For adjustment, each component may be blended all at once, or each component may be dissolved or dispersed in an organic solvent and then blended sequentially. For example, a dispersion is produced by adding a colorant (A), an alkali-soluble resin (B), an organic solvent (P), etc., and performing a dispersion treatment. Thereafter, the polymerizable compound (C), the polymerization initiator (D), and the compound (E) represented by the general formula (1) are added to the dispersion and mixed. Note that the timing of blending each material is arbitrary. Moreover, the dispersion step can also be performed multiple times.

Examples of the dispersing machine that performs the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

The average dispersed particle size (secondary particle size) of the colorant (A) in the photosensitive coloring composition is preferably 30 to 200 nm, more preferably 40 to 200 nm. When the particle size is appropriate, it is easy to obtain a photosensitive coloring composition with high dispersion stability.

The average dispersed particle size (secondary particle size) can be measured using, for example, Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method). D. The particle shape is non-spherical, and the D50 particle diameter is the average diameter. It is preferable to use the organic solvent used for dispersion as the diluting solvent for measurement, and to measure the sample treated with ultrasonic waves immediately after sample preparation, because results with less variation can be easily obtained.

The photosensitive coloring composition is prepared by centrifugation, filtration using a sintered filter or a membrane filter, etc. to obtain coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and It is preferable to remove mixed dust. The photosensitive coloring composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<Membrane>
The film of the present invention is formed using the photosensitive coloring composition described above. Although the film is preferably a patterned film, it can also be used as a flat film.

[Membrane manufacturing method]
The method for manufacturing the membrane is not particularly limited, and any known method can be used. For example, it can be manufactured through a process of coating the photosensitive coloring composition of the present invention on a substrate.

Examples of the base material include substrates made of materials such as glass, resin, and silicon. An organic light-emitting layer may be formed on these substrates. Furthermore, an imaging device such as a CCD or CMOS may be formed on the base material. Further, an undercoat layer may be provided on the base material, if necessary, in order to improve adhesion between the upper layer and the layer, prevent substance diffusion, and flatten the substrate surface.

As the coating method, a known method can be used. Examples include a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexo printing, screen printing, gravure printing, offset printing, and the like.

The thickness of the film can be adjusted as appropriate depending on the purpose. The thickness of the film is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

Next, a pattern is formed. Examples of methods for forming the pattern include photolithography and dry etching, with photolithography being preferred. Note that when used as a flat film, there is no need to perform the step of forming a pattern, and after coating, drying or exposing the entire surface to light is performed as necessary.

Hereinafter, a method for forming a pattern will be described in detail.

When forming a pattern by photolithography, a layer formed by coating the photosensitive coloring composition of the present invention on a substrate is prebaked as necessary, and then exposed to light in a pattern through a mask (exposure step). ), and after removing the unexposed portions by alkaline development (development step), the pattern is heat-treated (post-bake step).

[Exposure process]
In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. Examples of active energy rays used for exposure include ultraviolet rays such as g-line (wavelength: 436 nm), h-line (wavelength: 405 nm), and i-line (wavelength: 365 nm). Furthermore, light having a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm).
Furthermore, during exposure, exposure may be performed by continuously irradiating light, or exposure may be performed by repeatedly irradiating and pausing light in short cycles (e.g., millisecond level or less) (pulse exposure). .

[Development process]
Next, by performing an alkaline development treatment, the unexposed portions of the layer are eluted into an alkaline aqueous solution, leaving only the hardened portions to form a patterned film.
Examples of alkaline developers include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. , pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the alkaline developer is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed and the residual film rate after development can be improved.
Examples of the developing method include a dip method, a spray method, and a paddle method. The developing temperature is preferably 15 to 40°C. Note that after alkaline development, it is preferable to wash with pure water.

[Post-bake process]
After development, heat treatment (post-bake) is performed. Post-baking improves the resistance of the membrane.
The temperature is preferably 80 to 300°C. Further, the time is preferably about 2 minutes to 1 hour. When a material with low heat resistance is used for the base material or when a base material having an organic electroluminescent element is used as a light emitting layer, the temperature is preferably 150°C or lower, more preferably 130°C or lower.

<Color filter>
The film of the present invention can be used for color filters. The color filter of the present invention can be used in solid-state imaging devices such as CCDs and CMOSs, image display devices, and the like. Color filters can be made into red color filters, green color filters, blue color filters, magenta color filters, cyan color filters, yellow color filters, gray color filters, and black color filters by appropriately selecting the colorant (A). Filters etc. can be obtained. The color filter can be manufactured in the same manner as the above-mentioned film.

<Solid-state image sensor>
The film of the present invention can be used for solid-state imaging devices. The form used for the solid-state image sensor is not particularly limited, but for example, a transfer device consisting of a plurality of photodiodes, polysilicon, etc. that constitute the light-receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a base material. It has an electrode, has a light-shielding film on the photodiode and transfer electrode with an opening only at the light-receiving part of the photodiode, and is made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a device protective film and a filter on the device protective film. Furthermore, there may be a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film below the filter (on the side closer to the base material), or a configuration in which the condensing means is provided on the filter. You can. Further, the filter may have a structure in which the film of the present invention forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition wall preferably has a low refractive index for each colored pixel.
An imaging device equipped with the solid-state imaging device of the present invention can be used in various applications such as, for example, a digital camera, an electronic device having an imaging function (smartphone, tablet terminal, etc.), an in-vehicle camera, a surveillance camera, a sensor, etc.

<Image display device>
The film of the present invention can be used for image display devices. Examples of the image display device include a liquid crystal display and an organic EL display. The form used in the image display device is not particularly limited, but it can be used as a color filter or a black matrix.
The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994) can be mentioned.
For the definition of image display devices and details of each image display device, see, for example, "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosenkai Co., Ltd., 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho. Co., Ltd., published in 1989).

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to these. Note that "part" means "part by mass" and "%" means "% by mass." In addition, in the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass remaining after standing in an oven at 230° C. for 30 minutes.

Prior to Examples, each measurement method will be explained.

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters of the solution was injected. The molecular weight is a polystyrene equivalent value.

(acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, and use a 0.1 mol/L KOH aqueous solution as the titrant using an automatic titrator ("COM-555" Hiranuma Sangyo Co., Ltd.). The acid value (mgKOH/g) was measured. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

(amine value of resin)
The amine value of the resin is the value obtained by converting the total amine value (mgKOH/g) measured in accordance with the method of ASTM D 2074 into nonvolatile content.

<Production of colorant (A)>
(Colorant (A-7))
According to the description in JP-A No. 2014-12838, the molar ratio of Ni and Zn metal ions is 65:35, and the anion of the azo compound represented by the general formula (2) and its tautomeric structure is , a colorant (A-7) containing a compound represented by general formula (3) was obtained.

<Production of alkali-soluble resin (B)>
(Alkali-soluble resin (B1-1) having hydroxyl group-containing monomer unit (b1))
Pour 100 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) into a reaction container equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device in a separable 4-necked flask, and add 120 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) to the reaction container while injecting nitrogen gas into the container. ℃, and at the same temperature, 56.86 parts (0.4 mol) of glycidyl methacrylate, 66.09 parts (0.3 mol) of dicyclopentanyl methacrylate, and 31.25 parts (0.3 mol) of styrene were added from a dropping tube at the same temperature. A mixture of 3 mol) of azobisisobutyronitrile as a polymerization initiator and 5.0 parts of azobisisobutyronitrile dissolved in PGMAc was added dropwise over 2.5 hours to carry out a polymerization reaction.
After the dropwise addition was completed, the mixture was further stirred at 120° C. for 2 hours to obtain a precursor. Next, the inside of the flask was purged with air, and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 28.82 parts (0.4 mol) of acrylic acid as a modified compound, and the mixture was reacted at 120°C for 5 hours. I let it happen. Thereby, the epoxy group of glycidyl methacrylate and the carboxyl group of acrylic acid were reacted, and the epoxy group of glycidyl methacrylate was cleaved to generate a hydroxyl group, and at the same time, a polymerizable unsaturated group was introduced.
Next, 48.68 parts (0.32 moles) of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added as modification compounds, and the mixture was reacted at 120° C. for 4 hours. As a result, a part of the hydroxyl group generated by cleavage of the epoxy group of glycidyl methacrylate was reacted with tetrahydrophthalic anhydride to introduce a carboxyl group. Thereafter, PGMAc was added so that the nonvolatile content was 20% by mass to prepare an alkali-soluble resin (B1-1) having a hydroxyl group-containing monomer unit (b1). The weight average molecular weight (Mw) was 10,000, and the acid value was 77 mgKOH/g.

(Alkali-soluble resins (B1-2) to (B1-6) having hydroxyl group-containing monomer units (b1))
Alkali-soluble resins (B1-2) to (B1-6) having a hydroxyl group-containing monomer unit (b1) were synthesized by changing the blend type and amount so that the components and composition ratios were as shown in Table 1, PGMAc was added to make the nonvolatile content 20% by mass.

Aronix M-110 listed in Table 1 is paracumylphenol ethylene oxide modified acrylate manufactured by Toagosei Co., Ltd., and Karenz MOI-DEM is malonic acid-2-[[[[2-methyl-1-oxo -2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester).

(Alkali-soluble resin (B2-1) without hydroxyl group-containing monomer unit (b1))
Put 160 parts of PGMAc into a reaction container equipped with a thermometer, cooling tube, nitrogen gas introduction tube, and stirring device in a separable 4-necked flask, and heat it to 120°C while injecting nitrogen gas into the container. 109.25 parts (0.62 mol) of benzyl methacrylate, 24.1 parts (0.28 mol) of methacrylic acid, 22.03 parts (0.1 mol) of dicyclopentanyl methacrylate, and azobis which is a polymerization initiator. A mixture of 1.0 part of isobutyronitrile and PGMAc was added dropwise over 2.5 hours.
After the dropwise addition was completed, stirring was further performed at 120°C for 2 hours. Thereafter, PGMAc was added so that the nonvolatile content was 20% by mass to prepare an alkali-soluble resin (B2-1) having no hydroxyl group-containing monomer unit (b1). The weight average molecular weight was 17,500 and the acid value was 98 mgKOH/g.

<Production of polymerizable compound (C)>
(Polymerizable compound having urethane bond (C3-1))
400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, and the mixture was heated at 70°C. The temperature was raised to , and a mixture of 112 parts of hexamethylene diisocyanate and 112 parts of PGMAc was added dropwise from a dropping tube over 2 hours. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of isocyanate absorption at 2,180 cm ^-1 was confirmed by IR. PGMAc was added so that the nonvolatile content was 50% by mass to obtain a polymerizable compound (C3-1) having a urethane bond with an average number of polymerizable unsaturated groups of 6.

(Polymerizable compound having urethane bond (C3-2))
Into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged. The temperature was raised to .degree. C., and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from a dropping tube over 2 hours. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of isocyanate absorption at 2,180 cm ^-1 was confirmed by IR. PGMAc was added so that the nonvolatile content was 50% by mass to obtain a polymerizable compound (C3-2) having a urethane bond with an average number of polymerizable unsaturated groups of 10.

(Polymerizable compound having urethane bond (C3-3))
Into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged. The temperature was raised to .degree. C., and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from a dropping tube over 2 hours. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of isocyanate absorption at 2,180 cm ^-1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged, and the mixture was reacted at a temperature of 50 to 60°C for 6 hours. The nonvolatile content was adjusted to 50% by mass to obtain a polymerizable compound (C3-3) having an acidic group and a urethane bond with an average number of polymerizable unsaturated groups of 9.

<Manufacture of dispersed resin (G)>
(Dispersion resin (G-1))
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by non-volatile content measurement that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. . After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and PGMAc was added so that the nonvolatile content was 30% by mass to obtain a dispersion resin (G-1). Ta. The acid value was 70 mgKOH/g.

(Dispersion resin (G-2))
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C while flowing nitrogen. The mixture was stirred for 1 hour, and the atmosphere in the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to form the first block (B block). Polymerization started. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or more in terms of nonvolatile content, and the reaction solution was heated to room temperature. Polymerization was stopped by cooling. After cooling to room temperature, about 2 g was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added so that the nonvolatile content was 30% by mass to form the dispersion resin (G-2). Obtained. The amine value was 169.8 mgKOH/g.

<Production of dispersion>
(Dispersion 1)
After stirring and mixing the following raw materials so that they were uniform, they were dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm, and then the pore size was Dispersion 1 was prepared by filtration with a 1.0 μm filter.
Colorant (A-1): 15.0 parts Dispersion resin (G-2): 15.0 parts Organic solvent (Q-1): 70.0 parts

(Dispersions 2 to 13)
Dispersions 2 to 13 were prepared in the same manner as Dispersion 1 except that the components and amounts listed in Table 2 were changed.

The respective components listed in Tables 2-1 and 2-2 are as follows.

[Colorant (A)]
A-1:C. I. pigment green 58
A-2:C. I. pigment green 59
A-3:C. I. pigment green 63
A-4:C. I. pigment yellow 138
A-5:C. I. pigment yellow 139
A-6:C. I. pigment yellow 150
A-8:C. I. pigment red 254
A-9:C. I. pigment red 177
A-10:C. I. pigment blue 15:3
A-11:C. I. pigment blue 15:6
A-12:C. I. pigment violet 23
A-13: Carbon black

[Dye derivative (F)]

[Organic solvent (Q)]
Q-1: Propylene glycol monomethyl ether acetate

<Manufacture of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition 1)
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1.
Dispersion 1: 30.0 parts Dispersion 4: 10.0 parts Alkali-soluble resin (B1-1) having a hydroxyl group-containing monomer unit (b1)
: 12.0 parts Alkali-soluble resin without hydroxyl group-containing monomer unit (b1) (B2-1)
: 5.0 parts Polymerizable compound having a urethane bond (C3-2) : 1.6 parts Polymerizable compound having a urethane bond (C3-3) : 3.6 parts Other polymerizable compounds (C7-1) : 3 .2 parts Polymerization initiator (D-1): 0.5 parts Compound (E-1) represented by general formula (1): 5.0 parts Leveling agent (N): 1.0 parts Organic solvent (Q -1): 18.1 parts Organic solvent (Q-2): 10.0 parts

[Examples 2 to 43 and Comparative Examples 1 and 2]
(Photosensitive coloring compositions 2 to 45)
Photosensitive coloring compositions 2 to 45 were prepared in the same manner as in Example 1, except that photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts listed in Tables 3-1 to 3-5. did.

The raw materials listed in Tables 3-1 to 3-5 are as follows.

[Polymerizable compound (C)]
C1-1: Dipentaerythritol pentaacrylate C2-1: Aronix M-520 (manufactured by Toagosei Co., Ltd.)
C4-1: KAYARAD DCPA-30 (manufactured by Nippon Kayaku Co., Ltd.)
C7-1: Dipentaerythritol hexaacrylate [polymerization initiator (D)]
D-1: Compound (D-1) described above D-2: Compound (D-2) described above D-3: Compound (D-3) described above D-4: Compound (D-4) described above Compound D-5: Compound (D-5) described above D-6: Omnirad 907 (manufactured by IGM Resins)
D-7: The following compound

[Compound (E) represented by general formula (1)]
E-1: A 10% PGMAc solution of the compound (E-1) described above E-2: A 10% PGMAc solution of the compound (E-2) described above E-3: A solution of the compound (E-3) described above 10% PGMAc solution E-7: 10% PGMAc solution of the compound (E-7) mentioned above

[Leveling agent (N)]
One part each of BYK-330 (manufactured by BYK Chemie) and Megafac F-551 (manufactured by DIC) were mixed and dissolved in 98 parts of PGMAc, and a mixed solution was used as a leveling agent (N).

[Adhesion improver (P)]
3-glycidoxypropyltrimethoxysilane

[Organic solvent (Q)]
Q-1: Propylene glycol monomethyl ether acetate Q-2: Ethyl 3-ethoxypropionate

<Evaluation of photosensitive coloring composition>
The resulting photosensitive coloring compositions 1 to 45 were evaluated for adhesion, pattern shape, surface smoothness, and developability after storage using the following methods. The evaluation results are shown in Table 4.

[Adhesion evaluation]
The obtained photosensitive coloring composition was applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm long x 100 mm wide and 0.7 mm thick by spin coating so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, it was exposed to light using a high-pressure mercury lamp at an illuminance of 30 mW/cm ² and 50 mJ/cm ² through a photomask having a stripe pattern with a width of 5 μm. Thereafter, this substrate was spray developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and cleaned. A substrate for evaluation was obtained by heating at 230° C. for 30 minutes in an oven. Spray development was carried out for the shortest time in which a pattern could be formed without any development residue for the film formed with each photosensitive coloring composition, and this was defined as the appropriate development time.
Among the patterns on the evaluation substrate, fine line patterns with a width of 5 to 25 μm were observed with an optical microscope to confirm the remaining fine line patterns. The evaluation criteria are as follows, and 3 or more is practical.
5: Fine lines of 10 μm or less remain.
4: Fine lines of 15 μm or more remain.
3: Fine lines of 20 μm or more remain.
2: A thin line of 25 μm remains.
1: No fine lines remain.

[Pattern shape evaluation (1): linearity]
The obtained photosensitive coloring composition was applied to a 100 mm long x 100 mm wide, 0.7 mm thick glass substrate (Eagle 2000 manufactured by Corning) by a spin coating method so that the dry film thickness was 2.0 μm. , and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, it was exposed to ultraviolet light using an ultra-high pressure mercury lamp at an illuminance of 30 mW/cm ² and 50 mJ/cm ² through a photomask with a 100 μm wide stripe pattern. Thereafter, this substrate was spray developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and cleaned. A substrate for evaluation was obtained by heating at 230° C. for 30 minutes in an oven. Spray development was carried out for the shortest time in which a pattern could be formed without any development residue for the film formed with each photosensitive coloring composition, and this was defined as the appropriate development time.
The evaluation substrate was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon, and calculating the average thereof. The evaluation criteria are as follows, and 3 or more is practical.
5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths The difference is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[Pattern shape evaluation (2): Cross-sectional shape]
Using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Tech, Inc.), the cross-sectional shape of the pattern was confirmed on the substrate prepared in pattern shape evaluation (1). The cross-sectional shape was evaluated by capturing a SEM image of the cross-section of the pattern and measuring the taper angle between the base material and the end of the cross-section of the pattern. The evaluation criteria are as follows, and scores of 3 or higher are considered practical.
5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle of 50 degrees or more and less than 60 degrees 3: Taper angle of less than 30 degrees or 60 degrees or more and less than 70 degrees 2: Taper angle of 70 degrees or more and less than 90 degrees 1: Taper angle of 90 degrees that's all

[Surface smoothness evaluation]
Using an optical microscope ("BX-51" manufactured by Olympus Optical Co., Ltd., magnification: 200 times), the surface of the pattern was confirmed on the substrate prepared in pattern shape evaluation (1). 3 or more should be practical.
5: No wrinkles or unevenness observed on the surface of the pattern.
4: Very slight wrinkles or unevenness are observed on the surface of the pattern.
3: Slight wrinkles or unevenness are observed on the surface of the pattern.
2: Wrinkles or unevenness are observed on the surface of the pattern.
1: Severe wrinkles and unevenness are observed on the surface of the pattern.

[Evaluation of developability after storage]
The obtained photosensitive coloring composition was applied to a 100 mm long x 100 mm wide, 0.7 mm thick glass substrate (Eagle 2000 manufactured by Corning) by a spin coating method so that the dry film thickness was 2.0 μm. , and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, it was exposed to ultraviolet light using an ultra-high pressure mercury lamp at an illuminance of 30 mW/cm ² and 50 mJ/cm ² through a photomask with a 100 μm wide stripe pattern. Thereafter, this substrate was spray developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23° C., then washed with ion-exchanged water, and air-dried. Spray development was performed for the coating film of each photosensitive coloring composition for the shortest time possible to form a pattern without any development residue, and this was taken as the initial development time.
The photosensitive coloring composition was stored in a sealed container at 40° C. for one week, developed under the same conditions as the initial evaluation, and evaluated using the following criteria. 3 or more should be practical.
5: Development time after storage is in the range of 90% or more and 110% or less of the initial development time 4: Development time after storage is 80% or more and less than 90% of the initial development time, or more than 110% and 120% or less Range 3: Development time after storage is 70% or more and less than 80% of the initial development time, or more than 120% and 130% or less 2: Development time after storage is 60% or more and 70% of the initial development time % or more than 130% and less than 140% 1: Development time after storage is less than 60% or more than 140% of the initial development time

Claims (10)

A photosensitive coloring composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the following general formula (1).
General formula (1)

(In general formula (1), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer from 2 to 10.) The photosensitive coloring composition according to claim 1, comprising at least two kinds of compounds (E) represented by the general formula (1). The photosensitive coloring composition according to claim 1 or 2, wherein the compound (E) represented by the general formula (1) includes a compound where n=2. The photosensitive coloring composition according to claim 3, wherein the content of the compound where n=2 is 30% by mass or more based on 100% by mass of the compound (E) represented by the general formula (1). The photosensitive coloring composition according to claim 1 or 2, wherein the alkali-soluble resin (B) contains an alkali-soluble resin (B1) having a hydroxyl group-containing monomer unit (b1). The photosensitive coloring composition according to claim 1 or 2, wherein the polymerizable compound (C) contains a polymerizable compound (C1) having a hydroxyl group. A film comprising the photosensitive coloring composition according to claim 1 or 2. A color filter comprising the film according to claim 7. A solid-state image sensor comprising the color filter according to claim 7. An image display device comprising the color filter according to claim 7.