JP7739732B2 - Photosensitive coloring composition, cured film, and optical filter - Google Patents

Description

The present invention relates to a photosensitive coloring composition, a cured film, and an optical filter.

Optical filters are used for a variety of purposes, such as adjusting image brightness, improving image contrast, transmitting or reflecting specific wavelengths, and splitting an image into two independent images at a specific ratio. They are used in devices and equipment such as cameras, image display devices such as liquid crystal and organic electroluminescence, solid-state imaging devices such as C-MOS (Complementary Metal Oxide Semiconductor) image sensors and CCD (Charge Coupled Device) image sensors, infrared sensors, and biometric authentication sensors.

In recent years, optical filters have been required to have high color separation and high definition. To meet these demands, efforts have been made to increase the concentration of colorants contained in the compositions that form optical filters and to increase film thickness. However, increasing the colorant concentration or film thickness can lead to problems such as wrinkles forming on the film surface during curing and deterioration of developability and pattern formability. These problems become particularly pronounced when halide metal phthalocyanine pigments, which have high absorbance in the ultraviolet range and are difficult to transmit ultraviolet light, are used as colorants, and improvements have been sought.

Various efforts have been made to solve the above problems. Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble resin having an acryloyl group or an epoxy group, a photopolymerizable compound having an alkylene oxide structure, and an oxime ester compound as a photopolymerization initiator. Patent Document 2 also discloses a colored resin composition having a double bond equivalent of 400 g/mol or less and containing a photopolymerizable monomer having a bisphenol skeleton.

JP 2015-212738 A Japanese Patent Application Laid-Open No. 2019-183053

However, the compositions described in Patent Documents 1 and 2 are insufficient in terms of wrinkles during curing, developability, and pattern formability, particularly when the film thickness is increased. Furthermore, color separation is not taken into consideration.

The objective of the present invention is to provide a photosensitive coloring composition that produces minimal wrinkles during curing, has excellent developability and pattern formability, and exhibits excellent color separation properties, even when the film thickness is increased.

The present invention provides a photosensitive coloring composition comprising an organic pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and silica particles (E),
the organic pigment (A) comprises a halogenated metal phthalocyanine pigment (A-1) and an isoindoline pigment (A-2);
the polymerizable compound (C) contains a polymerizable compound (C-1) having a urethane bond,
The photosensitive coloring composition relates to a photosensitive coloring composition in which the content of the organic pigment (A) is 25% by mass or more based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

The present invention also relates to the above photosensitive coloring composition, in which the polymerizable compound (C) further contains a polymerizable compound (C-2) other than the polymerizable compound (C-1) having a urethane bond.

The present invention also relates to the photosensitive coloring composition, in which the mass ratio of the polymerizable compound (C-1) having a urethane bond to the polymerizable compound (C-2) is 80:20 to 20:80.

The present invention also relates to the above photosensitive coloring composition, wherein the polymerizable compound (C-1) having a urethane bond has an acid group.

The present invention also relates to the above-mentioned photosensitive coloring composition, in which the alkali-soluble resin (B) comprises an alkali-soluble resin (B-1) containing an alicyclic hydrocarbon structure-containing monomer unit (b1) and a carboxyl group-containing monomer unit (b2).

The present invention also relates to the photosensitive coloring composition, wherein the alkali-soluble resin (B-1) contains the alicyclic hydrocarbon structure-containing monomer unit (b1) in an amount of 5 to 60% by mass, based on 100% by mass of all structural units of the alkali-soluble resin (B-1).

The present invention also relates to the above photosensitive coloring composition, in which the mass ratio of the halogenated metal phthalocyanine pigment (A-1) to the isoindoline pigment (A-2) is 97:3 to 40:60.

The present invention also relates to the photosensitive coloring composition, wherein the content of the silica particles (E) is 5 to 30 mass % based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

The present invention also relates to the above photosensitive coloring composition, which further contains a near-infrared absorber (H).

The present invention also relates to a cured film obtained by curing the above-mentioned photosensitive coloring composition.

The present invention also relates to an optical filter having the above-mentioned cured film, wherein the film thickness of the cured film is 4.0 μm or more.

The present invention provides a photosensitive coloring composition that exhibits minimal wrinkles during curing, excellent developability, pattern formability, and excellent color separation, even when the film thickness is increased.

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

In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" refers to "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or
or methacrylate," or "acrylamide and/or methacrylamide." Also, "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.

<Photosensitive coloring composition>
The present invention provides a photosensitive coloring composition comprising an organic pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and silica particles (E),
the organic pigment (A) comprises a halogenated metal phthalocyanine pigment (A-1) and an isoindoline pigment (A-2);
the polymerizable compound (C) contains a polymerizable compound (C-1) having a urethane bond,
The photosensitive coloring composition has a content of the organic pigment (A) of 25% by mass or more in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

The mechanism by which the photosensitive coloring composition having the above-described configuration can solve the problems of the present invention is unclear, but the inventors speculate as follows.

When the concentration of the colorant is increased or the film thickness is increased, when the photosensitive coloring composition is exposed to light in the ultraviolet region and cured, the light does not reach the inside of the photosensitive coloring composition layer, and wrinkles occur on the surface due to a difference in the degree of cure shrinkage between the surface and the inside.
However, it is believed that the silica particles (E) have high transparency, and therefore create a path for light to pass through the composition layer, thereby improving the curability. Furthermore, it is believed that the urethane bond moiety of the polymerizable compound (C-1) having a urethane bond absorbs or suppresses shrinkage during curing, thereby suppressing the occurrence of wrinkles.
It is believed that by combining specific organic pigments and their contents, the transmittance of each wavelength region can be controlled, resulting in excellent color separation.

[Organic pigment (A)]
The photosensitive coloring composition of the present invention contains a halogenated metal phthalocyanine pigment (A-1) and an isoindoline pigment (A-2) as the organic pigment (A), and the content of the organic pigment (A) is 25% by mass or more in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

From the viewpoint of color separation and wrinkle suppression, the content of the organic pigment (A) in the photosensitive coloring composition of the present invention is more preferably 25 to 40% by mass, and particularly preferably 25 to 35% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

(Halogenated Metal Phthalocyanine Pigment (A-1))
The halogenated metal phthalocyanine pigment (A-1) is not particularly limited, and known pigments can be used. Specific examples include C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, and 63, and pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, Japanese Patent No. 4893859, JP-A-2016-57635, JP-A-2016-153481, and JP-A-2017-197685. Among these, from the viewpoint of color separability from the blue region (a region having high transmittance in the wavelength range of 400 to 500 nm), halogenated metal phthalocyanine pigments in which the central metal is zinc or aluminum are preferred, and halogenated metal phthalocyanine pigments in which the central metal is zinc are more preferred. Examples of halogenated metal phthalocyanine pigments in which the central metal is zinc include C.I. Pigment Green 58 and 59.

Halogenated metal phthalocyanine pigments (A-1) can be used alone or in combination of two or more types.

(Isoindoline pigment (A-2))
The isoindoline pigment (A-2) is not particularly limited, and known pigments can be used. Specific examples include C.I. Pigment Yellow 139 and 185, and from the viewpoint of color separation in the blue region, C.I. Pigment Yellow 139 is more preferred.

Isoindoline pigments (A-2) can be used alone or in combination of two or more types.

In terms of color separation between the blue region and the red region (a region having high transmittance on the wavelength side longer than 580 nm), the photosensitive coloring composition of the present invention preferably has a mass ratio of the halogenated metal phthalocyanine pigment (A-1) to the isoindoline pigment (A-2) of 97:3 to 40:60, more preferably 95:5 to 50:50.

(Other organic pigments (A-3))
The photosensitive coloring composition of the present invention may contain an organic pigment (A-3) other than the halogenated metal phthalocyanine pigment (A-1) and the isoindoline pigment (A-2).

Other organic pigments (A-3) 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, 18 4,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260, 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 red organic pigments such as pigments described in Japanese Patent No. 6368844,
Orange organic pigments such as C.I. Pigment Orange 36, 38, 43, 62, 64, 71, and 73;
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, 12 Yellow organic pigments such as those described in JP-A-2012-226110 and JP-A-2012-226110,
green organic pigments such as C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, and 55;
C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:
blue organic pigments such as 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;
Examples of purple organic 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.

From the viewpoint of color separation properties, the photosensitive coloring composition of the present invention preferably has a total content of the halogenated metal phthalocyanine pigment (A-1) and the isoindoline pigment (A-2) of 95% by mass or more, and more preferably 99% by mass or more, based on 100% by mass of the organic pigment (A).

[Inorganic pigments]
The photosensitive coloring composition of the present invention can contain an inorganic pigment.

The inorganic pigment is not particularly limited, and known inorganic pigments can be used. Examples include zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron (III) oxide red), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, and umber. Examples of black inorganic pigments include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of Group 4 metal elements such as titanium and zirconium, Group 5 metal elements such as vanadium and niobium, cobalt, chromium, copper, manganese, ruthenium, iron, nickel, tin, and silver, as well as carbon black.

[dye]
The photosensitive coloring composition of the present invention can contain a dye.

There are no particular limitations on the dye, and any known dye can be used. Examples include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Derivatives of these dyes and laked dyes are also acceptable.

Furthermore, in the case of an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, it is preferable to use the acid dye as a salt-forming compound obtained by salt formation using an inorganic salt of the acid dye, a salt-forming compound of the acid dye with a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound, or a resin component having these functional groups, or to use the acid dye as a sulfonamide compound, which results in a coloring composition having excellent fastness, since the coloring composition has excellent resistance.
Furthermore, a salt-forming compound of an acid dye with a compound having an onium salt group is also preferred because it has excellent fastness, and more preferably, the compound having an onium salt group is a resin having a cationic group in the side chain.

When in the form of a basic dye, it can be used after being salted with an organic acid, perchloric acid, or a metal salt thereof. Among these, salt-forming compounds of basic dyes are preferred due to their excellent resistance and compatibility with pigments. Even more preferred is a salt-forming compound obtained by salting a basic dye with a counter component that acts as a counter ion, such as an organic sulfonic acid, organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye.

Furthermore, when the dye skeleton has a polymerizable unsaturated group, the dye can have excellent durability.
preferable.

The chemical structure of dyes includes, 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, polymer dyes, etc. Examples of dye structures derived from dyes selected from tin dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), 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.

(Fine Pigment)
The pigment is preferably micronized before use. The micronization method is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle size of the micronized 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 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. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling pigment, it is possible to obtain pigments with extremely fine primary particle diameters and a narrow, sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the standpoint of cost. From the standpoints of both processing efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of pigment (A).

The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, because the temperature rises during salt milling and the solvent becomes more likely to evaporate, high-boiling solvents with a boiling point of 120°C or higher are preferred for safety reasons. Examples of water-soluble organic solvents that can be used include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, and more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

A resin may be added to the salt milling treatment as needed. 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, resins that are solid at room temperature, insoluble in water, and partially soluble in the organic solvents are preferred. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

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

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

Specific examples of diketopyrrolopyrrole dye derivatives include those disclosed in JP 2001-220520 A, WO 2009/081930 A, WO 2011/052617 A, WO 2012/102399 A, and WO 2017-156397 A; examples of phthalocyanine dye derivatives include those disclosed in JP 2007-226161 A, WO 2016/163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A; and examples of anthraquinone dye derivatives include those disclosed in JP 63-264 A. 674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009/025325, as quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, as dioxazine dye derivatives, JP-A-2011-162662, as thiazine indigo dye derivatives, JP-A-2007-314785, as triazine Examples of benzoisoindole dye derivatives include those disclosed in 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; examples of benzoisoindole dye derivatives include those disclosed in JP-A-2009-57478; examples of quinophthalone dye derivatives include those disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-226 Examples of known dye derivatives include those described in JP-A-110, JP-A-2012-208329 and JP-A-2014-5439 as naphthol dye derivatives, JP-A-2001-172520 and JP-A-2012-172092 as azo dye derivatives, JP-A-2004-307854 as acidic substituents, and JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc. Although these documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, the compounds having substituents such as acidic groups, basic groups, and neutral groups in the organic dye residues are synonymous with dye derivatives.

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

The content of the dye derivative (F) is preferably from 1 to 20 parts by mass, more preferably from 2 to 10 parts by mass, per 100 parts by mass of the organic pigment (A).

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

The dispersing resin (G) has an adsorption group that has a high affinity for the pigment. The adsorption group is preferably one or more of a cationic group and an anionic group.

Examples of resins having cationic groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium salt groups, and groups containing nitrogen atoms such as nitrogen-containing heterocycles.

Examples of resins having anionic groups include carboxyl groups, phosphate groups, and sulfonic acid groups. Among these, carboxyl groups and phosphate groups are preferred from the standpoint of adsorption to pigments.

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

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

Commercially available dispersion resins (G) 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, 2095, 2150, 2155, 2163, and 2164 manufactured by BYK Japan Co., Ltd. U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 2800 manufactured by Lubrizol Japan Co., Ltd. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4090, 41000, 41100, 41200, 41300, 41400, 41500, 41600, 41700, 41800, 41900, 42000, 42100, 42200, 42300, 42400, 42500, 42600, 42750, 42800, 42900, 43000, 43100, 43200, 43300, 43400, 43500, 43600, 43700, 43800, 44000, 44100, 44200, 44300, 44400, 44500, 44600, 44700, 44800, 44800, 44900, 45000, 452 ... 400, 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., Ajisuper PA111, PB711 manufactured by Ajinomoto Fine-Techno Co., Ltd.
Examples include resins such as PB821, PB822, and PB824 described in JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416.

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

From the viewpoint of dispersion stability, the content of the dispersing resin (G) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the organic pigment (A).

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

The alkali-soluble resin (B) may be any resin that dissolves in an alkaline developer, and known resins can be used. The alkali-soluble resin (B) can be classified into non-photosensitive alkali-soluble resins and photosensitive alkali-soluble resins. The alkali-soluble resin (B) has an alkali-soluble group such as a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, or a phenolic hydroxyl group. Among these, a carboxyl group is preferred.
Examples of the non-photosensitive alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/maleic acid (anhydride) copolymer. The photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. The alkali-soluble resin (B) may contain a thermosetting group such as an epoxy group or an oxetanyl group.

From the viewpoint of developability, the weight-average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 300,000, and particularly preferably 4,000 to 20,000. Furthermore, the Mw/Mn value is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves adhesion to the substrate and solubility in development.

The acid value of the alkali-soluble resin (B) is preferably 50 to 200 mgKOH/g, more preferably 70 to 180 mgKOH/g, and even more preferably 90 to 170 mgKOH/g. A moderate acid value improves adhesion to the substrate and solubility in development.

The content of alkali-soluble resin (B) is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of organic pigment (A).

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

From the viewpoint of pattern formability, the alkali-soluble resin (B) preferably contains a photosensitive alkali-soluble resin.

(Alkali-soluble resin (B-1))
The photosensitive coloring composition of the present invention preferably contains, as the alkali-soluble resin (B), an alkali-soluble resin (B-1) containing an alicyclic hydrocarbon structure-containing monomer unit (b1) and a carboxyl group-containing monomer unit (b2) from the viewpoint of pattern formability.

[Alicyclic hydrocarbon structure-containing monomer unit (b1)]
Examples of the alicyclic hydrocarbon structure-containing monomer that forms the alicyclic hydrocarbon structure-containing monomer unit (b1) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, from the viewpoint of pattern formability, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[Carboxyl group-containing monomer unit (b2)]
Examples of the carboxyl group-containing monomer that forms the carboxyl group-containing monomer unit (b2) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Furthermore, a monomer that contains a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, can also be used in combination. Among these, acrylic acid and methacrylic acid are preferred.

[Other monomer units (b3)]
The alkali-soluble resin (B-1) may contain other monomer units (b3) in addition to the alicyclic hydrocarbon structure-containing monomer (b1) and the carboxyl group-containing monomer units (b2).

Examples of other monomers forming the other monomer units (b3) include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate;
hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate;
Polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to a hydroxyalkyl(meth)acrylate, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone), and/or poly(12-hydroxystearic acid);
epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate;
(meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine;
styrene or styrenes such as α-methylstyrene;
vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate;
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-(
N-substituted maleimides such as N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, 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 thereof include phosphate group-containing (meth)acrylates such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

The alkali-soluble resin (B-1) may contain an alicyclic hydrocarbon structure-containing monomer unit (b1) and a carboxyl group-containing monomer unit (b2), and its synthesis method is not particularly limited; known methods can be used. For example, it can be synthesized by the following method (i) or method (ii).

<Method (i)>
In the method (i), for example, the alkali-soluble resin (B-1) can be synthesized by synthesizing a copolymer of an alicyclic hydrocarbon structure-containing monomer and a carboxyl group-containing monomer.

<Method (ii)>
In the method (ii), for example, a copolymer of an alicyclic hydrocarbon structure-containing monomer and an epoxy group-containing monomer is synthesized, and then a carboxyl group-containing monomer is added to the epoxy group of the copolymer, and the resulting hydroxyl group is esterified with a fatty acid anhydride to synthesize the alkali-soluble resin (B-1).

Epoxy group-containing monomers include those listed as other monomers that form other monomer units (b3), and examples include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Of these, glycidyl (meth)acrylate is preferred from the standpoint of reactivity.

Examples of fatty acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, and these can be used alone or in combination of two or more.

From the viewpoint of pattern formability, the content of the alicyclic hydrocarbon structure-containing monomer unit (b1) is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass, based on 100% by mass of all structural units of the alkali-soluble resin (B-1).

From the viewpoint of pattern formability, the content of alkali-soluble resin (B-1) is preferably 50% by mass or more, and more preferably 70% by mass or more, based on 100% by mass of alkali-soluble resin (B).

(Alkali-soluble resin (B-2))
The photosensitive coloring composition of the present invention may contain, as the alkali-soluble resin (B), an alkali-soluble resin (B-2) other than the alkali-soluble resin (B-1).

[Polymerizable compound (C)]
(Polymerizable compound (C-1) having a urethane bond)
The photosensitive coloring composition of the present invention contains a polymerizable compound (C-1) having a urethane bond as the polymerizable compound (C). The urethane bond portion of the polymerizable compound (C-1) having a urethane bond alleviates and suppresses cure shrinkage due to the difference in the degree of cure between the surface and the interior of the film during cure, and can more effectively prevent wrinkles from occurring on the surface.
The polymerizable compound (C) is a monomer, dimer, trimer, or oligomer containing a polymerizable unsaturated group, such as a vinyl group, a (meth)allyl group, a (meth)acryloyl group, or a (meth)acryloyloxy group.

The polymerizable compound (C-1) having a urethane bond is not particularly limited, and known compounds can be used. Examples include urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting it with a (meth)acrylate having a hydroxyl group.

The (meth)acrylate having a hydroxyl group is, for example, 2-hydroxyethyl (meth)acrylate.
acrylate, 4-hydroxybutyl(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

Examples of the polyfunctional isocyanate include aromatic diisocyanates such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene;
Aliphatic diisocyanates such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate;
Examples of alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane. Also included are biuret, isocyanate nurate, and trimethylolpropane adducts of these.

From the viewpoint of developability, the polymerizable compound (C-1) having a urethane bond preferably has an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Of these, a carboxyl group is preferred. The polymerizable compound (C-1) having an acid group and a urethane bond is preferably a compound represented by the following general formula (1):

General formula (1) (H ₂ C=C(R ¹ )COO) _m -X-(OCOCH(R ¹ )CH ₂ S(R ² )COOH) _n
In general formula (1), ^R1 represents a hydrogen atom or a methyl group, ^R2 represents a hydrocarbon group having 1 to 12 carbon atoms, X represents an (m+n)-valent organic group having a urethane bond having 3 to 60 carbon atoms, m represents an integer of 2 to 18, and n represents an integer of 1 to 3.

The compound represented by general formula (1) can be synthesized, for example, by first reacting the polyfunctional isocyanate compound with the (meth)acrylate having a hydroxyl group. Then, a mercapto compound having a carboxyl group is added to the product.

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

The number of polymerizable unsaturated groups in the polymerizable compound (C-1) having a urethane bond is preferably 3 to 15, and more preferably 5 to 12, from the viewpoints of pattern formability and wrinkle suppression.

From the perspective of preventing wrinkles, the polymerizable compound (C-1) having a urethane bond preferably contains an alicyclic or aromatic urethane (meth)acrylate, which is a reaction product of a (meth)acrylate having a hydroxyl group and an alicyclic diisocyanate or aromatic diisocyanate, and more preferably contains an aromatic urethane (meth)acrylate. Using an alicyclic or aromatic diisocyanate with a rigid structure makes it less likely for shrinkage to occur during curing, thereby preventing wrinkles.

Commercially available polymerizable compounds (C-1) having a urethane bond include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., U-15HA, UA-160TM, and 1100H manufactured by Shin-Nakamura Chemical Co., Ltd., UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and EBECRY220, 1290, 4513, and 5129 manufactured by Daicel-Allnex Corporation.

(Other polymerizable compounds (C-2))
From the viewpoint of pattern formability, the photosensitive coloring composition of the present invention preferably contains another polymerizable compound (C-2) in addition to the polymerizable compound (C-1) having a urethane bond.

Other polymerizable compounds (C-2) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. acrylate, tricyclodecane dimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO Examples of the acrylic acid ester include modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, and various acrylic acid esters and methacrylic acid esters such as epoxy (meth)acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile. Among these, those with 5 or more polymerizable unsaturated groups are preferred from the perspective of pattern formation.

Other commercially available polymerizable compounds (C-2) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, and M-31 manufactured by Toagosei Co., Ltd. Examples include M-3, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, M-5300, M-5400, M-5700, M-510, M-520, and M-521, Viscoat #2500P manufactured by Osaka Organic Chemicals, NK Ester ABE-300, A-DOG, A-DCP, and A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRY 40, 130, 140, and 145 manufactured by Daicel Allnex Corporation.

From the viewpoint of pattern formability and suppression of surface wrinkles, the mass ratio of the polymerizable compound (C-1) having a urethane bond to the other polymerizable compound (C-2) is preferably 80:20 to 20:80, and more preferably 70:30 to 30:70.

The content of the polymerizable compound (C) is preferably 5 to 50% by mass, and more preferably 5 to 30% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[Photopolymerization initiator (D)]
The photosensitive coloring composition of the present invention contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D), the photosensitive coloring composition can be cured by ultraviolet irradiation 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;
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,
triazine-based compounds such as 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, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;
Oxime ester 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 compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

Commercially available acetophenone compounds include "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), both manufactured by IGM Resins. Acylphosphine compounds include "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) and "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), and oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE-02), IRGACURE OXE-03, and IRGACURE OXE-04 manufactured by BASF, N-1919, NCI-730, NCI-831, and NCI-930 manufactured by ADEKA, and TRONLY TR-PBG-304 and TRONLY OXE-305 manufactured by Changzhou Strong New Materials Co., Ltd. Examples of suitable compounds include TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-345, and TRONLY TR-PBG-3054. Other examples include the oxime compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, and International Publication WO 2015/036910. Among these, oxime compounds are preferred from the standpoint of pattern formability, and the compound represented by the following chemical formula (2) is more preferred.

Chemical formula (2)

The method for producing the compound of chemical formula (2) is not particularly limited, and known methods can be used. For example, the method described in International Publication WO2015/036910 can be used.

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

From the viewpoints of photocurability and developability, the content of photopolymerization initiator (D) is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of organic pigment (A).

[Silica particles (E)]
The photosensitive coloring composition of the present invention contains silica particles (E).

The silica particles (E) are not particularly limited, and known silica particles can be used.

Silica particles (E) can be, for example, dry silica or wet silica such as colloidal silica, with colloidal silica being preferred as it is easy to control the particle size and shape.

The shape of the silica particles (E) is preferably spherical from the viewpoint of surface smoothness of the cured film.

From the viewpoint of wrinkle suppression, the average primary particle diameter of the silica particles (E) is preferably 1 to 100 nm, more preferably 5 to 50 nm, and particularly preferably 10 to 30 nm.

Commercially available silica particles (E) include, for example, PL-1-IPA, PL-1-TOL, PL-2L-PGME, and PL-2L-MEK manufactured by Fuso Chemical Co., Ltd., YA010C-LDI and YA050C-LHI manufactured by Admatechs Co., Ltd., and MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, MEK-ST-40, MEK-ST-UP, MIBK-ST, MIBK-ST-L, and CHO- manufactured by Nissan Chemical Industries, Ltd. ST-M, EAC-ST, PMA-ST, TOL-ST, DMAC-ST, MEK-AC-2140Y, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Z, PEM-AC-4130Y, MIBK-AC -4130Y, MIBK-AC-2140Y, MIBK-SD-L, MEK-EC-2130Y, MEK-EC-6150P, MEK-EC-7150P, EP-F2130Y, EP-F6140P, EP-F7150P, etc.

From the viewpoint of pattern formability and wrinkle suppression, the content of the silica particles (E) is preferably 5% by mass or more and 30% by mass or less, and more preferably more than 10% by mass and less than 25% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[Near-infrared absorber (H)]
When the photosensitive coloring composition of the present invention is used in a solid-state imaging device, it preferably contains a near-infrared absorber (H). This makes it possible to control the transmission of near-infrared light of a specific wavelength and improves the separation from the near-infrared region.
The near-infrared absorber (H) is a compound that absorbs light with a wavelength of 750 to 1,200 nm.

Examples of near-infrared absorbers (H) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, immonium compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds. Among these, cyanine compounds, pyrrolopyrrole compounds, and squarylium compounds are preferred.

Among the near-infrared absorbers (H), cyanine compounds are described in International Publication Nos. WO2006/006573, WO2010/073857, JP2013-241598A, JP2016-113501A, and JP2016-113504A; phthalocyanine compounds are described in JP4-23868A, JP06-192584A, JP2000-63691A, and WO2014/208514; naphthalocyanine compounds are described in JP11-152414A, JP2000-86919A, JP2009-29955A, and WO2018/186490; and immonium compounds are described in , JP 2005-336150 A, JP 2007-197492 A, JP 2008-88426 A; pyrrolopyrrole compounds are disclosed in JP 2009-263614 A, JP 2010-90313 A, JP 2011-068731 A; squarylium compounds are disclosed in JP 2011-132361 A , JP 2016-142891 A, WO 2017/135359 A, WO 2018/225837 A, JP 2019-001987 A, WO 2020/054718 A; examples of croconium compounds include those described in WO 2019/021767 A, etc.

Near-infrared absorbers (H) can be used alone or in combination of two or more types.

The content of the near-infrared absorber (H) is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, and particularly preferably 20 to 100 parts by mass, per 100 parts by mass of the organic pigment (A).

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

Examples of the sensitizer (I) include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of the compound include aryl ether derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

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

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

The content of sensitizer (I) is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of photopolymerization initiator (D). When an appropriate amount is included, photocurability and developability are improved.

[Thermosetting compound (J)]
The photosensitive coloring composition of the present invention can contain a thermosetting compound (J). This allows the thermosetting compound (J) to react in the heating step, increasing the crosslink density and improving the heat resistance.

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

(Epoxy compound (J-1))
Examples of the epoxy compound (J-1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, 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, methyl ... Examples of suitable epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine 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. Examples include VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, and 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004 and 1256, JER1032H60, 157S65, 157S70, 152, and 154 manufactured by Japan Epoxy Resins Co., Ltd., Celoxide 2021 and 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, and 721 manufactured by Nagase ChemteX Corporation, and TEPIC-L, H, and S manufactured by Nissan Chemical Industries, Ltd.

From the viewpoint of the heat resistance of the cured film, the content of epoxy compound (J-1) is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass, per 100 parts by mass of organic pigment (A).

(Oxetane Compound (J-2))
The oxetane compound (J-2) is a known compound having an oxetane group, and examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

Examples of the monofunctional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl-3-
Examples thereof include 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-hydroxymethyloxetane, 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- 1,4-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, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

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

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.

The content of the oxetane compound (J-2) is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

Melamine compounds are compounds that have a melamine ring structure. Methylol-type or ether-type melamine compounds are preferred, and melamine compounds with an average of 5.0 or more methylol groups and/or ether groups per melamine ring are more preferred. Having an appropriate number of methylol groups or ether groups makes it easier to achieve just the right amount of heat resistance.

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

Among these, products with an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more, such as Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, and MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, and 350 manufactured by Nippon Cytec Industries Co., Ltd., are preferred in terms of increasing crosslink density.

Thermosetting compounds (J) can be used alone or in combination of two or more types.

[Curing agent (curing accelerator)]
The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermosetting compound (J). 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.).

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

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

[Thiol-based chain transfer agent (K)]
The photosensitive coloring composition of the present invention can contain a thiol-based chain transfer agent (K). When the thiol-based chain transfer agent (K) is used in combination with the photopolymerization initiator (D), during radical polymerization after irradiation with light, a thiyl radical that is not easily inhibited by oxygen is generated, and the photosensitivity of the photosensitive coloring composition is improved.

The thiol chain transfer agent (K) is preferably a multifunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent have four or more SH groups. Increasing the number of functional groups makes it easier for the film to be photocured 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 include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

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

The content of the thiol chain transfer agent (K) is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass, per 100 parts by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is included, photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

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

The polymerization inhibitor (L) may be, for example, an alkyl catechol compound 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, or 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, or 2-n- Examples of suitable compounds include alkyl resorcinol compounds such as butyl resorcinol, 4-n-butyl resorcinol, 2-t-butyl resorcinol, and 4-t-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, t-butyl hydroquinone, and 2,5-di-t-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucin.

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

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

The ultraviolet absorber (M) is an organic compound that has ultraviolet absorbing properties, and examples thereof 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, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl ester mixture, 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 Examples of suitable hydroxybenzoates 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, 32 manufactured by BASF Japan Ltd.
No. 6,329,384-2,900,928,99-2,1130, Adekastab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA Corporation, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)glycidic acid ester. Examples 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 Co., Ltd., and TINUVIN 400, 405, 460, 477, 479, 1577ED, and AD manufactured by BASF Japan Ltd.
ADK STAB LA-46, LA-F70 manufactured by EKA Corporation, CYASORB manufactured by Sun Chemical Company
UV-1164 and the like.

Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-hydrate, 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, and 12 manufactured by Chemipro Chemicals.
, 111, SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., Adekastab 1413 manufactured by ADEKA Corporation, and UV-12 manufactured by Sun Chemical Co., Ltd.

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

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

[Antioxidant (N)]
The photosensitive coloring composition of the present invention can contain an antioxidant (N). The antioxidant (N) prevents the photopolymerization initiator (D) and thermosetting compound (J) contained in the photosensitive coloring composition from yellowing due to oxidation during the thermal process of thermal curing or ITO annealing. In particular, when the concentration of the organic pigment (A) in the photosensitive coloring composition is high, the content of the polymerizable compound (C) is relatively reduced, and if the amount of the photopolymerization initiator (D) is increased or a thermosetting compound is added to address this, the cured film is likely to yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

Examples of the antioxidant (N) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Note that, in this specification, antioxidants preferably do not contain halogen atoms.

Of 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), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl) 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, Adekastab 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 Company.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2 , 6,6-tetramethyl-4-piperidyl methacrylate, 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-tetramethyl- 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-pyridyl sebacate 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 Co., Ltd.

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 diphenol 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, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA Corporation, IRGAFOS 168 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], 3,3'-thiobisditridecylpropionate, 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 Kasei Co., Ltd.

Antioxidants (N) can be used alone or in combination of two or more types.

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

[Leveling agent (O)]
The photosensitive coloring composition of the present invention can contain a leveling agent (O). This further improves the wettability to the substrate during coating and the drying property. Examples of the leveling agent (O) 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 terminals.

Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie, and FZ-7002 and 211 manufactured by Dow Corning Toray. Examples include 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, and KP-341.

Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

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.

Nonionic surfactants include, for example, 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 nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. acrylate, 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 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, LATEMURU PD-420, PD-430, PD-430S, PD-450, Rheodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, C Examples include H-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Corporation's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical Co., Ltd.'s (meth)acrylic acid (co)polymer Polyflow No. 75, No. 90, No. 95.

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

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 alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters.

Commercially available products include, for example, Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol 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 dimethylaminoacetic acid 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.

Leveling agents (O) can be used alone or in combination of two or more types.

The content of the leveling agent (O) 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 non-volatile content of the photosensitive coloring composition. Being within this range further improves the balance between the coatability and adhesion of the photosensitive coloring composition.

[Storage stabilizer (P)]
The photosensitive coloring composition of the present invention can contain a storage stabilizer (P). This stabilizes the viscosity of the photosensitive coloring composition over time. Examples of the storage stabilizer (P) include quaternary ammonium chlorides such as benzyl trimethyl 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 (P) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the organic pigment (A).

[Adhesion improver (Q)]
The photosensitive coloring composition of the present invention may contain an adhesion improver (Q). This improves the adhesion between the cured film and the substrate. It also makes it easier to form narrow patterns by photolithography.

Examples of the adhesion improver (Q) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) silane coupling agents such as aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

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

The content of the adhesion improver (Q) is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the organic pigment (A).

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

Examples of organic solvents (R) 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, and n-butyl Alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether 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 Examples of the propylene glycol monomethyl ether include 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 viewpoints of pigment dispersibility and alkali-soluble resin solubility, 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 benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

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

[Method for producing photosensitive coloring composition]
The photosensitive coloring composition of the present invention can be produced by, for example, adding an organic pigment (A), a dispersing resin (G), an organic solvent (R), etc., and performing a dispersion treatment to produce a dispersion. The dispersion can then be mixed with an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and silica particles (E). The timing of blending each material is optional. The dispersion process can also be performed multiple times.

Dispersing machines used for the dispersion process include, for example, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, and attritors.

The average dispersed particle size (secondary particle size) of the organic pigment (A) in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easier to obtain a photosensitive coloring 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) with particle permeability set to absorption mode, particle shape set to non-spherical, and the D50 particle size taken as the average diameter. The organic solvent used for dispersion should be 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 yield results with little variation.

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

<Cured film>
The cured film of the present invention can be obtained by curing a film formed using the photosensitive coloring composition of the present invention. The cured film also includes a patterned cured film.

[Method of producing cured film]
The method for producing the cured film is not particularly limited, and for example, the cured film can be produced by carrying out the following steps: a step (1) of applying a photosensitive coloring composition onto a substrate to form a layer of the composition; a step (2) of exposing the layer to light in a pattern through a mask; a step (3) of developing the unexposed parts with an alkali to form a patterned cured film; and a step (4) of heat-treating (post-baking) the pattern.

The method for producing the cured film will be described in detail below.
(Step (1))
In the step (1) of forming a composition layer, the photosensitive coloring composition is applied onto a substrate by, for example, spin coating, roll coating, slit coating, casting coating, inkjet coating, or the like, and then dried (pre-baked) at a temperature of 50 to 120°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 and a silicon substrate. The silicon substrate may have an imaging element such as a CCD or a CMOS formed on its surface. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with an upper layer, prevent diffusion of substances, and flatten the substrate surface.
From the viewpoint of color separation, the layer is preferably coated so that the thickness after drying is 4.0 μm or more, more preferably 6.0 μm or more.

(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-rays, h-rays, and i-rays.

(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 eluted in an alkaline aqueous solution, leaving only the cured areas, thereby obtaining 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 developer is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11 to 13, more preferably 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 the developing method include a dipping method, a spraying method, a paddle method, etc. The developing temperature is preferably 15 to 40° C. After alkaline development, it is preferable to wash with pure water.

(Step (4))
The heat treatment (post-baking) is performed by heating the patterned cured film obtained in step (3) to sufficiently cure it. The heating temperature for post-baking is preferably 100 to 300° C., more preferably 150 to 250° C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

From the viewpoint of color separation, the cured film obtained by curing the photosensitive coloring composition of the present invention preferably has a thickness of 4.0 μm or more, more preferably 6.0 μm or more. There is no particular upper limit, but 10.0 μm or less is preferred.

The method for measuring the film thickness of the cured film is as follows:

(Film Thickness Measurement)
The photosensitive coloring composition of the present invention was applied to a glass substrate by spin coating so that the film thickness after drying would be 6.0 μm, and after drying on a hot plate at 70° C. for 1 minute, the entire surface was exposed to 250 mJ/cm ² using an ultra-high pressure mercury lamp. Thereafter, the substrate was subjected to a 0.2 mass%
After spray development using an aqueous sodium carbonate solution, the resist was washed with ion-exchanged water, air-dried, and heated (post-baked) in a clean oven at 230° C. for 30 minutes to obtain a cured film.
The obtained cured film was measured at five randomly selected points using a Dektak 3030 (manufactured by Nippon Shinku Gijutsu Co., Ltd.), and the average value was taken as the film thickness.
The thickness of 6.0 μm includes the range of tolerance acceptable in the technical field to which the present invention pertains, specifically, a thickness of 6.0 μm±0.2 μm.

<Optical filter>
The cured film of the present invention can be used for an optical filter. The cured film prepared using the photosensitive coloring composition of the present invention has no wrinkles on the film surface and has excellent color separation. The optical filter of the present invention can be produced by the same method as the above-mentioned cured film.

The optical filter of the present invention can be used, for example, in cameras, image display devices such as liquid crystal and organic electroluminescence devices, solid-state imaging devices such as C-MOS image sensors and CCD image sensors, infrared sensors, and biometric authentication sensors.

The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass."

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 are as follows:

(Average molecular weight of alkali-soluble resin and dispersing resin)
The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the alkali-soluble resin and dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation). Two separation columns were connected in series, and both columns were packed with "TSK-GEL SUPER HZM-N" packings. The oven temperature was 40°C, and the eluent was a tetrahydrofuran (THF) solution. The measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and 20 microliters was injected. The molecular weight is a polystyrene equivalent value.

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

(Amine value of dispersing resin)
The amine value of the dispersing resin is the total amine value (mgKOH/g) measured in accordance with the method of ASTM D 2074 and converted into solid content.

<Production of organic pigment (A)>
(Finely divided halogenated metal phthalocyanine pigment (A-1-1))
100 parts of C.I. Pigment Green 58 (manufactured by DIC Corporation, "FASTGEN GREEN A110") whose central metal is zinc, 1,200 parts of ground sodium chloride,
and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3,000 parts of warm water and stirred for 1 hour while heating to 70° C. to form a slurry, which was then filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain a finely divided halogenated metal phthalocyanine pigment (A-1-1).

(Finely divided halogenated metal phthalocyanine pigment (A-1-2))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1,500 parts of concentrated sulfuric acid in an ice bath. Then, 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 20°C for 8 hours. Subsequently, this sulfuric acid solution was poured into 9,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water again, in that order, and then dried to obtain 159 parts of compound (a).
Next, 1,000 parts of 1-methyl-2-pyrrolidinone, 100 parts of compound (a), and 32 parts of diphenyl phosphate were added to a reaction vessel. After reacting at 85°C for 3 hours, the solution was poured into 8,000 parts of water. The reaction product was filtered, washed with 16,000 parts of water, and then dried overnight at 60°C under reduced pressure to obtain 112 parts of a product. Next, the obtained product was added to 600 parts of propylene glycol monomethyl ether acetate, and heated at 120°C for 2 hours. The product was filtered and dried overnight at 60°C under reduced pressure to obtain a halogenated metal phthalocyanine pigment (A-1-2) in which the central metal is aluminum.
Thereafter, 100 parts of the halogenated metal phthalocyanine pigment (A-1-2), 1,000 parts of pulverized 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 poured into 3,000 parts of warm water, and stirred for about 1 hour with a high-speed mixer while heating to about 70° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove the sodium chloride and solvent, and then dried at 80° C. for 24 hours to obtain a finely divided halogenated metal phthalocyanine pigment (A-1-2).

(Finely divided isoindoline pigment (A-2-1))
100 parts of C.I. Pigment Yellow 139 (Clariant "Novoperm Yellow P-M3R"), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 12 hours at 70 ° C. This mixture was added to 3,000 parts of hot water, and stirred for about 1 hour with a high-speed mixer while heating to about 70 ° C. to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the slurry was dried at 80 ° C. overnight to obtain a finely divided isoindoline pigment (A-2-1).

(Micronized isoindoline pigment (A-2-2))
100 parts of C.I. Pigment Yellow 185 ("Palitol Yellow D1155" manufactured by BASF Japan Ltd.), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80°C. Next, this kneaded mixture was poured into 8 liters of warm water and stirred for 2 hours while heating to 80°C to form a slurry. After repeatedly filtering and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried at 85°C for one day and night to obtain a finely divided isoindoline pigment (A-
2-2) was obtained.

(Finely divided organic pigment (A-3-1))
100 parts of C.I. Pigment Yellow 138 (BASF "Paliotol Yellow K0960-HD"), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80°C. This mixture was added to 2,000 parts of warm water and stirred for 1 hour while heating to 80°C to form a slurry, which was then filtered and washed repeatedly with water to remove the salt and solvent, and then dried overnight at 80°C to obtain a finely divided organic pigment (A-3-1).

(Finely divided organic pigment (A-3-2))
100 parts of C.I. Pigment Yellow 150 ("E4GN" manufactured by Lanxess AG), 700 parts of pulverized 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 added to 2,000 parts of warm water, and stirred for 1 hour while heating to 80 ° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove the salt and solvent, and then dried overnight at 80 ° C. to obtain a finely divided organic pigment (A-3-2).

<Production of alkali-soluble resin (B)>
(Alkali-soluble resin (B-1-1) solution)
Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 333 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was introduced, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and then a solution obtained by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol (100 mol% relative to the glycidyl groups of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask, and the reaction was continued for 6 hours at 110 ° C., and the reaction was terminated when the nonvolatile acid value reached 1 mg KOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120 ° C. to obtain a photosensitive transparent resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized photosensitive transparent resin solution so that the nonvolatile content was 40% by mass, thereby preparing a photosensitive alkali-soluble resin (B-1-1) solution. The mass average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (B-1-2) solution)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 182 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol), 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 136 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% relative to the carboxyl group of the methacrylic acid used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol and 0.145 parts of hydroquinone were added to the flask, and the reaction was continued for 6 hours at 110 ° C. to obtain a photosensitive transparent resin solution having an acid value of 79 mg KOH / g. After cooling to room temperature, approximately 2 parts of the photosensitive transparent resin solution was sampled and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized photosensitive transparent resin solution so that the nonvolatile content was 40% by weight, and a photosensitive alkali-soluble resin (B-1-2) solution was prepared. The weight average molecular weight (Mw) was 13,000.

(Alkali-soluble resin (B-2-1) solution)
A separable four-necked flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 196 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80 ° C. and purged with nitrogen. From the dropping tube, a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd., "Aronix M110"), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 40%, to prepare a non-photosensitive alkali-soluble resin (B-2-1) solution. The weight average molecular weight (Mw) was 26,000.

<Production of polymerizable compound (C-1) having a urethane bond>
(Polymerizable compound (C-1-1) having a urethane bond)
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 112 parts of hexamethylene diisocyanate and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 cm ^-1 was confirmed by IR. PGMAc was added so that the nonvolatile content was 50% by mass, and an aliphatic urethane acrylate solution having 6 polymerizable unsaturated groups was obtained.

(Polymerizable compound (C-1-2) having a urethane bond)
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 148 parts of isophorone diisocyanate and 100 parts of PGMAc was added dropwise over 2 hours from the dropping tube. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 ^cm was confirmed by IR. PGMAc was added so that the nonvolatile content was 50% by mass, yielding an alicyclic urethane acrylate solution having 6 polymerizable unsaturated groups.

(Polymerizable compound (C-1-3) having a urethane bond)
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 107 parts of 1,3-phenylene diisocyanate and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 cm ^-1 was confirmed by IR. PGMAc was added so that the nonvolatile content was 50% by mass, yielding an aromatic urethane acrylate solution having 6 polymerizable unsaturated groups.

(Polymerizable compound (C-1-4) having a urethane bond)
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 66 parts of toluene diisocyanate (a mixture of 2,4 and 2,6 isomers) and 100 parts of PGMAc was added dropwise over 2 hours from the dropping tube. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 cm ^-1 was confirmed by IR. PGMAc was added so that the nonvolatile content was 50% by mass, and an aromatic urethane acrylate solution having 10 polymerizable unsaturated groups was obtained.

(Polymerizable compound (C-1-5) having a urethane bond)
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 112 parts of hexamethylene diisocyanate and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 cm ^-1 was confirmed by IR. Next, 13 parts of mercaptopropionic acid and 0.4 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60°C for 6 hours. PGMAc was added so that the nonvolatile content was 50% by mass, and an aliphatic urethane acrylate solution having an average of 5 polymerizable unsaturated groups and an acid group was obtained as the compound represented by general formula (1).

(Polymerizable compound (C-1-6) having a urethane bond)
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 116 parts of toluene diisocyanate (a mixture of 2,4 and 2,6 isomers) and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 cm ^-1 was confirmed by IR. Next, 13 parts of mercaptopropionic acid and 0.4 parts of 4-methoxyphenol were charged and allowed to react for 6 hours at a temperature of 50 to 60°C. PGMAc was added so that the nonvolatile content was 50% by mass, and an aromatic urethane acrylate solution having an average number of polymerizable unsaturated groups containing acid groups and 5 was obtained as the compound represented by general formula (1).

(Polymerizable compound (C-1-7) having a urethane bond)
A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 61 parts of 1,3-phenylenediisocyanate and 61 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of the isocyanate absorption at 2180 cm ^-1 was confirmed by IR. Next, 20 parts of mercaptopropionic acid and 0.6 parts of 4-methoxyphenol were charged and allowed to react for 6 hours at a temperature of 50 to 60°C. PGMAc was added so that the nonvolatile content was 50% by mass, and an aromatic urethane acrylate solution having an average number of polymerizable unsaturated groups containing an acid group of 9 was obtained as the compound represented by general formula (1).

<Production of Dispersion Resin (G)>
(Dispersion resin (G-1) solution)
A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and 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 the atmosphere was replaced 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 and 90 parts of PGMAc was added, and the reaction was carried out for 7 hours. Measurement of the nonvolatile content confirmed that 95% had reacted. 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 after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the solution was diluted with PGMAc so that the nonvolatile content was 30% by measuring the nonvolatile content, thereby obtaining a dispersion resin (G-1) solution having an acid value of 70 mgKOH/g and a weight average molecular weight of 8,500.

(Dispersion resin (G-2) solution)
250 parts by weight of tetrahydrofuran (THF) and 5.81 parts by weight of dimethylketene methyltrimethylsilyl acetal (initiator) were added via the addition funnel to a 500 mL round-bottom, four-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the atmosphere was thoroughly purged with nitrogen. 0.5 parts by weight of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate (catalyst) was injected using a syringe, and 19.7 parts by weight of solvent-philic blocking monomers (2-hydroxyethyl methacrylate, 7.5 parts by weight of 2-ethylhexyl methacrylate, 12.9 parts by weight of n-butyl methacrylate, 10.7 parts by weight of benzyl methacrylate, and 30.9 parts by weight of methyl methacrylate) were added dropwise over 60 minutes using the addition funnel. The temperature of the reaction flask was maintained below 40°C by cooling in an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, a monomer for the colorant-adsorbing functional block, was added dropwise over 20 minutes. After 1 hour of reaction, 1 part by mass of methanol was added to terminate the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered, and purified by vacuum drying.
Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottom flask, and 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalents relative to dimethylaminopropyl methacrylamide), which is a salt-forming component, was added. The mixture was stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to adjust the content, thereby obtaining a dispersion resin (G-2) solution with a nonvolatile content of 30%.

<Production of near-infrared absorber (H)>
(Near-infrared absorber (H-1))
400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water produced during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling the toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water produced during the reaction was removed from the reaction system by azeotropic distillation.
After completion of the reaction, the solvent was distilled, and 200 parts of hexane was added while stirring the resulting reaction mixture. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a near-infrared absorber (H-1) represented by the following chemical formula (3). 50 parts of the obtained near-infrared absorber (H-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was poured into hot water and stirred for 1 hour while heating to about 80°C to form a slurry, which was then filtered and washed with water to remove the sodium chloride and diethylene glycol. The mixture was then dried overnight at 80°C and pulverized to obtain a finely divided near-infrared absorber (H-1).

Chemical formula (3)

<Preparation of Dispersion>
(Dispersion 1)
The following raw materials were mixed and stirred to a uniform consistency, then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (Q-1) was PGMAc.
Micronized halogenated phthalocyanine pigment (A-1-1): 20.0 parts Dispersion resin (G-1) solution: 9.3 parts Dispersion resin (G-2) solution: 9.2 parts Organic solvent (R-1): 61.5 parts

(Dispersions 2 to 7)
Dispersions 2 to 7 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 1 were changed.

<Production of Photosensitive Coloring Composition>
[Example 1]
(Photosensitive coloring 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 a photosensitive coloring composition 1.
Dispersion 1: 37.5 parts Dispersion 3: 3.25 parts Alkali-soluble resin (B-1-1) solution: 20.75 parts Alkali-soluble resin (B-1-2) solution: 3.0 parts Polymerizable compound (C-1-1): 8.0 parts Photopolymerization initiator (D-1): 0.4 parts Silica particles (E): 9.7 parts Polymerization inhibitor (L): 0.01 parts Antioxidant (N): 0.1 parts Leveling agent (O): 1.0 parts Storage stabilizer (P): 0.2 parts Organic solvent (R): 16.09 parts

[Examples 2 to 31, Comparative Examples 1 to 7]
(Photosensitive coloring compositions 2 to 38)
Photosensitive coloring compositions 2 to 38 were prepared in the same manner as in Example 1, except that the photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts described in Tables 2-1 to 2-3.

The ingredients listed in Tables 2-1 to 2-3 are as follows:

[Polymerizable compound (C)]
(Other polymerizable compounds (C-2))
C-2-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, non-volatile content 100%)
C-2-1: Aronix M-521 (manufactured by Toagosei Co., Ltd., number of polymerizable unsaturated groups: 5, non-volatile content: 100%)
C-2-3: Aronix M-309 (manufactured by Toagosei Co., Ltd., number of polymerizable unsaturated groups: 3, non-volatile content: 100%)

[Photopolymerization initiator (D)]
D-1: Compound represented by the above chemical formula (2) D-2: Irgacure 907 (manufactured by BASF)

[Silica particles (E)]
PMA-ST (Nissan Chemical Industries, Ltd., primary particle size 12 nm, non-volatile content 30%)

[Sensitizer (I)]
I-1: Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)
I-2: CHEMARK DEABP (manufactured by Chemark Chemical)
The above (I-1) and (I-2) were mixed in equal amounts to prepare sensitizer (I).

[Thiol-based chain transfer agent (K)]
Pentaerythritol tetrakis(3-mercaptopropionate)

[Polymerization inhibitor (L)]
L-1: 4-methylcatechol L-2: methylhydroquinone L-3: t-butylhydroquinone The above (L-1) to (L-3) were mixed in equal amounts to prepare a polymerization inhibitor (L).

[Antioxidant (N)]
N-1: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] N-2: dioctadecyl 3,3'-thiodipropanoate N-3: tris[2,4-di-(t)-butylphenyl]phosphine N-4: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate N-5: p-octylphenyl salicylate Equal amounts of the above (N-1) to (N-5) were mixed together to form antioxidant (N).

[Leveling agent (O)]
O-1: BYK-330 (manufactured by BYK-Chemie)
O-2: Megafac F-551 (DIC Corporation)
One part each of (O-1) and (O-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution, which was used as a leveling agent (O).

[Storage stabilizer (P)]
P-1: 2,6-bis(1,1-dimethylethyl)-4-methylphenol P-2: Triphenylphosphine Equal amounts of (P-1) and (P-2) were mixed together to prepare a storage stabilizer (P).

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

<Evaluation of Photosensitive Coloring Composition>
The resulting photosensitive coloring compositions 1 to 38 were evaluated for developability, pattern formability, surface wrinkles, and color separation by the following methods. The evaluation results are shown in Table 3.

[Evaluation of developability]
The obtained photosensitive coloring compositions 1 to 38 were applied to a 100 mm x 100 mm x 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 6.0 μm, and then 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 250 mJ/cm ² through a photomask with a 100 μm wide stripe pattern. After cooling to room temperature, the substrate was spray-developed using a 0.2% by mass aqueous sodium carbonate solution at two development times (50 seconds and 100 seconds), washed with ion-exchanged water, and air-dried. The obtained substrate was post-baked in a clean oven at 230°C for 30 minutes to form a striped pattern on the substrate. The pattern was observed using an optical microscope to evaluate the presence or absence of development residue and chipping in unexposed areas. The results are shown below, with a value of 2 or higher being practical.
3: After a development time of 100 seconds, there was no development residue in the unexposed areas and no pattern defects.
2: After a development time of 100 seconds, development residues or pattern defects were observed in the unexposed areas.
1: After a development time of 50 seconds, development residues or pattern defects were observed in the unexposed areas.

[Evaluation of Pattern Formability (1): Adhesion]
The obtained photosensitive coloring compositions 1 to 38 were applied by spin coating to a 100 mm long x 100 mm wide, 0.7 mm thick glass substrate (Corning Eagle 2000) so that the film thickness after drying was 6.0 μm, and then dried on a hot plate at 70 ° C. for 1 minute. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp was used, and the substrate was exposed at an illuminance of 30 mW / cm ² and 250 mJ / cm ² through a photomask with a 100 μm wide (pitch 200 μm) and 10 μm wide (pitch 20 μm) stripe pattern. Thereafter, the substrate was spray-developed using a 0.2 mass% aqueous sodium carbonate solution, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 30 minutes to obtain a substrate for adhesion evaluation. Spray development was performed for each photosensitive coloring composition coating for the shortest time possible to form a pattern without residual development, and this was determined to be the appropriate development time.
Of the patterns on the substrate for evaluating adhesion, fine line patterns with widths of 6 to 25 μm were observed under an optical microscope to confirm the minimum line width of the remaining fine line patterns.
5: Fine lines of 10 μm or less remain.
4: Fine lines of 15 μm or less remain.
3: Fine lines of 20 μm or less remain.
2: Fine lines of 25 μm or less remain.
1: No fine lines remain.

[Pattern Formation Evaluation (2): Linearity]
The substrate prepared in the pattern formability evaluation (1) was evaluated by measuring the maximum and minimum line widths of 10 stripe patterns using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with a score of 3 or higher being practical.
5: The difference between the maximum and minimum line widths is less than 0.5 μm. 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm. 3: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm. 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm. 1: The difference between the maximum and minimum line widths is 2.0 μm or more.

[Surface wrinkle evaluation]
The pattern surface of the substrate prepared for the adhesion evaluation was observed using an optical microscope (Olympus Optical Co., Ltd. "BX-51", magnification: 200 times). The evaluation criteria are as follows, with 3 or more being practical.
5: No wrinkles are observed on the surface of the pattern. 4: Very slight wrinkles are observed on the surface of the pattern. 3: Slight wrinkles are observed on the surface of the pattern. 2: Wrinkles are observed on the surface of the pattern. 1: Severe wrinkles are observed on the surface of the pattern.

[Color Separability Evaluation]
The obtained photosensitive coloring compositions 1 to 38 were applied by spin coating to a glass substrate (Eagle 2000 manufactured by Corning Incorporated) measuring 100 mm in length x 100 mm in width and 0.7 mm in thickness, so that the film thickness after drying was 6.0 μm, and then dried on a hot plate at 70 °C for 1 minute. Next, the entire surface was exposed to light at an exposure dose of 50 mJ/ ^cm2 using an ultra-high pressure mercury lamp, and then post-baked in a clean oven at 230 °C for 30 minutes to obtain a substrate for evaluating color separation. The obtained substrate for evaluating color separation was measured for maximum transmittance at wavelengths of 450 to 510 nm and 580 to 700 nm in the thickness direction of the coating using an OSP-SP100 (manufactured by Olympus Corporation). The evaluation criteria were as follows, with a score of 2 or higher being practical.
4: The maximum transmittance at wavelengths of 450 to 510 nm is less than 30%, and the maximum transmittance at wavelengths of 580 to 700 nm is less than 30%. 3: The maximum transmittance at wavelengths of 450 to 510 nm is less than 40%, and the maximum transmittance at wavelengths of 580 to 700 nm is less than 40%. 2: The maximum transmittance at wavelengths of 450 to 510 nm is less than 50%, and the maximum transmittance at wavelengths of 580 to 700 nm is less than 50%. 1: The maximum transmittance at wavelengths of 450 to 510 nm is 50% or more, or the maximum transmittance at wavelengths of 580 to 700 nm is 50% or more.

In addition, photosensitive coloring compositions 10, 18, and 35 were coated so that the film thickness after drying was 4.0 μm, and the evaluation substrates described above were prepared. Development properties, pattern formability, surface wrinkles, and color separation were evaluated for Examples 32, 33, and Comparative Example 8.

Claims (13)

Organic pigment (A), alkali-soluble resin (B), polymerizable compound (C), photopolymerization initiator (D
), and silica particles (E),
the organic pigment (A) comprises a halogenated metal phthalocyanine pigment (A-1) and an isoindoline pigment (A-2);
the polymerizable compound (C) contains a polymerizable compound (C-1) having a urethane bond,
The content of the organic pigment (A) is 25% by mass or more in 100% by mass of the nonvolatile content of the photosensitive coloring composition,
The silica particles (E) contain silica particles having an average primary particle diameter of 10 to 30 nm.
Photosensitive coloring composition. Organic pigment (A), alkali-soluble resin (B), polymerizable compound (C), photopolymerization initiator (D
), and silica particles (E),
The organic pigment (A) is a halogenated metal phthalocyanine pigment (A-1) and isoin
Contains a dorin pigment (A-2),
the polymerizable compound (C) contains a polymerizable compound (C-1) having a urethane bond,
The content of the organic pigment (A) is 25 mass % based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.
% or more,
the polymerizable compound (C-1) having a urethane bond comprises an alicyclic urethane (meth)acrylate which is a reaction product of a (meth)acrylate having a hydroxyl group and an alicyclic diisocyanate, or an aromatic urethane (meth)acrylate which is a reaction product of a (meth)acrylate having a hydroxyl group and an aromatic diisocyanate;
The photosensitive coloring composition further comprises the alicyclic urethane (meth)acrylate or aromatic urethane (meth)acrylate having an acid group. Organic pigment (A), alkali-soluble resin (B), polymerizable compound (C), photopolymerization initiator (D
), and silica particles (E),
The organic pigment (A) is a halogenated metal phthalocyanine pigment (A-1) and isoin
Contains a dorin pigment (A-2),
the polymerizable compound (C) contains a polymerizable compound (C-1) having a urethane bond,
The content of the organic pigment (A) is 25 mass % based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.
% or more,
The photosensitive coloring composition further comprises a near-infrared absorber (H), and the near-infrared absorber (H) comprises at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, and a squarylium compound. Photosensitive coloring composition. The polymerizable compound (C) further contains the polymerizable compound (C-1) having a urethane bond.
The photosensitive coloring composition according to any one of claims 1 to 3, further comprising a polymerizable compound (C-2) other than the above. The photosensitive coloring composition according to claim 4 , wherein the mass ratio of the polymerizable compound (C-1) having a urethane bond to the polymerizable compound (C-2) is 80:20 to 20:80. The photosensitive coloring composition according to claim 1 or 3 , wherein the polymerizable compound (C-1) having a urethane bond has an acid group. The photosensitive coloring composition according to any one of claims 1 to 6, wherein the alkali-soluble resin (B) comprises an alkali-soluble resin (B-1) containing an alicyclic hydrocarbon structure-containing monomer unit ( b1 ) and a carboxyl group-containing monomer unit (b2 ) . The alkali-soluble resin (B-1) contains the alicyclic hydrocarbon structure-containing monomer unit (b1
) in an amount of 5 to 60% by mass relative to 100% by mass of all structural units of the alkali-soluble resin (B-1).
The photosensitive coloring composition of claim 7 , comprising: The photosensitive coloring composition according to any one of claims 1 to 8 , wherein the mass ratio of the halogenated metal phthalocyanine pigment (A-1) to the isoindoline pigment (A-2) is 97:3 to 40:60. The content of the silica particles (E) is 5 to 100% by mass of the nonvolatile content of the photosensitive coloring composition.
The photosensitive coloring composition according to any one of claims 1 to 9 , wherein the content of the coloring agent is 30% by mass. The photosensitive coloring composition according to claim 1 or 2 , further comprising a near-infrared absorber (H). A cured film obtained by curing the photosensitive coloring composition according to any one of claims 1 to 11 . 13. An optical filter having the cured film according to claim 12 , wherein the film thickness of the cured film is 4.0
An optical filter having a thickness of 1 μm or more.