Photosensitive composition, optical filter, fingerprint authentication sensor, and image display device

A photosensitive composition with a controlled pigment content and specific components forms a coating that addresses noise and pattern issues in optical fingerprint sensors, enhancing authentication accuracy and reducing foreign matter, thus improving sensor and display device performance.

JP7718231B2Active Publication Date: 2025-08-05TOYO INK MFG CO LTD +1
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Patent Information

Application Number
JP2021176226
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Filing Date
2021-10-28
Publication Date
2025-08-05
Estimated Expiration
2041-10-28

AI Technical Summary

Technical Problem

Optical fingerprint authentication sensors in smartphones are affected by external light with a wavelength of around 660 nm, causing noise and reducing authentication accuracy, and the photolithography method used in forming optical filters leads to issues such as thicker pattern lines and foreign matter generation.

Method used

A photosensitive composition comprising a pigment (A) with a specific formula, an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), where the pigment content is less than 20% by mass, forms a coating with improved transmittance at 450 to 570 nm and reduced transmittance at 630 to 690 nm, minimizing foreign matter generation.

Benefits of technology

The composition forms a coating that suppresses the transmission of 660 nm light, enhances pattern formability, and reduces foreign matter, thereby improving fingerprint authentication accuracy and display device performance.

✦ Generated by Eureka AI based on patent content.

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Abstract

To provide a photosensitive resin composition which enables an optical filter that suppresses permeation of light in the vicinity of a wavelength of 660 nm and can permeate light of a wide wavelength region on a wavelength side lower than a wavelength of 600 nm, and is excellent in fingerprint authentication accuracy, is excellent in pattern formation property, and generates little foreign matter.SOLUTION: A photosensitive composition enables formation of a film which has film thickness of 2.0 μm, transmittance at a wavelength of 450-570 nm of 50% or more, and transmittance at a wavelength of 630-690 nm of 15% or less, in which the photosensitive composition contains a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), the pigment (A) contains a phthalocyanine-based pigment (A1) represented by a specific formula, the photopolymerization initiator (D) contains an acetophenone-based compound (D1), and a content of the pigment (A) is less than 20 mass% in 100 mass% of a non-volatile content of the photosensitive composition.SELECTED DRAWING: Figure 1
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Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition for use in fingerprint authentication sensors, image display devices, and the like. [Background technology]

[0002] In recent years, fingerprint authentication sensors have been incorporated into mobile devices such as smartphones and tablets. Fingerprint authentication sensors are available in optical and ultrasonic types, with the optical type being widely used as it is inexpensive and easy to install.

[0003] 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 a captured image based on the light reflected from the finger. Optical filters used in fingerprint authentication sensors are generally formed by photolithography using a photosensitive composition containing a pigment. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-196319 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when an optical fingerprint authentication sensor is incorporated into the display of a smartphone or other device, external light with a wavelength of around 660 nm passes through body tissue, generating noise and preventing the generation of a correct captured image, resulting in reduced fingerprint authentication accuracy.

[0006] Furthermore, in the photolithography method, when the pigment concentration in the photosensitive composition is low, the active energy rays (such as i-rays) are easily transmitted, which causes problems such as the line width of the pattern becoming thicker, deteriorating the pattern shape, and generating foreign matter.

[0007] The present invention aims to provide a photosensitive composition that can form a coating that suppresses the transmission of light with a wavelength of around 660 nm and is capable of transmitting light in a wide wavelength range below 600 nm, and that has excellent pattern formability and generates little foreign matter. [Means for solving the problem]

[0008] The photosensitive composition of the present invention can form a coating having a thickness of 2.0 μm and a transmittance of 50% or more at a wavelength of 450 to 570 nm and a transmittance of 15% or less at a wavelength of 630 to 690 nm, the photosensitive composition comprises a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D); The pigment (A) contains a pigment (A1) represented by the following general formula (1): the photopolymerization initiator (D) contains an acetophenone-based compound (D1), The content of the pigment (A) is less than 20% by mass in 100% by mass of the nonvolatile content of the photosensitive composition. General formula (1) [ka] (In general formula (1), X represents a halogen atom, and n represents 0 to 16.) [Effects of the Invention]

[0009] According to the present invention described above, it is possible to form a coating that suppresses the transmission of light with a wavelength of around 660 nm and that is capable of transmitting light in a wide wavelength range below 600 nm, and it is possible to provide a photosensitive composition, an optical filter, a fingerprint authentication sensor, and an image display device that are excellent in pattern formability and generate little foreign matter. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device that includes a fingerprint authentication sensor inside an image display. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0012] 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. Also, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. A monomer is a compound that forms a resin upon polymerization. A monomer is in an unreacted state, and a monomer unit is a monomer that forms a resin after polymerization. A polymerizable compound is a compound that forms a coating upon polymerization.

[0013] <Photosensitive composition> The photosensitive composition of the present invention is a photosensitive composition capable of forming a coating having a thickness of 2.0 μm and a transmittance of 50% or more at wavelengths of 450 to 570 nm and a transmittance of 15% or less at wavelengths of 630 to 690 nm, the photosensitive composition comprises a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D); The pigment (A) contains a pigment (A1) represented by the following general formula (1): the photopolymerization initiator (D) contains an acetophenone-based compound (D1), The content of the pigment (A) is less than 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition. The photosensitive composition of the present invention can be used for various applications in which patterns are formed by photolithography, and is preferably used for filters for fingerprint authentication sensors.

[0014] General formula (1) [ka] (In general formula (1), X represents a halogen atom, and n represents 0 to 16.)

[0015] The mechanism by which the photosensitive coloring composition having the above-mentioned constitution can solve the problems of the present invention is not clear, but is speculated as follows. By suppressing the content of pigment (A) to less than 20 mass% of the total nonvolatile content of the photosensitive composition and including pigment (A1) represented by general formula (1), transmittance at wavelengths of 450 to 570 nm can be improved and transmittance at wavelengths of 630 to 690 nm can be suppressed. Furthermore, even when the pigment content is suppressed, by using an acetophenone-based compound (D1) with low sensitivity as the photopolymerization initiator (D), the line width of the developed pattern is unlikely to be wider than the line width of the photomask, and the generation of foreign matter can also be suppressed.

[0016] Pigment The pigment (A) contains a pigment (A1) represented by general formula (1), and the content of the pigment (A) is less than 20% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0017] (Pigment (A1) represented by general formula (1)) In the general formula (1), X represents a halogen atom, and n represents 0 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.

[0018] Examples of the halogen atom represented by X in general formula (1) include fluorine, bromine, chlorine, and iodine. The halogen atoms can be used alone or in combination of two or more. Among these, bromine and chlorine are preferred, with bromine being more preferred, from the viewpoint of transmittance at wavelengths of 450 to 570 nm.

[0019] In general formula (1), n is preferably 0 to 12, more preferably 0 to 10, and particularly preferably 4 to 10, from the viewpoint of transmittance at wavelengths of 450 to 570 nm.

[0020] The pigment (A1) can be used alone or in combination of two or more kinds.

[0021] From the viewpoint of transmittance, the content of the pigment (A1) is preferably 95% by mass or more, more preferably 99% by mass or more, and particularly preferably 100% by mass, based on 100% by mass of the pigment (A).

[0022] <Method for producing pigment (A1) represented by general formula (1)> The method for producing the pigment (A1) represented by general formula (1) is not particularly limited and can be produced by known methods, examples of which are shown below.

[0023] A compound represented by the following chemical formula (3) is halogenated and then hydrolyzed to synthesize a compound represented by the following general formula (4), which is then reacted with diphenyl phosphate to synthesize a pigment (A1) represented by the general formula (1).

[0024] [ka]

[0025] The halogenated compound represented by chemical formula (3) can be synthesized by, for example, the chlorosulfonic acid method or the dissolution method described in The Phthalocyanines Volume II Manufacture and Applications (CRC Press, Inc., 1983).

[0026] In the chlorosulfonic acid method, the compound represented by the chemical formula (3) is dissolved in a sulfur oxide solvent such as chlorosulfonic acid or sulfuric acid, and then halogenated using a halogenating agent. The reaction temperature is preferably about 20 to 120°C, and the reaction time is preferably about 1 to 10 hours.

[0027] An example of the dissolution method is a method described in Japanese Patent Laid-Open No. 51-64534 in which a phthalocyanine compound is halogenated 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 alkaline earth metal halide (hereinafter referred to as an alkali(earth) metal halide) such as sodium chloride or sodium bromide, or thionyl chloride.

[0028] The halogenating agent used for halogenation is a fluorinating agent, a chlorinating agent, a brominating agent, or an iodinating agent, such as fluoroxytrifluoromethane, cesium fluoride sulfate, acetyl hypofluorite, N-fluorosulfonamide, diethylaminosulfur trifluoride, or N-fluoropyridinium salt. Examples of the chlorinating agent include chlorine (Cl2), 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 (Br2), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetylhypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexa-2,5-dienone, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, and 1,3-dibromo-5,5-dimethylhydantoin. Examples of the iodinating agent include iodine (I2), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodite, iodine-periodic acid, ethylene iodochloride, and N-iodosuccinimide.

[0029] The compound represented by general formula (4) has the properties of a pigment. Therefore, in order to improve the reaction efficiency with diphenyl phosphate, it is preferable to perform 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 (4) is micronized in advance, the pigment (A1) represented by general formula (1) synthesized from it is also likely to be obtained in the form of fine particles.

[0030] The reaction between the compound represented by general formula (4) and diphenyl phosphate is carried out, for example, by mixing and stirring in an organic solvent, and then the organic solvent is removed to obtain the pigment (A1) represented by general formula (1).

[0031] 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 suitable solvents include lower monoalkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monoethyl (or butyl) ether; polyether solvents such as ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), and triethylene glycol dimethyl ether (triglyme); sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, and 3-sulfolene; polyfunctional solvents such as diacetone alcohol and diethanolamine; carboxylic acid solvents such as acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, and trifluoroacetic acid; sulfonic acid solvents such as methanesulfonic acid and trifluorosulfonic acid; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these, monohydric alcohol solvents such as methanol, ethanol, and isopropyl alcohol, and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and 1-methyl-2-pyrrolidinone are preferred because they dissolve diphenyl phosphate well. The organic solvents can be used alone or in combination of two or more kinds.

[0032] The method for removing the organic solvent is not particularly limited, 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 addition, 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.

[0033] (Other pigments (A2)) The pigment (A) may contain a pigment other than the pigment (A1) represented by general formula (1) (hereinafter also referred to as other pigment (A2)). There are no particular restrictions on the other pigment (A2), and any known pigment may be used.

[0034] Other pigments (A2) include, for example, CI 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, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, Yellow pigments described in JP 2012-226110 A and JP 6432077 A; CI 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, 64 3:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 2 1,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259 ,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 CI 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 CI 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; Purple pigments such as CI 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; Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0035] The other pigments (A2) can be used alone or in combination of two or more kinds.

[0036] From the viewpoint of transmittance, the content of the pigment (A) is preferably 8% by mass or more and 18% by mass or less, and more preferably 10% by mass or more and 18% by mass or less, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0037] (Fine particle size 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, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter 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 diameter is more preferably 10 to 70 nm.

[0038] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heat 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. Optimizing the conditions for salt milling a pigment can produce a pigment with an extremely fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0039] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the viewpoint of cost. From the viewpoints of both treatment 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 the pigment (A).

[0040] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. Examples of water-soluble organic solvents that can be used include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment (A).

[0041] A resin may be added to the salt milling treatment as needed. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, resins that are solid at room temperature and insoluble in water are preferred, and those that are partially soluble in the organic solvents are preferred. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0042] (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. Also included are dye derivatives and lake pigments obtained by converting dyes into lakes.

[0043] The dye is preferably used as a salt-forming compound. Examples of the salt-forming compound include a salt-forming compound of an acid dye with a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a salt-forming compound of an acid dye with a resin component having an amino group; a salt-forming compound of an acid dye with a compound having an onium salt group; and a salt-forming compound of a basic dye with an organic acid, perchloric acid, or a metal salt thereof. Among these, a salt-forming compound of a basic dye is preferred because of its excellent resistance to various types of resistance and compatibility with pigments. The compound having an onium salt group is preferably a resin having a cationic group in the side chain.

[0044] The chemical structure of the dye may be, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, etc. Examples of the dye structure include dyes derived from dyes selected from the group consisting of oxonol-based dyes, merocyanine-based dyes, arylidene-based dyes, styryl-based dyes, cyanine-based dyes, squarylium-based dyes, and croconium-based dyes, quinophthalone-based dyes, phthalocyanine-based dyes, subphthalocyanine-based dyes, perinone-based dyes, indigo-based dyes, thioindigo-based dyes, quinoline-based dyes, nitro-based dyes, nitroso-based dyes, rhodamine-based dyes, and metal complex dyes thereof.

[0045] 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.

[0046] [Alkali-soluble resin (B)] The alkali-soluble resin (B) may be any resin that dissolves in an alkaline developer, and known resins can be used. The alkali-soluble resin (B) preferably has an alkali-soluble group such as a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, or a phenolic hydroxyl group. Among these, a carboxyl group is preferred. Examples of the alkali-soluble resin (B) include an alkali-soluble resin (B1) having an alicyclic hydrocarbon-containing monomer unit (b1) and a polymerizable unsaturated group-containing monomer unit (b2) (hereinafter referred to as alkali-soluble resin (B1)), an alkali-soluble resin (B2) having an alicyclic hydrocarbon-containing monomer unit (b1) but not a polymerizable unsaturated group-containing monomer unit (b2) (hereinafter referred to as alkali-soluble resin (B2)), and an alkali-soluble resin (B3) other than the alkali-soluble resin (B1) and the alkali-soluble resin (B2) (hereinafter referred to as other alkali-soluble resin (B3)).

[0047] The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably from 4,000 to 40,000, more preferably from 4,000 to 35,000.

[0048] The acid value of the alkali-soluble resin (B) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g, from the viewpoint of developability.

[0049] The content of the alkali-soluble resin (B) is preferably from 1 to 80% by mass, more preferably from 5 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0050] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0051] The alkali-soluble resin (B) preferably contains an alkali-soluble resin (B1) from the viewpoint of pattern formability, and preferably contains an alkali-soluble resin (B2) from the viewpoint of suppressing foreign matter.

[0052] The total content of the alkali-soluble resin (B1) and the alkali-soluble resin (B2) is preferably from 60 to 100 mass %, more preferably from 80 to 100 mass %, based on 100 mass % of the alkali-soluble resin (B).

[0053] (Alkali-soluble resin (B1)) The alkali-soluble resin (B1) is an alkali-soluble resin having an alicyclic hydrocarbon-containing monomer unit (b1) and a polymerizable unsaturated group-containing monomer unit (b2). The alkali-soluble resin (B1) may be any known alkali-soluble resin as long as it contains these monomer units. Examples of the alkali-soluble resin (B1) include copolymers of a monomer forming the alicyclic hydrocarbon-containing monomer unit (b1) with a monomer forming the polymerizable unsaturated group-containing monomer unit (b2), copolymers obtained by reacting a copolymer of a monomer forming the alicyclic hydrocarbon-containing monomer unit (b1) with another monomer copolymerizable therewith with a compound having a polymerizable unsaturated group to introduce the polymerizable unsaturated group-containing monomer unit (b2), and copolymers obtained by the method described in JP 2008-165059 A.

[0054] [Alicyclic hydrocarbon-containing monomer unit (b1)] Examples of the monomer forming the alicyclic hydrocarbon-containing monomer unit (b1) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, from the viewpoint of pattern formability, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0055] From the viewpoint of pattern formability, the content of the alicyclic hydrocarbon-containing monomer unit (b1) is preferably from 1 to 60 mol %, more preferably from 1 to 40 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0056] [Polymerizable unsaturated group-containing monomer unit (b2)] The alkali-soluble resin (B1) can be made to contain the polymerizable unsaturated group-containing monomer unit (b2) by, for example, the following methods (i) to (iii).

[0057] <Method (i)> In the method (i), for example, a polymer (precursor) of an epoxy group-containing monomer and other monomers is first synthesized, and then a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

[0058] 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.

[0059] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Among these, acrylic acid and methacrylic acid are preferred.

[0060] From the viewpoint of developability, a monomer unit having a moiety in which an acid anhydride is further reacted with a moiety in which a carboxyl group of a carboxyl group-containing monomer is added to an epoxy group of an epoxy group-containing monomer unit is preferred as the polymerizable unsaturated group-containing monomer unit (b2).

[0061] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0062] <Method (ii)> In the method (ii), for example, a polymer (precursor) of a carboxyl group-containing monomer and other monomers is first synthesized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0063] <Method (iii)> In the method (iii), for example, a polymer (precursor) of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers is first synthesized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0064] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate.

[0065] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0066] From the viewpoint of pattern formability, the content of the polymerizable unsaturated group-containing monomer unit (b2) is preferably from 5 to 80 mol %, more preferably from 10 to 80 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0067] [Aromatic ring-containing monomer unit (b3) having a homopolymer glass transition temperature of 80°C or higher] From the viewpoint of pattern formability, the alkali-soluble resin (B1) preferably contains an aromatic ring-containing monomer unit (b3) (hereinafter referred to as aromatic ring-containing monomer unit (b3)) whose homopolymer has a glass transition temperature of 80°C or higher. The glass transition temperature of the homopolymer is the value shown in "Polymer Handbook, Third Edition, John Wiley & Sons, 1989" edited by Brandrup, J. and Immergut, EH.

[0068] Examples of aromatic ring-containing monomers include styrene, α-methylstyrene, vinylnaphthalene, etc. Among these, styrene and α-methylstyrene are preferred from the viewpoint of reactivity.

[0069] From the viewpoint of pattern formability, the content of the aromatic ring-containing monomer unit (b3) is preferably from 1 to 50 mol %, more preferably from 1 to 40 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0070] [Other monomer units (b4)] The alkali-soluble resin (B1) can contain monomer units other than (b1) to (b3) (hereinafter also referred to as other monomer units (b4)).

[0071] Examples of other monomers include acrylic acid esters such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or PO-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate; Epoxy group-containing (meth)acrylates such as oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate; (meth)acrylates containing a blocked isocyanate group, such as 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, and benzoic acid-4-[[[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester; Unsaturated carboxylic acids such as (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2-acryloyloxyethylhexylhydrophthalic acid; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. These monomers can be used alone or in combination of two or more.

[0072] The alkali-soluble resin (B1) can be used alone or in combination of two or more kinds.

[0073] The weight average molecular weight (Mw) of the alkali-soluble resin (B1) is preferably from 4,000 to 40,000, more preferably from 4,000 to 35,000.

[0074] The acid value of the alkali-soluble resin (B1) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g.

[0075] (Alkali-soluble resin (B2)) The alkali-soluble resin (B2) is an alkali-soluble resin that has an alicyclic hydrocarbon-containing monomer unit (b1) but does not have a polymerizable unsaturated group-containing monomer unit (b2). The alkali-soluble resin (B2) is not particularly limited as long as it is an alkali-soluble resin that has an alicyclic hydrocarbon-containing monomer unit (b1) but does not have a polymerizable unsaturated group-containing monomer unit (b2), and known alkali-soluble resins can be used. For example, alkali-soluble resins that have the above-mentioned alicyclic hydrocarbon-containing monomer unit (b1) and other monomer units (b4) can be used.

[0076] From the viewpoint of suppressing foreign matter, the content of the alicyclic hydrocarbon-containing monomer unit (b1) is preferably 1 to 60 mol %, more preferably 1 to 40 mol %, of all the constituent units of the alkali-soluble resin (B2).

[0077] The alkali-soluble resin (B2) can be used alone or in combination of two or more kinds.

[0078] The weight average molecular weight (Mw) of the alkali-soluble resin (B2) is preferably from 4,000 to 40,000, more preferably from 4,000 to 35,000.

[0079] The acid value of the alkali-soluble resin (B2) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g.

[0080] From the viewpoint of suppressing foreign matter, the content of the alkali-soluble resin (B2) is preferably 40 to 95 mass%, more preferably 60 to 95 mass%, relative to 100 mass% of the total content of the alkali-soluble resin (B1) and the alkali-soluble resin (B2).

[0081] (Other alkali-soluble resins (B3)) The other alkali-soluble resin (B3) is an alkali-soluble resin other than the alkali-soluble resin (B1) and the alkali-soluble resin (B2). Known resins can be used as the other alkali-soluble resin (B3). Examples of such resins include α-olefin / maleic anhydride copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic anhydride copolymers.

[0082] [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 (C1) having a urethane bond, a polymerizable compound (C2) having 3 or 4 polymerizable unsaturated groups (excluding the polymerizable compound (C1)), and other polymerizable compounds (C3) (excluding the polymerizable compound (C1) and the polymerizable compound (C2)).

[0083] (Polymerizable compound (C1) having a urethane bond) The use of a polymerizable compound (C1) having a urethane bond improves pattern formability. Examples of the polymerizable compound (C1) having a urethane bond include a urethane (meth)acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a urethane (meth)acrylate obtained by reacting a product of a polyhydric alcohol with a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group.

[0084] 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.

[0085] Examples of polyfunctional isocyanates include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; and biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adducts thereof.

[0086] From the viewpoint of developability, it is also preferable that the polymerizable compound (C1) having a urethane bond further has an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0087] The acid group can be introduced into the polymerizable compound (C1) having a urethane bond by, for example, first reacting a (meth)acrylate having a hydroxyl group with the above-mentioned polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0088] Examples of mercapto compounds having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0089] Commercially available polymerizable compounds (C1) having a urethane bond include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0090] The number of polymerizable unsaturated groups in the polymerizable compound (C1) having a urethane bond is preferably from 3 to 15, more preferably from 5 to 12, from the viewpoint of pattern formability.

[0091] From the viewpoint of pattern formability, the content of the polymerizable compound (C1) having a urethane bond is preferably from 5 to 80 mass %, more preferably from 10 to 70 mass %, in 100 mass % of the polymerizable compound (C).

[0092] (Polymerizable Compound (C2) Having 3 or 4 Polymerizable Unsaturated Groups) When a polymerizable compound (C2) having 3 or 4 polymerizable unsaturated groups is used, the pattern formability is further improved.

[0093] Examples of the polymerizable compound (C2) having 3 or 4 polymerizable unsaturated groups include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, ditrimethylolpropane EO-modified tri(meth)acrylate, Examples of such an alkyl acrylate include ditrimethylolpropane PO-modified tri(meth)acrylate, ditrimethylolpropane EO-modified tetra(meth)acrylate, ditrimethylolpropane PO-modified tetra(meth)acrylate, pentaerythritol EO-modified tri(meth)acrylate, pentaerythritol PO-modified tri(meth)acrylate, pentaerythritol EO-modified tetra(meth)acrylate, pentaerythritol PO-modified tetra(meth)acrylate, diglycerin EO-modified tri(meth)acrylate, diglycerin PO-modified tri(meth)acrylate, diglycerin EO-modified tetra(meth)acrylate, diglycerin PO-modified tetra(meth)acrylate, and isocyanuric acid EO-modified tri(meth)acrylate.

[0094] Commercially available polymerizable compounds (C2) having 3 or 4 polymerizable unsaturated groups include Aronix M-309, M-310, M-321, M-350, M-360, M-306, M-305, M-450, M-408, and M-510 manufactured by Toagosei Co., Ltd.; KAYARAD GPO-303, TMPTA, PET-30, T-1420(T), and RP-1040 manufactured by Nippon Kayaku Co., Ltd.; NK Ester A-TMPT, A-TMPT-3EO, AT-20E, A-GLY-3E, A-TMM-3, ATM-4EL, ATM-4PL, A-TMMT, ATM-4E, and AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.; Viscoat #295 and #300 manufactured by Osaka Organic Chemical Industry Co., Ltd.; and Miramer manufactured by Miwon Specialty Chemical Co., Ltd. Examples include M300, M3130, M3160, M3190, M360, M370, M4004, M410, and M420.

[0095] From the viewpoint of pattern formability, the content of the polymerizable compound (C2) having 3 or 4 polymerizable unsaturated groups is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, based on 100 mass % of the polymerizable compound (C).

[0096] (Other polymerizable compounds (C3)) Examples of other polymerizable compounds (C3) 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, polypropylene glycol di(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,6-hexanediol diglyceride, Examples of suitable acrylic acid esters and methacrylic acid esters include bisphenol A 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 esters of methylolated melamine, and epoxy (meth)acrylate; styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0097] Other commercially available polymerizable compounds (C3) include Aronix M-101A, M-111, M-120, M-140, M-208, M-215, M-220, M-240, M-403, M-400, M-402, M-404, M-405, M-5300, M-5400, M-520, and M-521 manufactured by Toagosei Co., Ltd.; KAYARAD R-128H, NPGDA, PEG400DA, FM-400, R-167, HX-200, R-551, R-721, R-604, R-684, DPHA, DPEA-12, D-310, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.; and NK Ester manufactured by Shin-Nakamura Chemical Co., Ltd. A-DPH, A-9550, A-DPH-12E, Miramer M500, M600, HR6060, HR6100, HR6200 manufactured by Miwon Specialty Chemical Co., Ltd., OGSOL EA-0200, EA-0300 manufactured by Osaka Gas Chemicals Co., Ltd., and the like.

[0098] The polymerizable compound (C) can be used alone or in combination of two or more kinds.

[0099] The content of the polymerizable compound (C) is preferably from 5 to 70 mass %, more preferably from 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0100] [Photopolymerization initiator (D)] (Acetophenone-based compounds (D1) The photopolymerization initiator (D) includes an acetophenone-based compound (D1).

[0101] Examples of the acetophenone compound (D1) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylprop-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane, 2-hydroxy-1-(4-(4-2-hydroxy-2-methylpropynyl)benzyl)phenyl)-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone, and compounds represented by general formula (2).

[0102] Commercially available acetophenone compounds (D1) include Omnirad 907, 369E, 379EG, 184, 1173, 2959, and 127 manufactured by IGM Resins.

[0103] [Compound represented by general formula (2)] From the viewpoint of pattern formability and suppression of foreign matter, the photosensitive composition of the present invention preferably contains a compound represented by the following general formula (2) as the acetophenone-based compound (D1).

[0104] General formula (2) [ka]

[0105] In the general formula (2), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Among these, from the viewpoint of the pattern shape, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0106] In general formula (2), R3 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Substituents that the benzoyl group or thenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0107] Examples of methods for producing the compound represented by general formula (2) include the methods described in JP-A-2019-507108 and JP-A-2019-528331.

[0108] Specific examples of the compound represented by formula (2) are shown below, but the present invention is not limited to these.

[0109] [ka]

[0110] Chemical formula (7) [ka]

[0111] Among the compounds of chemical formulas (5) to (7), the compound of chemical formula (5) is preferred from the viewpoint of pattern forming properties and suppression of foreign matter.

[0112] The acetophenone-based compound (D1) can be used alone or in combination of two or more kinds.

[0113] From the viewpoint of pattern formability, the content of the acetophenone compound (D1) is preferably from 50 to 100 mass %, more preferably from 70 to 100 mass %, based on 100 mass % of the photopolymerization initiator (D).

[0114] (Other photopolymerization initiators (D2)) The photopolymerization initiator (D) may contain a photopolymerization initiator (D2) other than the acetophenone-based compound (D1) (hereinafter also referred to as other photopolymerization initiator (D2)) within the range that does not impair the effects of the present invention.

[0115] Other examples of the photopolymerization initiator (D2) include benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; 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; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis( biimidazole compounds such as 2,2'-bis(o-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

[0116] The other photopolymerization initiators (D2) can be used alone or in combination of two or more.

[0117] From the viewpoint of pattern formability, the content of the photopolymerization initiator (D) is preferably from 1 to 10 parts by mass, more preferably from 2 to 8 parts by mass, relative to 100 parts by mass of the polymerizable compound (C).

[0118] [Near-infrared absorbing dye (E)] The photosensitive composition of the present invention may contain a near-infrared absorbing dye (E), which can block near-infrared light that is highly permeable to body tissues, thereby improving the accuracy of fingerprint authentication.

[0119] The near-infrared absorbing dye (E) is a compound having a maximum absorption in a wavelength range of 700 to 2,000 nm, and may be a pigment (also called a near-infrared absorbing pigment) or a dye (also called a near-infrared absorbing dye). A near-infrared absorbing pigment and a near-infrared absorbing dye may also be used in combination. From the viewpoint of heat resistance, a near-infrared absorbing pigment is preferred. In the present invention, the near-infrared absorbing pigment preferably has a solubility in 100 g of propylene glycol monomethyl ether acetate at 25° C. of less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

[0120] From the viewpoint of solvent resistance, the near-infrared absorbing dye (E) preferably has a π-conjugated plane containing a monocyclic or fused aromatic ring. The π-π interaction between the aromatic rings causes association of the near-infrared absorbing dyes (E) with each other, thereby suppressing elution into organic solvents.

[0121] The π-conjugated plane of the near-infrared absorbing dye (E) preferably contains 2 to 100 monocyclic or condensed aromatic rings, more preferably 3 to 50, still more preferably 4 to 40, and particularly preferably 5 to 30. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, a quaterrylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, a fluorene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a triazole ring, a benzotriazole ring, an oxazole ring, a benzoxazole ring, an imidazoline ring, a pyrazine ring, a quinoxaline ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an indole ring, an isoindole ring, a carbazole ring, and fused rings having these rings.

[0122] Specific examples of the near-infrared absorbing dye (E) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, oxonol compounds, pyrromethene compounds, azomethine compounds, triarylmethane compounds, dibenzofuranone compounds, etc. Among these, from the viewpoint of heat resistance, it is preferable to include at least one selected from the group consisting of naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds.

[0123] Cyanine compounds are disclosed in WO 2006 / 006573, WO 2010 / 073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; phthalocyanine compounds are disclosed in JP 4-23868, JP 06-192584, JP 2000-63691, WO 2014 Naphthalocyanine compounds are disclosed in JP-A-11-152414, JP-A-2000-86919, JP-A-2009-29955, WO-A-2017 / 002920, WO-A-2018 / 186490, etc.; indigo compounds are disclosed in JP-A-2012-224593, JP-A-2013-87233, JP-A-2013-230412, etc. Immonium compounds are disclosed in JP 2005-336150 A, JP 2007-197492 A, JP 2008-88426 A, etc.; anthraquinone compounds are disclosed in JP 62-903 A, JP 1-172458 A, etc.; pyrrolopyrrole compounds are disclosed in JP 2009-263614 A, JP 2010-90313 A, JP 2011-068731 A Examples of squarylium compounds include those described in JP 2011-132361 A, JP 2016-142891 A, WO 2017 / 135359 A, WO 2018 / 225837 A, JP 2019-001987 A, WO 2020 / 054718 A, etc. Examples of croconium compounds include those described in WO 2019 / 021767 A, etc.

[0124] (Squarylium compounds) The squarylium compound is preferably a compound represented by the following general formula (8).

[0125] General formula (8) [ka]

[0126] In general formula (8), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 10 , -COR 11 , -COOR 12 , -OCOR 13 , -NR 14 R 15 , -NHCOR 16 , -CONR 17 R 18 , -NHCONR 19 R 20 , -NHCOOR 21 , -SR 22 , -SO2R 23 , -SO2OR 24 , -NHSO2R 25 , -SO2NR 26 R 27 , -B(OR 28 )2, and -NHBR 29 R 30 Represents R 10 ~R 30 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. 12 R 12 When -SO2OR is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in the form of a salt. 24 R 24When R is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt. 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.

[0127] The "substituent" is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 100 , -COR 101 , -COOR 102 , -OCOR 103 , -NR 104 R 105 , -NHCOR 106 , -CONR 107 R 108 , -NHCONR 109 R 110 , -NHCOOR 111 , -SR 112 , -SO2R 113 , -SO2OR 114 , -NHSO2R 115 or -SO2NR 116 R 117 Examples include: R 100 ~R 117 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. 102 R 102 When -SO2OR is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in the form of a salt. 114 R 114 When is a hydrogen atom (ie, a sulfo group), the hydrogen atom may be dissociated (ie, a sulfonate group) or may be in the form of a salt.

[0128] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkynyl group may be linear, branched, or cyclic. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms. The alkyl portion of the aralkyl group is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the aryl group described above. The aralkyl group preferably has 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, and particularly preferably 7 to 25 carbon atoms. The heteroaryl group is preferably a monocyclic ring or a fused ring, more preferably a monocyclic ring or a fused ring having 2 to 8 rings, and particularly preferably a monocyclic ring or a fused ring having 2 to 4 rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12. The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, and aralkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the "substituents" described above.

[0129] From the viewpoint of light resistance and heat resistance, the squarylium compound is more preferably a compound represented by the following general formula (9).

[0130] General formula (9) [ka]

[0131] In general formula (9), R 5 ~R 8 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 50 , -COR 51 , -COOR 52 , -OCOR 53 , -NR 54 R 55 , -NHCOR 56 , -CONR 57 R 58 , -NHCONR 59 R 60 , -NHCOOR 61 , -SR 62 , -SO2R 63 , -SO2OR 64 , -NHSO2R 65 or -SO2NR 66 R 67 , -B(OR 68 )2, and -NHBR 69 R 70 Represents R 50 ~R 70 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. 52 R 52 When -SO2OR is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group) or may be in the form of a salt. 64 R 64 When R is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt. 5 and R 6 , R 7 and R 8 may be bonded to each other to form a ring.

[0132] The "substituent" has the same meaning as the "substituent" described above.

[0133] Specific examples of squarylium compounds are shown below, but the present invention is not limited to these.

[0134] [ka]

[0135] [ka]

[0136] (Pyrrolopyrrole compounds) The pyrrolopyrrole compound is preferably a compound represented by the following general formula (10).

[0137] General formula (10) [ka]

[0138] In general formula (10), R 1x and R 1y each independently represents an alkyl group, an aryl group, or a heteroaryl group; R 2 and R 3 each independently represents a hydrogen atom or a substituent, R 2 and R 3 may be bonded to each other to form a ring, R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4x R 4y or a metal atom, R 4 is R 1x , R 1y and R 3 may be covalently or coordinately bonded to at least one selected from the group consisting of R 4x R 4y each independently represents a substituent. General formula (10) is described in JP-A-2009-263614, JP-A-2011-68731, and WO 2015 / 166873.

[0139] R 1x and R1y are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. 1x and R 1y The alkyl group, aryl group, and heteroaryl group represented by may have a substituent or may be unsubstituted. The substituent may be an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR 11 , -SOR 12 , -SO2R 13 etc. R 11 ~R 13 each independently represents a hydrocarbon group or a heteroaryl group. Examples of the substituent include those described in paragraphs 0020 to 0022 of JP-A No. 2009-263614. Among these, examples of the substituent include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR 11 , -SOR 12 , -SO2R 13 is preferred. 1x and R 1y is an alkoxy group having a branched alkyl group, or -OCOR 11 An aryl group having as a substituent a group represented by the following formula: embedded image is preferred. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.

[0140] R 2 and R 3 At least one of R is preferably an electron-withdrawing group. 2 represents an electron-withdrawing group, and R 3represents a heteroaryl group. The electron-withdrawing group represents an electron-withdrawing group having a Hammett σp value of 0.2 or more, and examples thereof include a cyano group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfinyl group, an arylsulfinyl group, and a heteroaryl group. These electron-withdrawing groups may be further substituted. The heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a monocyclic or fused ring, more preferably a monocyclic or fused ring having 2 to 8 rings, and more preferably a monocyclic or fused ring having 2 to 4 rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 or 2. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms. When two R 2 The two R in the general formula (10) may be the same or different. 3 They may be the same or different.

[0141] R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or -BR 4x R 4y is preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by -BR 4x R 4y A group represented by -BR 4x R 4y Particularly preferred is a group represented by R 4x R 4y The substituent represented by is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. 4 They may be the same or different.

[0142] Specific examples of pyrrolopyrrole compounds are shown below. In the following structural formulas, Me represents a methyl group, and Ph represents a phenyl group. Examples of pyrrolopyrrole compounds include the compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, paragraphs 0037 to 0052 of JP 2011-68731 A, paragraphs 0014 to 0027 of JP 2014-130343 A, and paragraphs 0010 to 0033 of WO 2015 / 166873 A. However, the present invention is not limited thereto.

[0143] [ka]

[0144] (Naphthalocyanine compounds) The naphthalocyanine compound is preferably a compound represented by the following general formula (11).

[0145] General formula (11) [ka]

[0146] In general formula (11), X1~X8, Y l Each of Y8 independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonic acid group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. X1 to X8 may also be bonded to each other to form an aromatic ring which may have a substituent. However, any one or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 may be bonded to each other to form an aromatic ring which may have a substituent. Z is a polymer moiety containing a monomer unit represented by the following general formula (12) or a phosphorus compound moiety represented by the following general formula (13), and * is a bond to Al.

[0147] Examples of the "alkyl group" in the alkyl group which may have a substituent include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, a 2-ethylhexyl group, etc. Examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, a 2,4-dichlorobenzyl group, etc.

[0148] Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

[0149] Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like. Examples of the "substituted cycloalkyl group" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, and the like.

[0150] Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group, and examples of the "heterocyclic group having a substituent" include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

[0151] Examples of the "alkoxyl group" in the alkoxyl group which may have a substituent include linear or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group. Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

[0152] Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, etc. Examples of the "substituted aryloxy group" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

[0153] Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

[0154] Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

[0155] Examples of the substituent on the aromatic ring which may have a substituent include a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent.

[0156] General formula (12) [ka]

[0157] In the general formula (12), X is -CONH-R 25 -,-COO-R 26 -, -CONH-R 27 -O-, -COO-R 28 -O-, R 25 ~R 28 represents an alkylene group or an arylene group in which carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. 31 represents hydrogen or a methyl group.

[0158] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, a terphenylene group, and an anthrylene group.

[0159] The monomer unit represented by the general formula (12) can be obtained by polymerizing a monomer such as (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxypropyl) acid phosphate, or (2-(meth)acryloyloxyisopropyl) acid phosphate. The polymer moiety containing the monomer unit represented by the general formula (12) can contain other monomer units in addition to the monomer unit represented by the general formula (12).

[0160] Examples of other monomers include (meth)acrylic acid esters, crotonate esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth)acrylonitrile, acid group-containing monomers, and thermally crosslinkable group-containing monomers.

[0161] The weight average molecular weight of the polymer portion is preferably 5,000 to 20,000, and more preferably 8,000 to 15,000. Having an appropriate molecular weight improves the optical properties and heat resistance.

[0162] The glass transition temperature (Tg) of the polymer portion is preferably from −50 to 150° C., more preferably from 20 to 80° C. An appropriate Tg improves the optical properties.

[0163] Phosphorus compound moiety represented by general formula (13) [ka]

[0164] In general formula (13), R 29 and R 30each independently represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent; R 29 and R 30 may be bonded to each other to form a ring.

[0165] Examples of the "alkyl group" of an alkyl group which may have a substituent, the "aryl group" of an aryl group which may have a substituent, the "alkoxyl group" of an alkoxyl group which may have a substituent, and the "aryloxy group" of an aryloxy group which may have a substituent are the same as those exemplified in the description of general formula (11) above.

[0166] General formula (13) is R 29 and R 30 At least one of R is preferably an aryl group which may have a substituent or an aryloxy group which may have a substituent, 29 and R 30 are more preferably all aryl groups or aryloxy groups, and R 29 and R 30 More preferably, all of are a phenyl group or a phenoxy group.

[0167] The naphthalocyanine compound is more preferably a compound represented by the following general formula (14).

[0168] General formula (14) [ka]

[0169] In general formula (14), Y9~Y 16 , R8~R 21each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z is a polymer moiety containing a monomer unit represented by general formula (12) or a phosphorus compound moiety represented by general formula (13), and * is a bond to Al.

[0170] The alkyl group which may have a substituent, the aryl group which may have a substituent, the cycloalkyl group which may have a substituent, the heterocyclic group which may have a substituent, the alkoxy group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, the arylthio group which may have a substituent, the phthalimidomethyl group which may have a substituent, and the sulfamoyl group which may have a substituent are as explained above in relation to general formula (11).

[0171] In general formula (14), Y9~Y 16 , R8~R 21 From the viewpoint of dispersibility and color properties, is preferably a hydrogen atom, a halogen atom, or an alkoxyl group which may have a substituent.

[0172] Specific examples of naphthalocyanine compounds are shown below, but the present invention is not limited to these.

[0173] [ka] [ka] [ka] [ka]

[0174] (indigo compounds) The indigo compound is preferably a compound represented by the following general formula (15) and / or general formula (16).

[0175] [ka]

[0176] In the general formula (15) and the general formula (16), X1 to X 40 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted arylalkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an amino group, an optionally substituted alkylamino group, an optionally substituted arylamino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO3H; -COOH; and monovalent to trivalent metal salts of these acidic groups; and alkylammonium salts. M represents a metal atom.

[0177] Examples of the "alkyl group" in the alkyl group which may have a substituent include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, a 2-ethylhexyl group, etc. Examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, a 2,4-dichlorobenzyl group, etc.

[0178] Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

[0179] Examples of the "alkoxyl group" in the alkoxyl group which may have a substituent include linear or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group. Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

[0180] Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, etc., and examples of the "aryloxy group having a substituent" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

[0181] Examples of the "arylalkyl group which may have a substituent" include a benzyl group, a 2-phenylpropan-yl group, a styryl group, a diphenylmethyl group, and a triphenylmethyl group.

[0182] Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, etc.

[0183] Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

[0184] Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

[0185] Examples of the "alkylamino group" in the alkylamino group optionally having a substituent include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a dodecylamino group, an octadecylamino group, an isopropylamino group, an isopentylamino group, a sec-butylamino group, a tert-butylamino group, a sec-pentylamino group, a tert-pentylamino group, a tert-octylamino group, a neopentylamino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantamino group, and a 2-adamantamino group.

[0186] Examples of the "arylamino group" of the arylamino group which may have a substituent include an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidino group, a p-toluidino group, a 2-biphenylamino group, a 3-biphenylamino group, a 4-biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, and a p-terphenylamino group.

[0187] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

[0188] Examples of the acidic group include -SO3H and -COOH, and examples of the monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Examples of the alkylammonium salts of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, and quaternary alkylammonium salts such as palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium, and distearyldimethylammonium salts.

[0189] Among the above substituents, X1 to X 40 Preferred substituents include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, and -SO3H.

[0190] M represents a metal atom, such as Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, or Ba. Among these, divalent metal atoms are preferred, with Zn, Co, or Ni being more preferred.

[0191] Specific examples of indigo compounds are shown below, but the present invention is not limited to these.

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] The near-infrared absorbing dye (E) can be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to use at least two compounds with different maximum absorption wavelengths. This broadens the absorption spectrum waveform compared to when a single near-infrared absorbing dye (E) is used, allowing near-infrared light to be absorbed over a wide wavelength range.

[0197] From the viewpoint of near-infrared absorbing properties, the content of the near-infrared absorbing dye (E) is preferably from 0.5 to 70 mass %, more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0198] [Dye derivative (F)] The photosensitive composition of the present invention may contain a dye derivative (F), which improves dispersion stability.

[0199] The dye derivative (F) is a compound having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples of the dye derivative (F) include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, 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.

[0200] Specifically, diketopyrrolopyrrole dye derivatives are disclosed 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 disclosed in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are disclosed in JP 63-264 A. 674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009 / 025325, quinacridone dye derivatives are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine dye derivatives are disclosed in JP-A-2011-162662, thiazine indigo dye derivatives are disclosed in JP-A-2007-314785, triazine Indole-based dye derivatives are 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; benzisoindole-based dye derivatives are disclosed in JP-A-2009-57478; quinophthalone-based dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-22 Examples of known dye derivatives include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc., and examples of known dye derivatives include those described in JP-A-2002-208329 and JP-A-2014-5439 for naphthol dye derivatives, JP-A-2001-172520 and JP-A-2012-172092 for azo dye derivatives, JP-A-2001-172520 and JP-A-2012-172092 for acidic substituents, and JP-A-2004-307854 for basic substituents. In these documents, the dye derivative is sometimes referred to as a derivative, a pigment derivative, a dispersant, a 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.

[0201] The dye derivative (F) can be used alone or in combination of two or more kinds.

[0202] The content of the dye derivative (F) is preferably from 1 to 15 parts by mass, more preferably from 2 to 10 parts by mass, relative to 100 parts by mass of the pigment (A).

[0203] [Dispersion resin (G)] The photosensitive composition of the present invention may contain a dispersing resin (G).

[0204] The dispersing resin (G) is preferably a resin having an adsorptive group that has a high affinity for the pigment (A). The adsorptive group preferably has at least one type of basic group and acidic group.

[0205] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0206] Examples of the acidic group include a carboxyl group, a phosphate group, a sulfonic acid group, etc. Among these, the carboxyl group and the phosphate group are preferred from the viewpoint of adsorption onto the pigment and developability.

[0207] Examples of resin types for the dispersion resin (G) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0208] Examples of the structure of the dispersing resin (G) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, the block structure or the comb structure is preferred from the viewpoint of dispersion stability.

[0209] Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, and 2164 manufactured by BYK Japan, as well as Anti-Terra-U203 and 204, and BYK-P104 and 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, 36 600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 455 manufactured by BASF Japan 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., Inc., and resins described in JP-A Nos. 2008-029901, 2009-155406, 2010-185934, 2011-157416, etc.

[0210] The dispersing resin (G) can be used alone or in combination of two or more kinds.

[0211] From the viewpoint of dispersion stability, the content of the dispersing resin (G) is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the pigment (A).

[0212] [Sensitizer (H)] The photosensitive composition of the present invention may contain a sensitizer (H).

[0213] Examples of the sensitizer (H) include chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and polymethine dyes such as oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples of the compound include compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, and benzophenone compounds. Among these, thioxanthone compounds and benzophenone compounds are preferred from the viewpoint of pattern formability.

[0214] Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferred.

[0215] Examples of benzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0216] The sensitizer (H) can be used alone or in combination of two or more kinds.

[0217] From the viewpoint of pattern formability, the content of the sensitizer (H) is preferably from 10 to 400 parts by mass, more preferably from 20 to 300 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (D).

[0218] [Thermosetting compound (I)] The photosensitive composition of the present invention may contain a thermosetting compound (I), which reacts in the heating step to increase the crosslink density and improve the heat resistance.

[0219] The thermosetting compound (I) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (I) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0220] (Epoxy compound (I1)) The content of the epoxy compound (I1) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0221] (Oxetane compound (I2)) The oxetane compound (I2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0222] The content of the oxetane compound (I2) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0223] The melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol 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.

[0224] The thermosetting compound (I) can be used alone or in combination of two or more kinds.

[0225] [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 (I). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds.

[0226] The curing agents can be used alone or in combination of two or more.

[0227] The content of the curing agent is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting compound (I).

[0228] [Thiol-based chain transfer agents (J)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (J). When the thiol chain transfer agent (J) is used in combination with the photopolymerization initiator (D), it generates thiyl radicals that are resistant to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive composition.

[0229] The thiol chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably a polyfunctional thiol having four or more thiol groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0230] 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 the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0231] The thiol chain transfer agent (J) can be used alone or in combination of two or more kinds.

[0232] The content of the thiol chain transfer agent (J) is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0233] [Polymerization inhibitor (K)] The photosensitive composition of the present invention may contain a polymerization inhibitor (K).

[0234] Examples of the polymerization inhibitor (K) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol; alkylresorcinol compounds such as 4-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucin.

[0235] The content of the polymerization inhibitor (K) is preferably 0.01 to 0.4% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0236] [Ultraviolet absorber (L)] The photosensitive composition of the present invention may contain an ultraviolet absorber (L).

[0237] The ultraviolet absorber (L) is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0238] The content of the ultraviolet absorber (L) is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (L).

[0239] [Antioxidant (M)] The photosensitive composition of the present invention may contain an antioxidant (M). The antioxidant (M) prevents the photopolymerization initiator (D) and thermosetting compound (I) in the photosensitive composition from oxidizing and yellowing during thermal processes such as thermal curing and ITO annealing. The antioxidant (M) is preferably a compound that does not contain a halogen atom.

[0240] Examples of the antioxidant (M) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, etc. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0241] The antioxidant (M) can be used alone or in combination of two or more kinds.

[0242] The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[0243] [Leveling Agent (N)] The photosensitive composition of the present invention may contain a leveling agent (N), which further improves the wettability to the substrate during application and the drying property.

[0244] Examples of the leveling agent (N) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0245] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0246] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0247] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0248] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0249] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. 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, and the like.

[0250] Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and L manufactured by Kao Corporation. S-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, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0251] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0252] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0253] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0254] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0255] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine; and alkylamine oxides such as lauryldimethylamine oxide.

[0256] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

[0257] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0258] The content of the leveling agent (N) is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the balance between the coatability and adhesion of the photosensitive composition is further improved.

[0259] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O), which stabilizes the viscosity of the photosensitive composition over time.

[0260] Examples of the storage stabilizer (O) include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0261] The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the pigment (A).

[0262] [Adhesion improver (P)] The photosensitive composition of the present invention may contain an adhesion promoter (P), which improves the adhesion between the cured film and the substrate and also makes it easier to form narrow patterns by photolithography.

[0263] Examples of the adhesion improver (P) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) silane coupling agents such as aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0264] The adhesion improver (P) can be used alone or in combination of two or more kinds.

[0265] The content of the adhesion improver (P) is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, relative to 100 parts by mass of the pigment (A).

[0266] [Organic solvent (Q)] The photosensitive composition of the present invention may contain an organic solvent (Q).

[0267] Examples of the organic solvent (Q) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy- 3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-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-butyro Lactone, 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, 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,Examples of the alkyl esters include dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol 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.

[0268] The organic solvent (Q) can be used alone or in combination of two or more kinds.

[0269] <Method for producing photosensitive composition> The photosensitive composition of the present invention can be produced by, for example, preparing a dispersion by adding a pigment (A), a dispersing resin (G), an organic solvent (Q), and the like and carrying out a dispersion treatment. The dispersion can then be blended and mixed with an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The timing of blending each material is optional. The dispersion process can also be carried out multiple times.

[0270] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0271] 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. If the particle size is appropriate, a photosensitive composition with high dispersion stability is easily obtained.

[0272] The average dispersed particle size (secondary particle size) is measured using, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and the D50 particle size set to the average size. The dilution solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to provide results with little variation.

[0273] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, and more preferably coarse particles of 0.5 μm or larger, as well as any dust particles that have been mixed in, by means of centrifugation, filtration through a sintered filter or membrane filter, etc. The photosensitive composition for a fingerprint authentication sensor of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0274] [Optical filter] The optical filter of the present invention comprises a substrate and a coating formed from a photosensitive composition, and the coating is preferably patterned by photolithography.

[0275] <Method of manufacturing optical filters> A method for manufacturing an optical filter includes, for example, step (1) of applying a photosensitive composition onto a substrate to form a layer (coating) of the composition, step (2) of exposing the coating to light in a pattern through a mask, step (3) of developing the unexposed portions with an alkali to form a patterned hardened coating, and step (4) of heat-treating (post-baking) the pattern.

[0276] The method for manufacturing the optical filter will now be described in detail.

[0277] (Process (1)) In the step (1) of forming a coating, the photosensitive composition is applied to a substrate by, for example, 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 needed. Examples of the substrate include a glass substrate, a resin substrate, and a silicon substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light-emitting layer may be formed on these substrates. For example, an imaging element such as a CCD or a CMOS may be formed on the surface of the silicon substrate. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with upper layers, prevent diffusion of substances, and flatten the substrate surface. The coating is preferably applied so that the film thickness after drying is 0.05 to 5.0 μm, more preferably 0.3 to 4.0 μm.

[0278] (Process (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 cured coating. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Using KrF rays or ArF rays allows for the formation of finer patterns than using i-rays. Furthermore, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pauses of light in short cycles (for example, milliseconds or less) (pulse exposure).

[0279] (Step (3)) The cured coating obtained in step (2) is subjected to an alkali development treatment, whereby the unexposed portions are dissolved in an alkaline aqueous solution, leaving only the cured portions, thereby obtaining a patterned cured coating. Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses pattern roughening and peeling, and improves the remaining film rate after development.

[0280] Examples of the developing method include a dipping method, a spraying method, a puddling method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0281] (Step (4)) In the heat treatment (post-baking), the patterned cured coating obtained in step (3) is sufficiently cured by heating. The heating temperature for post-baking is preferably 100 to 300° C., more preferably 150 to 250° C. The heating time is preferably 2 minutes to 1 hour, more preferably 3 minutes to 30 minutes.

[0282] Next, the transmittance in each wavelength region of the film formed from the photosensitive composition of the present invention will be described.

[0283] [Transmittance at wavelengths of 450 to 570 nm] The photosensitive composition of the present invention has a transmittance of 50% or more at a wavelength of 450 to 570 nm when a coating having a thickness of 2.0 μm is formed. From the viewpoint of fingerprint authentication accuracy, the transmittance at wavelengths of 450 to 570 nm is preferably 60% or more. By increasing the transmittance of light at wavelengths lower than 600 nm, fingerprint authentication accuracy improves.

[0284] The method for measuring the spectral characteristics and film thickness of the coating is described below.

[0285] (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 would be 2.0 μm, and after drying on a hot plate at 90°C for 2 minutes, it was exposed to light using an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm through a photomask with a 100 μm square pattern. 2 , 50mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated (post-baked) in a clean oven at 230°C for 15 minutes to form a square pattern on the substrate. Spray development was performed for each photosensitive composition coating for the shortest time possible to form a pattern without residual development. Measurements were then taken at five random locations using a Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.), and the average of the measurements was used to determine the film thickness. The thickness of 2.0 μm includes the tolerance range acceptable in the technical field to which the present invention pertains, specifically, a thickness of 2.0 μm±0.07 μm.

[0286] (Transmittance measurement) The film thickness was measured, and the transmittance in the thickness direction of the film at each wavelength was measured using OSP-SP100 (manufactured by Olympus Corporation).

[0287] [Transmittance at wavelengths of 630 to 690 nm] The photosensitive composition of the present invention has a transmittance of 15% or less at wavelengths of 630 to 690 nm when formed into a coating having a thickness of 2.0 μm. By suppressing the transmission of light having a wavelength of around 660 nm, which has a relatively high transmittance through body tissue, the accuracy of fingerprint authentication is improved. From the viewpoint of fingerprint authentication accuracy, it is preferable that the transmittance at wavelengths of 630 to 690 nm is 10% or less.

[0288] [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 optical filter of the present invention is configured to have a substrate on which are mounted a plurality of photodiodes constituting the light receiving area of a CCD image sensor, a CMOS image sensor, an organic CMOS image sensor, or the like, and transfer electrodes 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 electrodes; a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes; and Furthermore, a configuration may be adopted in which a focusing means (e.g., a microlens, etc.; the same applies hereinafter) 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, etc. Japanese Patent Application Laid-Open Nos. 2015-196465, 2017-194676, and 2019-512762 can be referred to.

[0289] The organic CMOS image sensor is composed of a thin-film 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 extracts the electrical signal to the outside, and in principle, can achieve a 100% aperture ratio for incident light.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.

[0290] [Image display device] The image display device of the present invention includes a 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, Japanese Patent Application Laid-Open Nos. 2015-196465, 2020-35327, and 2020-92080 can be referred to. FIG. 1 is a schematic cross-sectional view of an example of an image display device including a fingerprint authentication sensor inside the image display. The display panel 100 includes a substrate 11, a drive layer 10, a fingerprint authentication sensor layer 20, an OLED (organic light-emitting diode) light-emitting layer 30, and a cover glass layer 40.

[0291] The substrate 11 may be made of glass, plastic, or the like.

[0292] 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 light 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 to and from the fingerprint authentication sensor layer 20 and the OLED light emitting layer 30.

[0293] The OLED light-emitting layer 30 includes one or more OLEDs 31 that emit light 33, and serves as an area for displaying images and also as an area for emitting light for fingerprint authentication. The OLED 31 has an organic light-emitting portion and electrodes above and below it.

[0294] The fingerprint authentication sensor layer 20 includes at least one fingerprint authentication sensor 21, and the fingerprint authentication sensor 21 senses at least a portion of the light 23 emitted from the OLED 31 and reflected by a finger 50 that is the authentication target.

[0295] On top of the OLED light-emitting layer 30, a cover glass layer 40 is disposed to protect the underlying structure and form the display surface.

[0296] The image display device of the present invention can be used without any restrictions in devices that require fingerprint authentication, such as smartphones, tablet terminals, and notebook PCs. [Example]

[0297] 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."

[0298] Before describing the examples, each measurement method will be explained.

[0299] (Identification of pigment (A1)) Pigment (A1) in the present invention was identified by checking whether the molecular ion peak in the mass spectrum obtained using a time-of-flight mass spectrometer (Autoflex III (TOF-MS), manufactured by Bruker Daltonics) matched the calculated mass number, and whether the ratios of carbon, hydrogen, and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin-Elmer) matched the theoretical values. The number of halogen atoms substituted was determined by combusting pigment (A-1) using the oxygen combustion flask method, absorbing the combustion product into water, and quantifying the amount of halogen in the liquid using an ion chromatograph (ICS-2000 ion chromatograph, manufactured by DIONEX). The resultant liquid was then converted into the number of halogen atoms substituted.

[0300] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows:

[0301] (average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (Tosoh Corporation). Two separation columns were connected in series, with both columns packed with TSK-GEL SUPER HZM-N. Measurements were performed at an oven temperature of 40°C, a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0302] (resin acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mg KOH / g) was measured. The acid value per unit of nonvolatile content of the resin was then calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0303] (Amine value of resin) The amine value of the resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into solid content.

[0304] <Production of pigment (A1) represented by general formula (1)> (Pigment (A1-1) represented by general formula (1)) In a reaction vessel, 100 parts of chloroaluminum phthalocyanine were added to 1,500 parts of concentrated sulfuric acid in an ice bath. Then, 296 parts of 1,3-dibromo-5,5-dimethylhydantoin were gradually added, and the mixture was stirred at 20°C for 8 hours. Subsequently, this sulfuric acid solution was poured into 9,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water again, and then dried to obtain 159 parts of compound (a1-1) represented by general formula (4), where X = bromine and n = 10. Next, 1,000 parts of 1-methyl-2-pyrrolidinone, 100 parts of compound (a1-1), and 32 parts of diphenyl phosphate were added to a reaction vessel. After reacting at 85°C for 3 hours, the solution was poured into 8,000 parts of water. The reaction product was filtered, washed with 16,000 parts of water, and dried overnight at 60°C under reduced pressure to obtain 112 parts of a product. Next, 600 parts of the resulting product was added to propylene glycol monomethyl ether acetate and heated at 120°C for 2 hours. The product was filtered and dried overnight at 60°C under reduced pressure to obtain pigment (A1-1) represented by general formula (1). The resulting pigment (A1-1) had X = bromine and n = 10. Then, 100 parts of pigment (A1-1), 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 warm water, and stirred for about 1 hour with a high-speed mixer while heating to about 70° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove the sodium chloride and solvent, and then dried at 80° C. for 24 hours and pulverized to make it finer.

[0305] (Pigment (A1-2) represented by general formula (1)) Pigment (A1-2) represented by general formula (1) was obtained in the same manner as in the synthesis of pigment (A1-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 215 parts. In the obtained pigment (A1-2), X = bromine and n = 8. Then, it was micronized in the same manner as in the synthesis of pigment (A1-1).

[0306] (Pigment (A1-3) represented by general formula (1)) Pigment (A1-3) was obtained in the same manner as in the synthesis of pigment (A1-1), except that 296 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 107 parts. In the obtained pigment (A1-3), X = bromine and n = 4. Thereafter, it was pulverized in the same manner as in the synthesis of pigment (A1-1).

[0307] (Pigment (A1-4) represented by general formula (1)) 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 pigment (A1-4) represented by general formula (1). The obtained pigment (A1-4) had n = 0. It was then micronized using the same method as for pigment (A1-1).

[0308] <Production of other pigments (A2)> (Other pigments (A2-1)) 100 parts of CI Pigmen 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 mixture was poured into 3,000 parts of warm water and stirred for 1 hour while heated to 70°C to form a slurry. The sodium chloride and diethylene glycol were removed by repeated filtration and water washing, and the mixture was then dried overnight at 80°C and pulverized to a fine powder.

[0309] <Production of alkali-soluble resin (B)> (Alkali-soluble resin (B1-1) solution) A reaction vessel equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, which was a separable four-neck flask, was charged with 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc), and the vessel was heated to 120°C while nitrogen gas was injected into the vessel. At the same temperature, a mixture of 10.42 parts of styrene (hereinafter, St), 85.29 parts of glycidyl methacrylate (hereinafter, GMA), 66.01 parts of dicyclopentanyl methacrylate (hereinafter, DCPMA), and 0.5 parts of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 43.24 parts of acrylic acid (hereinafter referred to as AA), 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, followed by a reaction at 120°C for 5 hours. This caused the epoxy group of GMA to react with the carboxyl group of AA, introducing polymerizable unsaturated group-containing monomer unit (b2) (hereinafter referred to as GMA+AA). Further, 52.64 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours. This caused an esterification reaction between the hydroxyl groups of GMA + AA and TPHA, introducing fatty acid anhydride-modified polymerizable unsaturated group-containing monomer units (b2) (hereinafter referred to as GMA + AA + TPHA). Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass, and an alkali-soluble resin (B1-1) solution was prepared.

[0310] (Alkali-soluble resin (B1-2) and (B1-3) solutions, alkali-soluble resin (B2-1) and (B2-2) solutions) The types and amounts of monomers were varied to achieve the composition and molar ratios shown in Table 1, and alkali-soluble resins (B1-2), (B1-3), (B2-1), and (B2-2) were synthesized. PGMAc was added to adjust the nonvolatile content to 40% by mass.

[0311] [Table 1]

[0312] GLM+MOI in Table 1 represents a polymerizable unsaturated group-containing monomer unit (b2) obtained by reacting a hydroxyl group derived from polymerized glycerin monomethacrylate (hereinafter, GLM) with an isocyanate group of 2-methacryloyloxyethyl isocyanate (hereinafter, MOI).

[0313] <Production of polymerizable compound (C)> (Polymerizable compound (C1-1) solution having a urethane bond) A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 112 parts of hexamethylene diisocyanate and 112 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the chromatogram was measured at 2180 cm by IR. -1 PGMAc was added so that the nonvolatile content was 50% by mass, to obtain a solution of a polymerizable compound (C1-1) having an average of 6 polymerizable unsaturated groups and urethane bonds.

[0314] (Polymerizable compound (C1-2) solution having a urethane bond) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR reading was 2180 cm. -1 The disappearance of the isocyanate absorption was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted for 6 hours at a temperature of 50 to 60°C. The nonvolatile content was adjusted to 50% by mass, and a solution of a polymerizable compound (C1-2) having an average of 9 polymerizable unsaturated groups and urethane bonds was obtained.

[0315] <Production of near-infrared absorbing dye (E)> (Near-infrared absorbing dye (E-1)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the toluene was distilled to obtain a dark brown solid, which was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled off, and 200 parts of hexane was added to the resulting reaction mixture while stirring. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain near-infrared absorbing dye (A-1) represented by the following chemical formula (17). 50 parts of the resulting near-infrared absorbing dye (E-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. The kneaded mixture was then poured into warm water and stirred for 1 hour while heated to approximately 80°C to form a slurry. The mixture was then filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80°C to be pulverized into fine particles.

[0316] Chemical formula (17) [ka]

[0317] (Near-infrared absorbing dye (E-2)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 50.1 parts of 2-hydroxy-9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the toluene was distilled to give a dark brown solid, which was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, to which 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was heated and stirred under a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and the resulting reaction mixture was stirred and 200 parts of hexane was added. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a near-infrared absorbing dye (E-2) represented by the following chemical formula (18). The near-infrared absorbing dye (E-1) was pulverized in the same manner as in the near-infrared absorbing dye (E-1).

[0318] Chemical formula (18) [ka]

[0319] <Production of Dispersion Resin (G)> (Dispersion resin (G-1) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 3 parts trimellitic anhydride, 1 part 3-mercapto-1,2-propanediol, 50 parts PGMAc, and 0.1 parts dimethylbenzylamine. After purging with nitrogen gas, the reactor was heated to 120°C and reacted for 4 hours, followed by 2 hours at 80°C. Next, 30 parts tert-butyl acrylate, 20 parts ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate, manufactured by Ube Industries), 5 parts methacrylic acid, 40 parts ethyl acrylate, and 10 parts PGMAc were charged. While maintaining the reactor at 80°C, 0.2 parts 2,2'-azobisisobutyronitrile was added in 15 increments every 30 minutes. One hour after the final addition, the nonvolatile content was measured, confirming that 95% of the monomers 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 with an acid value of 51 mg KOH / g per nonvolatile content and a weight average molecular weight (Mw) of 24,000 was obtained.

[0320] (Dispersion resin (G-2) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged 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 4 hours of polymerization, a sample was taken from the polymerization solution and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as the second block (A block) monomer were added to the reactor, and the reaction was continued with stirring at 110 °C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was taken and the nonvolatile content was measured. The conversion rate of the second block (A block) was confirmed to be 98% or higher based on the nonvolatile content. The reaction solution was then cooled to room temperature to terminate the polymerization. The nonvolatile content was then diluted with PGMAc to a nonvolatile content of 30% by mass, yielding a dispersion resin (G-2) solution with an amine value of 57 mg KOH / g and a number-average molecular weight (Mn) of 4,500.

[0321] (Dispersion resin (G-3) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst. The mixture was stirred at 50 °C for 1 hour under a nitrogen stream, and the system was then purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were added. The temperature was raised to 110 °C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, a sample was taken of the polymerization solution and the nonvolatile content was measured. Based on the nonvolatile content, the polymerization conversion was confirmed to be 98% or higher. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethyl benzyl dimethyl ammonium chloride were added to the reactor. The reaction was continued at 110 °C under a nitrogen atmosphere with stirring. Two hours after addition, the polymerization solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or higher. The reaction solution was then cooled to room temperature to terminate the polymerization. GPC analysis revealed that the polymer had a weight-average molecular weight of 20,000, a molecular weight distribution (Mw / Mn) of 1.4, and a reaction conversion rate of 98.5%. In this way, a dispersion resin (G-3) with an amine value per nonvolatile content of 169.8 mg KOH / g was obtained. After cooling to room temperature, approximately 2 g was sampled and dried by heating at 180 °C for 20 minutes. The nonvolatile content was measured, and PGMAc was added to obtain a dispersion resin (G-3) solution with a nonvolatile content of 30% by mass.

[0322] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The organic solvent (Q-1) was PGMAc. Pigment (A1-1) represented by general formula (1): 12.0 parts Dispersion resin (G-1) solution: 13.3 parts Dispersion resin (G-2) solution: 6.7 parts Organic solvent (Q-1): 68.0 parts

[0323] (Dispersion 2~7) Dispersions 2 to 7 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 2 were changed.

[0324] [Table 2]

[0325] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. Dispersion 1: 20.00 parts Alkali-soluble resin (B1-1) solution: 2.75 parts Alkali-soluble resin (B2-1) solution: 12.50 parts Polymerizable compound (C1-1) solution having a urethane bond: 7.00 parts Polymerizable compound (C2-1) having 3 or 4 polymerizable unsaturated groups: 2.80 parts Polymerizable compound (C2-4) having 3 or 4 polymerizable unsaturated groups: 0.70 parts Compound (D1-1-1) represented by general formula (2): 0.30 parts Leveling agent (N): 1.00 parts Organic solvent (Q): 52.95 parts

[0326] [Examples 2 to 30, Comparative Examples 1 to 3] (Photosensitive compositions 2-33) Photosensitive compositions 2 to 33 were prepared in the same manner as in Example 1, except that the raw materials and amounts of photosensitive composition 1 in Example 1 were changed to those shown in Tables 3-1 to 3-4.

[0327] [Table 3-1] [Table 3-2] [Table 3-3] [Table 3-4]

[0328] The raw materials listed in Tables 3-1 to 3-4 are as follows:

[0329] [Polymerizable compound (C)] (Polymerizable Compound (C2) Having 3 or 4 Polymerizable Unsaturated Groups) C2-1: Pentaerythritol triacrylate C2-2: Trimethylolpropane PO modified triacrylate C2-3: Aronix M-510 (manufactured by Toagosei Co., Ltd., a polymerizable compound having an acidic group and three polymerizable unsaturated groups) C2-4: Pentaerythritol tetraacrylate

[0330] (Other polymerizable compounds (C3)) C3-1: Dipentaerythritol hexaacrylate

[0331] [Photopolymerization initiator (D)] (Acetophenone-based compound (D1)) D1-1: Compound of the above chemical formula (5) D1-2: Compound of the above chemical formula (6) D1-3: Omnirad 369E (IGM Resins) D1-4: Omnirad 907 (IGM Resins)

[0332] (Other photopolymerization initiators (D2)) D2-1: Irgacure OXE02 (BASF Japan)

[0333] [Leveling Agent (N)] N-1: BYK-330 (BYK-Chemie) N-2: Megafac F-554 (DIC) One part each of (N-1) and (N-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution, which was used as a leveling agent (N).

[0334] [Organic solvent (Q)] Q-1: Propylene glycol monomethyl ether acetate 30 parts Q-2: 30 parts cyclohexanone Q-3: 10 parts of ethyl 3-ethoxypropionate Q-4: Propylene glycol monomethyl ether 10 parts Q-5: Cyclohexanol acetate 10 parts Q-6: Dipropylene glycol methyl ether acetate 10 parts The above (Q-1) to (Q-6) were mixed in the above-mentioned parts by mass to obtain organic solvent (Q).

[0335] <Evaluation of Photosensitive Composition> The photosensitive compositions thus obtained were evaluated for pattern formability (adhesion, line width, and residual film rate), foreign matter, spectral characteristics, and fingerprint authentication by the methods described below. The evaluation results are shown in Table 4.

[0336] [Pattern Formability Evaluation (1): Adhesion] The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to apply a stripe pattern of 5 to 25 μm widths at 5 μm intervals to the substrate at an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 15 minutes. Spray development was carried out for the shortest time possible to form a pattern without leaving any residual development residue on the coating of each photosensitive composition. The resulting patterns on the substrates with widths of 5, 10, 15, 20, and 25 μm were observed under an optical microscope to confirm the minimum line width of the remaining patterns. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or more remain. 3: Fine lines of 20 μm or more remain. 2: 25 μm fine lines remain. 1: No fine lines remain.

[0337] [Pattern Formability Evaluation (2): Line Width] The obtained photosensitive coloring composition was applied by spin coating to a 100mm x 100mm x 0.7mm thick glass substrate (Corning Eagle 2000) so that the dried film thickness was 2.0μm, and then dried on a hot plate at 70°C for 1 minute. The substrate was then cooled to room temperature and exposed to ultraviolet light using a high-pressure mercury lamp through a photomask with a 25μm wide stripe pattern. The exposure dose was adjusted so that the average width of the line portions of the pattern obtained after development was 25μm at 50 locations. The substrate was then spray-developed using an aqueous developer containing 0.12% by weight of a nonionic surfactant and 0.04% by weight of potassium hydroxide at 23°C, then washed with ion-exchanged water, and air-dried. The resulting substrate was subjected to measurement of the line width of the pattern at 50 locations using a Nikon ECLIPSE LV100POL Model optical microscope to determine the line width variation (3σ). The evaluation criteria are as follows, with 3 or more being practical. 5: Line width variation is less than 1.0 μm 4: Line width variation is 1.0 μm or more and less than 1.5 μm 3: Line width variation is 1.5 μm or more and less than 3.0 μm 2: Line width variation is 3.0 μm or more and less than 3.5 μm 1: Line width variation is 3.5 μm or more

[0338] [Pattern Formability Evaluation (3): Residual Film Rate] The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, after cooling the substrate to room temperature, the substrate was irradiated with a high-pressure mercury lamp at an illumination intensity of 30 mW / cm through a photomask having a 100 μm-wide stripe pattern. 2 , 50mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, and the coating film was washed with ion-exchanged water and air-dried, after which the film thickness was measured. This film thickness is the post-development film thickness. The substrate was then heated in a clean oven at 230°C for 15 minutes, and the film thickness was measured at the same location as the post-development film thickness. This film thickness is the post-post-bake film thickness. The remaining film thickness was calculated from the two film thicknesses using the following formula. A ratio of 3 or more is considered practical. The film thickness was measured using a Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.). Formula: Remaining film rate (%) = film thickness after post-baking ÷ film thickness after development × 100 5: Remaining film rate 85% or more 4: Remaining film rate: 80% or more but less than 85% 3: Remaining film rate: 75% or more but less than 80% 2: Remaining film rate: 70% or more but less than 75% 1: Less than 70% remaining film

[0339] [Foreign matter evaluation] The obtained photosensitive composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, after cooling the substrate to room temperature, the substrate was irradiated with a high-pressure mercury lamp at an illumination intensity of 30 mW / cm through a photomask having a 100 μm-wide stripe pattern. 2 , 50 mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 15 minutes. The resulting substrate was subjected to surface observation of the pattern using a metallurgical microscope "BX60" (Olympus Systems Corporation). The magnification was set to 500x, and the number of foreign particles observable in any five fields of view was counted in transmission light. The evaluation criteria are as follows, with a score of 3 or higher being practical. 5: Fewer than 5 foreign objects 4: 5 or more but less than 10 foreign objects 3: 10 or more but less than 15 foreign objects 2: The number of foreign objects is 15 or more but less than 20 1: 20 or more foreign objects

[0340] <Preparation of substrate for evaluating spectroscopic characteristics> The photosensitive composition thus obtained was applied by spin coating onto a 100 mm x 100 mm x 0.7 mm thick glass substrate (Eagle 2000 manufactured by Corning Incorporated) so that the film thickness after post-baking would be 2.0 μm. After drying on a hot plate at 70°C for 1 minute, the composition was exposed to light using an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm through a photomask with a 100 μm square pattern. 2 , 50 mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 15 minutes. The spray development was carried out for the shortest time possible to form a pattern without residual development.

[0341] [Transmittance of wavelengths from 450 to 570 nm] The transmittance of the obtained substrate for evaluating spectral characteristics at wavelengths of 450 to 570 nm was measured in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation).The evaluation criteria were as follows. 3: Transmittance is 60% or more at wavelengths of 450 to 570 nm 2: Transmittance is 50% or more at wavelengths of 450 to 570 nm 1: There are areas with transmittance of less than 50% at wavelengths between 450 and 570 nm

[0342] [Transmittance of wavelengths 630-690nm] The transmittance of the obtained substrate for evaluating spectral characteristics at wavelengths of 630 to 690 nm was measured in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation).The evaluation criteria were as follows. 3: Transmittance is 10% or less at wavelengths of 630 to 690 nm 2: Transmittance is 15% or less at wavelengths of 630 to 690 nm 1: There are areas where the transmittance exceeds 15% at wavelengths of 630 to 690 nm

[0343] <Creating an optical filter for fingerprint authentication evaluation> The photosensitive composition thus obtained was applied by spin coating onto a 100 mm x 100 mm x 0.7 mm thick glass substrate (Eagle 2000 manufactured by Corning Incorporated) so that the film thickness after post-baking would be 2.0 μm. After drying on a hot plate at 70°C for 1 minute, the composition was exposed to light using an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm through a photomask with a 100 μm square pattern. 2 , 50mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 15 minutes to obtain an optical filter for fingerprint authentication evaluation.

[0344] [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, and a fingerprint image was captured to evaluate the image performance. The evaluation criteria are as follows, with a score of 2 or higher being practical. 3: Fingerprints are clearly recognizable 2: Fingerprints can be recognized 1: Fingerprint not recognized

[0345] [Table 4] [Explanation of symbols]

[0346] 10 Driving Layer 11 Circuit Board 20 Fingerprint authentication sensor layer 21 Fingerprint authentication sensor 23 Reflected Light 30 OLED light-emitting layer 31 OLED 33 light 40 cover glass layers 50 fingers 100 Display Panel

Claims

1. Can a coating be formed under the following formation conditions, with a film thickness of 2.0 μm, having a transmittance of 60% or more in the wavelength range of 450 to 570 nm and a transmittance of 10% or less in the wavelength range of 630 to 690 nm? Under the following formation conditions, a coating can be formed that has a film thickness of 2.0 μm and a transmittance of 50% or more and less than 60% at wavelengths of 450 to 570 nm and a transmittance of 10% or less at wavelengths of 630 to 690 nm, or Under the following conditions, a coating can be formed that has a thickness of 2.0 μm and a transmittance of 60% or more at wavelengths of 450 to 570 nm, and a transmittance of more than 10% and not more than 15% at wavelengths of 630 to 690 nm.

1. A photosensitive composition comprising: the photosensitive composition contains a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D); The pigment (A) contains a pigment (A1) represented by the following general formula (1): the photopolymerization initiator (D) contains an acetophenone-based compound (D1), The acetophenone-based compound (D1) includes a compound represented by the following general formula (2): A photosensitive composition, wherein the content of the pigment (A) is less than 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition. General formula (1) 【Chemical 1】 (In general formula (1), X represents a halogen atom, and n represents 0 to 16.) General formula (2) 【Chemistry 2】 (In general formula (2), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R 3 represents a hydrogen atom or a monovalent substituent.) 《Formation conditions》 The photosensitive composition is applied to a glass substrate by spin coating so that the film thickness after drying is 2.0 μm, and after drying on a hot plate at 90°C for 2 minutes, it is exposed to light at an illuminance of 30 mW / cm2 and 50 mJ / cm2 using an ultra-high pressure mercury lamp through a photomask with a 100 μm square pattern.The substrate is then spray-developed at 23°C using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 15 minutes.

2. 2. The photosensitive composition according to claim 1, wherein the content of the pigment (A1) is 95% by mass or more based on 100% by mass of the pigment (A).

3. 3. The photosensitive composition according to claim 1, wherein the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having an alicyclic hydrocarbon-containing monomer unit (b1) and a polymerizable unsaturated group-containing monomer unit (b2), and an alkali-soluble resin (B2) having an alicyclic hydrocarbon-containing monomer unit (b1) but not a polymerizable unsaturated group-containing monomer unit (b2).

4. 4. The photosensitive composition according to claim 3, wherein the content of the alkali-soluble resin (B2) is 40 to 95 mass% relative to 100 mass% of the total content of the alkali-soluble resin (B1) and the alkali-soluble resin (B2).

5. 5. The photosensitive composition according to claim 1, wherein the polymerizable compound (C) comprises a polymerizable compound (C1) having a urethane bond.

6. The photosensitive composition according to any one of claims 1 to 5, wherein the polymerizable compound (C) includes a polymerizable compound (C2) (excluding the polymerizable compound (C1)) having 3 or 4 polymerizable unsaturated groups.

7. The photosensitive composition according to any one of claims 1 to 6, further comprising a near-infrared absorbing dye (E).

8. A photosensitive composition described in any one of claims 1 to 7, which is for use in a fingerprint authentication sensor.

9. An optical filter comprising a substrate and a coating formed from the photosensitive composition according to any one of claims 1 to 8.

10. A fingerprint authentication sensor comprising the optical filter according to claim 9.

11. An image display device comprising the fingerprint authentication sensor according to claim 10 inside an image display.

Citation Information

Patent Citations

  • Imaging device, authentication processing device, imaging method, authentication processing method, and program

    JP2017196319A