Photosensitive composition, film, optical filter, solid-state imaging element, image display device, and infrared sensor

Abstract

To provide a photosensitive composition which enables formation of a film that is excellent in pattern formability and light resistance, and has excellent resistance (high temperature and high humidity resistance, and solvent resistance) in low temperature heating.SOLUTION: A photosensitive composition contains a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the alkali-soluble resin (B) contains an alkali-soluble resin (B1) having an alkoxysilyl group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2), and the polymerization initiator (D) contains a polymerization initiator (D1) having an absorption coefficient of light at a wavelength of 365 nm in propylene glycol monomethyl ether acetate of 5.0×103 L / mol cm or more.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive composition used to form an optical filter for use in a solid-state imaging device, an image display device, or the like. [Background technology]

[0002] The demand for optical filters used in liquid crystal display devices, digital cameras, smartphones, infrared sensors, etc. is growing due to the widespread use of these devices. In order to make these devices light, thin, and energy-efficient, organic EL (Electro-Luminescence) display devices using OLEDs (Organic Light Emitting Diodes) and other devices that do not require backlighting, and the use of organic materials for the photoelectron conversion film in image sensors, are being considered.

[0003] Since the heat resistance of an organic light-emitting layer used in an organic EL display device or the like is generally low, it is preferable that the heating process of the photosensitive composition for forming an optical filter used in an organic EL display device is performed at a low temperature, for example, 150° C. or less. Therefore, in order to study the production of an optical filter at a low temperature, an attempt has been made to sufficiently cure the composition in an exposure process using a highly sensitive polymerization initiator. For example, Patent Document 1 discloses a colored photosensitive composition that contains a colorant, a polymerizable compound, and a photopolymerization initiator, and the photopolymerization initiator has an absorbance of 0.45 or more at a wavelength of 340 nm when the photopolymerization initiator is dissolved in acetonitrile at 0.001% by mass. Patent Document 2 discloses a photosensitive resin composition that contains an alkali-soluble resin, a polymerizable compound, a fluorene structure-containing oxime ester photopolymerization initiator, and a solvent. Patent Document 3 discloses a photosensitive colored resin composition containing a colorant, a (meth)acrylate copolymer-based dispersant, an alkali-soluble resin, a photopolymerizable compound, an oxime ester photopolymerization initiator having a specific structure, and a solvent.

[0004] Patent Document 4 discloses a coloring composition that contains a red colorant, a resin having a repeating unit containing a blocked isocyanate group, a polymerizable compound, and a photopolymerization initiator as a coloring composition that can form a cured film in which mixing with other colors is suppressed even when an image is formed by a low-temperature process. Patent Document 5 discloses a coloring composition that contains a colorant, a polymer, and a polymerizable compound as a coloring composition that can obtain a cured film with excellent storage stability, low-temperature curing properties, and solvent resistance, and at least one selected from the group consisting of the colorant, polymer, and polymerizable compound has a specific structure, and at least one selected from the group consisting of the colorant, polymer, and polymerizable compound has a hydroxyl group. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 038708 [Patent Document 2] JP 2019-200226 A [Patent Document 3] Patent Publication No. 2021-167893 [Patent Document 4] International Publication No. 2021 / 054248 [Patent Document 5] Patent Publication No. 2021-102759 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the compositions described in Patent Documents 1 to 5 were unable to satisfy certain levels of pattern formability, light resistance, and resistance to low-temperature heating.

[0007] An object of the present invention is to provide a photosensitive composition capable of forming a film having excellent pattern formability and light resistance, and having excellent resistance (high temperature and high humidity resistance, solvent resistance) upon low temperature heating. [Means for solving the problem]

[0008] The present invention relates to a photosensitive composition comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having an alkoxysilyl group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2); The polymerization initiator (D) has an absorption coefficient of 5.0×10 at 365 nm in propylene glycol monomethyl ether acetate. 3 The present invention relates to a photosensitive composition comprising a polymerization initiator (D1) having a viscosity of 1000 sq. m / mol·cm or more. Effect of the Invention

[0009] According to the present invention, it is possible to provide a photosensitive composition capable of forming a film having excellent pattern formability and light resistance, and excellent resistance (high temperature and high humidity resistance, solvent resistance) by low temperature heating. The present invention also provides a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of an infrared sensor having an optical filter of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, the embodiment 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 embodiment, and can be modified within the scope of the problem that can be solved.

[0012] In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively means "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compound in the present invention, for low molecular weight compounds whose molecular weight can be specified, the molecular weight is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and for compounds having a molecular weight distribution, the molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. A monomer is a compound that will polymerize to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that will polymerize to form a resin.

[0013] <Photosensitive composition> A photosensitive composition according to one embodiment of the present invention is a photosensitive composition comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having an alkoxysilyl group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2); The polymerization initiator (D) has an absorption coefficient of 5.0×10 at 365 nm in propylene glycol monomethyl ether acetate. 3 L / mol cm or more of a polymerization initiator (D1).

[0014] The mechanism by which the photosensitive composition having the above-mentioned configuration can solve the problems of the present invention is not clear, but is speculated as follows.

[0015] In the alkali-soluble resin (B1) having an alkoxysilyl group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2), the alkoxysilyl group is hydrolyzed in the development step, and the resulting silanol group forms a hydrogen bond with the functional group on the substrate surface or with the functional group of another component contained in the photosensitive composition. Then, in the heating step, a siloxane bond is formed by a dehydration condensation reaction. This is presumably what makes the film stronger. Furthermore, the absorption coefficient of light with a wavelength of 365 nm in propylene glycol monomethyl ether acetate is 5.0 x 10 3 Since polymerization initiator (D1) with a density of 1000 L / mol cm or more has a high absorption capacity for light around 365 nm, which is the main wavelength of the ultra-high pressure mercury lamp used in the production of optical filters, it is assumed that photocuring proceeds sufficiently to the bottom of the film where light is difficult to reach, and that unreacted components are unlikely to remain, improving light resistance. It is also assumed that film resistance can be maintained even when heated at low temperatures because photocuring proceeds.

[0016] Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

[0017] Pigment The photosensitive composition of the present invention contains a pigment (A), which makes it possible to control the spectral characteristics of the optical filter.

[0018] The pigment (A) is not particularly limited, and examples thereof include chromatic pigments, white pigments, black pigments, and near-infrared absorbing pigments. The pigment (A) may be colorless. In the present invention, the solubility of the pigment (A) in 100 g of propylene glycol monomethyl ether acetate at 25° C. is preferably less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less.

[0019] When the photosensitive composition of the present invention is used for a color filter, the pigment (A) is preferably a chromatic pigment. The chromatic pigment may be used alone or in combination of two or more. When the photosensitive composition of the present invention is used for a near-infrared cut filter, the pigment is preferably a near-infrared absorbing pigment. The near-infrared absorbing pigment may be used alone or in combination of two or more. When used for a near-infrared transmission filter, the pigment (A) is preferably used as a black pigment or a combination of two or more chromatic pigments to produce a black color. Furthermore, a near-infrared absorbing pigment may be used in combination.

[0020] (chromatic pigments) The chromatic pigment is not particularly limited, and any known chromatic pigment can be used, for example, a compound classified as a pigment in the Color Index.

[0021] Chromatic pigments include, for example, 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, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,1 81,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260, Nos. 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, JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844.

[0022] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0023] CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 1 No. 27,128,129,138,139,147,150,151,152, 153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,192,193,194,196,198,199,213,214,231,233, and JP-A-2012-226110.

[0024] Further, examples of yellow pigments include metal azo pigments containing one or more anions selected from the group consisting of azo compounds represented by the following general formula (1) and mono-, di-, tri-, and tetraanions of azo compounds having a tautomeric structure thereof, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (2).

[0025] General formula (1) [ka]

[0026] In general formula (1), two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and two R2s each independently represent -OH or -NH2.

[0027] General formula (2) [ka]

[0028] In general formula (2), three R3's each independently represent a hydrogen atom or an alkyl group.

[0029] Examples of the metal azo pigment include those described in JP-A-2014-12838, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, and JP-A-2022-61494.

[0030] Examples of green pigments include 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, 63, 64, 65, and 66.

[0031] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, 87, and 88.

[0032] Examples of purple pigments include 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, and 50.

[0033] The chromatic pigments can be used alone or in combination of two or more kinds. For example, in the case of black, in addition to using the black pigment described later, two or more chromatic pigments selected from the group consisting of red pigments, yellow pigments, green pigments, blue pigments, and purple pigments can be used (combined) to obtain the color. Examples of the combination include the following modes. (1) Contains yellow and purple pigments. (2) Contains red, yellow, and purple pigments. (3) Contains red, yellow, and blue pigments. (4) Contains red, yellow, and green pigments. (5) Contains yellow pigment, blue pigment, and purple pigment. (6) Contains red pigment, yellow pigment, blue pigment, and purple pigment. (7) Contains yellow pigment, blue pigment, green pigment, and purple pigment.

[0034] An example of the above embodiment (1) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233, and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (2) is an embodiment in which the red pigment is one or more selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow pigment is one or more selected from CI Pigment Yellow 139, 185, 231, and 233; and the purple pigment is CI Pigment Violet 23. An example of the above embodiment (3) is an embodiment containing one or more red pigments selected from CI Pigment Red 177, 254, 291, 295, and 296, one or more yellow pigments selected from CI Pigment Yellow 139, 185, 231, and 233, and one or more blue pigments selected from CI Pigment Blue 15:3, 15:4, and 15:6. An example of the above embodiment (4) is an embodiment containing one or more red pigments selected from CI Pigment Red 177, 254, 291, 295, and 296, one or more yellow pigments selected from CI Pigment Yellow 139, 185, 231, and 233, and one or more green pigments selected from CI Pigment Green 7, 36, 58, 59, and 63. In the above embodiment (5), for example, the yellow pigment is CI Pigment Yellow 139,185. , 231, 233; the blue pigment is one or more selected from CI Pigment Blue 15:3, 15:4, 15:6; and the purple pigment is CI Pigment Violet 23. An example of the above embodiment (6) is an embodiment in which the red pigment contains one or more selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (7) is an embodiment in which the yellow pigment contains one or more selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains one or more selected from CI Pigment Blue 15:3, 15:4, and 15:6; the green pigment contains one or more selected from CI Pigment Green 7, 36, 58, 59, and 63; and the purple pigment contains CI Pigment Violet 23.

[0035] Table 1 shows the preferred mass ratios (mass %) of each chromatic pigment in each embodiment.

[0036] [Table 1]

[0037] The above combinations of chromatic pigments (1) to (7) are preferred when the photosensitive composition of the present invention is used for a near-infrared transmission filter.

[0038] (White pigment) The white pigment is not particularly limited, and any known white pigment can be used. Examples of the white pigment include titanium oxide, magnesium oxide, zirconium oxide, aluminum oxide, antimony oxide, barium sulfate, calcium carbonate, silica, zinc oxide, mica, talc, kaolin, clay, strontium titanate, barium tungstate, zinc phosphate, aluminum hydroxide, aluminum silicate, hollow resin particles, and compounds described in JP2011-075786A, WO2013 / 061621A, JP2015-047520A, and JP2015-164881A. Further, examples of compounds classified as pigments in the Color Index include CI Pigment White 1, 2, 3, 4, 5, 6, 6:1, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 18:1, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 32, and 33.

[0039] (Black pigment) The black pigment is not particularly limited, and known black pigments can be used. Examples of the black pigment include carbon black, titanium black, acetylene black, lamp black, graphite, aniline black, cyanine black, perylene black, and compounds described in JP-A-1-170601, JP-A-2-34664, JP-A-2007-302836, JP-T-2010-534726, and JP-T-2012-515233. Further, examples of compounds classified as pigments in the Color Index include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0040] (Near infrared absorbing pigment) The near-infrared absorbing pigment is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm, and may be either an organic pigment (also called a near-infrared absorbing organic pigment) or an inorganic pigment (also called a near-infrared absorbing inorganic pigment). In addition, a near-infrared absorbing organic pigment and a near-infrared absorbing inorganic pigment may be used in combination.

[0041] The near infrared absorbing organic pigment is not particularly limited, and known near infrared absorbing organic pigments can be used. For example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, porphyrin compounds, etc. can be mentioned. Among these, from the viewpoint of near infrared absorbing property and heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferred, and naphthalocyanine compounds, squarylium compounds, and indigo compounds are more preferred.

[0042] Cyanine compounds are disclosed in WO 2006 / 006573, WO 2010 / 073857, JP 2013-241598 A, JP 2016-113501 A, JP 2016-113504 A, etc.; phthalocyanine compounds are disclosed in JP 4-23868 A, JP 06-192584 A, JP 2000-63691 A, WO 2014 / 208514 A, JP 2022-022070 A, JP 2022-110 262, etc.; naphthalocyanine compounds are described in JP-A-11-152414, JP-A-2000-86919, JP-A-2009-29955, WO 2018 / 186490, JP-A-2022-123689, JP-A-2022-091099, JP-A-7182049, etc.; indigo compounds are described in JP-A-2013-230412, etc.; immonium compounds are described in JP-A-2005-336150, JP-A-2007-19749 2, JP 2008-88426 A, JP 2022-184710 A, JP 2023-01394 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, and WO 2021 / 039205; squarylium compounds are disclosed in JP 2011-13236 A 1, JP 2016-142891 A, WO 2017 / 135359 A, WO 2018 / 225837 A, JP 2019-001987 A, WO 2020 / 054718 A, WO 2020 / 189459 A, etc.; croconium compounds are described in WO 2019 / 021767; porphyrin compounds are described in JP 2006-209059 A, WO 2022 / 131191 A, etc.

[0043] The near infrared absorbing inorganic pigment is not particularly limited, and any known near infrared absorbing inorganic pigment can be used, such as indium tin oxide, antimony tin oxide, zinc oxide, aluminum-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, lanthanum boride, copper, nickel, silver, gold, or other metal oxide particles or metal particles.

[0044] The pigment (A) can be used alone or in combination of two or more kinds.

[0045] The content of the pigment (A) is preferably from 0.5 to 60 mass %, and more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0046] The pigment (A) is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoint of dispersibility, the average primary particle size is more preferably 10 to 70 nm.

[0047] In the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment (A) is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in organic solvents. The amount of the resin added is preferably 2 to 200 parts by mass relative to 100 parts by mass of the pigment (A).

[0048] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B).

[0049] The alkali-soluble resin (B) is not particularly limited as long as it dissolves in the alkali developer described below, and any known resin can be used, such as (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, and cyclic olefin resin.

[0050] The weight average molecular weight of the alkali-soluble resin (B) is preferably from 3,000 to 100,000.

[0051] The acid value of the alkali-soluble resin (B) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0052] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0053] The content of the alkali-soluble resin (B) is preferably from 1 to 90 mass %, and more preferably from 5 to 80 mass %, in 100 mass % of the nonvolatile content of the photosensitive composition.

[0054] (Alkali-soluble resin (B1) having an alkoxysilyl group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2)) The photosensitive composition of the present invention contains, as the alkali-soluble resin (B), an alkali-soluble resin (B1) having an alkoxysilyl group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2).

[0055] The alkali-soluble resin (B1) having the alkoxysilyl group-containing monomer unit (b1) and the acidic group-containing monomer unit (b2) (hereinafter also simply referred to as the alkali-soluble resin (B1)) is not particularly limited, and can be a known resin. For example, the monomer forming the alkoxysilyl group-containing monomer unit (b1), the monomer forming the acidic group-containing monomer unit (b2), and the copolymer with other monomers that can be copolymerized arbitrarily can be mentioned.

[0056] [Alkoxysilyl group-containing monomer unit (b1)] The alkoxysilyl group-containing monomer unit (b1) may have an alkoxysilyl group, and can be formed, for example, from a monomer represented by the following general formula (3).

[0057] General formula (3) [ka]

[0058] In general formula (3), R1 represents a hydrogen atom or a methyl group.

[0059] In the general formula (3), R2 represents an alkylene group having 1 to 10 carbon atoms. Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propyl group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, etc. Among these, a methylene group, an ethylene group, an n-propylene group, and an isopropylene group are preferred.

[0060] In general formula (3), R3 to R5 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that at least one of R3 to R5 is an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, etc. Among these, from the viewpoint of resistance to low-temperature heating, a methoxy group and an ethoxy group are preferred. From the viewpoint of resistance to low-temperature heating, at least two of R3 to R5 in general formula (3) are preferably alkoxy groups having 1 to 6 carbon atoms.

[0061] Examples of the compound represented by general formula (3) include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, and 8-(meth)acryloyloxyoctyltrimethoxysilane.

[0062] From the viewpoint of resistance to low-temperature heating, the content of the alkoxysilyl group-containing monomer units (b1) is preferably 5 to 90 mol %, more preferably 10 to 80 mol %, of all monomer units in the alkali-soluble resin (B1).

[0063] [Acidic group-containing monomer unit (b2)] Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexyl hydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0064] The content of the acidic group-containing monomer unit (b2) is preferably from 1 to 40 mol %, more preferably from 5 to 30 mol %, of all the constituent units of the alkali-soluble resin (B1) from the viewpoint of pattern formability. It is nice.

[0065] The alkali-soluble resin (B1) may have a monomer unit other than the alkoxysilyl group-containing monomer unit (b1) and the acidic group-containing monomer unit (b2). The monomer unit other than the alkoxysilyl group-containing monomer unit (b1) and the acidic group-containing monomer unit (b2) is not particularly limited as long as it is a monomer unit formed from an alkoxysilyl group-containing monomer and a monomer copolymerizable with the acidic group-containing monomer. For example, a blocked isocyanate group-containing monomer unit (b3), a polymerizable unsaturated group-containing monomer unit (b4), an aliphatic condensed ring structure-containing monomer unit (b5), a hydroxyl group-containing monomer unit (b6), an epoxy group-containing monomer unit (b7), and other monomer units (b8) can be mentioned.

[0066] [Blocked isocyanate group-containing monomer unit (b3)] The blocked isocyanate group-containing monomer is a compound in which the isocyanate group in the isocyanate group-containing monomer is protected with a compound that is eliminated by heat (hereinafter, also referred to as a blocking agent). The elimination temperature of the blocking agent is preferably 60 to 160°C, more preferably 80 to 140°C.

[0067] Examples of isocyanate group-containing monomers include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. Also usable are equimolar reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compound. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0068] Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0069] Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is preferred. Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred. The pyrazole compound is, for example, pyrazole, methylpyrazole, 3,5-dimethylpyrazole, Of these, 3,5-dimethylpyrazole is preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compound include succinimide, maleimide, maleimide, and phthalimide. Examples of the urea compound include urea, thiourea, and ethyleneurea. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

[0070] The blocking agents can be used alone or in combination of two or more kinds.

[0071] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and from the viewpoint of protection reaction and deprotection reaction, one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferable, and from the viewpoint of resistance to low-temperature heating, active methylene compounds are particularly preferable. The desorption temperature of the active methylene compound or the temperature of the ester exchange reaction is low at 80 to 110°C, and the reaction is sufficient even at low-temperature heating, improving resistance.

[0072] Examples of the blocked isocyanate group-containing monomer include the following compounds, although the present invention is not limited thereto.

[0073] [ka]

[0074] Commercially available blocked isocyanate group-containing monomers include Karenz MOI-DEM (blocking agent desorption temperature: 85 to 95°C), MOI-BP (blocking agent desorption temperature: 105 to 115°C), and MOI-BM (125 to 135°C), all manufactured by Showa Denko K.K.

[0075] The blocked isocyanate group-containing monomer unit (b3) is also preferably formed from a monomer represented by the following general formula (4).

[0076] General formula (4) [ka]

[0077] In general formula (4), R1 represents a hydrogen atom or a methyl group.

[0078] In the general formula (4), R2 represents an alkylene group having 1 to 10 carbon atoms. Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propyl group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, and a 2-methylhexylene group.

[0079] In the general formula (4), R3 and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[0080] In the general formula (4), R5 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[0081] The monomer represented by general formula (4) can be obtained, for example, by the method described in WO 2022 / 145298.

[0082] [Polymerizable unsaturated group-containing monomer unit (b4)] Methods for incorporating the polymerizable unsaturated group-containing monomer unit (b4) into the alkali-soluble resin (B1) include, for example, the following methods (i) to (iii).

[0083] <Method (i)> In the method (i), for example, first, a precursor having an epoxy group-containing monomer unit (b7) described later is synthesized, and then a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

[0084] 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.

[0085] The epoxy group of the epoxy group-containing monomer unit (b7) to which the carboxyl group of a carboxyl group-containing monomer has been added can be further reacted with an acid anhydride.

[0086] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0087] <Method (ii)> In the method (ii), for example, a precursor having an acidic group-containing monomer unit (b2) in which the acidic group is a carboxyl group is first synthesized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group.

[0088] 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.

[0089] <Method (iii)> In the method (iii), for example, a precursor having a hydroxyl group-containing monomer (b6) described later 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).

[0090] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0091] [Aliphatic condensed ring structure-containing monomer unit (b5)] Examples of the aliphatic condensed ring structure-containing monomer include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0092] [Hydroxyl group-containing monomer unit (b6)] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

[0093] [Epoxy group-containing monomer unit (b7)] Examples of epoxy group-containing monomers include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate.

[0094] [Other monomer units (b8)] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Acrylic acid esters such as ethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 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, diethylaminoethyl (meth)acrylate, etc.; aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, etc.; (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 acetate or vinyl propionate or other vinyl fatty acids; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5 -Methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N N-substituted maleimides such as -(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; 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 di(2-ethyl)-2,2'-[oxybis(methylene)]bis-2-propenoate (hexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. The other monomers can be used alone or in combination of two or more.

[0095] The weight average molecular weight of the alkali-soluble resin (B1) is preferably from 3,000 to 50,000, and more preferably from 3,000 to 20,000.

[0096] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the alkali-soluble resin (B1) is preferably from 1.3 to 3.0, more preferably from 1.5 to 2.8.

[0097] The acid value of the alkali-soluble resin (B1) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0098] The molar ratio of the alkoxysilyl group-containing monomer unit (b1) and the acidic group-containing monomer unit (b2) in the alkali-soluble resin (B1) is preferably b1:b2=20:80 to 80:20.

[0099] The silyl group equivalent of the alkali-soluble resin (B1) is preferably 200 to 4,000 g / mol, more preferably 250 to 3,000 g / mol. The silyl group equivalent is a value obtained by dividing the molecular weight of the alkali-soluble resin (B1) by the average number of silyl groups per molecule, and is calculated based on the amount of the monomer that forms the alkoxysilyl group-containing monomer unit (b1). The calculated value shall be used.

[0100] The method for producing the alkali-soluble resin (B1) is not particularly limited, and a known method can be used. For example, the methods described in WO 2018 / 110097, WO 2022 / 085389, etc. can be mentioned.

[0101] The alkali-soluble resin (B1) can be used alone or in combination of two or more kinds.

[0102] The content of the alkali-soluble resin (B1) is preferably from 10 to 100 mass %, more preferably from 20 to 80 mass %, in 100 mass % of the alkali-soluble resin (B), from the viewpoints of pattern formability and resistance to low-temperature heating.

[0103] (Alkali-soluble resin (B2) not having alkoxysilyl group-containing monomer unit (b1)) From the viewpoint of pattern formability, the photosensitive composition of the present invention preferably contains an alkali-soluble resin (B2) (hereinafter, simply referred to as alkali-soluble resin (B2)) that does not have an alkoxysilyl group-containing monomer unit (b1) as the alkali-soluble resin (B). It is presumed that the absence of an alkoxysilyl group-containing monomer unit (b1) allows the interaction with the functional groups on the substrate surface and the functional groups of other components contained in the photosensitive composition to be adjusted, thereby improving pattern formability.

[0104] The alkali-soluble resin (B2) is not particularly limited as long as it does not have an alkoxysilyl group-containing monomer unit (b1), and a known alkali-soluble resin can be used. For example, an alkali-soluble resin having at least one of the above-mentioned monomer units (b2) to (b8) can be used. Among these, from the viewpoint of resistance to low-temperature heating, the alkali-soluble resin (B2) more preferably has at least one monomer unit selected from the group consisting of the above-mentioned blocked isocyanate group-containing monomer unit (b3) and the polymerizable unsaturated group-containing monomer unit (b4), and particularly preferably has the blocked isocyanate group-containing monomer unit (b3).

[0105] The content of the blocked isocyanate group-containing monomer unit (b3) is preferably from 1 to 50 mol %, more preferably from 3 to 40 mol %, in the total monomer units of the alkali-soluble resin (B2).

[0106] The content of the polymerizable unsaturated group-containing monomer unit (b4) is preferably from 5 to 80 mol %, more preferably from 10 to 80 mol %, in all the monomer units of the alkali-soluble resin (B2).

[0107] Furthermore, from the viewpoint of resistance, the alkali-soluble resin (B2) preferably contains the above-mentioned aliphatic fused ring structure-containing monomer unit (b5).

[0108] From the viewpoint of resistance, the content of the aliphatic fused ring structure-containing monomer unit (b5) is preferably 1 to 40 mol % in all the constituent units of the alkali-soluble resin (B2).

[0109] The weight average molecular weight of the alkali-soluble resin (B2) is preferably from 3,000 to 50,000, more preferably from 3,000 to 20,000.

[0110] The acid value of the alkali-soluble resin (B2) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0111] The alkali-soluble resin (B2) can be used alone or in combination of two or more kinds.

[0112] The content of the alkali-soluble resin (B2) is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, based on 100% by mass of the alkali-soluble resin (B) from the viewpoints of pattern formability and resistance to low-temperature heating. 0% by mass is more preferable.

[0113] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0114] The polymerizable compound (C) is not particularly limited, and may be a known compound. For example, a monomer or oligomer having a polymerizable unsaturated group may be used. The polymerizable unsaturated group may be a vinyl group, (meth)allyl group, (meth)acryloyl group, or acryloyloxy group having an ethylenically unsaturated double bond.

[0115] Examples of the polymerizable compound (C) include a polymerizable compound (C1) having a hydroxyl group, a polymerizable compound (C2) having an amine structure, a polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure, a polymerizable compound (C4) having an acidic group, a polymerizable compound (C5) having a urethane bond, a lactone-modified polymerizable compound (C6), and other polymerizable compounds (C7). Among these, it is preferable to include at least one selected from the group consisting of a polymerizable compound (C1) having a hydroxyl group, a polymerizable compound (C2) having an amine structure, and a polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure.

[0116] The polymerizable compound (C) may be used alone or in combination of two or more kinds.

[0117] The content of the polymerizable compound (C) is preferably from 1 to 80 mass %, and more preferably from 5 to 70 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0118] (Polymerizable compound having a hydroxyl group (C1)) From the viewpoint of resistance to low-temperature heating, the photosensitive composition of the present invention preferably contains a polymerizable compound (C1) having a hydroxyl group as the polymerizable compound (C). It is presumed that the resistance is improved by the reaction between the hydroxyl group of the polymerizable compound (C1) having a hydroxyl group and the alkoxysilyl group of the alkali-soluble resin (B1).

[0119] Examples of the polymerizable compound (C1) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, EO isocyanuric acid, or the like. Examples of the acrylic acid ester include PO-modified (meth)acrylate, isocyanuric acid EO or PO-modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, and epoxy (meth)acrylate obtained by reacting an epoxy group of an epoxy compound with a carboxyl group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0120] Examples of commercially available polymerizable compounds (C1) having a hydroxyl group include KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd., ARONIX M-5700 and M-920 manufactured by Toagosei Co., Ltd., NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P, Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0121] The polymerizable compound (C1) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0122] The content of the polymerizable compound (C1) having a hydroxyl group is preferably from 10 to 90 mass %, and more preferably from 20 to 80 mass %, in 100 mass % of the polymerizable compound (C).

[0123] (Polymerizable compound having an amine structure (C2)) From the viewpoint of pattern forming property and resistance to low-temperature heating, the photosensitive composition of the present invention preferably contains a polymerizable compound (C2) having an amine structure. It is presumed that the polymerizable compound (C2) having an amine structure has an amine structure in the molecule, and thus hydrogen is easily extracted to generate a carbon radical. Therefore, the generated peroxy radical extracts hydrogen from the polymerizable compound (C2) having an amine structure, and the newly generated carbon radical starts polymerization. In addition, the generated carbon radical can also capture oxygen, which has the effect of reducing the oxygen concentration. It is presumed that these mechanisms suppress polymerization inhibition by oxygen, and polymerization proceeds sufficiently, resulting in sufficient adhesion and resistance. It is also presumed that the amine structure has polarity, which improves adhesion to the substrate.

[0124] The amine structure of the polymerizable compound (C2) having an amine structure may be any of a primary amine, secondary amine, and tertiary amine structures, but is preferably a secondary or tertiary amine structure, provided that the amine structure of the polymerizable compound (C2) having an amine structure does not include an amide structure, an imide structure, or a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0125] Examples of the polymerizable compound (C2) having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0126] Examples of the (meth)acrylate compound (X) 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, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta ...hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples of the alkylene oxide-modified tetra(meth)acrylate include phosphorus tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerol alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0127] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0128] The amine compound (Y) is, for example, n-propylamine, n-butylamine, n-hexylamine, primary amines such as diamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0129] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0130] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and a known method can be used. For example, the methods described in International Publication No. 2006 / 075754, JP-A-2008-545859, JP-A-2017-066347, etc. can be mentioned.

[0131] The polymerizable compound (C2) having an amine structure may have an acidic group and / or a hydroxyl group. Examples of a method for introducing an acidic group and / or a hydroxyl group include a method of using a compound having an acidic group and / or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

[0132] Commercially available polymerizable compounds (C2) having an amine structure include, for example, ARONIX MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL 80 and 7100 manufactured by Daicel-Allnex Corporation, and CN371NS, 372, 374, 383 and 386 manufactured by Arkema.

[0133] The polymerizable compound (C2) having an amine structure preferably further has a urethane bond. This forms a chemical crosslinked structure by polymerization as well as a physical crosslinked structure by intermolecular hydrogen bonds between the urethane bonds and between the urethane bonds and the functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds in the urethane bonds is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes flexible and strong due to the interaction between the urethane bonds, improving its resistance.

[0134] The urethane bond can be introduced, for example, by a urethane reaction between a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0135] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclo polyisocyanate compounds having an alicyclic structure, such as norbornane diisocyanate, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane; 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0136] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0137] The method of the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and a known method can be used. For example, the method described in JP-A-2018-517797 can be mentioned.

[0138] An example of a commercially available polymerizable compound (C2) having an amine structure and a urethane bond is CN9906NS manufactured by Arkema.

[0139] The polymerizable compound (C2) having an amine structure can be used alone or in combination of two or more kinds.

[0140] The content of the polymerizable compound (C2) having an amine structure is preferably from 0.1 to 80 mass %, and more preferably from 0.5 to 60 mass %, in 100 mass % of the polymerizable compound (C).

[0141] (Polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure) From the viewpoint of resistance to low-temperature heating, the photosensitive composition of the present invention preferably contains a polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure. The polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure has a closer distance between polymerizable groups in the molecule and a higher density than general linear polymerizable compounds. Therefore, it is less susceptible to oxygen inhibition and chain transfer of solvents, and is expected to react sufficiently even when the amount of polymerization initiator or the amount of exposure is small, improving resistance.

[0142] A compound having a dendrimer structure has a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, and a polymerizable unsaturated group is bonded to the end of the branch, and the compound has a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of the dendrimer structure.

[0143] Commercially available polymerizable compounds (C3) having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) and SIRUS-501 (dendrimer structure, average number of acryloyl groups: 18) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by SARTOMER Co., Ltd., and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), 6363 (hyperbranched structure, average number of acryloyl groups: 16), and DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials.

[0144] The polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more kinds.

[0145] The content of the polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure is preferably from 0.5 to 80 mass %, and more preferably from 1 to 60 mass %, in 100 mass % of the polymerizable compound (C).

[0146] (Polymerizable compound having an acidic group (C4)) Examples of the polymerizable compound (C4) having an acidic group include an esterification product of a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid; an esterification product of a polycarboxylic acid and a monohydroxyalkyl (meth)acrylate, and the like.

[0147] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0148] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0149] Examples of the polyvalent carboxylic acid include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0150] Commercially available products of the polymerizable compound (C4) having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and β-CEA manufactured by Daicel-Allnex Corporation.

[0151] (Polymerizable compound having a urethane bond (C5)) Examples of the polymerizable compound (C5) having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the polyhydric alcohol with a hydroxyl group-containing (meth)acrylate.

[0152] Examples of the hydroxyl group-containing (meth)acrylate 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 (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, 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.

[0153] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanates such as isophorone diisocyanate, as well as biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adduct derivatives thereof.

[0154] The polymerizable compound (C5) having a urethane bond may have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, the carboxyl group is preferred.

[0155] The method for introducing an acidic group into the polymerizable compound (C5) having a urethane bond can be, for example, synthesized by first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0156] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0157] Commercially available polymerizable compounds (C5) having a urethane bond include, for example, 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.

[0158] (Lactone-modified polymerizable compound (C6)) The lactone-modified polymerizable compound (C6) is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound (C6) is obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0159] Commercially available lactone-modified polymerizable compounds (C6) include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0160] (Other polymerizable compounds (C7)) Examples of other polymerizable compounds (C7) include methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane EO or PO modified tri(meth)acrylate, isocyanuric acid. Examples of the methacrylic acid ester include EO- or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, and (meth)acrylic acid ester of methylolated melamine; styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0161] Other commercially available polymerizable compounds (C7) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-21 manufactured by Toagosei Co., Ltd. 1B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., OGSOL manufactured by Osaka Gas Chemical Co., Ltd. Examples of such esters include EA-0200, EA-0300, Miramer HR6060, 6100, and 6200 manufactured by Miwon Specialty Chemical Co., Ltd., and NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, and AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0162] Further examples include (meth)acrylates having a hydroxyl group and an acidic group, (meth)acrylates having a hydroxyl group and a urethane bond, and lactone-modified (meth)acrylates having a hydroxyl group.

[0163] [Polymerization initiator (D)] The photosensitive composition of the present invention contains a polymerization initiator (D).

[0164] The polymerization initiator (D) is not particularly limited, and any known compound can be used. For example, a compound that generates radicals by the action of light or heat to initiate or promote a radical polymerization reaction can be used. The polymerization initiator that generates radicals by light (hereinafter, also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals by light rays in the ultraviolet to visible light range. The polymerization initiator that generates radicals by heat (hereinafter, also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0165] Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 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, 2,4-trichloromethyl-(4' -Methoxystyryl)-6-triazine and other triazine compounds; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; and carbazole-based compounds.

[0166] Commercially available products include acetophenone compounds such as Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime compounds such as IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, ADEKA Arcles N-1919, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of such adhesives include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemistrys. Further, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855 A, JP 2022-5115524 A, and the like are also included.

[0167] Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), Dimethyl-2,2'-azobis(2-methyl propionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl) azo compounds such as 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, Examples of the organic peroxides include acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide.

[0168] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0169] The content of the polymerization initiator (D) is preferably from 0.1 to 20 mass %, more preferably from 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0170] (The absorption coefficient of light with a wavelength of 365 nm in propylene glycol monomethyl ether acetate is 5.0 × 10 3 L / mol cm or more polymerization initiator (D1) The photosensitive composition of the present invention contains a polymerization initiator (D) having an absorption coefficient of 5.0×10 3 L / mol cm or more of a polymerization initiator (D1) (hereinafter simply referred to as polymerization initiator (D1)).

[0171] The absorption coefficient of the polymerization initiator (D1) in propylene glycol monomethyl ether acetate at a wavelength of 365 nm is 5.0 × 10 3 ~5.0×10 4 mL / gcm is preferred, and 1.0×10 4 ~4.0×10 4 It is more preferable that the density is in the range of 100 to 200 nm.

[0172] The polymerization initiator (D1) is not particularly limited, and known compounds can be used. For example, compounds described in International Publication No. 2008 / 078678, JP 2009-134289 A, Japanese Patent No. 4600600 A, JP 2011-132215 A, JP 2014-500852 A, JP 2015-523318 A, International Publication No. 2015 / 036910 A, International Publication No. 2017 / 051680 A, International Publication No. 2021 / 175855 A, and JP 2022-515524 A can be mentioned. Among them, it is preferable to include a compound having one oxime ester group, and it is more preferable to include a compound having two oxime ester groups. By having two oxime ester groups, the radical generating ability is high and it is difficult to be inhibited by oxygen. This promotes photocuring, improving pattern formability and resistance to low-temperature heating.

[0173] Specific examples of the polymerization initiator (D1) are shown below, but the present invention is not limited to these.

[0174] [ka]

[0175] [ka]

[0176] The polymerization initiator (D1) can be used alone or in combination of two or more kinds.

[0177] The content of the polymerization initiator (D1) is preferably from 10 to 100 mass%, and more preferably from 20 to 100 mass%, in 100 mass% of the polymerization initiator (D).

[0178] [Thermosetting compound (E)] The photosensitive composition of the present invention contains a thermosetting compound (E) from the viewpoint of resistance to low-temperature heating. This is preferable. By this, the thermosetting compound (E) is crosslinked by heating, and the resistance is improved. In this specification, the thermosetting compound (E) is not included in the alkali-soluble resin (B) and the polymerizable compound (C).

[0179] The thermosetting compound (E) is not particularly limited as long as it is a compound having a thermosetting group, and a known compound can be used. For example, a compound having an epoxy group, a compound having a blocked isocyanate group, a compound having an oxetanyl group, a compound having a methylol group, a compound having a phenol group, a compound having an alkoxyalkyl group, etc. can be mentioned. Among these, it is preferable to include at least one selected from the group consisting of a compound having an epoxy group and a compound having a blocked isocyanate group.

[0180] The thermosetting compound (E) can be used alone or in combination of two or more kinds.

[0181] The content of the thermosetting compound (E) is preferably from 0.5 to 40 mass %, and more preferably from 1 to 30 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0182] (Compound (E1) having an epoxy group) The photosensitive composition of the present invention preferably contains a compound (E1) having an epoxy group as the thermosetting compound (E), whereby the epoxy group is crosslinked by heating, and resistance is further improved.

[0183] The epoxy group is a group having a three-membered cyclic ether structure, including an alicyclic epoxy group. The compound having an epoxy group is not particularly limited, and known compounds can be used. For example, polyglycidyl ether compounds of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as bis(3,4-epoxycyclohexylmethyl)-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone; Examples include an adduct of 2,2-bis(hydroxymethyl)-1-butanol with 1,2-epoxy-4-(2-oxiranyl)cyclohexane.

[0184] Commercially available products of the compound (E1) having an epoxy group include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, and EPICLON manufactured by DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500.

[0185] The compound (E1) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0186] The epoxy equivalent of the compound (E1) having an epoxy group is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of an epoxy group.

[0187] From the viewpoint of resistance to low-temperature heating, the compound (E1) having an epoxy group more preferably contains a compound represented by the following general formula (5).

[0188] General formula (5) [ka]

[0189] In formula (5), R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0190] R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol. The group obtained by removing m hydroxyl groups from the m-hydric alcohol is preferably an alkyl group having 2 to 20 carbon atoms, which may be linear, branched, cyclic, or a combination of these. Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2,2-dimethylpropyl group, a butyl group, an isobutyl group, a tert-butyl group, a 3,3-dimethylbutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable.

[0191] m represents an integer of 1 to 6, and n represents an integer of 1 to 30. When m is 2 or more, n in each group in parentheses in general formula (5) may be the same or different.

[0192] A specific example of the compound represented by the general formula (5) is a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0193] The compound (E1) having an epoxy group can be used alone or in combination of two or more kinds.

[0194] The content of the compound (E1) having an epoxy group is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, in 100 mass % of the thermosetting compound (E).

[0195] (Compound (E2) Having a Blocked Isocyanate Group) The photosensitive composition of the present invention preferably contains a compound (E2) having a blocked isocyanate group as the thermosetting compound (E).

[0196] The compound (E2) having a blocked isocyanate group is a compound in which the isocyanate group of a compound having an isocyanate group is protected with a blocking agent. The desorption temperature of the blocking agent of the blocked isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 100°C.

[0197] The compound (E2) having a blocked isocyanate group can be obtained by reacting a compound having an isocyanate group with a blocking agent by a known method, for example, as described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, JP-A-2012-012567, etc.

[0198] Examples of the blocking agent include the above-mentioned compounds. Among these, at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds is preferred, at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferred, and from the viewpoint of resistance to low-temperature heating, active methylene compounds are particularly preferred. The elimination temperature of the active methylene compound or the temperature of the ester exchange reaction is as low as 80 to 110°C, and the reaction is sufficient even at low-temperature heating, improving resistance.

[0199] Examples of the compound having an isocyanate group include compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclo Compounds having an alicyclic structure, such as norbornane diisocyanate, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane; 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Examples of the aromatic compounds include 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene. Further examples include biuret forms, isocyanurate forms, adduct forms, allophanate forms, and reaction products of these compounds with polyols.

[0200] The compound having an isocyanate group is preferably a biuret, isocyanurate, adduct or allophanate of a compound having an aliphatic structure or a compound having an alicyclic structure.

[0201] Examples of the compound (E2) having a blocked isocyanate group include the following compounds: In the following structural formulas, X represents a blocked isocyanate group, but the present invention is not limited thereto.

[0202] [ka]

[0203] Examples of X (blocked isocyanate group) in the above compound include the following structures (X-1) to (X-6). In the following structures, * represents a bond. However, the present invention is not limited to these.

[0204] [ka]

[0205] Commercially available products of the compound (E2) having a blocked isocyanate group include, for example, compounds having an aliphatic structure, such as Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882 manufactured by Mitsui Chemicals, Inc., and BI7960, BI7961, BI7982, BI7991, and BI7992 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an alicyclic structure include Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation, and BI7950, BI7951, and BI7990 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an aromatic structure include Takenate B-830 and B-815N manufactured by Mitsui Chemicals.

[0206] The compound (E2) having a blocked isocyanate group preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0207] The weight average molecular weight of the compound (E2) having a blocked isocyanate group is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0208] The acid value of the compound (E2) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0209] The compound (E2) having a blocked isocyanate group can be used alone or in combination of two or more kinds.

[0210] The content of the compound (E2) having a blocked isocyanate group is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, in 100 mass % of the thermosetting compound (E).

[0211] From the viewpoint of resistance to low-temperature heating, the photosensitive composition of the present invention more preferably uses, as the thermosetting compound (E), a compound (E1) having an epoxy group and a compound (E2) having a blocked isocyanate group in combination. The mass ratio of the compound (E1) having an epoxy group to the compound (E2) having a blocked isocyanate group is preferably from 5:95 to 95:5, and more preferably from 10:90 to 90:10.

[0212] [Ultraviolet absorber (F)] From the viewpoint of pattern formability, the photosensitive composition of the present invention preferably contains an ultraviolet absorber (F), which reduces the influence of changes in exposure dose and the type and amount of polymerization initiator used, thereby improving pattern formability.

[0213] The ultraviolet absorber (F) is not particularly limited, and known compounds can be used. For example, benzotriazole compounds, benzophenone compounds, triazine compounds, conjugated diene compounds, methyldibenzoyl compounds, coumarin compounds, acrylonitrile compounds, benzothiazole compounds, salicylate compounds, etc. can be mentioned. Among these, it is preferable to include at least one selected from the group consisting of benzotriazole compounds, benzophenone compounds, and triazine compounds, and it is more preferable to include at least one selected from the group consisting of benzotriazole compounds and benzophenone compounds.

[0214] The ultraviolet absorbents (F) can be used alone or in combination of two or more kinds.

[0215] The content of the ultraviolet absorber (F) is preferably from 30 to 300 parts by mass, and more preferably from 60 to 200 parts by mass, based on 100 parts by mass of the polymerization initiator (D).

[0216] (Benzotriazole compound (F1)) Benzotriazole compounds (F1) include, for example, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, ester compounds of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and linear alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, and the like. Examples of commercially available products include Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT manufactured by BASF Japan Ltd., and Adeka STAB LA-31RG and LA-31G manufactured by ADEKA Corporation.

[0217] Benzotriazole compounds (F1) include the following compounds, but the present invention is not limited thereto.

[0218] [ka]

[0219] (Benzophenone compounds (F2)) The benzophenone compound (F2) may be, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, diethylamino hydroxybenzoyl hexyl benzoate, 4,4'-bis(dimethylamino)benzyloxy ... Benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone Examples include phenone. Examples of commercially available products include Ubinal A, 3049, 3050, and UVA-935LH manufactured by BASF Japan Ltd., and Adeka STAB 1413 manufactured by ADEKA Corporation.

[0220] Examples of the benzophenone compound (F2) include the following compounds, although the present invention is not limited thereto.

[0221] [ka]

[0222] (Triazine compounds (F3)) Examples of the triazine compound (F3) include a reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl with [(C10-C16 (mainly C12-C13) alkyloxy)methyl]oxirane, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2, Examples of such phenols include 4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol. Examples of commercially available products include Tinuvin 400, 405, 406, 477, and 479 manufactured by BASF Japan, and Adeka STAB LA-46 and LA-F70 manufactured by ADEKA Corporation.

[0223] Examples of the triazine compound (F3) include the following compounds, but the present invention is not limited thereto.

[0224] [ka]

[0225] [Thiol-based chain transfer agents (G)] From the viewpoint of resistance to low-temperature heating, the photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent (G), which is presumably responsible for the generation of thiyl radicals that are not easily inhibited by oxygen during the exposure step, which promotes photocuring and improves resistance to low-temperature heating.

[0226] Examples of the thiol-based chain transfer agent (G) include monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds having a hydroxyl group or an acidic group, such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid; 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 tetrakis(3-mercaptopropionate), trime Examples of suitable polyfunctional thiol compounds include tris(2-hydroxyethyl)isocyanate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0227] The thiol chain transfer agent (G) preferably contains a monofunctional thiol compound having an acidic group.

[0228] The thiol chain transfer agent (G) can be used alone or in combination of two or more kinds.

[0229] The content of the thiol chain transfer agent (G) is preferably from 0.5 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0230] [Silane coupling agent (H)] From the viewpoint of pattern formability and resistance to low-temperature heating, the photosensitive composition of the present invention preferably contains a silane coupling agent (H). It is presumed that the silane coupling agent (H) reacts with functional groups on the substrate surface and functional groups of other components contained in the photosensitive composition, improving the pattern formability and resistance to low-temperature heating.

[0231] The silane coupling agent (H) is a compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of hydrolysis and condensation reactions. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. From the viewpoint of reactivity, the alkoxy group is preferably a methoxy group or an ethoxy group. Examples of the other functional groups include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, and a ureido group. In this specification, the silane coupling agent (H) is not included in the alkali-soluble resin (B) and the polymerizable compound (C).

[0232] Examples of the silane coupling agent (H) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and the like.

[0233] Commercially available products of the silane coupling agent (H) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, and KBE -1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-1048, X-12-50, etc.

[0234] The silane coupling agent (H) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0235] The polysiloxane type is a compound in which the hydrolyzable group and the other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Silicone Co., Ltd.

[0236] The organic polymer type is a silane coupling agent (H) in which the hydrolyzable group and the other functional groups are bonded to an organic polymer whose main chain is an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L manufactured by Shin-Etsu Silicone Co., Ltd.

[0237] The silane coupling agent (H) preferably contains a compound represented by the following general formula (6). The compound represented by general formula (6) has a urethane bond, and therefore forms hydrogen bonds between the urethane bonds and with functional groups of other components contained in the photosensitive composition, forming a strong film. In addition, it is presumed that the urethane bond has flexibility, resulting in a strong yet flexible film.

[0238] General formula (6) [ka]

[0239] In general formula (6), three R1s each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, Q represents a group represented by the following general formulas (Q-1) to (Q-4), and n represents an integer of 1 to 10.

[0240] [ka]

[0241] In the general formula (Q-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In the general formulae (Q-1) to (Q-4), R4 represents a hydrogen atom or a methyl group. * represents a bond to an oxygen atom.

[0242] In the general formula (5), the three R1's are preferably methyl groups.

[0243] In the general formula (5), Q is preferably any of the general formulae (Q-1) to (Q-3).

[0244] The molecular weight or weight average molecular weight of the silane coupling agent (H) is preferably from 100 to 3,000, and more preferably from 150 to 1,500.

[0245] The acid value of the silane coupling agent (H) is preferably 10 mgKOH / g or less.

[0246] The silane coupling agent (H) can be used alone or in combination of two or more kinds.

[0247] The content of the silane coupling agent (H) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0248] [Dye (I)] The photosensitive composition of the present invention can contain a dye (I).

[0249] The dye (I) is not particularly limited, and any known compound can be used. Examples include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, derivatives of these dyes and lake pigments obtained by converting dyes into lakes can also be used.

[0250] The acid dye preferably has an acid group such as a sulfo group or a carboxyl group. In addition, a salt-forming compound which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferred. In addition, a salt-forming compound which is a salt of a resin component having these functional groups and an acid dye is also preferred. In addition, the salt-forming compound is easily modified into a sulfonamide compound to obtain a photosensitive composition having excellent resistance (light resistance, solvent resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0251] Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because it has excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion component acting as a counter ion in the salt-forming compound of the basic dye is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compound is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0252] The chemical structure of the dye (I) may be, for example, an azo dye, a disazo dye, an azomethine dye (such as an indoaniline dye or an indophenol dye), a dipyrromethene dye, a quinone dye (such as a benzoquinone dye, a naphthoquinone dye, anthraquinone dye, or an anthrapyridone dye), a carbonium dye (such as a diphenylmethane dye, a triphenylmethane dye, a xanthene dye, or an acridine dye), a quinoneimine dye (such as an oxazine dye or a thiazine dye), an azine dye, Examples of the dye structure include those derived from dyes selected from polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0253] Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0254] The dyes (I) can be used alone or in combination of two or more kinds.

[0255] The content of the dye (I) is preferably from 0.5 to 60 mass %, and more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0256] [Pigment Derivatives (J)] The photosensitive composition of the present invention may contain a pigment derivative (J), which allows the pigment (A) to be stably dispersed.

[0257] The pigment derivative (J) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. can be mentioned. Specifically, compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, etc., and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group can be mentioned. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, and naphthalocyanine compounds.

[0258] Specifically, pyrrolopyrrole pigment derivatives are described in JP 2001-220520 A, WO 2009 / 081930 A, WO 2011 / 052617 A, WO 2012 / 102399 A, JP 2017-156397 A, and WO 2018 / 101189 A, phthalocyanine pigment derivatives are described in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone pigment derivatives are described in JP 63-2 64674, JP09-272812A, JP10-245501A, JP10-265697A, JP2007-079094A, WO 2009 / 025325A, quinacridone pigment derivatives are shown in JP48-54128A, JP03-9961A, and JP2000-273383A, dioxazine pigment derivatives are shown in JP2011-162662A, thiazine indigo pigment derivatives are shown in JP2007-314785A, triazine pigment derivatives are shown in Examples of benzoisoindole pigment derivatives include JP-A-2009-57478, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-226110. Examples of naphthol pigment derivatives include Examples of squarylium pigment derivatives include those described in JP 2012-208329 A and JP 2014-5439 A; examples of azo pigment derivatives include those described in JP 2001-172520 A and JP 2012-172092 A; examples of acidic substituents include those described in JP 2004-307854 A; and examples of basic substituents include those described in JP 2002-201377 A, JP 2003-171594 A, JP 2005-181383 A, JP 2005-213404 A, and the like.In these documents, the term "derivative," "dye derivative," "dispersant," "dispersing aid," "pigment dispersant," or simply "compound" is sometimes used, but these terms are synonymous with the pigment derivative (J).

[0259] The pigment derivative (J) is preferably added during the above-mentioned micronization of the pigment (A) or during the dispersion treatment of the pigment (A) described below. The average primary particle size of the pigment derivative (J) is preferably 5 to 200 nm.

[0260] The pigment derivative (J) can be used alone or in combination of two or more kinds.

[0261] The content of the pigment derivative (J) is preferably from 1 to 50 parts by mass, and more preferably from 2 to 40 parts by mass, based on 100 parts by mass of the pigment (A).

[0262] [Dispersion resin (K)] The photosensitive composition of the present invention may contain a dispersing resin (K), which allows the pigment (A) to be stably dispersed. In this specification, the dispersing resin (K) is not included in the alkali-soluble resin (B).

[0263] The dispersing resin (K) is preferably a resin having an adsorptive group having a high affinity for the pigment (A). The adsorptive group preferably has at least one type of basic group and acidic group.

[0264] 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.

[0265] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0266] Examples of the resin type of the dispersion resin (K) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0267] Examples of the structure of the dispersing resin (K) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, the block structure, the graft structure, and the comb structure are preferred.

[0268] From the viewpoint of resistance to low-temperature heating, the dispersing resin (K) preferably has a thermosetting group and / or a polymerizable unsaturated group. Examples of the thermosetting group include a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, and a blocked isocyanate group.

[0269] Examples of the dispersing resin (K) include the resins described in paragraphs 0122 to 0155 of WO 2013175978, the resins described in paragraphs 0317 to 0321 of JP 2019-78878 A, the resins described in paragraphs 0083 of WO 2018 / 139534, the resins described in paragraphs 0167 to 0191 of WO 2019 / 163505, the resins described in paragraphs 0299 ​​to 0310 of WO 2021 / 131927, the resins described in paragraphs 0080 to 0085 of WO 2022 / 102367, and the resins described in paragraphs 0099 to 0109 of WO 2022 / 172607.

[0270] Commercially available dispersion resins (K) 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, 2164, Anti-Terra-U203, 204, and BYK-P1 manufactured by BYK-Chemie Japan Co., Ltd. 04, P104S, 220S, Lactimon, Lactimon-WS, 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, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 7 EFKA-6500 manufactured by BASF Japan, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503 manufactured by Ajinomoto Fine-Techno Co., Ltd., Aji-Super - PA111, PB711, PB821, PB822, PB824, and the like, resins described in JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, JP1996-143651A, and the like.

[0271] The dispersing resin (K) can be used alone or in combination of two or more kinds.

[0272] From the viewpoint of dispersion stability, the content of the dispersing resin (K) is preferably from 3 to 200 parts by mass, and more preferably from 5 to 150 parts by mass, relative to 100 parts by mass of the pigment (A).

[0273] [Sensitizer (L)] The photosensitive composition of the present invention can contain a sensitizer (L).

[0274] Examples of the sensitizer (L) include polymethine dyes such as 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 oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples of the compounds include compounds having a fluorine atom, ...

[0275] The sensitizers (L) can be used alone or in combination of two or more kinds.

[0276] The content of the sensitizer (L) is preferably from 10 to 400 parts by mass, and more preferably from 20 to 300 parts by mass, based on 100 parts by mass of the polymerization initiator (D).

[0277] [Hardening agent (curing accelerator)] In the photosensitive composition of the present invention, a curing agent (curing accelerator) can be used in combination to assist the curing of the thermosetting compound (E). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)- N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0278] The curing agents can be used alone or in combination of two or more kinds.

[0279] The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound (E).

[0280] [Polymerization inhibitor (M)] The photosensitive composition of the present invention may contain a polymerization inhibitor (M).

[0281] Examples of the polymerization inhibitor (M) 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, and 2-n- alkyl resorcinol compounds such as butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-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 phloroglucine.

[0282] The content of the polymerization inhibitor (M) is preferably from 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0283] [Antioxidant (N)] The photosensitive composition of the present invention may contain an antioxidant (N). The antioxidant (N) prevents the polymerization initiator (D) and the thermosetting compound (E) in the photosensitive composition from being oxidized and yellowed by heat during the heating process or ITO annealing.

[0284] Examples of the antioxidant (N) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based and hydroxylamine-based compounds. Of these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0285] Examples of the hindered phenol antioxidant include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'- t-Butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5- Methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate stearyl, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4 ,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethyl bis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylene bisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthiomethyl)-o-cresol ethylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and the like.

[0286] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0287] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, and 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol with 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi 1,2,2,6,6-pentamethyl-4-pyridyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-Hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0288] Examples of commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd., and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

[0289] Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylide diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples of such phosphite include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-t-butyl-6-methylphenyl)phosphite.

[0290] Commercially available products include, for example, ADEKA STAB PEP-36, PEP-8, and HP- 10, 2112, 1178, 1500, C, 135A, 3010, TPP, IRGAFOS168 manufactured by BASF Japan, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0291] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0292] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0293] The antioxidants (N) can be used alone or in combination of two or more kinds.

[0294] The content of the antioxidant (N) is preferably from 0.5 to 5.0% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0295] [Leveling agent (O)] The photosensitive composition of the present invention may contain a leveling agent (O), which improves the wettability and drying property of the composition with respect to a substrate during application.

[0296] Examples of the leveling agent (O) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0297] 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 ends.

[0298] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341.

[0299] The fluorosurfactant may be, for example, a surfactant or a leveling agent having a fluorocarbon chain.

[0300] 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.

[0301] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxy Ethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan Examples of such sorbitan monooleate include 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 alkylamines, alkyl alkanolamides, and alkyl imidazolines.

[0302] 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, LATEMURU 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), Ami-to 102, Examples of such polymers include 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 Polyfluor No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0303] Examples of the cationic surfactant include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0304] Commercially available products include, for example, Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0305] Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, lauryl Examples of the monomer units include ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

[0306] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adeka Col TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0307] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethyl amino acetate betaine; and alkyl amine oxides such as lauryl dimethyl amine oxide.

[0308] Commercially available products include Anhythol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0309] The leveling agent (O) can be used alone or in combination of two or more kinds.

[0310] The content of the leveling agent (O) is preferably from 0.001 to 2.0% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0311] [Storage stabilizer (P)] The photosensitive composition of the present invention may contain a storage stabilizer (P), which stabilizes the viscosity of the photosensitive composition over time.

[0312] Examples of the storage stabilizer (P) include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0313] The content of the storage stabilizer (P) is preferably from 0.05 to 5% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0314] [Organic solvent (Q)] The photosensitive composition of the present invention may contain an organic solvent (Q).

[0315] 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, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, and 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, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, gamma-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl Ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol 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, dibasic acid esters, and the like.Among these, from the viewpoints of resin solubility and coatability, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0316] From the viewpoint of the environment, the photosensitive composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.) Substantially not containing means that the content of such organic solvents in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0317] The organic solvent (Q) can be used alone or in combination of two or more kinds.

[0318] The content of the organic solvent (Q) is preferably an amount such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0319] [Specific metal element content] The photosensitive composition of the present invention preferably has a total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) of 500 mass ppm or less.

[0320] When the total amount of the specific metal elements in the photosensitive composition is within the above range, the composition has excellent dispersion stability and sensitivity even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0321] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less.

[0322] When the water content of the photosensitive composition is within the above range, the composition has excellent dispersion stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0323] [Method of producing photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photosensitive composition, the components may be mixed at once, or each component may be dissolved or dispersed in the polymerizable compound (C) or the organic solvent (Q) and then mixed successively. For example, a dispersion is produced by adding a pigment (A), a dispersing resin (K), an organic solvent (Q), etc., and carrying out a dispersion treatment. Then, an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), etc. are blended and mixed with the dispersion to produce the dispersion. The timing of blending each material is arbitrary. The dispersion process can also be carried out multiple times.

[0324] 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.

[0325] The average dispersed particle size (secondary particle size) of the particles in the dispersion is preferably from 30 to 200 nm, more preferably from 40 to 200 nm. If the particles have an appropriate particle size, a photosensitive composition having high dispersion stability is easily obtained.

[0326] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack 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 D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasonic waves immediately after sample preparation, as this tends to give results with less variation.

[0327] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0328] The photosensitive composition of the present invention can be preferably used for forming a pattern by a photolithography method, although the present invention is not limited thereto.

[0329] <Membrane> The film of the present invention is a film formed from the above-mentioned photosensitive composition. The film is preferably a patterned film, but can also be used as a flat film.

[0330] [Membrane manufacturing method] The method for producing the film is not particularly limited, and known methods can be used. In the present invention, the heating temperature throughout the entire process of film production is preferably 150°C or less, more preferably 130°C or less. By heating at 150°C or less, the performance of the image display device can be maintained when an organic EL element is used as the light source of the image display device, when the photoelectric conversion film of the image sensor is made of an organic material, when a heat-sensitive base material such as a plastic film is used, etc. The heating temperature is preferably 50°C or more.

[0331] In the production of the film, the photosensitive composition of the present invention is first applied onto a substrate. Examples of the substrate include substrates made of materials such as glass, resin, and silicon. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or CMOS may be formed on the substrate. Also, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0332] The coating method may be a known method, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0333] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0334] Next, a pattern is formed. Examples of a method for forming a pattern include a photolithography method and a dry etching method. Among these, a photolithography method is preferable. When the film is used as a flat film, the step of forming a pattern is not necessary, and after coating, the film is dried or the entire surface is exposed to light as necessary.

[0335] A method for forming a pattern by photolithography will be described in detail below.

[0336] When forming a pattern by photolithography, a layer formed by coating the photosensitive composition of the present invention on a substrate is dried at a temperature of 150°C or less as necessary, and then exposed to light in a pattern through a mask (exposure step). The unexposed parts are removed by alkaline development (development step), and the pattern is then heat-treated (heating step).

[0337] [Exposure process] In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. Examples of active energy rays used for exposure include ultraviolet rays such as g-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). In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure). Moreover, a plurality of active energy rays can be combined, or exposure can be carried out in a plurality of separate steps.

[0338] [Development process] Next, the layer is treated with an alkaline developer, whereby the unexposed portions are dissolved in the alkaline developer, leaving only the hardened portions to obtain a patterned film. Examples of alkaline developers 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 0.001 to 10% by mass, more preferably 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 roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0339] [Heating process] After development, a heat treatment is performed, which improves the resistance of the film. The heating temperature is preferably equal to or lower than 150° C., more preferably equal to or lower than 130° C. The heating time is preferably about 2 minutes to 2 hours.

[0340] <Optical filters> The optical filter of the present invention has the above-mentioned film. The optical filter is used, for example, in a color filter, a black matrix, a light-shielding filter, an anti-reflection filter, an infrared cut filter, an infrared transmission filter, a microlens, etc. The optical filter of the present invention can be manufactured by the same method as the above-mentioned film.

[0341] <Solid-state imaging element> The solid-state imaging device of the present invention has the above optical filter. The solid-state imaging device is not particularly limited as long as it includes the optical filter of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0342] The substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light shielding film with only the light receiving portion of the photodiode open on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving portion of the photodiode, and the optical filter (color filter) of the present invention on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the optical filter (the side closer to the substrate), or a light collecting means on the optical filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partitions, for example, in a lattice shape. In this case, the partitions preferably have a low refractive index with respect to each color pixel. An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, and surveillance cameras.

[0343] <Image display device> The image display device of the present invention includes the above optical filter. Examples of the image display device include a liquid crystal display and an organic EL display. The form of the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0344] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form of the infrared sensor used is not particularly limited as long as it is provided with the optical filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0345] A solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) is mounted on the board. The device has a plurality of photodiodes constituting an area and a transfer electrode made of polysilicon or the like. A light-shielding film with only the light receiving portion of the photodiodes open is provided on the photodiodes and the transfer electrodes. A device protective film is provided on this light-shielding film, and the optical filter of the present invention is provided on this device protective film. Furthermore, the device may have a configuration in which a focusing means (e.g., a microlens, etc., the same applies below) is provided on the device protective film and below the optical filter (the side closer to the substrate), or a configuration in which a focusing means is provided on the optical filter.

[0346] 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with an optical filter of the present invention. The infrared sensor shown in FIG.

[0347] The imaging area provided on the solid-state imaging element 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

[0348] The infrared cut filter 111 can be formed using the photosensitive composition of the present invention. The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm).

[0349] The color filter 112 is a color filter having pixels formed therein that transmit and absorb light of specific wavelengths in the visible light region, and for example, a color filter having red (R), green (G), and blue (B) pixels formed therein is used.

[0350] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 that is capable of transmitting light of a wavelength that has passed through the infrared transmission filter 113 is disposed.

[0351] The infrared transmission filter 113 can be formed using the photosensitive composition of the present invention, and is a filter that has a visible light shielding property and transmits infrared rays of a specific wavelength. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

[0352] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed so as to cover the microlens 115.

[0353] In the embodiment shown in FIG. 1, the resin film 114 is disposed, but instead of the resin film 114, an infrared transmission filter 113 may be formed.

[0354] This infrared sensor can simultaneously capture image information, making it possible to perform motion sensing that recognizes the object whose movement is to be detected. In addition, this infrared sensor can obtain distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor. EXAMPLES

[0355] 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". In the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0356] Before describing the examples, each measurement method will be described.

[0357] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and extinction coefficient (L / mol cm) of the resin are measured as follows: .

[0358] (molecular weight) The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0359] (Acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of sample solution, and the solution was stirred to dissolve uniformly. The solution was titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) was measured. The acid value per unit of nonvolatile content was calculated from the acid value of the solution and the concentration of nonvolatile content in the solution.

[0360] (amine value) The amine value is the total amine value (mgKOH / g) measured according to the method of ASTM D 2074 and converted into non-volatile content.

[0361] (Extinction coefficient) 0.001 g of polymerization initiator was dissolved in 0.01 L of propylene glycol monomethyl ether acetate to prepare a 0.1 mass% measurement solution. The 0.1 mass% measurement solution was then diluted with propylene glycol monomethyl ether acetate to prepare 0.01 mass% and 0.001 mass% measurement solutions. The absorbance of each concentration of the measurement solution was measured at a wavelength of 365 nm using a spectrophotometer (Hitachi High-Technologies Corporation, "U-3010"), and the extinction coefficient (L / mol cm) was calculated from the slope when the horizontal axis was the molar concentration and the vertical axis was the absorbance.

[0362] <Production of Pigment (A)> (Near infrared absorbing pigment (A-12)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added while stirring the resulting reaction mixture. The resulting black-brown precipitate was filtered off, washed with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a near-infrared absorbing pigment (A-12) represented by the following chemical formula (7). 50 parts of the obtained near-infrared absorbing pigment (A-12), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C for 12 hours. Next, the kneaded mixture was poured into hot water, heated to about 80 ° C and stirred for 1 hour to form a slurry, filtered, and washed with ion-exchanged water several times, then dried overnight at 80 ° C and pulverized to obtain a finely divided near-infrared absorbing pigment (A-12).

[0363] Chemical formula (7) [ka]

[0364] (Near infrared absorbing pigment (A-13)) In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and 34 parts of aluminum trichloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of ion-exchanged water while stirring, to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of ion-exchanged water, and dried to obtain compound a. Next, in a reaction vessel, 140 parts of compound a were added to 1,500 parts of concentrated sulfuric acid in an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, and washed with water, and then dried to obtain compound b. 5 parts of diphenyl phosphate was added to 200 parts of N-methylpyrrolidone, thoroughly mixed and heated to 50°C. 10 parts of compound b was gradually added to this solution, and then stirred at 90°C for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto filter paper and determining that no bleeding had occurred. Subsequently, this reaction solution was poured into 2,000 parts of ion-exchanged water, and the resulting precipitate was filtered and washed with ion-exchanged water several times, and then dried to obtain a near-infrared absorbing pigment (A-13) which is a mixture of compounds represented by the following chemical formula (8) (mass ratio: n1:n2:n3:n4=7:19:59:15). Next, it was finely divided by the same method as for the near-infrared absorbing pigment (A-12).

[0365] Chemical formula (8) [ka]

[0366] (Near infrared absorbing pigment (A-14)) According to the description of WO 2019 / 058882, a near infrared absorbing pigment (A-14) represented by the following chemical formula (9) was obtained. The near infrared absorbing pigment (A-12) was then micronized in the same manner as in the near infrared absorbing pigment (A-12).

[0367] Chemical formula (9) [ka]

[0368] (Near infrared absorbing pigment (A-15)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / l toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo were added and refluxed for 10 hours. After the reaction was completed, methanol was added and filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound c. In a reaction vessel, 13.5 parts of compound c, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and the mixture was heated and stirred at 40°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into 500 parts of methanol while stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, washed several times with 500 parts of ion-exchanged water, and dried to obtain a near-infrared absorbing pigment (A-15) which is a mixture of compounds represented by the following chemical formula (10) (mass ratio of dimer: trimer: tetramer = 81:17:2). Next, it was finely divided by the same method as for the near-infrared absorbing pigment (A-12).

[0369] Chemical formula (10) [ka]

[0370] <Production of alkali-soluble resin (B)> (Solution of alkali-soluble resin (B1-1) having alkoxysilyl group-containing monomer unit (b1) and acidic group-containing monomer unit (b2)) 300 parts of 3-methoxy-1-butanol was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 105°C. Next, a mixture of 106.9 parts of 3-methacryloyloxypropyltrimethoxysilane, 40.8 parts of methacrylic acid and 125 parts of methyl methacrylate, and 27.3 parts of dimethyl 2,2'-azobis(isobutyrate) as a polymerization initiator was added dropwise from the dropping funnel into the flask. After the dropwise addition, the mixture was reacted for 2 hours while stirring at 105°C. Then, propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by mass, and an alkali-soluble resin (B1-1) solution was prepared. The alkali-soluble resin (B1-1) had an acid value of 99 mgKOH / g and a weight average molecular weight of 7,100. In Table 2, the blending amounts are expressed in mole percent.

[0371] (Alkali-soluble resin (B1-2) to (B1-11) solutions) Alkali-soluble resins (B1-2) to (B1-11) were synthesized in the same manner as for alkali-soluble resin (B1-1), varying the type and amount of monomer used to obtain the composition ratio and weight-average molecular weight shown in Table 2, and propylene glycol monomethyl ether was added to adjust the non-volatile content to 40 mass%. The weight-average molecular weight of the resin was adjusted by varying the amount of polymerization initiator used.

[0372] [Table 2]

[0373] (Solution of alkali-soluble resin (B2-1) not having alkoxysilyl group-containing monomer unit (b1)) Into a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser was added 28.5 parts of diethyl malate, 0.01 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.05 parts of dibutyltin urate was added, stirred, and cooled to 15-20°C. Then, the temperature was maintained at 15-20°C, and 23.3 parts of 2-methacryloyloxyethyl isocyanate was added dropwise from the dropping funnel while stirring. After the dropwise addition was completed, the mixture was stirred at 25°C for 13 hours to react. The disappearance of the peak of the isocyanate group was confirmed by IR, and a monomer represented by the following chemical formula (11) was obtained.

[0374] Chemical formula (11) [ka]

[0375] Next, 200 parts of PGMAc was placed in a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 90°C. Next, a mixture of 41.7 parts of a monomer represented by chemical formula (11), 14 parts of methacrylic acid, 86 parts of n-butyl acrylate and 76 parts of methyl methacrylate, and a mixture of 24 parts of 2,2'-azobis(isobutyric acid)dimethyl (hereinafter, V-601) as a polymerization initiator added and dissolved in 50 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, a solution of 4 parts of V-601 dissolved in 16 parts of PGMAc was dropped and reacted for 3 hours. Then, PGMAc was added so that the non-volatile content was 40% by mass, and a precursor 1 solution was obtained. Next, 0.1 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 was added to 100 parts of the precursor 1 solution, and the temperature was raised to 80°C while stirring. After that, the reaction was carried out at 80°C for 30 minutes, and then cooled to terminate the reaction. As a result, an alkali-soluble resin (B2-1) having a monomer unit formed from a monomer represented by the following chemical formula (12) was obtained. The alkali-soluble resin (B2-1) had an acid value of 60 mgKOH / g and a weight average molecular weight of 9,000. In Table 3, the blending amounts are expressed in mol%.

[0376] Chemical formula (12) [ka]

[0377] (Solution of alkali-soluble resin (B2-2) not having alkoxysilyl group-containing monomer unit (b1)) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc), which was stirred while replacing with nitrogen and heated to 78° C. Next, a mixture of 25.2 parts of KarenzMOI-DEM (2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester of malonic acid (manufactured by Showa Denko K.K.), 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid and 27.0 parts of methyl methacrylate, and 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc was dropped into the flask from the dropping funnel. After the dropwise addition was completed, the mixture was stirred at 78°C for 3 hours. Then, propylene glycol monomethyl ether was added so that the non-volatile content was 40% by mass. The alkali-soluble resin (B2-2) had an acid value of 74 mg KOH / g and a weight average molecular weight of 8,000. In Table 3, the blending amounts are shown in mol %.

[0378] (Alkali-soluble resin (B2-3) to (B2-8) solutions) Solutions of alkali-soluble resins (B2-3) to (B2-8) were synthesized by changing the type and amount of monomer used to obtain the composition ratio and weight average molecular weight shown in Table 3, and propylene glycol monomethyl ether was added to adjust the non-volatile content to 40 mass%. The weight average molecular weight of the resin was adjusted by changing the amount of polymerization initiator used.

[0379] [Table 3]

[0380] Karenz MOI-BP in Table 3 is a pyrazole compound, 2-(3,5-diethylpyrazol-1-yl)carbonylaminoethyl methacrylate manufactured by Showa Denko K.K. Karenz MOI-BM is an oxime compound, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate manufactured by Showa Denko K.K. Nix M-110 is a paracumylphenol EO modified acrylate manufactured by Toagosei Co., Ltd. GMA+AA represents a polymerizable unsaturated group-containing monomer unit (b4) in which the epoxy group of glycidyl methacrylate (GMA) is reacted with the carboxyl group of acrylic acid (AA), GMA+AA+THPA represents a polymerizable unsaturated group-containing monomer unit (b4) in which the hydroxyl group of GMA+AA is reacted with tetrahydrophthalic anhydride (THPA), and GLM+MOI represents a polymerizable unsaturated group-containing monomer unit (b4) in which the hydroxyl group of glycerol monomethacrylate (GLM) is reacted with the isocyanate group of 2-isocyanatoethyl methacrylate (MOI).

[0381] <Production of Silane Coupling Agent (H)> (Silane coupling agent (H-1)) In a 1L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 116g of hydroxyethyl acrylate was charged and heated to 80°C. 205g of 3-isocyanatepropyltrimethoxysilane was added dropwise thereto and heated and stirred at 80°C for 4 hours. After that, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and instead an absorption peak derived from a urethane bond had been generated, and a silane coupling agent (H-1) whose main component is represented by the following chemical formula (13) was obtained. In addition, as a secondary component, a dimer to decamer which is a condensation product of the chemical formula (13) was included.

[0382] Chemical formula (13) [ka]

[0383] <Production of dye (I)> (Dye (I-1)) A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were mixed uniformly, then charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the end of the dropping, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight was 6,830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50° C. for 2 hours, then the temperature was raised to 80° C. over 1 hour, and the mixture was reacted for 2 hours to obtain Resin 1. Next, 30 parts of resin 1 in terms of non-volatile content was added to 2,000 parts of water, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water, and the solution was gradually dropped into the resin 1 solution. After the dropwise addition, the mixture was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, the mixture was filtered by suction, washed with water, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer to obtain dye (I-1), which is a salt-forming compound of 32 parts of CI Acid Red 52 and resin 1. At this time, the content of the component derived from CI Acid Red 52 in dye (I-1) was 25% by mass.

[0384] <Production of Dispersion Resin (K)> (Dispersed resin (K-1) solution) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 parts of hydroquinone were charged, and IR showed a 2,270 cm 3 reaction based on the isocyanate group. -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After cooling, PGMAc was added so that the non-volatile content was 30 mass %, to obtain a dispersion resin (K-1) solution having a polymerizable unsaturated group. The acid value was 68 mg KOH / g, and the weight average molecular weight was 13,000.

[0385] (Dispersed resin (K-2) solution) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a dispersion resin (K-2) solution was obtained. The acid value was 70 mgKOH / g and the weight average molecular weight was 8,500.

[0386] (Dispersed resin (K-3) solution) In a reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the non-volatile content. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a dispersion resin (K-3) solution was prepared. The amine value was 169.8 mg KOH / g.

[0387] (Dispersion resin (K-4) solution) According to Example A3 of WO 2022 / 172607, a dispersion resin (K-4) having a polymerizable unsaturated group was synthesized, and PGMAc was added so that the non-volatile content was 30% by mass. The amine value was 67 mg KOH / g and the weight average molecular weight was 5,600.

[0388] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The non-volatile content was 21.1% by mass. Pigment (A-1): 15.0 parts Pigment derivative (J-1): 1.0 part Dispersion resin (K-1) solution: 8.5 parts Dispersion resin (K-2) solution: 8.5 parts Organic solvent (Q-1): 67.0 parts

[0389] (Dispersion 2~16) Dispersion was carried out in the same manner as Dispersion 1, except that the raw materials and amounts shown in Tables 4-1 and 4-2 were changed. Bodies 2 to 16 were prepared.

[0390] [Table 4-1]

[0391] [Table 4-2]

[0392] The components listed in Tables 4-1 and 4-2 are as follows.

[0393] Pigment A-1: CI Pigment Blue 15:3 A-2: CI Pigment Blue 15:6 A-3: CI Pigment Violet 23 A-4: CI Pigment Green 58 A-5: CI Pigment Green 36 A-6: CI Pigment Green 62 A-7: CI Pigment Red 177 A-8: CI Pigment Yellow 138 A-9: CI Pigment Yellow 139 A-10: CI Pigment Yellow 150 A-11: CI Pigment Red 254

[0394] All of the pigments (A-1) to (A-11) were finely milled by salt milling, and thoroughly washed and dried before use.

[0395] [Dye derivative (J)] [ka]

[0396] [Organic solvent (Q)] Q-1: PGMAc

[0397] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain Photosensitive Composition 1. The nonvolatile content was 15.0% by mass. Dispersion 2: 1.0 part Dispersion 5: 21.0 parts Dispersion 9: 3.0 parts Alkali-soluble resin (B1-1) solution: 5.6 parts Alkali-soluble resin (B2-2) solution: 5.8 parts Hydroxyl-containing polymerizable compound (C1-1): 1.4 parts Polymerizable compound having an amine structure (C2-2): 0.5 parts Other polymerizable compounds (C7-1): 0.6 parts Polymerization initiator (D1-1): 0.15 parts Compound having an epoxy group (E1-1): 0.4 parts Compound having a blocked isocyanate group (E2-1): 1.8 parts Benzotriazole compound (F1-1): 0.15 parts Benzophenone compound (F2-1): 0.15 parts Thiol chain transfer agent (G-1): 0.15 parts Thiol chain transfer agent (G-2): 0.15 parts Silane coupling agent (H-1): 0.45 parts Leveling agent (O): 1.0 part Organic solvent (Q): 56.7 parts

[0398] [Examples 2 to 58 and Comparative Examples 1 and 2] (Photosensitive composition 2-60) Photosensitive compositions 2 to 60 were prepared in the same manner as in Example 1, except that the photosensitive composition 1 in Example 1 was changed to the raw materials and amounts shown in Tables 5-1 to 5-6.

[0399] [Table 5-1]

[0400] [Table 5-2]

[0401] [Table 5-3]

[0402] [Table 5-4]

[0403] [Table 5-5]

[0404] [Table 5-6]

[0405] The respective raw materials listed in Tables 5-1 to 5-6 are as follows.

[0406] [Polymerizable compound (C)] (Polymerizable compound having a hydroxyl group (C1)) C1-1: Pentaerythritol triacrylate C1-2: Dipentaerythritol pentaacrylate C1-3: Glycerol diacrylate

[0407] (Polymerizable compound having an amine structure (C2)) C2-1: Aronix MT-3041 (manufactured by Toagosei Co., Ltd., a multifunctional acrylate having a tertiary amine structure) C2-2: CN9906NS (Arkema, multifunctional urethane acrylate with a tertiary amine structure)

[0408] (Polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure) C3-1: Miramer SP-1106 (Miwon Specialty Chemical Co., Ltd., a compound having a dendrimer structure with an average number of 18 acryloyl groups) C3-2: SIRIUS-501 (Osaka Organic Chemical Industry Co., Ltd., a compound having a dendrimer structure with an average number of 18 acryloyl groups, non-volatile content 50% by mass)

[0409] (Other polymerizable compounds (C7)) C7-1: Pentaerythritol tetraacrylate C7-2: Dipentaerythritol hexaacrylate C7-3: Dipentaerythritol EO modified hexaacrylate

[0410] [Polymerization initiator (D)] (The absorption coefficient of light at a wavelength of 365 nm in PGMAc is 5.0×10 3 L / mol cm or more polymerization initiator (D1) D1-1: The above compound (D1-1) (absorption coefficient of light with a wavelength of 365 nm is 18,334 L / mol cm) D1-2: The above compound (D1-2) (absorption coefficient of light with a wavelength of 365 nm is 27,257 L / mol cm) D1-5: The above compound (D1-5) (absorption coefficient of light with a wavelength of 365 nm is 13,410 L / mol cm) D1-6: The above compound (D1-6) (absorption coefficient of light with a wavelength of 365 nm is 14,214 L / mol cm) D1-10: The above compound (D1-10) (absorption coefficient of light at a wavelength of 365 nm is 18,767 L / mol cm) D1-12: The above compound (D1-12) (absorption coefficient of light at a wavelength of 365 nm is 7,051 L / mol cm)

[0411] (Polymerizable compound (D2) other than polymerizable compound (D1)) D2-1:TRONLY TR-PBG-3057 (manufactured by Changzhou Strong New Materials Co., Ltd.) D2-2: IRGACURE OXE-02 (BASF Japan)

[0412] [Thermosetting compound (E)] (Compound (E1) having an epoxy group) E1-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by general formula (5), with an average of 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq) E1-2: Denacol EX-611 (manufactured by Nagase ChemteX Corporation, average number of epoxy groups: 4, epoxy equivalent: 155-175g / eq)

[0413] (Compound (E2) Having a Blocked Isocyanate Group) E2-1: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, isocyanurate of hexamethylene diisocyanate blocked with an active methylene compound, non-volatile content 60% by mass) E2-2: BI7982 (manufactured by Baxenden Chemical, isocyanurate of hexamethylene diisocyanate blocked with a pyrazole compound, non-volatile content 70% by mass) E2-3: BI7984 (manufactured by Baxenden Chemical, an oxime compound) Blocked hexamethylene diisocyanate isocyanurate, non-volatile content 75% by mass

[0414] [Ultraviolet absorber (F)] (Benzotriazole compound (F1)) F1-1: The above-mentioned compound (F1-1) (Benzophenone compounds (F2)) F2-1: The above-mentioned compound (F2-1) (Triazine compounds (F3)) F3-1: The above-mentioned compound (F3-1)

[0415] [Thiol chain transfer (G)] G-1: Mercaptosuccinic acid G-2: Pentaerythritol tetrakis(3-mercaptopropionate)

[0416] [Silane coupling agent (H)] H-2: KBM-803 (Shin-Etsu Silicone Co., Ltd., 3-mercaptopropyltrimethoxysilane) H-3: KBM-403 (Shin-Etsu Silicone Co., Ltd., 3-glycidoxypropyltrimethoxysilane)

[0417] [Leveling agent (O)] A solution in which 1 part of BYK-330 (manufactured by BYK-Chemie) was dissolved in 99 parts of PGMAc was used as a leveling agent (O).

[0418] [Organic solvent (Q)] Q-1: PGMAc Q-2: Cyclohexanone Q-3: Ethyl 3-ethoxypropionate The above Q-1, Q-2, and Q-3 were mixed in a mass ratio of 8:1:1 to obtain an organic solvent (Q).

[0419] <Evaluation of Photosensitive Composition> The following evaluations were carried out on the obtained photosensitive compositions 1 to 60. The evaluation results are shown in Table 6.

[0420] [Pattern Formation Evaluation (1): Developability] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a 100 μm-wide stripe pattern at an illumination intensity of 30 mW / cm. 2 , 100mJ / cm2 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, and air-dried. The substrate was observed under an optical microscope to confirm the presence or absence of residues in the unexposed areas. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: When developed in the shortest time possible for pattern formation, no residue was left in the unexposed areas. 4: No residue was left in the unexposed areas after development for 5 seconds longer than the shortest time possible for pattern formation. 3: No residue was left on the unexposed areas after development for 10 seconds longer than the shortest possible time for pattern formation. 2: No residue was left on the unexposed areas after development for 15 seconds longer than the shortest possible time for pattern formation. 1: Even after development for 20 seconds longer than the shortest time possible for pattern formation, residue was still present in the unexposed areas.

[0421] [Pattern Formation Evaluation (2): 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 film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern of 5 to 25 μm in 5 μm increments at an illumination intensity of 30 mW / cm. 2 , 100mJ / 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 then washed with ion-exchanged water and air-dried. The spray development was carried out for each photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The resulting patterns of 5, 10, 15, 20, and 25 μm in width were observed with an optical microscope to confirm the minimum line width of the remaining pattern. The evaluation criteria are as follows, with 3 or more 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.

[0422] [Pattern Formation Evaluation (3): Linearity] 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 dry film thickness was 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, the substrate was irradiated with light at an illumination intensity of 30 mW / cm using an ultra-high pressure mercury lamp through a photomask with a 100 μm-wide stripe pattern. 2 , 100mJ / 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 90° C. for 60 minutes. The spray development was carried out for each photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The obtained substrate was evaluated by measuring the maximum and minimum line widths of 10 stripe patterns using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with 3 or more being practical. 5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[0423] [Light resistance 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 film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Then, after cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm. 2 , 100mJ / cm 2 Thereafter, the substrate was subjected to a heat treatment at 90° C. for 60 minutes in a clean oven to obtain a substrate for evaluation. The chromaticity ([L*(1), a*(1), b*(1)]) of the obtained substrate under C light source was measured using a microspectrophotometer (Olympus Optical Co., Ltd., "OSP-SP100"). After that, a light resistance test was performed by irradiating light from a xenon lamp (100,000 lux) for 50 hours. The chromaticity ([L*(2), a*(2), b*(2)]) of the light source was measured, and the color difference ΔEab* was calculated using the following formula. The evaluation criteria are as follows, with 3 or more considered practical: ΔEab*=((L*(2)-L*(1)) 2 +(a*(2)-a*(1)) 2 +(b*(2)-b*(1)) 2 ) 1 / 2 5: ΔEab* is less than 1 4: ΔEab* is 1 or more and less than 2 3: ΔEab* is 2 or more and less than 3 2: ΔEab* is 3 or more and less than 5 1: ΔEab* is 5 or more

[0424] [High temperature and humidity resistance 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 film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Then, after cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm. 2 , 100mJ / 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 90° C. for 60 minutes. The spray development was carried out for each photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The obtained substrate was stored for 200 hours under conditions of a temperature of 85°C and a humidity of 85%. After storage, the film was cut with a cutter knife to create a lattice pattern of 1 mm squares (total of 100 squares), and a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was firmly pressed against the film and peeled off in a direction of about 180 degrees. The state of the lattice patterns was observed, and the number of peeled lattice patterns was counted. The evaluation criteria are as follows, with 3 or more being considered practical. 5: Less than 2 4: 2 or more but less than 5 3: 5 to less than 10 2: 10 or more but less than 15 1:15 pieces or more

[0425] [Solvent resistance 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 film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, the substrate was irradiated with light at an illumination intensity of 30 mW / cm using an ultra-high pressure mercury lamp through a photomask with a 100 μm-wide stripe pattern. 2 , 100mJ / 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 90° C. for 60 minutes. The spray development was carried out for each photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The obtained substrate was immersed in PGMAc at room temperature for 15 minutes, washed with ion-exchanged water, air-dried, and the stripe pattern portion with a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, with 3 or more being considered practical. 5: No change in appearance or color. 4: Slight wrinkles etc. occur, but there is no change in color. 3: Some wrinkles or other imperfections occur, but there is no change in color. 2: Wrinkles and other imperfections appear all over the surface, and the color fades slightly. 1: Peeling or fading occurs.

[0426] [Table 6] [Explanation of symbols]

[0427] 100 Infrared Sensor 110 Solid-state image sensor 111 Infrared cut filter 112 Color Filter 113 Infrared transmission filter 114 Resin Film 115 Micro Lens 116 Flat membrane

Claims

1. A photosensitive composition comprising a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), and a polymerization initiator (D), the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having an alkoxysilyl group-containing monomer unit (b1) and an acidic group-containing monomer unit (b2); The polymerization initiator (D) has an absorption coefficient of 5.0×10 at 365 nm in propylene glycol monomethyl ether acetate. ３ A photosensitive composition comprising a polymerization initiator (D1) having a viscosity of 1000 sq. m or more.

2. 2. The photosensitive composition according to claim 1, wherein the alkali-soluble resin (B) further comprises an alkali-soluble resin (B2) having no alkoxysilyl group-containing monomer unit (b1).

3. The photosensitive composition according to claim 2, wherein the alkali-soluble resin (B2) has one or more monomer units selected from the group consisting of a blocked isocyanate group-containing monomer unit (b3) and a polymerizable unsaturated group-containing monomer unit (b4).

4. The photosensitive composition according to claim 3 , wherein the alkali-soluble resin (B2) further contains an aliphatic fused ring structure-containing monomer unit (b5).

5. 2. The photosensitive composition according to claim 1, wherein the polymerizable compound (C) comprises at least one selected from the group consisting of a polymerizable compound (C1) having a hydroxyl group, a polymerizable compound (C2) having an amine structure, and a polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure.

6. The photosensitive composition according to claim 1 , further comprising a thermosetting compound (E).

7. The photosensitive composition according to claim 1 , further comprising an ultraviolet absorber (F).

8. A film formed from the photosensitive composition according to claim 1 or 2.

9. An optical filter comprising the film according to claim 8.

10. A solid-state imaging device comprising the optical filter according to claim 9.

11. An image display device comprising the optical filter according to claim 9.

12. An infrared sensor comprising the optical filter according to claim 9.

Images