JP7631783B2 - Photosensitive composition for fingerprint authentication sensor, optical filter, fingerprint authentication sensor, and image display device - Google Patents

Description

The present invention relates to a photosensitive composition for use in a fingerprint authentication sensor.

In recent years, mobile devices such as smartphones and tablet computers have been equipped with user authentication functions that use biometric information such as fingerprints, faces, irises, or voice. Fingerprint authentication in particular offers the convenience of unlocking the device simply by placing your finger on it, and it is small and inexpensive, allowing for enhanced security, so the adoption of fingerprint authentication sensors in smartphones is expanding.

In the past, capacitive fingerprint authentication sensors were placed in the bezel area (the outside of the image display) of smartphones, but with the trend towards larger displays, the bezel area has disappeared and full-screen displays have become the norm. This has created a need to install fingerprint authentication sensors inside the display. However, capacitive fingerprint authentication sensors require the finger to be placed directly on the sensor, so they will not work if placed inside the display. Fingerprint authentication sensors that can be installed inside displays include optical and ultrasonic types, and optical types, which are inexpensive and easy to install, are being considered in particular.

Patent Document 1 discloses an optical fingerprint authentication sensor that performs fingerprint authentication by irradiating a finger with green light having a wavelength of about 570 nm or blue light having a wavelength shorter than 570 nm and generating an image based on the light reflected from the finger.

JP 2017-196319 A

However, when an optical fingerprint authentication sensor is installed inside the display of a smartphone or other device, there is no cover to block external light, so light with a wavelength of around 660 nm passes through bodily tissue. This causes noise due to the external light passing through bodily tissue, which makes it impossible to generate a correct captured image, resulting in a problem of reduced fingerprint authentication accuracy.

The present invention aims to provide a photosensitive composition for fingerprint authentication sensors that can form an optical filter that suppresses the transmission of light with a wavelength of around 660 nm and has good transmittance for light in a wide wavelength range below 600 nm.

The photosensitive composition for fingerprint authentication sensors of the present invention is capable of forming a coating having a transmittance of 50% or more at wavelengths of 450 to 540 nm and a transmittance of 5% or less at wavelengths of 620 to 690 nm at a film thickness of 1.0 μm,
The composition contains a pigment (A) including a pigment (A-1) represented by the following general formula (1), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
General formula (1)

(In general formula (1), X represents a halogen atom, and n represents 4 to 16.)

According to the present invention, it is possible to provide a photosensitive composition for a fingerprint authentication sensor, an optical filter, a fingerprint authentication sensor, and an image display device that can form an optical filter that suppresses the transmission of light with a wavelength of around 660 nm and has good transmittance for light in a wide wavelength range below 600 nm.

FIG. 1 is a schematic cross-sectional view of an image display device having a fingerprint authentication sensor inside the image display.

The following is a detailed description of the embodiment of the photosensitive composition for fingerprint authentication sensors of the present invention. Note that the present invention is not limited to the following embodiment, and can be modified in various ways within the scope of the gist of the invention.

In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively. In addition, "C.I." means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.

<Photosensitive composition for fingerprint authentication sensor>
The photosensitive composition for fingerprint authentication sensors of the present invention (hereinafter also referred to as photosensitive composition) is a photosensitive composition for fingerprint authentication sensors capable of forming a coating having a transmittance of 50% or more at wavelengths of 450 to 540 nm and a transmittance of 5% or less at wavelengths of 620 to 690 nm at a film thickness of 1.0 μm,
The composition contains a pigment (A) including a pigment (A-1) represented by the following general formula (1), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
General formula (1)

(In general formula (1), X represents a halogen atom, and n represents 4 to 16.)

The coating formed from the photosensitive composition of the present invention is preferably used as a component of a fingerprint authentication sensor. Examples of fingerprint authentication sensors include optical fingerprint authentication sensors. The photosensitive composition of the present invention contains the pigment (A-1) represented by general formula (1), which suppresses the transmission of light with a wavelength of about 660 nm, and can form a coating with good transmittance for light in a wide wavelength range below 600 nm.

[Pigment (A)]
(Pigment (A-1))
The photosensitive composition of the present invention contains, as the pigment (A), the pigment (A-1) represented by the above general formula (1).

In the general formula (1), X represents a halogen atom, and n represents an integer of 4 to 16.
When general formula (1) contains a plurality of compounds each having a different number of halogen atoms represented by X, n is the average value of the plurality of compounds.

The halogen atom represented by X in general formula (1) can be fluorine, bromine, chlorine, or iodine. Two or more types of halogen atoms can be contained. From the viewpoint of transmittance at wavelengths of 450 to 540 nm, the halogen atom is preferably bromine or chlorine, and more preferably bromine.

In general formula (1), n is preferably 6 to 10, and more preferably 7 to 10, from the viewpoint of transmittance at wavelengths of 450 to 540 nm.

Pigments (A-1) can be used alone or in combination of two or more types.

The content of pigment (A-1) is preferably 95% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass, based on 100% by mass of pigment (A). When an appropriate amount is contained, a coating with good light transmittance over a wide wavelength range below 600 nm can be formed.

<Method for producing pigment (A-1) represented by formula (1)>
The pigment (A-1) represented by the general formula (1) can be produced by any known method without any particular limitation. The following methods are exemplified.

The compound represented by the following chemical formula (2) is halogenated and then hydrolyzed to synthesize the compound represented by the following general formula (3), which is then reacted with diphenyl phosphate to synthesize the pigment (A-1) represented by general formula (1).

The halogenated compound represented by chemical formula (2) can be synthesized, for example, by the chlorosulfonic acid method, dissolution method, or other method described in The Phthalocyanines Volume II Manufacture and Applications (CRC Press, Inc., 1983), etc.

The chlorosulfonic acid method involves dissolving the compound represented by chemical formula (2) in a sulfur oxide-based solvent such as chlorosulfonic acid or sulfuric acid, and then halogenating the compound using a halogenating agent. The reaction temperature in this case is preferably about 20 to 120°C, and the reaction time is preferably about 1 to 10 hours.

As described in JP-A-51-64534, for example, the dissolution method involves halogenating a phthalocyanine compound in a melt at about 10 to 170°C of one or a mixture of two or more halogenating agents, such as an aluminum halide such as aluminum chloride or aluminum bromide, a titanium halide such as titanium tetrachloride, an alkali metal halide or an alkaline earth metal halide such as sodium chloride or sodium bromide (hereinafter referred to as an alkali (earth) metal halide), or thionyl chloride.

The halogenating agent used for the halogenation is a fluorinating agent, a chlorinating agent, a brominating agent, or an iodinating agent, and examples of the fluorinating agent include fluoroxytrifluoromethane, cesium fluoride sulfate, acetyl hypofluorite, N-fluorosulfonamide, diethylaminosulfur trifluoride, and N-fluoropyridinium salt.
Examples of the chlorinating agent include chlorine (Cl ₂ ), N-chlorosuccinimide, sulfuryl chloride, trichloroisocyanuric acid, sodium dichloroisocyanurate, 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone, 2,3,4,4,5,6-hexachloro-2,5-cyclohexadienone, N-chlorotriethylammonium chloride, and benzeneselenenyl chloride.
Examples of brominating agents include bromine (Br ₂ ), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexa-2,5-dienone, hydrogen bromide-dimethylsulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, and 1,3-dibromo-5,5-dimethylhydantoin.
Examples of the iodinating agent include iodine (I ₂ ), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodite, iodine-periodic acid, ethylene iodochloride, and N-iodosuccinimide.

The compound represented by general formula (3) has the properties of a pigment. Therefore, in order to improve the efficiency of the reaction with diphenyl phosphate, it is preferable to use the compound after performing a micronization treatment using a method such as acid pasting or solvent salt milling prior to the reaction. If the compound represented by general formula (3) is micronized in advance, the pigment (A-1) represented by general formula (1) synthesized from it is also easy to obtain fine particles.

The reaction between the compound represented by general formula (3) and diphenyl phosphate is carried out, for example, by mixing and stirring in an organic solvent. The organic solvent is then removed to obtain the pigment (A-1) represented by general formula (1).

Examples of the organic solvent include monohydric alcohol solvents such as methanol, ethanol, isopropanol, and t-butanol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, and trimethylolpropane; amide solvents such as 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, urea, and tetramethylurea; and others. Examples of the solvent include lower monoalkyl ether solvents of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether, polyether solvents such as ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether (triglyme), sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, or 3-sulfolene, polyfunctional solvents such as diacetone alcohol or diethanolamine, carboxylic acid solvents such as acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, or trifluoroacetic acid, sulfonic acid solvents such as methanesulfonic acid or trifluorosulfonic acid, and aromatic hydrocarbon solvents such as benzene, toluene, or xylene. Among these, monohydric alcohol solvents such as methanol, ethanol, or isopropyl alcohol, and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, or 1-methyl-2-pyrrolidinone are preferred because they dissolve diphenyl phosphate well. Organic solvents can be used alone or in combination of two or more types.

There are no particular limitations on the method for removing the organic solvent, but it is preferable to perform suction filtration or pressure filtration, wash with an organic solvent that is compatible with the organic solvent used and has a low boiling point, and then dry and remove the organic solvent. In the case of a water-soluble organic solvent, it is preferable to mix it with water and then remove it by washing with water.

(Other pigments (A-2))
The pigment (A) may contain other pigments (A-2) in addition to the pigment (A-1). The other pigments (A-2) are not particularly limited, and any known pigments may be used.

Other pigments (A-2) include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 12 Yellow pigments described in JP-A-2012-226110 and JP-A-6432077;
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: 2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,11 3,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181 , 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231 , 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in JP 2014-134712 A, red pigments described in JP 6368844 A;
green 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, 55, 58, 59, 62;
Blue pigments such as C.I. Pigment Blue 1, 1:2, 9, 14, 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, 79;
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, 50 and other violet pigments;
Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, and 73.

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

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

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while being heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing 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 the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution range, and a 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 standpoint 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 is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves (is miscible with) water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling point solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety. For example, 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, liquid polypropylene glycol, etc. may be used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

In the salt milling treatment, a resin may be added as necessary. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in the organic solvent. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

(dye)
The photosensitive composition of the present invention may contain a dye. Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, examples of the dye include dye derivatives and lake pigments obtained by converting dyes into lakes.

It is preferable to use the dye as a salt-forming compound. Examples of salt-forming compounds include salt-forming compounds of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; salt-forming compounds of a resin component having an amino group and an acid dye, etc.; salt-forming compounds of an acid dye and a compound having an onium base; salt-forming compounds of a basic dye and an organic acid, perchloric acid, or a metal salt thereof. Among these, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types of substances and compatibility with pigments. In addition, the compound having an onium base is preferably a resin having a cationic group on the side chain.

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.), azido dyes, Examples of the dye structure include dyes derived from dyes selected from the group consisting of amine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

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

[Alkali-soluble resin (B)]
The photosensitive composition of the present invention contains an alkali-soluble resin (B).
The alkali-soluble resin (B) is a resin that dissolves in an alkali developer, and is preferably a resin that has a transmittance of 80% or more over the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 μm is formed. The transmittance is preferably 95% or more.
The alkali-soluble resin (B) can be classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin. From the viewpoint of developability, the alkali-soluble resin (B) preferably has an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group. Among these, a carboxyl group is preferred. The alkali-soluble resin (B) can also contain a thermosetting group such as an epoxy group or an oxetanyl group.

(Non-photosensitive alkali-soluble resin)
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, an isobutylene/maleic acid (anhydride) copolymer, etc. Among these, an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer are preferred.

(Photosensitive alkali-soluble resin)
The photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. The photosensitive alkali-soluble resin is preferably a resin synthesized by the following method (i) or (ii). When cured with active energy rays, the resin is three-dimensionally crosslinked, increasing the crosslink density and improving chemical resistance.

[Method (i)]
In the method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the generated hydroxyl group to obtain a photosensitive alkali-soluble resin.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of other monomers include 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, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy (meth)acrylates such as diethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol;
(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 acetate, vinyl propionate, or other vinyl fatty acids;
Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichloro N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine;
Examples of the monomer include phosphate group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds in which a hydroxyl group of a hydroxyl group-containing monomer described below is reacted with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

Examples of monocarboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. If necessary, the remaining anhydride groups can be hydrolyzed using a tricarboxylic dianhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic anhydride.

In addition, a method similar to method (i) can be used in which, for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized. Then, an epoxy group-containing monomer is added to some of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin.

[Method (ii)]
In the method (ii), for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers is synthesized, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly-γ-valerolactone, poly-ε-caprolactone, and/or poly-12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred in terms of the resistance to foreign matter generation in the coating. Glycerol mono(meth)acrylate is also preferred in terms of photosensitivity.

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

The monocarboxyl group-containing monomer and other monomers can be the compounds mentioned above.

The raw materials used in the synthesis of the alkali-soluble resin (B) can be used alone or in combination of two or more kinds. In addition, the alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

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 even more preferably 4,000 to 20,000. The value of Mw/Mn is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and solubility in alkaline 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 alkaline development.

The content of the 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 the pigment (A).

[Polymerizable compound (C)]
The photosensitive composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a monomer, dimer, trimer, or oligomer containing a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Examples of the polymerizable compound (C) include a polymerizable compound (C-1) having an acid group, a polymerizable compound (C-2) having a urethane bond and an acid group (excluding (C-1)), and other polymerizable compounds (C-3).

(Polymerizable Compound (C-1) Having an Acid Group)
The photosensitive composition of the present invention preferably contains a polymerizable compound (C-1) having an acid group as the polymerizable compound (C). This makes it possible to suppress development residues during pattern formation by photolithography, thereby improving the accuracy of fingerprint authentication. Examples of the acid group of the polymerizable compound (C-1) having an acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, a carboxyl group is preferred.

Examples of the polymerizable compound (C-1) having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; and esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates.
Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.
Examples of polyvalent carboxylic acids include trimellitic acid and pyromellitic acid.
Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

Commercially available products of the polymerizable compound (C-1) having an acid group include Viscoat #2500P manufactured by Osaka Organic Industries, and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd.

The content of the polymerizable compound (C-1) having an acid group is preferably 5 to 80 mass %, and more preferably 25 to 80 mass %, of 100 mass % of the polymerizable compound (C), from the viewpoint of development residues during pattern formation.

(Polymerizable compound having a urethane bond and an acid group (C-2))
From the viewpoint of pattern formability, the photosensitive composition of the present invention more preferably contains, as the polymerizable compound (C), a polymerizable compound (C-2) having a urethane bond and an acid group.

The polymerizable compound (C-2) having a urethane bond and an acid group is, for example, a compound represented by the following general formula (4).

General formula (4) (H ₂ C=C(R ¹ )COO) _m -X-(OCOCH(R ¹ )CH ₂ S(R ² )COOH) _n
In general formula (4), ^R1 is a hydrogen atom or a methyl group, ^R2 is a hydrocarbon group having 1 to 12 carbon atoms, X is an (m+n)-valent organic group having a urethane bond having 3 to 60 carbon atoms, m is an integer of 2 to 18, and n is an integer of 1 to 3.

The compound represented by general formula (4) can be synthesized, for example, by first reacting a polyfunctional isocyanate compound with a hydroxyl group-containing (meth)acrylate, and then adding a mercapto compound having a carboxyl group to the product.

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, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)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, bis(isocyanatemethyl)cyclohexane, etc. Also included are biuret products, isocyanate nurate products, trimethylolpropane adduct products, etc. of these.

Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)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 mercapto compounds having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

From the viewpoint of pattern formability, the polymerizable compound (C-2) having a urethane bond and an acid group is particularly preferably a compound having an acid group in 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 an aromatic diisocyanate.

From the viewpoints of development residues during pattern formation and pattern formability, the content of the polymerizable compound (C-2) having a urethane bond and an acid group is preferably 5 to 80 mass % and more preferably 25 to 80 mass % in 100 mass % of the polymerizable compound (C).

(Other polymerizable compounds (C-3))
Examples of other polymerizable compounds (C-3) include 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, 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 modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate ) 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, epoxy (meth)acrylate, various acrylic acid esters and methacrylic acid esters such as urethane acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, acrylonitrile, and the like.

Other commercially available polymerizable compounds (C-3) include, for example, KAYARAD manufactured by Nippon Kayaku Co., Ltd. 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, DPCA-120, and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-4 ...4, M-405, M-406, M-409, M-500, M-501, M-502, M-503, M-504, M-505, M-506, M-507, M-508, M-509, M-510, M-511, M-512, M-513, M-515, M-5 -403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Co., Ltd., NK Ester A-9300, UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., etc.

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

The content of the polymerizable compound (C) is preferably 1 to 60 mass %, and more preferably 2 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[Photopolymerization initiator (D)]
The photosensitive composition of the present invention contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D), the photosensitive composition can be cured by irradiation with ultraviolet light to produce an optical filter.

Examples of the photopolymerization initiator (D) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone;
Triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;
Oxime 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);
Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.

Commercially available products include acetophenone compounds manufactured by IGM Resins such as "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), and phosphine compounds manufactured by IGM Resins such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) and "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), and oxime compounds such as IRGACURE OXE-01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)]), IRGACURE OXE 02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)), IRGACURE OXE 03, and IRGACURE OXE 04 manufactured by BASF Japan, N-1919, NCI-730, NCI-831, and NCI-930 manufactured by ADEKA, and TRONLY TR-PBG-304 and TRONLY manufactured by Changzhou Strong New Materials Co., Ltd. Examples of such photopolymerization initiators include TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-345, and TRONLY TR-PBG-3054. Examples of such photopolymerization initiators include oxime ester-based photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, and JP-A-2011-020998.

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

The content of the 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 the pigment (A) from the viewpoints of photocurability and developability.

[Triarylsulfonium compound (E)]
The photosensitive composition of the present invention preferably contains a triarylsulfonium compound (E). By using the triarylsulfonium compound (E), the transmittance in the wavelength range of 700 to 730 nm can be effectively suppressed.

The triarylsulfonium compound (E) includes a compound represented by the following general formula (5):

General formula (5)

In formula (5), R ₁ to R ₃ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent, and X ⁻ represents a monovalent counter anion.

In general formula (5), R ₁ to R ₃ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group that may have a substituent include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl groups, and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups, as well as alkyl groups having a substituent such as trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl groups.

Examples of alkoxyl groups that may have a substituent include linear alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, 2,3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, branched alkoxyl groups, and cyclic alkoxyl groups such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and cyclohexyloxy, as well as alkoxyl groups having a substituent such as trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.

Aryl groups which may have a substituent include aryl groups such as phenyl, naphthyl, and anthranyl groups, as well as aryl groups having a substituent such as p-methylphenyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinonyl, and 2-aminoanthraquinonyl.

Among these, from the viewpoint of suppressing the transmittance in the wavelength range of 700 to 730 nm, it is preferable that at least one of R ₁ to R ₃ is a hydrogen atom.

In the general formula (5), X ⁻ represents a monovalent counter anion. Examples of X ⁻ include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , and compounds represented by the following general formulae (6) to (11).

General formula (6) MY _a ^-
In formula (6), M represents a phosphorus atom, a boron atom, or an antimony atom, Y represents a halogen atom, and a represents an integer of 4 to 6.

Examples of the compound represented by the general formula (6) include PF ₆ ^- , BF ₆ ^- and SbF ₆ ^- . Of these, PF ₆ is preferred.

General formula (7) (Rf) _b PF _6-b ^-
In the general formula (7), Rf represents an alkyl group having 1 to 8 carbon atoms in which 80 mol % or more of the hydrogen atoms are substituted with fluorine atoms. The alkyl group may be linear, branched or cyclic. b represents an integer of 1 to 5.

Examples of compounds represented by general formula (7) include _{( CF3CF2} ) _2PF ^- _{4 ,} ( _CF3CF2 ) ^3PF3- _{, ( CF3CF2CF2 ) 2PF4-} ^{, (} ( _CF3 ) _2CF ) _{3PF3- ,} ( ^CF3CF2CF2 _{) 2PF4- , and the like .}

General formula (8) R ⁴ _c LY _c ^-
In formula (8), ^R4 represents a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, L represents a boron atom or a gallium atom, and c represents an integer of 1 to 4.

Examples of compounds represented by general formula (8) include (C ₆ F ₅ )B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ )B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , (C ₆ H ₃ F ₂ ) ₄ Ga ^{− ,} and the like.

General formula (9) R ⁵ SO ₃ ⁻
In general formula (9), ^R5 represents an alkyl group having 1 to 12 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group and the perfluoroalkyl group may be linear, branched, or cyclic, and the aryl group may be unsubstituted or may have a substituent.

Examples of the compound represented by general formula (9) include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nanofluorobutanesulfonate anion, pentafluorophenylsulfonate anion, p-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, and butanesulfonate anion.

General formula (10) (R ⁶ SO ₂ ) ₃ C ^-
In general formula (10), ^R6 represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, the alkyl group and the perfluoroalkyl group may be linear, branched, or cyclic, and the aryl group may be unsubstituted or may have a substituent.

Examples of the compound represented by general formula (10) include (CF ₃ SO ₂ ) ₃ C ^- , (C ₂ F ₅ SO ₂ ) ₃ C ^- , (C ₃ F ₇ SO ₂ ) ₃ C ^- , (C ₄ F ₉ SO ₂ ) ₃ C ^{- ,} and the like.

General formula (11) (R ⁷ SO ₂ ) ₂ N ⁻
In general formula (11), ^R7 represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, the alkyl group and the perfluoroalkyl group may be linear, branched, or cyclic, and the aryl group may have a substituent.

Examples of the compound represented by general formula (11) include (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₃ F ₇ SO ₂ ) ₂ N ^- , (C ₄ F ₉ SO ₂ ) ₂ N ^{- ,} and the like.

In addition to the above anions, perhalogen acid ions (ClO ₄ ^- , BrO ₄ ^- , etc.), halogenated sulfonate ions (FSO ₃ ^- , ClSO ₃ ^- , etc.), sulfate ions (CH ₃ SO ₄ ^- , CF ₃ SO ₄ ^- , HSO ₄ ^{- ,} etc.), carbonate ions (HCO ₃ ^- , CH ₃ CO ₃ ^{- ,} etc.), aluminate ions (AlCl ₄ ^- , AlF ₄ ^{- ,} etc.), carboxylate ions (CHCOO ^- , CF ₃ COO ^- , C ₆ H ₅ COO - , CH ₃ C ₆ H ₄ COO ^- , C ₆ F ₅ COO ^- , etc.), aryl borate ions (B(C ₆ H ₅ ) ₄ ^{- ,} etc.), ^- , etc.), anions described in JP-A-2013-092657, JP-A-2013-080245, JP-A-2013-080240, JP-A-2013-047211, JP-A-2013-033161, etc.

Among these, from the viewpoint of suppressing the transmittance in the wavelength range of 700 to 730 nm, X ⁻ is preferably Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₆ ⁻ , a trifluoromethanesulfonate anion, or a nonafluorobutanesulfonate anion.

Examples of the triarylsulfonium compound (E) represented by general formula (5) include the following compounds.

Commercially available triarylsulfonium compounds (E) include, for example, WPAG-336, 367, 370, 469, and 638 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., SP-056 and 066 manufactured by ADEKA Corporation, TS-91 manufactured by Sanwa Chemical Co., Ltd., and T1608 and 1609 manufactured by Tokyo Chemical Industry Co., Ltd.

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

From the viewpoint of suppressing the transmittance at wavelengths of 700 to 730 nm, the content of the triarylsulfonium compound (E) is preferably 0.1 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the pigment (A-1) represented by general formula (1).

[Dye derivative (F)]
The photosensitive composition of the present invention may contain a dye derivative (F) as necessary, which improves the dispersion stability.

The dye derivative (F) is a compound having an acidic group, a basic group, a neutral group, etc. in an 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.

Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009/081930 A, WO 2011/052617 A, WO 2012/102399 A, and JP 2017-156397 A; phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016/163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A; and anthraquinone dye derivatives are described 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, quinacridone dye derivatives are shown in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383, dioxazine dye derivatives are shown in JP-A-2011-162662, thiazineindigo dye derivatives are shown in JP-A-2007-314785, and triazine Examples of benzoisoindole-based 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 quinophthalone-based dye derivatives include those disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-2261. Examples of known dye derivatives include those described in 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, and JP-A-2005-213404 as basic substituents. In these documents, the dye derivative may be described as a derivative, pigment derivative, dispersant, pigment dispersant, or simply as a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

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

The content of the dye derivative (F) is preferably 1 to 15 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the pigment (A).

[Dispersion Resin (G)]
The photosensitive composition of the present invention may contain a dispersing resin (G) as required.
The dispersing resin (G) has an adsorptive group having a high affinity for the pigment, and the adsorptive group is preferably one or more of a cationic group and an anionic group.

Examples of the cationic groups of the resin having a cationic group include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and groups containing nitrogen atoms such as nitrogen-containing heterocycles.

Examples of the anionic group of the resin having an anionic group include a carboxyl group, a phosphate group, and a sulfonic acid group. Among these, the carboxyl group and the phosphate group are preferred from the viewpoint of adsorption to the pigment.

The resin type of the dispersion resin (G) may be, for example, urethane resin, polycarboxylate ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylate (partial) amine salt, polycarboxylate ammonium salt, polycarboxylate alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylate ester, modified products thereof, amides formed by the reaction of poly(lower alkylene imine) with polyesters having free carboxyl groups, salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphates.

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

Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, manufactured by BYK Japan Co., Ltd. 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, 2164, or Anti-Terra-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, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 455 manufactured by BASF Japan Ltd. 0, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd., and resins described in JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, etc. are included.

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 pigment (A).

[Near infrared absorbing agent (H)]
The photosensitive composition of the present invention may contain a near-infrared absorbing agent (H). This allows the composition to block near-infrared light, which has high permeability to body tissue, and therefore improves the accuracy of fingerprint authentication. The near-infrared absorbing agent (H) is a compound having a maximum absorption wavelength in the wavelength range of 750 to 1,200 nm.

Examples of near-infrared absorbents (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 disclosed in International Publication Nos. WO2006/006573, WO2010/073857, JP2013-241598A, JP2016-113501A, and JP2016-113504A; phthalocyanine compounds are disclosed in JP4-23868A, JP06-192584A, JP2000-63691A, and WO2014/208514; naphthalocyanine compounds are disclosed in JP11-152414A, JP2000-86919A, JP2009-29955A, and WO2018/186490; immonium compounds are disclosed 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, International Publication No. WO 2017/135359, International Publication No. WO 2018/225837, JP 2019-001987 A, International Publication No. WO 2020/054718; examples of croconium compounds include those described in International Publication No. WO 2019/021767, etc.

The near infrared absorbing agent (H) can be used alone or in combination of two or more types.

[Sensitizer (I)]
The photosensitive 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, tetrapyrazinoporphyra, and the like. 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. As the sensitizer (I) compound, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc. are preferred.

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

The content of the 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 the photopolymerization initiator (D). When an appropriate amount is contained, the photocurability and developability are improved.

[Thermosetting compound (J)]
The photosensitive composition of the present invention may contain a thermosetting compound (J), which reacts in the heating step after the formation of the coating film to increase the crosslink density and improve 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. Among 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, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). Examples of such epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, 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, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. 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 coating, the content of the 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 the pigment (A).

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

Examples of the monofunctional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.
Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bis(3-ethyl-3-oxetanylmethyl) ether, Examples of bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether 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.
Examples of 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 mass %, and more preferably 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

A melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol type or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and/or ether groups per melamine ring. Having an appropriate number of methylol groups or ether groups makes it easier to obtain 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, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 manufactured by Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and/or ether groups per melamine ring, are preferred in terms of increasing crosslink density.

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

[Curing agent (curing accelerator)]
The photosensitive composition of the present invention may contain 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.).

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

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

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

The thiol chain transfer agent (K) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the coating becomes easier to photocure from the surface to the deepest part.

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

The thiol chain transfer agent (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 composition. When an appropriate amount is contained, the photosensitivity is improved and wrinkles are less likely to occur on the coating surface.

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

The polymerization inhibitor (L) is, 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 such 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 phloroglucinol.

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

[Ultraviolet absorber (M)]
The photosensitive composition of the present invention may contain an ultraviolet absorber (M). Examples of the ultraviolet absorber (M) 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 These include octyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

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

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

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

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

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

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

The content of the ultraviolet absorber (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 composition of the present invention may contain an antioxidant (N). The antioxidant (N) prevents the photopolymerization initiator (D) and the thermosetting compound (J) contained in the photosensitive composition from yellowing due to oxidation during the thermal process of heat curing or ITO annealing, and can suppress a decrease in the transmittance of the coating. In particular, when the pigment concentration of the photosensitive composition is high, the content of the photopolymerizable compound is relatively reduced, and the coating is likely to yellow if the amount of the photopolymerization initiator is increased or a thermosetting compound is added. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a decrease in the transmittance of the coating can be suppressed.

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

Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-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 Adeka STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by ChemiPro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan, and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2 ,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis(tetramethylbutyl)amino, Bis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridylsebake ester, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

Commercially available products include Adeka STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals, Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan, and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical.

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

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

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

Commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOX PLS manufactured by Chemipro Chemicals.

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

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

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

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

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

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

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. late, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, etc.

Commercially available products include Kao's 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-106. , LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW -L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH -60(K), Ami-to 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd., etc.

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

Commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyletherdisulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

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

Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl 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.

The leveling agent (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 mass %, and more preferably 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition. By being within this range, the balance between the coatability, pattern adhesion, and transmittance of the photosensitive composition is further improved.

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

The content of the storage stabilizer (P) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the pigment (A).

[Adhesion improver (Q)]
The photosensitive composition of the present invention may contain an adhesion improver (Q). This improves the adhesion between the coating 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 vinyl trimethoxysilane and vinyl triethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and other aminosilanes, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane, etc. silane coupling agents.

The adhesion improver (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 pigment (A).

[Organic solvent (R)]
The photosensitive composition of the present invention may contain an organic solvent (R).
Examples of the organic solvent (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, 3-ethoxyethyl propionate, 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 diglycerol 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 composition for fingerprint authentication sensor>
The photosensitive composition of the present invention is produced by, for example, adding a pigment (A), an alkali-soluble resin (B), and, if necessary, a dye derivative (F), a dispersing resin (G), an organic solvent (R), etc., and carrying out a dispersion treatment. The composition can then be produced by adding and mixing a polymerizable compound (C) and a photopolymerization initiator (D) to the dispersion. The timing of mixing each material is arbitrary. The dispersion process can also be carried out multiple times.

Dispersing machines used for dispersion processing 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 pigment (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A moderate particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

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

It is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more, as well as contaminated dust, from the photosensitive composition by means of centrifugation, filtration with a sintered filter or membrane filter, etc. It is preferable that the photosensitive composition for the fingerprint authentication sensor of the present invention does not substantially contain particles of 0.5 μm or more, and it is more preferable that it does not contain particles of 0.3 μm or less.

<Optical filter>
The optical filter of the present invention includes a substrate and a coating formed from a photosensitive composition for a fingerprint authentication sensor. The coating is preferably patterned by a photolithography method.

[Method of manufacturing optical filters]
The optical filter can be produced, for example, by carrying out the steps of: (1) applying a photosensitive composition onto a substrate to form a coating; (2) exposing the coating to light in a pattern through a mask; (3) developing and removing the unexposed portions to form a pattern; and (4) heat-treating the pattern.

(Step (1))
In the step (1) of forming a coating, the photosensitive composition is applied onto a substrate by a method such as rotary coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (prebaked) 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 image sensor such as a CCD or a CMOS formed on the 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.
The coating thickness is about 0.05 to 2.0 μm.

(Step (2))
In the exposure step, the coating obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a hardened coating.
Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

(Step (3))
The cured coating obtained in step (2) is subjected to an alkali development treatment, whereby the unexposed areas of the coating are dissolved in an aqueous alkaline solution, leaving only the cured areas.
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, and more preferably from 0.01 to 1% by mass.
The pH of the alkaline developer is preferably from 11 to 13, more preferably from 11.5 to 12.5. When used at an appropriate pH, roughening and peeling of the pattern is suppressed, and the remaining film rate after development is improved.

The development method may be, for example, the dip method, the spray method, or the paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

(Step (4))
The pattern obtained in step (3) is subjected to a heat treatment (post-baking) to sufficiently harden the coating. 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.

Next, we will explain the transmittance in each wavelength range of the coating formed from the photosensitive composition of the present invention.

[Wavelengths with transmittance of 50% or more]
The photosensitive composition of the present invention has a transmittance of 50% or more at wavelengths of 450 to 540 nm when a coating having a thickness of 1.0 μm is formed.
From the viewpoint of fingerprint authentication accuracy, the transmittance is preferably 50% or more at wavelengths of 440 to 550 nm, and more preferably 50% or more at wavelengths of 430 to 560 nm. By transmitting light in a wide wavelength range below 600 nm, the accuracy of fingerprint authentication is improved.

The method for measuring the spectroscopic characteristics and film thickness of the coating is shown below.

(Film Thickness Measurement)
The photosensitive composition of the present invention was applied to a glass substrate by spin coating so that the film thickness after drying was 1.0 μm, and after drying on a hot plate at 90° C. for 2 minutes, the substrate was exposed to light at an exposure dose of 50 mJ/cm ² through a photomask with a square pattern of 100 μm squares using an ultra-high pressure mercury lamp to prepare a substrate. The substrate was then spray-developed using a 0.04 mass% potassium hydroxide aqueous solution at 23° C., washed with ion-exchanged water, air-dried, and heated (post-baked) at 230° C. for 30 minutes in a clean oven to form a square pattern on the substrate. The spray development was performed for the coating of each photosensitive composition for the shortest possible time for pattern formation without residual development. Then, using Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.), measurements were taken at five arbitrary locations, and the average value was taken as the film thickness.
The above-mentioned film thickness of 1.0 μm includes the range of error permitted in the technical field to which the present invention pertains. Specifically, the film thickness is within the range of 1.0 μm±0.1 μm.

(Transmittance Measurement)
The film thickness was then measured, and the transmittance in the thickness direction of the film was measured at each wavelength using OSP-SP100 (manufactured by Olympus Corporation).

[Transmittance at wavelengths of 620 to 690 nm]
The photosensitive composition of the present invention has a transmittance of 5% or less at wavelengths of 620 to 690 nm when a coating having a thickness of 1.0 μm is formed.
From the viewpoint of fingerprint authentication accuracy, the transmittance at wavelengths of 620 to 690 nm is preferably 4% or less, and more preferably 3% or less.
By suppressing the transmission of light having a wavelength of about 660 nm, which has a relatively high transmittance through body tissue, the accuracy of fingerprint authentication is improved.

[Wavelengths with transmittance of 80% or more]
From the viewpoint of fingerprint authentication accuracy, the photosensitive composition of the present invention, when a coating having a thickness of 1.0 μm is formed, preferably has a transmittance of 80% or more at wavelengths of 450 to 540 nm, more preferably has a transmittance of 80% or more at wavelengths of 440 to 550 nm, and further preferably has a transmittance of 80% or more at wavelengths of 430 to 560 nm. By transmitting light in a wide wavelength range below 600 nm and achieving high transmittance, fingerprint authentication accuracy is improved.

[Transmittance at wavelengths of 700 to 730 nm]
When the photosensitive composition of the present invention is used to form a coating having a thickness of 1.0 μm, the transmittance at wavelengths of 700 to 730 nm is preferably 50% or less, more preferably 40% or less, from the viewpoint of fingerprint authentication accuracy. This transmittance can be easily obtained by including the triarylsulfonium compound (E).

<Fingerprint authentication sensor>
The fingerprint authentication sensor of the present invention includes the optical filter of the present invention. The fingerprint authentication sensor of the present invention may have the following configuration, for example.
The configuration has a substrate on which are provided a plurality of photodiodes constituting a light receiving area of a CCD image sensor, a CMOS image sensor, an organic CMOS image sensor or the like, and a transfer electrode made of polysilicon or the like, a light-shielding film made of tungsten or the like with only the light receiving portions of the photodiodes being opened on the photodiodes and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the photodiode light receiving portions, and the optical filter of the present invention on the device protection film.
Furthermore, the device may have a configuration in which a focusing means (e.g., a microlens, etc.; the same applies below) is provided on the device protection layer and below the optical filter (on the side closer to the substrate), or a configuration in which a focusing means is provided on the optical filter. In addition, JP-A-2015-196465, JP-A-2017-194676, and JP-T-2019-512762 can be referred to.

The organic CMOS image sensor is composed of a thin panchromatic organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material captures light and converts it into an electrical signal, while the inorganic material takes on the role of extracting the electrical signal to the outside. In principle, the aperture ratio for incident light can be made 100%. The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication and is suitable for miniaturizing pixels.

<Image display device>
The image display device of the present invention includes the fingerprint authentication sensor of the present invention inside the image display. The configuration of the image display device of the present invention is not particularly limited as long as fingerprint authentication can be performed on the image display. For example, JP 2015-196465 A, JP 2020-35327 A, and JP 2020-92080 A can be referred to. FIG. 1 is a schematic cross-sectional view of an image display device including the fingerprint authentication sensor of the present invention inside the image display. The display panel 100 includes a substrate 11, a driving layer 10, a fingerprint authentication sensor layer 20, an OLED (organic light emitting diode) light emitting layer 30, and a cover glass layer 40.

The substrate 11 may be made of glass or plastic.

The driving layer 10 is provided between the substrate 11 and the fingerprint authentication sensor layer 20 so as not to impair the light emitting and receiving functions of the OLED light emitting layer 30 and the fingerprint authentication sensor layer 20, and includes an interlayer insulating film provided with various transistor arrays and multilayer wiring for inputting and outputting electrical signals of the fingerprint authentication sensor layer 20 and the OLED light emitting layer 30.

The OLED light-emitting layer 30 includes one or more OLEDs 31 that emit light 33, and is an area for displaying an image and an area for emitting light for fingerprint authentication. The OLED 31 has an organic light-emitting portion and electrodes above and below it.

The fingerprint authentication sensor layer 20 includes at least one fingerprint authentication sensor 21, and the fingerprint authentication sensor 21 detects at least a portion of the light 23 that is reflected by a finger, which is the authentication target, out of at least a portion of the light 33 emitted by the OLED 31.

A cover glass layer 40 is placed on top of the OLED light-emitting layer 30 to protect the underlying structure and form the display surface.

The image display device of the present invention can be used without restrictions in devices that require fingerprint authentication, such as smartphones, tablet terminals, and notebook PCs.

The present invention will be described 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.

(Identification of Pigment (A-1))
The pigment (A-1) in the present invention was identified based on the agreement between the molecular ion peak in the mass spectrum obtained using a time-of-flight mass spectrometer (AutoflexIII (TOF-MS), manufactured by Bruker Daltonics) and the mass number obtained by calculation, and also based on the agreement between the ratios of carbon, hydrogen and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin-Elmer) and the theoretical values. The number of substitutions of halogen atoms was obtained by burning the pigment (A-1) by the oxygen combustion flask method, absorbing the combustion product into water, quantifying the amount of halogen in the liquid using an ion chromatograph (ICS-2000 ion chromatograph, manufactured by DIONEX), and converting the amount into the number of substitutions of halogen atoms.

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 the dispersed resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The apparatus used was HLC-8220GPC (manufactured by Tosoh Corporation), two separation columns were connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were 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 the alkali-soluble resin and the dispersed resin solution, and the mixture was stirred to dissolve uniformly, and titrated with an automatic titrator ("COM-555", Hiranuma Sangyo Co., Ltd.) using a 0.1 mol/L KOH aqueous solution as the titrant to measure the acid value (mg KOH/g). The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

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

<Production of Pigment (A-1) Represented by General Formula (1)>
(Finely divided pigment (A-1-1))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1,500 parts of concentrated sulfuric acid under 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, in that order, and then dried to obtain 159 parts of a compound (a-1-1) represented by the general formula (3) in which X=bromine and n=10.
Next, 1,000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the compound (a-1-1) represented by the general formula (3), and 32 parts of diphenyl phosphate were added to the 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 at 60°C under reduced pressure for 24 hours 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 at 60°C under reduced pressure for 24 hours to obtain a pigment (A-1-1) represented by the general formula (1). The obtained pigment (A-1-1) had X = bromine and n = 10.
Thereafter, 100 parts of pigment (A-1-1), 1,000 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was added to 3,000 parts of warm water, and stirred for about 1 hour with a high-speed mixer while heating to about 70° C. to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A-1-1).

(Finely divided pigment (A-1-2))
A pigment (A-1-2) represented by general formula (1) was obtained in the same manner as in the synthesis of the pigment (A-1-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 175 parts. In the obtained pigment (A-1-2), X = bromine and n = 6. Thereafter, a finely divided pigment (A-1-2) was obtained in the same manner as in the synthesis of the finely divided pigment (A-1-1).

(Finely divided pigment (A-1-3)
A pigment (A-1-3) represented by general formula (1) was obtained in the same manner as in the synthesis of the pigment (A-1-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 215 parts. In the obtained pigment (A-1-3), X = bromine and n = 8. Then, a finely divided pigment (A-1-3) was obtained in the same manner as in the synthesis of the finely divided pigment (A-1-1).

(Finely divided pigment (A-1-4)
Pigment (A-1-4) represented by general formula (1) was obtained in the same manner as in the synthesis of pigment (A-1-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 358 parts. In the obtained pigment (A-1-4), X = bromine and n = 12. Then, a finely divided pigment (A-1-4) was obtained in the same manner as in the synthesis of the finely divided pigment (A-1-1).

(Finely divided pigment (A-1-5)
Pigment (A-1-5) represented by general formula (1) was obtained in the same manner as in the synthesis of pigment (A-1-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 152 parts of trichloroisocyanuric acid. In the obtained pigment (A-1-5), X = chlorine and n = 10. Then, a finely divided pigment (A-1-5) was obtained in the same manner as in the synthesis of the finely divided pigment (A-1-1).

(Finely divided pigment (A-1-6)
In a reaction vessel, 1,500 parts of concentrated sulfuric acid was added with 100 parts of chloroaluminum phthalocyanine under ice bath. Then, 75 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 20°C for 3 hours. Then, 148 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25°C for 4 hours. Then, 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 in this order, and dried to obtain 159 parts of a compound (a-1-6) represented by the general formula (3), where X = bromine and chlorine, and n = 10 (5 bromine and 5 chlorine).
Next, 1,000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the compound (a-1-6) represented by the general formula (3), and 32 parts of diphenyl phosphate were added to the 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 at 60°C under reduced pressure for 24 hours 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 at 60°C under reduced pressure for 24 hours to obtain a pigment (A-1-6) represented by the general formula (1). The obtained pigment (A-1-6) had X = bromine and chlorine, and n = 10 (5 bromine and 5 chlorine).
Thereafter, a finely divided pigment (A-1-6) was obtained in the same manner as in the case of the finely divided pigment (A-1-1).

<Production of other pigments (A-2)>
(Finely divided pigment (A-2-1))
100 parts of C.I. Pigment Blue 15:3 ("Lionol Blue FG7351" manufactured by Toyo Color Co., Ltd.), 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 added to 3,000 parts of hot water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and the solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A-2-1).

(Finely divided pigment (A-2-2))
100 parts of C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 1,000 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was added to 3,000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and the solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A-2-2).

(Finely divided pigment (A-2-3))
100 parts of C.I. Pigment Green 7 ("Lionol Green 8390" manufactured by Toyo Color Co., Ltd.), 1,000 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was added to 3,000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and the solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A-2-3).

(Finely divided pigment (A-2-4))
100 parts of C.I. Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Color Co., Ltd.), 1,000 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was added to 3,000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove sodium chloride and the solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A-2-4).

(Finely divided pigment (A-2-5))
100 parts of C.I. Pigment Green 58 (DIC Corporation "FASTGEN GREEN A110"), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3,000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain a finely divided pigment (A-2-5).

(Finely divided pigment (A-2-6))
100 parts of C.I. Pigment Green 59 (DIC Corporation "FASTGEN GREEN C100"), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3,000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain a finely divided pigment (A-2-6).

(Finely divided pigment (A-2-7))
A reaction vessel was charged with 1,000 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine, and 49.5 parts of diphenyl phosphate, and the mixture was heated to 40° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol and then with water, and dried to obtain 114 parts of pigment (A-2-7) represented by the following chemical formula (12).
Chemical Formula (12)


100 parts of pigment (A-2-7), 1,200 parts of 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 added to 3,000 parts of warm water and stirred for 1 hour while heating to 70° C. to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to produce a finely divided pigment (A-2-7) represented by chemical formula (12).

(Finely divided pigment (A-2-8))
100 parts of C.I. Pigment Yellow 150 ("Yellow Pigment E4GN" manufactured by Lanxess), 1,000 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50 ° C. This mixture was added to 3,000 parts of hot water, heated to about 70 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and the solvent, and then dried at 80 ° C. for 24 hours to obtain a finely divided pigment (A-2-8).

(Finely divided pigment (A-2-9))
100 parts of C.I. Pigment Red 177 (Synix Red SR3C manufactured by Synix), 1,000 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was added to 3,000 parts of hot water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and the solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A-2-9).

<Production Example of Alkali-Soluble Resin (B)>
(Alkali-soluble resin (B-1) solution)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, 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 substituted with nitrogen in the reaction vessel. 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 ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was added to the previously synthesized resin solution so that the non-volatile content was 20%, to prepare an alkali-soluble resin (B-1) solution. The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin (B-2) solution)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20% to prepare an alkali-soluble resin (B-2) solution. The weight average molecular weight (Mw) was 18,000.

(Alkali-soluble resin (B-3) solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80 ° C., and the inside of the flask was replaced with nitrogen, and then a mixture of 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours from the dropping tube. After the dropping, the mixture was further reacted at 100 ° C. for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued for another 1 hour at 100 ° C. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups) was added to the container with 0.5 parts of trisdimethylaminophenol and 0.1 parts of hydroquinone. The reaction was continued for 6 hours at 120 ° C., and the reaction was terminated when the non-volatile acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 20% by mass to prepare an alkali-soluble resin (B-3) solution. The weight average molecular weight (Mw) was 19,000.

(Alkali-soluble resin (B-4) solution)
A separable flask equipped with a cooling tube was prepared as a reaction vessel. Meanwhile, a thoroughly stirred mixture of 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy 2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats), and 40 parts of PGMAc was prepared as a monomer dropping vessel. A thoroughly stirred mixture of 8 parts of n-dodecanethiol and 32 parts of PGMAc was prepared as a chain transfer agent dropping vessel.
395 parts of PGMAc was charged into the reaction vessel, and after replacing with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. Dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C. 60 minutes after the end of dropping, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5 / 95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110 ° C. for 12 hours. Then, 150 parts of PGMAc was added and cooled to room temperature, and about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20 mass%, to obtain an alkali-soluble resin (B-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile content was 2 mgKOH/g.

(Alkali-soluble resin (B-5) solution)
Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 333 parts of PGMAc were 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 dropped into the flask from the dropping funnel 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 moles, (100 mol% relative to the glycidyl group of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol and 0.145 parts of hydroquinone were charged into the flask, and the reaction was continued for 6 hours at 110 ° C., and the reaction was terminated when the non-volatile acid value became 1 mgKOH / g. Next, 60.9 parts (0.40 moles) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was carried out at 120 ° C. for 3.5 hours to obtain a photosensitive resin with an acid value of 80 mgKOH / g. After cooling to room temperature, about 2 parts of the photosensitive resin was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the photosensitive resin synthesized earlier so that the non-volatile content was 20 mass% to prepare an alkali-soluble resin (B-5) solution. The weight average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (B-6) solution)
Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 182 parts of PGMAc were 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, 43.0 parts (0.5 mol), dicyclopentanyl methacrylate, 22.0 parts (0.10 mol), and 136 parts of PGMAc was dropped from the dropping funnel into the flask over 2 hours, and stirring was continued for another 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 moles, (50 moles 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 charged into the flask, and the reaction was continued for 6 hours at 110 ° C. to obtain a photosensitive resin with an acid value of 79 mg KOH / g. After cooling to room temperature, about 2 parts of the photosensitive resin was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the photosensitive resin synthesized earlier so that the non-volatile content was 20 mass% to prepare an alkali-soluble resin (B-6) solution. The mass average molecular weight (Mw) was 13,000.

<Production Example of Polymerizable Compound (C-2) Having Urethane Bond and Acid Group>
(Polymerizable compound having a urethane bond and an acid group (C-2-1))
In a four-neck flask, 400 parts of dipentaerythritol pentaacrylate, 61 parts of 1,3-tolylene diisocyanate, and 0.5 parts of N,N-dimethylbenzylamine were charged and reacted for 8 hours at a temperature of 50 to 70°C, 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 reacted for 6 hours at a temperature of 50 to 60°C, to obtain an aromatic urethane acrylate having an average of 9 polymerizable unsaturated groups having an acid group as the compound represented by general formula (4).

(Polymerizable compound having a urethane bond and an acid group (C-2-2))
In a four-neck flask, 400 parts of dipentaerythritol pentaacrylate, 85 parts of isophorone diisocyanate, and 0.5 parts of N,N-dimethylbenzylamine were charged and reacted for 8 hours at a temperature of 50 to 70°C, 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 reacted for 6 hours at a temperature of 50 to 60°C, to obtain an alicyclic urethane acrylate having an average of 9 polymerizable unsaturated groups having an acid group as the compound represented by general formula (4).

(Polymerizable compound having a urethane bond and an acid group (C-2-3))
In a four-neck flask, 400 parts of dipentaerythritol pentaacrylate, 64 parts of hexamethylene diisocyanate, and 0.5 parts of N,N-dimethylbenzylamine were charged and 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, 20 parts of mercaptopropionic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60°C for 6 hours to obtain an aliphatic urethane acrylate having an average of 9 polymerizable unsaturated groups having an acid group as the compound represented by general formula (4).

<Production Example of Dispersion Resin (G)>
(Dispersion resin (G-1) solution)
A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 parts of dimethylbenzylamine. After replacing with nitrogen gas, the reaction vessel was heated to 120°C and reacted for 4 hours, and then reacted at 80°C for 2 hours. Further, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA (methacrylate (3-ethyloxetan-3-yl) methyl, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were charged, and 0.2 parts of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes while maintaining the reaction vessel at 80°C. The nonvolatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomer had reacted. PGMAc was added to dilute the solution so that the nonvolatile content was 30% by nonvolatile content measurement, and a dispersion resin (G-1) solution having an acid value of 51 mgKOH/g and a weight average molecular weight (Mw) of 24,000 per nonvolatile content was obtained.

(Dispersion resin (G-2) solution)
In a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reaction vessel, and the mixture was stirred while maintaining 110° C. under a nitrogen atmosphere to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added to dilute the mixture so that the nonvolatile content was 30% in the nonvolatile content measurement, and a dispersion resin (G-2) solution having a piperidyl skeleton with an amine value of 57 mgKOH/g per nonvolatile content and a number average molecular weight of 4,500 (Mn) was obtained.

<Preparation of Dispersion>
(Dispersion 1)
The following raw materials were mixed and stirred to be uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (R-1) was PGMAc.
Finely divided pigment (A-1-1): 12.0 parts Dispersion resin (G-1) solution: 13.3 parts Dispersion resin (G-2) solution: 6.7 parts Alkali-soluble resin (B-1) solution: 10.0 parts Organic solvent (R-1): 58.0 parts

(Dispersions 2 to 18)
Dispersions 2 to 18 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts thereof were changed as shown in Tables 1-1 and 1-2.

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

[Triarylsulfonium compound (E)]
E-1: SP-066 (manufactured by ADEKA Corporation: triphenylsulfonium trifluoromethanesulfonate) E-2: SP-056 (manufactured by ADEKA Corporation: triphenylsulfonium nonafluorobutanesulfonate) E-3: TS-01 (manufactured by SANWA CHEMICAL Co., Ltd.: tris(4-methylphenyl)sulfonium trifluoromethanesulfonate

<Production of Photosensitive Composition for Fingerprint Authentication Sensor>
[Example 1]
(Photosensitive Composition 1)
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain Photosensitive Composition 1.
Dispersion 1: 25.0 parts Alkali-soluble resin (B) solution: 12.5 parts Polymerizable compound (C-2-1): 2.5 parts Polymerizable compound (C-3-1): 2.5 parts Photopolymerization initiator (D-1): 0.5 parts Photopolymerization initiator (D-2): 0.5 parts Sensitizer (I): 0.17 parts Epoxy compound (J-1): 1.0 parts Thiol-based chain transfer agent (K): 0.1 parts Polymerization inhibitor (M): 0.01 parts UV absorber (L): 0.1 parts Antioxidant (N): 0.1 parts Leveling agent (O): 1.0 parts Organic solvent (R): 53.62 parts

[Examples 2 to 28, Comparative Examples 1 to 7]
(Photosensitive compositions 2 to 35)
Photosensitive compositions 2 to 35 were prepared in the same manner as in Example 1, except that the photosensitive composition 1 in Example 1 was changed to the raw materials and amounts shown in Tables 2-1 to 2-4. In this specification, Examples 1 to 25 are reference examples.

The ingredients listed in Tables 2-1 to 2-4 are as follows:

[Alkali-soluble resin (B) solution]
The alkali-soluble resin (B-2) to (B-6) solutions were mixed in equal amounts to prepare an alkali-soluble resin (B) solution.

[Polymerizable compound (C)]
(Polymerizable Compound (C-1) Having an Acid Group)
C-1-1: Aronix M-510 (manufactured by Toagosei Co., Ltd.)
C-1-2: Aronix M-520 (manufactured by Toagosei Co., Ltd.)
C-1-3: Aronix M-521 (manufactured by Toagosei Co., Ltd.)

(Other polymerizable compounds (C-3))
C-3-1: Aronix M-402 (manufactured by Toagosei Co., Ltd.)

[Photopolymerization initiator (D)]
D-1: Irgacure 907 (manufactured by BASF Japan)
D-2: Irgacure 379 (manufactured by BASF Japan)
D-3: Irgacure OXE02 (manufactured by BASF Japan)
D-4: Irgacure OXE04 (manufactured by BASF Japan)

[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).

[Epoxy compound (J-1)]
J-1-1: EHPE-3150 (manufactured by Daicel Corporation)
J-1-2: Denacol EX611 (manufactured by Nagase ChemteX Corporation)
J-1-3: Triglycidyl isocyanurate The above (J-1-1) to (J-1-3) were mixed in equal amounts to obtain epoxy compound (J-1).

[Thiol-based chain transfer agent (K)]
K-1: Trimethylolethane tris(3-mercaptobutyrate)
K-2: Trimethylolpropane tris(3-mercaptobutyrate)
K-3: Pentaerythritol tetrakis(3-mercaptopropionate)
K-4: Trimethylolpropane tris(3-mercaptopropionate)
K-5: Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate The above (K-1) to (K-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (K).

[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).

[Ultraviolet absorber (M)]
M-1: TINUVIN 400 (manufactured by BASF Japan)
M-2: TINUVIN900 (manufactured by BASF Japan)
The above (M-1) and (M-2) were mixed in equal amounts to prepare an ultraviolet absorber (M).

[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 The above (N-1) to (N-5) were mixed in equal amounts to give antioxidant (N).

[Leveling agent (O)]
O-1: BYK-330 (manufactured by BYK-Chemie)
O-2: Megafac F-551 (manufactured by DIC)
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).

[Organic solvent (R)]
R-1: Propylene glycol monomethyl ether acetate 30 parts R-2: Cyclohexanone 30 parts R-3: 3-ethoxyethyl propionate 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 obtain organic solvent (R).

<Evaluation of Photosensitive Composition>
The photosensitive compositions thus obtained were evaluated for development residue, pattern formation (linearity), spectral characteristics, and fingerprint authentication by the methods described below. The evaluation results are shown in Table 3.

[Evaluation of Development Residue]
The obtained photosensitive composition was applied to a TFT type liquid crystal driving substrate having a length of 100 mm, width of 100 mm, and a thickness of 0.7 mm using a spin coater so that the dry film thickness was 2.0 μm, and pre-baked at 90 ° C for 120 seconds. Next, an ultra-high pressure mercury lamp was used to perform ultraviolet exposure at an integrated light amount of 100 mJ / cm ² , and ultraviolet exposure was performed through a photomask with a 100 μm wide stripe pattern. Furthermore, after cooling the substrate to room temperature, it was spray-developed using a 0.04% potassium hydroxide aqueous solution at 23 ° C for two levels of development time (40 seconds, 70 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 with an optical microscope to evaluate the presence or absence of development residue and chipping in the unexposed parts. The results are as follows, and 2 or more is practical.
3: After 70 seconds of development, there was no development residue in the unexposed area and no pattern loss. 2: After 70 seconds of development, development residue occurred in the unexposed area or pattern loss occurred. 1: After 40 seconds of development, development residue occurred in the unexposed area or pattern loss occurred.

[Pattern formation evaluation (linearity)]
The obtained photosensitive composition was applied to a TFT type liquid crystal driving substrate having a length of 100 mm, width of 100 mm, and a thickness of 0.7 mm using a spin coater so that the dry film thickness was 2.0 μm, and pre-baked at 90 ° C for 120 seconds. Next, after cooling the substrate to room temperature, the substrate was exposed to light at an illuminance of 30 mW / cm ² and 100 mJ / cm ² using an ultra-high pressure mercury lamp through a photomask with a stripe pattern of 100 μm width (pitch 200 μm) and 10 μm width (pitch 20 μm). Thereafter, the substrate was spray-developed using a 0.04% potassium hydroxide aqueous solution at 23 ° C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C for 30 minutes to obtain a substrate for evaluation. The spray development was performed for each photosensitive composition coating for the shortest time possible to form a pattern without residual development, and this was determined as the appropriate development time.
The evaluation substrate thus prepared was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using a Nikon Eclipse LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with 3 or more 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.

<Preparation of substrate for evaluating spectroscopic characteristics>
The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Corporation) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm, so that the film thickness after post-baking was 1.0 μm. Next, after drying on a hot plate at 90° C. for 2 minutes, a substrate was prepared by exposing the substrate to 100 mJ/cm ² through a photomask having a square pattern of 100 μm squares using an ultra-high pressure mercury lamp. Thereafter, the substrate was spray-developed using a 0.04 mass% potassium hydroxide aqueous solution at 23° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230° C. for 30 minutes. The spray development was performed for the shortest time possible for forming a pattern without residual development.

[Measurement of wavelength range in which transmittance is 50% or more]
The obtained substrate for evaluating spectral characteristics was measured for wavelengths at which the transmittance was 50% or more in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation). The evaluation criteria were as follows, with 2 or more being practical.
4: The transmittance is 50% or more at wavelengths of 430 to 560 nm. 3: The transmittance is 50% or more at wavelengths of 440 to 550 nm. 2: The transmittance is 50% or more at wavelengths of 450 to 540 nm. 1: There are some areas where the transmittance is less than 50% at wavelengths of 450 to 540 nm.

[Measurement of transmittance at wavelengths of 620 to 690 nm]
The obtained substrate for evaluating spectral characteristics was measured for transmittance at wavelengths of 620 to 690 nm in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation). The evaluation criteria are as follows, with 2 or more being practical.
4: The transmittance is 3% or less at wavelengths of 620 to 690 nm. 3: The transmittance is 4% or less at wavelengths of 620 to 690 nm. 2: The transmittance is 5% or less at wavelengths of 620 to 690 nm. 1: There are some areas where the transmittance exceeds 5% at wavelengths of 620 to 690 nm.

[Measurement of wavelength range in which transmittance is 80% or more]
The obtained substrate for evaluating spectral characteristics was measured for the wavelength at which the transmittance was 80% or more in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation). The evaluation criteria were as follows.
4: The transmittance is 80% or more at wavelengths of 430 to 560 nm. 3: The transmittance is 80% or more at wavelengths of 440 to 550 nm. 2: The transmittance is 80% or more at wavelengths of 450 to 540 nm. 1: There are some areas where the transmittance is less than 80% at wavelengths of 450 to 540 nm.

[Measurement of transmittance at wavelengths of 700 to 730 nm]
The obtained substrate for evaluating spectral characteristics was measured for transmittance at wavelengths of 700 to 730 nm in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation). The evaluation criteria were as follows.
3: The transmittance is 30% or less at wavelengths of 700 to 730 nm. 2: The transmittance is 40% or less at wavelengths of 700 to 730 nm. 1: There are some areas where the transmittance exceeds 40% at wavelengths of 700 to 730 nm.

<Creating optical filters for fingerprint authentication evaluation>
A resist solution for planarization film (HL-18s manufactured by Nippon Steel Chemical Co., Ltd.) was applied onto a 6-inch silicon wafer by spin coating, and the wafer was heated on a hot plate at 100° C. for 6 minutes, and then heated in an oven at 230° C. for 1 hour to harden the coating film and obtain a silicon wafer with a planarization film.
Next, the obtained photosensitive composition was applied by spin coating on the planarizing film so that the film thickness after drying was 1.0 μm, and the film was prebaked for 1 minute on a hot plate at 100 ° C., and pattern exposure was performed at an exposure dose of 150 mJ / cm ² through a photomask for forming a pattern of 1.0 μm square at a wavelength of 365 nm using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon). The exposed coating film was subjected to paddle development with an organic alkaline developer. After paddle development, the wafer was washed with pure water in a spin shower for 20 seconds, and the water droplets remaining on the wafer were blown off with high-pressure air.
Further, a heat treatment (post-baking) was carried out on a hot plate at 200° C. for 5 minutes to obtain a silicon wafer having a pattern as an optical filter.

[Fingerprint authentication evaluation]
The obtained optical filter was incorporated into a fingerprint authentication sensor according to JP 2020-92080 A. The obtained fingerprint authentication sensor was irradiated with light having an emission wavelength of 470 nm, a fingerprint image was captured, and the image performance was evaluated. The evaluation criteria are as follows, with 2 or more being practical.
3: Fingerprint is clearly recognized 2: Fingerprint is recognized 1: Fingerprint is not recognized

10 Driving layer 11 Substrate 20 Fingerprint authentication sensor layer 21 Fingerprint authentication sensor 23 Reflected light 30 OLED light emitting layer 31 OLED
33 Light 40 Cover glass layer 50 Finger 100 Display panel

Claims (5)

A photosensitive composition for a fingerprint authentication sensor capable of forming a coating having a transmittance of 50% or more at a wavelength of 450 to 540 nm and a transmittance of 5% or less at a wavelength of 620 to 690 nm at a thickness of 1.0 μm,
The composition includes a pigment (A) including a pigment (A-1) represented by the following general formula (1), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D) , and a triarylsulfonium compound (E) ,
The photosensitive composition for a fingerprint authentication sensor, wherein the triarylsulfonium compound (E) comprises a compound represented by general formula (5) :
General formula (1)


(In general formula (1), X represents a halogen atom, and n represents 4 to 16.)
General formula (5)

(In general formula (5), R ₁ to R ₃ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent. X ⁻ represents a compound represented by any one of the following general formulae (6) to (11).)
General formula (6) MY _a ^-
(In general formula (6), M represents a phosphorus atom, a boron atom, or an antimony atom; Y represents a halogen atom; and a represents an integer of 4 to 6.)
General formula (7) (Rf) _b PF _6-b ^-
(In general formula (7), Rf represents an alkyl group having 1 to 8 carbon atoms in which 80 mol % or more of the hydrogen atoms are substituted with fluorine atoms. The alkyl group may be linear, branched, or cyclic. b represents an integer of 1 to 5.)
General formula (8) R ⁴ _c LY _c ^-
(In the general formula (8), R4 ^represents a phenyl group in which at least one hydrogen atom is substituted with a halogen atom. L represents a boron atom or a gallium atom, and c represents an integer of 1 to 4.)
General formula (9) R ⁵ SO ₃ ^-
(In the general formula (9), R5 ^represents an alkyl group having 1 to 12 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; the alkyl group and the perfluoroalkyl group may be linear, branched, or cyclic; and the aryl group may be unsubstituted or may have a substituent.)
General formula (10) (R ⁶ SO ₂ ) ₃ C ^-
(In general formula (10), R6 ^represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; the alkyl group and the perfluoroalkyl group may be linear, branched, or cyclic; and the aryl group may be unsubstituted or may have a substituent.)
General formula (11) (R ⁷ SO ₂ ) ₂ N ⁻
(In general formula (11), R7 ^represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, the alkyl group and the perfluoroalkyl group may be linear, branched, or cyclic, and the aryl group may have a substituent.) The photosensitive composition for fingerprint authentication sensors according to claim 1, wherein the content of the pigment (A-1) is 95% by mass or more relative to 100% by mass of the pigment (A). An optical filter comprising a substrate and a coating formed from the photosensitive composition for a fingerprint authentication sensor according to claim 1 or 2 . A fingerprint authentication sensor comprising the optical filter according to claim 3 . An image display device having the fingerprint authentication sensor according to claim 4 inside an image display.

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