JP7707872B2 - Photosensitive composition, optical filter, image display device and solid-state image pickup device - Google Patents

Description

The present invention relates to a photosensitive composition and its uses.

2. Description of the Related Art Color filters, which are a type of optical filter, are used in image display devices, solid-state image pickup devices, and the like.
When a color filter is produced by photolithography, a post-bake is performed after the development step, in which the substrate is heated at a temperature of about 200 to 250° C. for about 10 to 60 minutes. However, when a conventional glass substrate is replaced with a flexible plastic substrate, or when a color filter is formed on an organic semiconductor element such as an organic electroluminescence display element (organic EL), post-bake at high temperatures is not possible due to the low heat resistance of these members. On the other hand, when post-bake is performed at low temperatures, the coating is not cured sufficiently, and there is a problem that the solvent resistance and high temperature and high humidity resistance of the cured film are reduced.

To solve the above problems, for example, Patent Document 1 discloses a coloring composition that contains a colorant including a red colorant, a resin having a repeating unit including a blocked isocyanate group, a polymerizable compound, and a photopolymerization initiator, and that specifies the ratio of the maximum and minimum absorbance values at a specific wavelength.

International Publication No. 2021/054248

However, the composition described in Patent Document 1 was unable to provide a cured film with a certain level of solvent resistance after low-temperature post-baking, or high-temperature and high-humidity resistance. In addition, there were problems with low line width stability, in which the line width of the pattern changes when the exposure dose is changed, and low adhesion.

The present invention aims to provide a photosensitive composition that can form a cured film that has excellent pattern line width stability and adhesion, and has excellent solvent resistance and high temperature and humidity resistance even after low-temperature post-baking.

The present invention relates to a photosensitive composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C) and a photopolymerization initiator (D),
the binder resin (B) contains a binder resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2);
The photosensitive composition according to the present invention relates to a polymerizable compound (C) containing a polymerizable compound (C1) having two (meth)acryloyl groups and a condensed ring structure.

According to the present invention, it is possible to provide a photosensitive composition capable of forming a cured film having excellent pattern line width stability and adhesion, excellent solvent resistance even after low-temperature post-baking, and high-temperature and high-humidity resistance. The present invention can also provide an optical filter, an image display device, and a solid-state imaging device.

The following describes in detail the embodiment of the photosensitive composition of the present invention. Note that the present invention is not limited to the following embodiment, and can be modified within the scope of the problem that can be solved.

In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide". In addition, "C.I." means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.
Regarding the molecular weight of the compound in the present invention, for a low molecular weight compound whose molecular weight can be specified, the molecular weight is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and for a compound having a molecular weight distribution, the molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.
A monomer is a compound that will polymerize to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that will polymerize to form a resin.
The fused ring structure means a structure in which two or more rings share an edge in a one-to-one relationship. A structure in which at least one ring is an aromatic ring is called an aromatic fused ring structure, and a structure in which all rings are aliphatic rings is called an aliphatic fused ring structure.

<Photosensitive composition>
The photosensitive composition of the present invention is a photosensitive composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C) and a photopolymerization initiator (D),
the binder resin (B) contains a binder resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2);
The polymerizable compound (C) is characterized in that it contains a polymerizable compound (C1) having two (meth)acryloyl groups and a condensed ring structure.

The mechanism by which the photosensitive composition having the above-mentioned structure can solve the problems of the present invention is unclear, but it is speculated as follows.

The binder resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2) is presumed to have a hydroxyl group-containing monomer unit (b2), so that even when heated at a relatively low temperature, the protective group (blocking agent) is released from the blocked isocyanate group to generate an isocyanate group, and then the isocyanate group and the hydroxyl group react to obtain a sufficiently cured film. And since the polymerizable compound (C1) having two (meth)acryloyl groups and a condensed ring structure has two functional groups, it has fewer crosslinking sites and a milder reaction than the penta- or hexa-functional (meth)acrylates that have been widely used in the color filter field, and even if the exposure dose is increased, the reaction is unlikely to proceed to the parts covered by the mask, and a pattern with the desired line width can be obtained. In addition, it is presumed that a pattern with high adhesion can be obtained because it has a condensed ring structure that is rigid, hydrophobic, and highly heat-resistant.

[Colorant (A)]
The photosensitive 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, which may be used in combination. From the viewpoints of light resistance, heat resistance, and solvent resistance, the colorant (A) is preferably a pigment.

(Pigment)
The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the Color Index. Examples of pigments are listed below.

Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2 , 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 1 84, 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, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are preferred, and C.I. Pigment Red 177,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are particularly preferred.

Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, and 73.

Yellow pigments include, for example, C.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, 1 27, 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 the pigments described in JP-A-2012-226110. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A-2012-226110 are preferred.

Examples of green pigments include C.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, and 63. Of these, C.I. Pigment Green 36, 58, 59, 62, and 63 are preferred.

Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

Examples of purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, C.I. Pigment Violet 19 and 23 are preferred.

Examples of black pigments include C.I. Pigment Black 1, 6, 7, 12, 20, and 31. Other examples include compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, JP-A-1-170601, and JP-A-2-34664.

Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

(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, sulfur dyes, etc. Furthermore, the dye may be in the form of a derivative of these dyes or a lake pigment obtained by making the dye into a lake.

The acid dye preferably has an acid group such as sulfonic acid or carboxylic acid. In addition, a salt-forming compound which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. In addition, a salt-forming compound which is a salt of a resin component having such a functional group and an acid dye is also preferable. In addition, the salt-forming compound is easily modified into a sulfonamide compound to obtain a photosensitive composition having excellent resistance (light resistance, solvent resistance).
In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

The basic dye is preferably a salt-forming compound that forms a salt with an organic acid or perchloric acid or a metal salt thereof. The salt-forming compound of the basic dye is preferred because it has excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion component acting as a counter ion in the salt-forming compound of the basic dye is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable group in the molecule.

In addition, if the dye skeleton contains a polymerizable unsaturated group, the durability of the dye is improved.

The chemical structure of the dyes can be, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, poly Examples of dye structures derived from dyes selected from methine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, and croconium dyes), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof, but are not particularly limited to these.

Among these dye structures, from the viewpoint of color properties such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

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

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

(Micronization of organic pigments)
The organic pigment is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while being heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by rinsing with water.

In the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment is coated with the resin, improving stability, light resistance, etc. 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 preferable for the resin to be solid at room temperature, insoluble in water, and partially soluble in the organic solvents mentioned above. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[Binder resin (B)]
(Binder resin (B1) having blocked isocyanate group-containing monomer unit (b1) and hydroxyl group-containing monomer unit (b2))
The photosensitive composition of the present invention contains, as the binder resin (B), a binder resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2) (hereinafter, also simply referred to as binder resin (B1)). This promotes the release of the blocking agent even in post-baking at a low temperature, and improves the resistance of the cured film.

[Blocked isocyanate group-containing monomer unit (b1)]
The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of an isocyanate group-containing monomer is protected with a compound that is eliminated by heat (hereinafter, also referred to as a blocking agent). The elimination temperature of the blocking agent is preferably 60 to 160°C, more preferably 80 to 140°C.

Examples of isocyanate group-containing monomers include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. Also usable are equimolar reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compounds. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

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 the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, and benzophenone oxime, and methyl ethyl ketoxime is preferred.
Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam.
Examples of the phenol compound include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, and p-nitrophenol, and 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred.
Examples of the alcohol compound 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, and carbazole.
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, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred.
Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan.
Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole.
Examples of the imide compound include succinimide, maleimide, maleimide, and phthalimide.
Examples of the urea compound include urea, thiourea, and ethyleneurea.
Examples of the imine compound include ethyleneimine and polyethyleneimine.
Examples of the bisulfite compound include sodium bisulfite, potassium bisulfite, etc. These blocking agents can be used alone or in combination of two or more kinds.

The blocking agent is preferably at least one 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, and from the viewpoint of protection reactions and deprotection reactions, at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferable.

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

Commercially available blocked isocyanate group-containing monomers include, for example, Showa Denko's Karenz MOI-DEM (blocking agent desorption temperature: 85-95°C), MOI-BP (blocking agent desorption temperature: 105-115°C), and MOI-BM (blocking agent desorption temperature: 125-135°C).

[Hydroxyl Group-Containing Monomer Unit (b2)]
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

From the viewpoints of solvent resistance in low-temperature post-baking, high-temperature and high-humidity resistance, and storage stability of the photosensitive composition, the total content of the blocked isocyanate group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2) is preferably 10 to 60 mol %, and more preferably 20 to 50 mol %, of all constituent units of the binder resin (B1).

The molar ratio of the blocked isocyanate group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2) is preferably 10:90 to 50:50, more preferably 15:85 to 45:55, from the viewpoints of solvent resistance in low-temperature post-baking and high-temperature and high-humidity resistance.

The binder resin (B1) may have a monomer unit other than the blocked isocyanate group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2). Examples include an aliphatic condensed ring structure-containing monomer unit (b3), an acidic group-containing monomer unit (b4), an epoxy group-containing monomer unit (b5), a polymerizable unsaturated group-containing monomer unit (b6), and other monomer units (b7). Among these, it is preferable to have an aliphatic condensed ring structure-containing monomer unit (b3) from the viewpoint of solvent resistance in low-temperature post-bake and high-temperature and high-humidity resistance, and it is preferable to have an acidic group-containing monomer unit (b4) from the viewpoint of developability.

[Aliphatic condensed ring structure-containing monomer unit (b3)]
Examples of the aliphatic condensed ring structure-containing monomer include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

From the viewpoints of solvent resistance in low-temperature post-baking and high-temperature and high-humidity resistance, the content of the aliphatic condensed ring structure-containing monomer unit (b3) is preferably 1 to 40 mol %, and more preferably 5 to 30 mol %, of all the constituent units of the binder resin (B1).

[Acidic group-containing monomer unit (b4)]
Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexyl hydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

From the viewpoint of developability, the content of the acidic group-containing monomer unit (b4) is preferably 1 to 40 mol %, and more preferably 5 to 30 mol %, of all the constituent units of the binder resin (B1).

[Epoxy group-containing monomer unit (b5)]
Examples of the epoxy group-containing monomer include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 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, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate.

[Polymerizable unsaturated group-containing monomer unit (b6)]
Examples of the polymerizable unsaturated group-containing monomer unit (b6) include units introduced by the following methods (i) to (iii).

<Method (i)>
There is a method (i) in which the above-mentioned epoxy group-containing monomer is added to the acidic group of a resin having an acidic group-containing monomer unit (b4).

<Method (ii)>
There is a method (ii) in which the above-mentioned acidic group-containing monomer is added to the epoxy group of a resin having an epoxy group-containing monomer unit (b5).

In addition, the polymerizable unsaturated group-containing monomer unit (b6) is also preferably a unit in which the hydroxyl group generated by the reaction of methods (i) and (ii) is further reacted with an acid anhydride.

Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc.

<Method (iii)>
There is a method (iii) in which the hydroxyl group of a resin having a hydroxyl group-containing monomer unit (b2) is reacted with the isocyanate group of an isocyanate group-containing monomer.

Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[Other monomer units (b7)]
Other monomers include, for example, acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of nonylphenol, EO or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene;
(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, and isobutyl vinyl ether;
vinyl acetate, vinyl propionate, or other vinyl fatty acids;
Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine;
Examples of such monomers include 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, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. These monomers can be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the binder resin (B1) is preferably 4,000 to 40,000, and more preferably 4,000 to 35,000.

The acid value of the binder resin (B1) is preferably 30 to 200 mg KOH/g, and more preferably 40 to 180 mg KOH/g.

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

From the viewpoints of solvent resistance in low-temperature post-baking and resistance to high temperature and humidity, the content of binder resin (B1) is preferably 50 to 100% by mass in 100% by mass of binder resin (B).

(Binder Resin (B2))
The photosensitive composition of the present invention may contain, as the binder resin (B), a binder resin other than the binder resin (B1) (hereinafter, simply referred to as binder resin (B2)).

There are no particular limitations on the binder resin (B2), and known resins can be used. Examples include acrylic resins having acidic groups, α-olefin/maleic acid (anhydride) copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers.

The content of the binder resin (B) is preferably 1 to 60% by mass, and more preferably 5 to 50% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[Polymerizable compound (C)]
(Polymerizable Compound (C1) Having Two (Meth)acryloyl Groups and a Condensed Ring Structure)
The photosensitive composition of the present invention contains, as the polymerizable compound (C), a polymerizable compound (C1) having two (meth)acryloyl groups and a condensed ring structure (hereinafter simply referred to as polymerizable compound (C1)).

The fused ring structure of the polymerizable compound (C1) may be either an aliphatic fused ring structure or an aromatic fused ring structure, but from the viewpoints of line width stability and adhesion of the pattern, an aliphatic fused ring structure is preferred.

Examples of the polymerizable compound (C1) include tricyclodecane dimethanol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, dicyclopentanyl di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 5,7-dimethyl-1,3-adamantanediol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-methacryloyloxyethoxy)phenyl]fluorene, and 9,9-bis[4-(2-methacryloyloxyethoxy)-3-methylphenyl]fluorene. Among these, tricyclodecane dimethanol di(meth)acrylate is preferred.

Commercially available polymerizable compounds (C1) include, for example, NK Ester A-DCP and DCP manufactured by Shin-Nakamura Chemical Co., Ltd., OGSOL EA-0200, EA-0300, GA-5060P, and GA-2800 manufactured by Osaka Gas Chemicals Co., Ltd., and Miramer HR6060, HR6100, and HR6200 manufactured by Miwon Specialty Chemical Co., Ltd.

The polymerizable compound (C1) can be used alone or in combination of two or more types.

From the viewpoint of line width stability and adhesion of the pattern, the content of the polymerizable compound (C1) is preferably 50 to 100 mass %, and more preferably 60 to 100 mass %, of 100 mass % of the polymerizable compound (C).

(Polymerizable compound (C2))
The photosensitive composition of the present invention can contain, as the polymerizable compound (C), a polymerizable compound (C2) (hereinafter, also simply referred to as polymerizable compound (C2)) other than the polymerizable compound (C1) as long as the effects of the present invention are not impaired.

Examples of the polymerizable compound (C2) include polymerizable compounds having one (meth)acryloyl group, such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, phenol EO-modified (meth)acrylate, 2-ethylhexyl EO-modified (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and monohydroxyethyl phthalate (meth)acrylate;
Polymerizable compounds having two (meth)acryloyl groups, such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, EO-modified bisphenol F di(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, and dioxane glycol di(meth)acrylate;
Polymerizable compounds having three (meth)acryloyl groups, such as trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and isocyanuric acid EO-modified tri(meth)acrylate;
Polymerizable compounds having four (meth)acryloyl groups, such as ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate;
Polymerizable compounds having five (meth)acryloyl groups, such as dipentaerythritol penta(meth)acrylate;
Examples of the polymerizable compound include a polymerizable compound having six (meth)acryloyl groups, such as dipentaerythritol hexa(meth)acrylate.
Other examples include polymerizable compounds having an acidic group, polymerizable compounds having a urethane bond, polymerizable compounds having a dendrimer structure or a hyperbranched structure, lactone-modified polymerizable compounds, etc. Among these, from the viewpoint of line width stability of the pattern, a polymerizable compound having two (meth)acryloyl groups is preferred, and a polymerizable compound having two (meth)acryloyl groups and a chain aliphatic structure is more preferred.

Examples of polymerizable compounds having two (meth)acryloyl groups and a chain aliphatic structure include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc. Among these, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate are preferred.

Commercially available polymerizable compounds having two (meth)acryloyl groups and a chain aliphatic structure include, for example, NK Ester A-HD-N, A-NOD-N, A-DOD-N, A-NPG, A-200, APG-200, and NPG manufactured by Shin-Nakamura Chemical Co., Ltd.

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 mass %, and more preferably 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[Photopolymerization initiator (D)]
The photosensitive composition of the present invention contains a photopolymerization initiator (D), which allows the photosensitive composition to be cured by irradiation with active energy rays to form a cured film.

Examples of the photopolymerization initiator (D) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone;
Triazine-based compounds such as 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)-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;
Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime);
Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.

Commercially available products include acetophenone compounds such as Omnirad 907, 369E, and 379EG manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 manufactured by BASF Japan, N-1919, NCI-730, 831, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of such resins include Omnirad 1312, 1314, and 1316 manufactured by Resins Co., Ltd., SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemistry Co., Ltd.
Further, acetophenone compounds described in JP-T-2019-507108 and JP-T-2019-528331, JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, WO 2015/036910, WO 2021/175855, and the like. Also mentioned are oxime compounds described therein.

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

From the viewpoint of photocurability, the content of the photopolymerization initiator (D) is preferably 1 to 100 parts by mass, and more preferably 3 to 50 parts by mass, per 100 parts by mass of the polymerizable compound (C).

[Dispersion resin (E)]
From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains a dispersing resin (E).

The dispersion resin (E) has an affinity site that has the property of adsorbing to the colorant (A) and a site that is compatible with the binder resin (B), and can be any known resin as long as it functions to adsorb to the colorant (A) and stabilize the dispersion in the binder resin (B). As is well known, the dispersion resin (E) is used when producing a dispersion of the colorant (A), which is a precursor of the photosensitive composition, and is distinguished from the binder resin (B).

It is preferable that the dispersing resin (E) has at least one of a basic group and an acidic group as a group that adsorbs to the colorant (A).

Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and groups containing nitrogen atoms such as nitrogen-containing heterocycles.

Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups.

Examples of the resin type of the dispersing resin (E) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphates.

The structure of the dispersing resin (E) may be, for example, a random structure, a block structure, a graft structure, a comb structure, or a star structure. Among these, from the viewpoint of dispersion stability, a block structure or a comb structure is preferred.

Commercially available dispersion resins (E) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, and 2095 manufactured by BYK Japan Co., Ltd. , 2150, 2155, 2163, 2164, Anti-Terra-U203, 204, BYK-P104, P104S, 220S, Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26 000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 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, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisuper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd., etc.

From the viewpoint of solvent resistance in low-temperature post-baking and high-temperature and high-humidity resistance, the dispersion resin (E) preferably has a polymerizable unsaturated group. Examples of dispersion resins having a polymerizable unsaturated group include the resins described in paragraphs 0317 to 0321 of JP 2019-78878 A, the resins described in paragraph 0083 of WO 2018/139534 A, the resins described in paragraphs 0167 to 0191 of WO 2019/163505 A, and the resins described in paragraphs 0299 to 0310 of WO 2021/131927 A.

From the viewpoint of storage stability, the content of the dispersing resin (E) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the colorant (A).

[Thiol-based chain transfer agent (F)]
The photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent (F) from the viewpoints of line width stability of the pattern, adhesion, solvent resistance in low-temperature post-baking, and high-temperature and high-humidity resistance. When the thiol-based chain transfer agent (F) is used in combination with the photopolymerization initiator (D), a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, thereby improving the photosensitivity of the photosensitive composition.

The thiol chain transfer agent (F) is preferably a multifunctional thiol having two or more thiol groups (SH groups), more preferably a multifunctional thiol having four or more thiol groups. As the number of functional groups increases, the film becomes easier to photocure from the surface to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of such thiopropionates include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, and the like.

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

From the viewpoints of line width stability of the pattern, adhesion, solvent resistance in low-temperature post-baking, and high-temperature and high-humidity resistance, the content of the thiol chain transfer agent (F) is preferably 0.1 to 1.0 mass %, and more preferably 0.2 to 0.8 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[Thermosetting compound (G)]
The photosensitive composition of the present invention preferably contains a thermosetting compound (G), which crosslinks during post-baking, and the solvent resistance and high-temperature and high-humidity resistance of the cured film are further improved.

The thermosetting compound (G) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (G) 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, from the viewpoint of suppressing foreign matter, epoxy compounds and oxetane compounds are preferred, and epoxy compounds are more preferred.

(Epoxy Compound)
The epoxy compound is preferably a compound having an aromatic ring and/or an aliphatic ring, and is more preferable than a compound having an aliphatic ring from the viewpoint of solvent resistance and high temperature and humidity resistance. The epoxy group is preferably bonded to the aromatic ring and/or the aliphatic ring via a single bond or a linking group. Examples of the linking group include an alkyl group, an arylene group, -O-, -NR- (R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent), -SO ₂ -, -CO-, -O-, and -S-. In the case of a structure having an aliphatic ring, it is more preferable that the epoxy group is bonded to the aliphatic ring via a single bond.

From the viewpoint of solvent resistance and high temperature and humidity resistance, the epoxy compound is preferably a compound having 5 to 50 epoxy groups in the molecule, and more preferably a compound having 10 to 30 epoxy groups.

Epoxy compounds include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, Examples of such epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celoxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., etc.

From the viewpoint of solvent resistance in low-temperature post-baking and high-temperature and high-humidity resistance, the content of the epoxy compound is preferably 0.5 to 20 mass %, and more preferably 1 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

(Oxetane Compounds)
The 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 higher oxetane compounds.

Examples of monofunctional oxetane compounds include (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, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

Commercially available products include, for example, OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Examples of bifunctional oxetane compounds include 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-hydroxymethyl oxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol 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 bis(3-ethyl-3-oxetanylmethyl) ether, Examples include 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 bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc.

Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei.

Examples of trifunctional or higher oxetane compounds include 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, and caprolactone-modified dipentaerythritol. Examples include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

From the viewpoint of solvent resistance in low-temperature post-baking and high-temperature and high-humidity resistance, the content of the oxetane compound is preferably 0.5 to 20 mass %, and more preferably 1 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

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

[Curing agent (curing accelerator)]
In the photosensitive composition of the present invention, a curing agent (curing accelerator) can be used in combination to assist the curing of the thermosetting compound (G). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., 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 salts thereof (e.g., imidazole, 2-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 (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 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 hardeners 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 per 100 parts by mass of the thermosetting compound (G).

[Dye derivative (H)]
The photosensitive composition of the present invention may contain a dye derivative (H).

The dye derivative (H) is not particularly limited, and a known compound can be used. For example, a compound having a structure in which a part of the dye is substituted with an acidic group, a basic group, a neutral group, or the like can be used. Specifically, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and an amine salt thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and a compound having a neutral substituent such as a phenyl group or a phthalimidoalkyl group can be used.
Examples of the dye include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, and naphthalocyanine compounds.

Specifically, pyrrolopyrrole dye derivatives are described, for example, in JP 2001-220520 A, WO 2009/081930 A, WO 2011/052617 A, WO 2012/102399 A, JP 2017-156397 A, and WO 2018/101189 A, phthalocyanine dye derivatives are described, for example, in JP 2007-226161 A, WO 2016/163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are described, for example, in JP 63-2 64674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009/025325; quinacridone dye derivatives are described, for example, in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine dye derivatives are described, for example, in JP-A-2011-162662; thiazineindigo dye derivatives are described, for example, in JP-A-2007-314785; and triazine dye derivatives are described, for example, in For example, see JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681; benzoisoindole dye derivatives are described, for example, in JP-A-2009-57478; quinophthalone dye derivatives are described, for example, in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-226110; and naphthol dye derivatives are described, for example, in JP-A-2012-226110. Examples of squarylium dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, and International Publication No. WO 2020/054718. Examples of azo dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092. Examples of acidic substituents include those described in JP-A-2004-307854. Examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In addition, although these documents may be described as derivatives, pigment derivatives, dispersants, dispersing aids, pigment dispersants, or simply compounds, they are synonymous with the dye derivative (H).

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

The content of the dye derivative (H) is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the colorant (A).

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

Sensitizers (I) include, for example, chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, and other polymethine dyes, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples of the compounds include compounds having a fluorine-containing compound, ...

Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Among these, 2,4-diethylthioxanthone is preferred.

Examples of benzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

Sensitizer (I) can be used alone or in combination of two or more types.

The content of the sensitizer (I) is preferably 10 to 400 parts by mass, and more preferably 20 to 300 parts by mass, per 100 parts by mass of the photopolymerization initiator (D).

[Polymerization inhibitor (J)]
The photosensitive composition of the present invention may contain a polymerization inhibitor (J).

Examples of the polymerization inhibitor (J) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n alkyl resorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkyl hydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol, phloroglucinol, and the like.

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

[Ultraviolet absorber (K)]
The photosensitive composition of the present invention may contain an ultraviolet absorber (K).

The ultraviolet absorber (K) is an organic compound having an ultraviolet absorbing function, and examples of such compounds include 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.

Benzotriazole compounds include, for example, 2-(5-methyl-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-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and straight chain 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-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-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 These include octyl-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-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan, Adeka STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA, KEMISORB 71, 73, 74, 79, and 279 manufactured by Chemipro Chemicals, and RUVA-93 manufactured by Otsuka Chemical.

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-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 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, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adeka STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3-water, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adeka STAB 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

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

The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (K).

[Antioxidant (L)]
The photosensitive composition of the present invention may contain an antioxidant (L). The antioxidant (L) prevents the photopolymerization initiator (D) and the thermosetting compound (G) in the photosensitive coloring composition from being oxidized and yellowed by the thermal process during heat curing or ITO annealing.

Examples of the antioxidant (L) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Examples of hindered phenol antioxidants include 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), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl 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-hydroxyphenylmethyl) nyl)-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)-phenol, etc.

Commercially available products include, for example, Adeka STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by ChemiPro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan, and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, 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, polycondensation product 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]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis(tetramethylbutyl)amino, Bis[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, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridylsebake ester, 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 esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

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, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals, Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan, and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical.

Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite.

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

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

Commercially available products include, for example, Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOX PLS manufactured by Chemipro Chemicals Co., Ltd.

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

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[Leveling Agent (M)]
The photosensitive composition of the present invention may contain a leveling agent (M). This improves the wettability and drying property of the composition to the substrate during application. Examples of the leveling agent (M) 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 have been introduced into the side chains or ends.

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, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Fluorine-based surfactants include, for example, surfactants or leveling agents having a fluorocarbon chain.

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

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. late, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, 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, alkyl imidazoline, 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, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, and LS- manufactured by Kao Corporation. 106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor 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, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, C Examples include H-60(K), Amit 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 manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and cetyl trimethyl ammonium chloride, and ethylene oxide adducts of these.

Commercially available products include, for example, Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate 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 alkyldiphenyletherdisulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

Commercially available products include, for example, Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adeka Col TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

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

Commercially available products include Kao Corporation's Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N.

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

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the balance between the coatability and adhesion of the photosensitive composition is further improved.

[Storage stabilizer (N)]
The photosensitive composition of the present invention may contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive composition over time. Examples of the storage stabilizer (N) include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

The content of the storage stabilizer (N) is preferably 0.05 to 5 mass % based on 100 mass % of the nonvolatile content of the photosensitive composition.

[Adhesion improver (O)]
The photosensitive composition of the present invention may contain an adhesion improver (O). This improves adhesion and also makes it easier to form a narrow pattern by photolithography.

Examples of the adhesion improver (O) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and other aminosilanes, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane, etc. silane coupling agents.

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

The content of the adhesion improver (O) is preferably 0.05 to 5 mass % based on 100 mass % of the nonvolatile content of the photosensitive composition.

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

There are no particular limitations on the organic solvent (P) as long as it satisfies the solubility and coatability of each component of the photosensitive composition of the present invention, and any known compound can be used.

Examples of organic solvents (P) include 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-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butylalcohol, Coal, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, 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 monopropyl ether, ethylene glycol monohexyl dimethyl 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 Lithium 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 monopropyl 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, propyl acetate, and dibasic acid esters. Among these, from the viewpoint of resin solubility and coatability, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone are preferred.

From an environmental perspective, the photosensitive composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). "Substantially not contained" means that the amount of such organic solvents in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

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

The content of the organic solvent (P) is preferably an amount such that the non-volatile content of the photosensitive composition is about 5 to 50 mass %.

[Method of producing photosensitive composition]
The photosensitive composition of the present invention can be produced by, for example, adding a colorant (A), a dispersion resin (E), an organic solvent (P), etc., and carrying out a dispersion treatment. Thereafter, the dispersion can be produced by blending and mixing a binder resin (B), a polymerizable compound (C), a photopolymerization initiator (D), etc. The timing of blending each material is arbitrary. The dispersion process can also be carried out multiple times.

Examples of dispersing machines used for the dispersion process include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

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

The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape aspheric, and the D50 particle size as the average size. The organic solvent used for dispersion is used as the dilution solvent for measurement, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to give results with less variation.

The photosensitive composition is preferably subjected to centrifugation, filtration with a sintered filter or membrane filter, or other means to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, as well as contaminated dust. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or more, and more preferably contains no particles of 0.3 μm or less.

<Optical filter>
The optical filter of the present invention includes a substrate and a cured film formed from a photosensitive composition. The cured film is preferably patterned by a photolithography method.

[Method of manufacturing optical filters]
The method for producing the optical filter is not particularly limited, and the optical filter can be produced by, for example, carrying out the steps of: (1) applying a photosensitive composition onto a substrate to form a layer of the composition; (2) exposing the layer to light through a mask in a pattern; (3) developing the unexposed portion with an alkali to form a patterned cured film; and (4) heat-treating (post-baking) the pattern. In the present invention, the optical filter is preferably produced at a temperature of 130° C. or less throughout all steps, and more preferably at a temperature of 100° C. or less.

The manufacturing method for optical filters is explained in detail below.

(Step (1))
In the step (1) of forming a composition layer, the photosensitive composition is applied onto a substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (prebaked) at a temperature of 50 to 100° C. for 10 to 120 seconds using an oven, a hot plate, or the like as necessary.
Examples of the substrate include a glass substrate, a resin substrate, and a silicon substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light-emitting layer may be formed on these substrates. For example, an imaging element such as a CCD or a CMOS may be formed on the surface of the silicon substrate. Furthermore, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the substrate surface.
The thickness of the layer is preferably from 0.05 to 10.0 μm, and more preferably from 0.3 to 5.0 μm.

(Step (2))
In the exposure step, the layer obtained in step (1) is exposed to light in a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a cured film.
Examples of radiation used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF (wavelength 193 nm).
In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure).

(Step (3))
The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is dissolved in an aqueous alkali solution, leaving only the cured areas to obtain a patterned cured film.
Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the alkaline developer is preferably from 0.001 to 10% by mass, and more preferably from 0.01 to 1% by mass.
The pH of the alkaline developer is preferably from 11 to 13, more preferably from 11.5 to 12.5. When used at an appropriate pH, roughening and peeling of the pattern is suppressed, and the remaining film rate after development is improved.

Examples of development methods include the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

(Step (4))
In the heat treatment (post-baking), the patterned cured film obtained in step (3) is sufficiently cured by heating. The heating temperature in the post-baking is preferably 130° C. or lower, more preferably 100° C. or lower. There is no particular lower limit to the heating temperature as long as it can promote curing, but it is preferably 50° C. or higher. The heating time is preferably 5 minutes to 2 hours, more preferably 5 minutes to 1 hour.

The optical filter of the present invention can be used for various purposes. Examples include anti-reflection filters, color filters, black matrices, infrared transmission filters, and light-shielding filters.

<Image display device>
The image display device of the present invention includes the optical filter of the present invention. Examples of the image display device include a liquid crystal display and an organic EL display.
The form of 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" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned.
The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

<Solid-state imaging element>
The solid-state imaging device of the present invention includes the optical filter of the present invention.
The form used for the solid-state imaging element is not particularly limited, but for example, a substrate is provided with a plurality of photodiodes constituting a light receiving area of a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light-shielding film with only the light receiving portion of the photodiodes opened on the photodiodes and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a filter on the device protection film. Furthermore, the device protection film may have a configuration in which a light-collecting means (e.g., a microlens, etc., the same below) is provided on the device protection film and below the filter (the side closer to the substrate), or a configuration in which a light-collecting means is provided on the filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each color pixel.
An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, surveillance cameras, and optical sensors.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass".
In the present invention, the non-volatile content or the non-volatile content concentration refers to the mass remaining after standing in an oven at 230° C. for 30 minutes.

Before going into the examples, we will explain each measurement method.

The weight average molecular weight (Mw), number average molecular weight (Mn), and acid value (mgKOH/g) of the resin were measured as follows:

(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. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and two "TSK-GEL SUPER HZM-N" packings were used as both packings connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

(Acid value of resin)
80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the resin solution, and the solution was stirred to dissolve uniformly, and titrated with an automatic titrator ("COM-555", Hiranuma Sangyo Co., Ltd.) using a 0.1 mol/L KOH aqueous solution as a titrant to measure the acid value (mgKOH/g). The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

<Production of Colorant (A)>
(Colorant (A-1))
100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60° C. This mixture was added to 3,000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80° C. overnight and pulverized to obtain a finely divided colorant (A-1).

(Colorant (A-2))
100 parts of C.I. Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was added to 3,000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80° C. overnight and pulverized to obtain a finely divided colorant (A-2).

(Colorant (A-3))
100 parts of C.I. Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 80° C. This mixture was poured into 3,000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, then dried at 80° C. for 24 hours and pulverized to obtain a finely divided colorant (A-3).
<Production of binder resin (B)>
(Binder resin (B1-1) solution)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed, and the mixture was stirred while replacing with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, a blocked isocyanate group-containing monomer, 31.2 parts of 2-hydroxyethyl methacrylate, a hydroxyl group-containing monomer, 37.5 parts of dicyclopentanyl methacrylate, an aliphatic condensed ring structure-containing monomer, 20.7 parts of methacrylic acid, an acidic group-containing monomer, and 27.0 parts of methyl methacrylate, another monomer unit, and 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc was dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 78 ° C. for 3 hours.
Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, and a binder resin (B1-1) solution was prepared. The binder resin (B1-1) had an acid value of 74 mgKOH/g and a weight average molecular weight of 8,000.

(Binder resin (B1-2) to (B1-10) solutions, binder resin (B2-1) and (B2-2) solutions)
Binder resins (B1-2) to (B1-10), (B2-1) and (B2-2) were synthesized so as to have the molar ratios of each of the constituent components shown in Tables 1-1 and 1-2, and PGMAc was added to adjust the non-volatile content to 40 mass%.

Karenz MOI-BP in Table 1-1 is 2-(3,5-diethylpyrazol-1-yl)carbonylaminoethyl methacrylate manufactured by Showa Denko K.K., and Karenz MOI-BM is 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate manufactured by Showa Denko K.K.

<Production of Dispersion Resin (E)>
(Dispersion resin (E-1) solution)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst, and then substituted with nitrogen gas, and reacted at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, the compound obtained in the first step was charged with 160 parts in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc, and the inside of the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% had reacted by measuring the non-volatile content. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm ⁻¹ due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a dispersion resin (E-1) solution having a polymerizable unsaturated group with a non-volatile content of 30% by mass. The dispersion resin (E-1) having a polymerizable unsaturated group had an acid value of 68 mg KOH/g and a weight average molecular weight of 13,000.

(Dispersion resin (E-2) solution)
A dispersion resin (E-2) solution having a polymerizable unsaturated group was obtained according to paragraph 0300 of WO 2021/131927. The dispersion resin (E-2) having a polymerizable unsaturated group had an acid value of 70 mg KOH / g and a weight average molecular weight of 17,200.

(Dispersion resin (E-3) solution)
A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the solution was diluted with PGMAc to a non-volatile content of 30% by mass to obtain a dispersion resin (E-3) solution. The dispersion resin (E-3) had an acid value of 70 mgKOH/g and a weight average molecular weight of 8,500.

<Preparation of Dispersion>
(Dispersion 1)
The following raw materials were mixed and stirred to be uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (P-1) was PGMAc.
Colorant (A-1): 12.0 parts Colorant (A-2): 0.8 parts Colorant (A-3): 2.2 parts Dispersion resin (E-1) solution: 17.5 parts Organic solvent (P-1): 67.6 parts

Dispersions 2 and 3
Dispersions 2 and 3 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts thereof shown in Table 2 were changed.

<Preparation of Photosensitive Composition>
[Example 1]
(Photosensitive composition 1)
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain Photosensitive Composition 1.
Dispersion 1: 40.0 parts Binder resin (B1-1) solution: 3.75 parts Polymerizable compound (C1-1): 4.50 parts Photopolymerization initiator (D-1): 0.30 parts Thiol-based chain transfer agent (F-1): 0.05 parts Thermosetting compound (G-1): 0.70 parts Leveling agent (M): 1.00 parts Organic solvent (P): 49.7 parts

[Examples 2 to 24, Comparative Examples 1 to 4]
(Photosensitive compositions 2 to 28)
Photosensitive compositions 2 to 28 were prepared in the same manner as in Example 1, except that the photosensitive composition 1 in Example 1 was changed to the raw materials and amounts shown in Tables 3-1 to 3-3.

The details of each ingredient listed in Tables 3-1 to 3-3 are as follows:

[Polymerizable compound (C)]
(Polymerizable compound (C1))
C1-1: Tricyclodecane dimethanol diacrylate C1-2: 1,3-adamantanediol diacrylate C1-3: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene

(Polymerizable compound (C2))
C2-1: Neopentyl glycol diacrylate C2-2: EO-modified bisphenol A diacrylate (EO number: 4)
C2-3: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate

[Photopolymerization initiator (D)]
D-1: Irgacure OXE-04 (manufactured by BASF Japan)
D-2: Omnirad907 (manufactured by IGM Resins)

[Thiol-based chain transfer agent (F)]
F-1: Pentaerythritol tetrakis(3-mercaptopropionate)

[Thermosetting compound (G)]
G-1: EHPE-3150 (manufactured by Daicel Corporation, a compound having an aliphatic ring with approximately 15 epoxy groups)

[Leveling Agent (M)]
M-1: BYK-330 (manufactured by BYK-Chemie)
M-2: Megafac F-554 (DIC)
One part each of (M-1) and (M-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution as a leveling agent (M).

[Organic solvent (P)]
P-1: Propylene glycol monomethyl ether acetate 30 parts P-2: Cyclohexanone 30 parts P-3: Ethyl 3-ethoxypropionate 10 parts P-4: Propylene glycol monomethyl ether 10 parts P-5: Cyclohexanol acetate 10 parts P-6: Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above parts by weight to obtain organic solvent (P).

<Evaluation of Photosensitive Composition>
The obtained photosensitive compositions 1 to 28 (Examples 1 to 24 and Comparative Examples 1 to 4) were evaluated as follows. The evaluation results are shown in Table 4.

[Line width stability evaluation]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm 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 the substrate to room temperature, the substrate was exposed through a photomask having a 100 μm wide stripe pattern at two levels of illuminance 30 mW/cm ² and exposure dose 50 mJ/cm ² and 100 mJ/cm ² using a high pressure mercury lamp. Thereafter, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., and then washed with ion-exchanged water and air-dried. The obtained substrate was post-baked in a clean oven at 100° C. for 60 minutes to obtain a substrate for evaluation.
The obtained evaluation substrate was measured for line width at an exposure dose of 50 mJ/ ^cm2 ( _CD50 ) and 100 mJ/ ^cm2 ( _CD100 ) using a Nikon Eclipse LV100POL Model optical microscope, and the line width difference (ΔCD) due to the difference in exposure dose was calculated using the following formula (1). The evaluation criteria are as follows, with 3 or more being considered practical.
Formula (1): ΔCD = CD ₁₀₀ - CD ₅₀
5: ΔCD is less than 2 μm 4: ΔCD is 2 μm or more and less than 3 μm 3: ΔCD is 3 μm or more and less than 5 μm 2: ΔCD is 5 μm or more and less than 6 μm 1: ΔCD is 6 μm or more

[Adhesion evaluation]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm 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 the substrate to room temperature, the substrate was exposed to light 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 to 25 μm and an interval of 5 μm. Thereafter, the substrate was spray-developed using an aqueous developer containing 0.12 mass % of a nonionic surfactant and 0.04 mass % of potassium hydroxide at 23 ° C., washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 100 ° C. for 60 minutes. The spray development was performed for each coating of the photosensitive composition for the shortest time possible to form a pattern without residual development.
The resulting patterns having widths of 5, 10, 15, 20 and 25 μm were observed with an optical microscope to confirm the minimum line width of the remaining pattern. The evaluation criteria are as follows, with a score of 3 or higher being considered 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.

[Solvent resistance evaluation (1)]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70° C. for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern at an illuminance of 30 mW/cm ² and 50 mJ/cm ² using a high pressure mercury lamp. Furthermore, after cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., and then washed with ion-exchanged water and air-dried. Then, it was post-baked in a clean oven at 130° C. for 60 minutes to obtain an evaluation substrate.
The obtained evaluation substrate was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, washed with ion-exchanged water, air-dried, and the stripe pattern portion having a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, with 3 or more being considered practical.
5: No change in appearance or color.
4: Slight wrinkles, etc., occur, but there is no change in color.
3: Some wrinkles or other imperfections occur, but there is no change in color.
2: Creases and other imperfections appear all over the surface, and the color fades slightly.
1: Peeling or fading occurs.

[Solvent resistance evaluation (2)]
The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70° C. for 1 minute. Then, after cooling the substrate to room temperature, it was exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern at an illuminance of 30 mW/cm ² and 50 mJ/cm ² using a high pressure mercury lamp. Furthermore, after cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C., and then washed with ion-exchanged water and air-dried. Then, it was post-baked in a clean oven at 100° C. for 60 minutes to obtain an evaluation substrate.
The obtained evaluation substrate was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, washed with ion-exchanged water, air-dried, and the stripe pattern portion having a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, with 3 or more being considered practical.
5: No change in appearance or color.
4: Slight wrinkles, etc., occur, but there is no change in color.
3: Some wrinkles or other imperfections occur, but there is no change in color.
2: Creases and other imperfections appear all over the surface, and the color fades slightly.
1: Peeling or fading occurs.

[High temperature and humidity resistance evaluation]
The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm, using a spin coater so that the dry film thickness was 2.0 μm, and dried on a hot plate at 70° C. for 1 minute. Next, using an ultra-high pressure mercury lamp, the coating was exposed to ultraviolet light at an illuminance of 30 mW/cm ² and 50 mJ/cm ² through a photomask having a 100 μm wide stripe pattern. Furthermore, after cooling the substrate to room temperature, the substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23° C., washed with ion-exchanged water, and air-dried. The obtained substrate was post-baked in a clean oven at 100° C. for 60 minutes to form a stripe pattern on the substrate.
The obtained substrate was stored for 200 hours under conditions of a temperature of 85° C. and a humidity of 85%. After storage, the number of foreign matters on the pattern was counted using an optical microscope. The evaluation criteria are as follows, with 3 or more being practical.
5: The number of foreign objects is less than 5 4: The number of foreign objects is 5 or more but less than 10 3: The number of foreign objects is 10 or more but less than 15 2: The number of foreign objects is 15 or more but less than 20 1: The number of foreign objects is 20 or more

[Evaluation of storage stability of photosensitive composition]
The obtained photosensitive composition was placed in a sealed container and stored at 40°C for one week, and the rate of change in viscosity before and after storage was calculated and evaluated using the following formula. The viscosity was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. The evaluation criteria are as follows, with 2 or more being practical.
[Change rate of viscosity over time] = |([initial viscosity] - [viscosity over time]) / [initial viscosity] | x 100
3: Change rate is less than 5% 2: Change rate is 5% or more but less than 10% 1: Change rate is 10% or more

Claims (9)

A photosensitive composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C) , a photopolymerization initiator (D) and a dispersion resin (E) ,
the binder resin (B) contains a binder resin (B1) having a blocked isocyanate group-containing monomer unit (b1) and a hydroxyl group-containing monomer unit (b2);
the polymerizable compound (C) contains a polymerizable compound (C1) having two (meth)acryloyl groups and a condensed ring structure,
The photosensitive composition , wherein the dispersing resin (E) has a polymerizable unsaturated group . The photosensitive composition according to claim 1, wherein the total content of the blocked isocyanate group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2) is 10 to 60 mol % of all the constituent units of the binder resin (B1). The photosensitive composition according to claim 1 or 2, wherein the molar ratio of the blocked isocyanate group-containing monomer unit (b1) and the hydroxyl group-containing monomer unit (b2) is 10:90 to 50:50. The photosensitive composition according to any one of claims 1 to 3, wherein the binder resin (B1) further contains an aliphatic condensed ring structure-containing monomer unit (b3). The photosensitive composition according to any one of claims 1 to 4, wherein the content of the polymerizable compound (C1) having two (meth)acryloyl groups and a condensed ring structure is 50 to 100 mass% in 100 mass% of the polymerizable compound (C). The photosensitive composition according to any one of claims 1 to 5 , further comprising a thiol-based chain transfer agent (F). An optical filter comprising a substrate and a cured film formed from the photosensitive composition according to any one of claims 1 to 6 . An image display device comprising the optical filter according to claim 7 . A solid-state imaging device comprising the optical filter according to claim 7 .