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

Abstract

To provide a photosensitive composition capable of forming a film that offers superior storage stability and exhibits superior resistance after low-temperature heating.SOLUTION: A photosensitive composition contains a pigment (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and an organic solvent (E). The alkali-soluble resin (B) contains an alkali-soluble resin (B1) with a thermally crosslinkable group-containing monomer unit (b1). The polymerization initiator (D) contains a bisoxime ester polymerization initiator (D1). Of the organic solvent (E) 100 mass%, 0.1-20 mass% is an organic solvent (E1) with a hydrogen bonding component of a Hansen solubility parameter of 10 MPa1 / 2 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 photosensitive composition for forming an optical filter used in an organic EL display device is heated at a low temperature, for example, at 150° C. or less. As an investigation into the production of an optical filter at a low temperature, for example, Patent Document 1 discloses a colored photosensitive composition containing a colorant, a polymerizable compound, and a photopolymerization initiator, in which the absorbance of a solution obtained by dissolving the photopolymerization initiator in acetonitrile at 0.001% by mass at a wavelength of 340 nm is 0.45 or more. Patent Document 2 discloses a photosensitive resin composition containing 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. 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 photosensitive resin composition that contains a resin having a constitutional unit having an α,β-unsaturated carbonyl group, a constitutional unit having an active methylene group or an active methine group, and a constitutional unit having an acid group as a curable resin composition that can form a cured film with excellent solvent resistance and adhesion even when the temperature of the post-bake process is 200° C. or less.

[0004] Furthermore, the quality of an optical filter is significantly reduced if there are foreign matters, defects, or differences in thickness. Therefore, it is necessary to suppress the deterioration of the quality of the photosensitive composition used in the manufacture of an optical filter as much as possible between immediately after the manufacture of the photosensitive composition and when the composition is stored and used in the manufacture of an optical filter. For example, Patent Document 6 discloses a radiation-sensitive resin composition having excellent stability of sensitivity over time, which contains an oxime ester compound having at least one type of group selected from a branched alkyl group and a cyclic alkyl group, and has a water content of 0.1 to 2 mass% relative to the mass of the radiation-sensitive resin composition. [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. 2022-10246 [Patent Document 6] International Publication No. 2017 / 099019 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the compositions described in Patent Documents 1 to 6 were unable to satisfy a certain level of storage stability and film resistance after low-temperature heating.

[0007] An object of the present invention is to provide a photosensitive composition which has excellent storage stability and is capable of forming a film having excellent resistance after 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), a polymerization initiator (D), and an organic solvent (E), the alkali-soluble resin (B) contains an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1), the polymerization initiator (D) comprises a bisoxime ester polymerization initiator (D1); In the organic solvent (E) 100% by mass, the hydrogen bond term of the Hansen solubility parameter is 10 MPa 1 / 2The present invention relates to a photosensitive composition containing 0.1 to 20 mass % of the above organic solvent (E1). 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 storage stability and excellent resistance after 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. Low temperature refers to temperatures below 150°C.

[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), a polymerization initiator (D), and an organic solvent (E), the alkali-soluble resin (B) contains an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1), the polymerization initiator (D) comprises a bisoxime ester polymerization initiator (D1); In the organic solvent (E) 100% by mass, the hydrogen bond term of the Hansen solubility parameter is 10 MPa 1 / 2 The composition is characterized in that it contains 0.1 to 20 mass % of the organic solvent (E1) described above.

[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] When the alkali-soluble resin (B) contains an alkali-soluble resin (B1) having a thermocrosslinkable group-containing monomer unit (b1), a crosslinking reaction occurs by heating, improving the resistance of the film. When a bisoxime ester polymerization initiator (D1) is used in combination as the polymerization initiator (D), it has two radical generating groups in the molecule, so radicals can be generated efficiently, and it is presumed that the photoreaction is likely to proceed and the film resistance can be maintained at the same level as when heated at a high temperature, even when heated at a low temperature. On the other hand, a photosensitive composition containing both an alkali-soluble resin (B1) having a thermocrosslinkable group-containing monomer unit (b1) and a bisoxime ester polymerization initiator (D1) is likely to undergo a reaction during storage, and the quality after storage decreases. However, when the hydrogen bond term of the Hansen solubility parameter is 10 MPa in an organic solvent (E), the photosensitive composition is more likely to undergo a reaction during storage, and the quality after storage decreases. 1 / 2 It is presumed that when the organic solvent (E1) is contained in a specific amount as described above, it acts on each component contained in the photosensitive composition and suppresses reactions during storage, thereby improving the quality after storage.

[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 compound 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 (8) 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 (9):

[0025] General formula (8) [ka]

[0026] In general formula (8), 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 (9) [ka]

[0028] In general formula (9), 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. An example of the above embodiment (5) 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; and the purple pigment contains 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 known compounds can be used. Examples 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 compounds can be used, such as 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 compounds 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 known compounds 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, and other metal oxide particles or metal particles.

[0044] Furthermore, as the pigment (A), metal pigments, hollow resin pigments, fluorescent pigments, pearl pigments, conductive pigments, etc. can also be used.

[0045] The pigment (A) can be used alone or in combination of two or more kinds.

[0046] 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.

[0047] 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.

[0048] 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).

[0049] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B).

[0050] 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. Examples of the alkali-soluble resin (B) include (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.

[0051] The weight average molecular weight of the alkali-soluble resin (B) is preferably 3,000 to 100,000.

[0052] 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.

[0053] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0054] 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.

[0055] (Alkali-soluble resin (B1) having a thermocrosslinkable group-containing monomer unit (b1)) The photosensitive composition of the present invention contains, as the alkali-soluble resin (B), an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1).

[0056] The alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1) (hereinafter also simply referred to as alkali-soluble resin (B1)) is not particularly limited, and known resins can be used. The thermally crosslinkable group is a group that undergoes a crosslinking reaction by heating to form a crosslink. Examples include a cyclic ether group, a methylol group, an isocyanate group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group. Among these, at least one selected from the group consisting of a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group is preferred from the viewpoints of storage stability and resistance after low-temperature heating. Examples of the alkali-soluble resin (B1) include a monomer that forms a thermally crosslinkable group-containing monomer unit (b1), and a copolymer optionally containing another copolymerizable monomer.

[0057] [Thermal crosslinkable group-containing monomer unit (b1)] From the viewpoints of storage stability and resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit (b1) is preferably formed from monomers represented by the following general formulas (1) to (5).

[0058] General formula (1) [ka]

[0059] In general formula (1), R 1 represents a hydrogen atom or a methyl group.

[0060] In general formula (1), R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0061] In general formula (1), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include a methylene group, an ethylene group, an n-propylene 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, and a tetramethylethylene group. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0062] In general formula (1), L 2 represents a single bond or an oxygen atom.

[0063] In general formula (1), L 3 and L 4 each independently represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include a methylene group, an ethylene group, an n-propylene 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, and a tetramethylethylene group. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0064] The method for producing the monomer represented by the general formula (1) is not particularly limited, and a known method can be used. For example, the methods described in JP-A-10-316643 and WO 2022 / 145298 can be mentioned.

[0065] Specific examples of the monomer represented by general formula (1) include compounds of formulas (1-1) to (1-14), although the present invention is not limited thereto.

[0066] [ka] TIFF2024174787000007.tif84158

[0067] From the viewpoint of resistance after low-temperature heating, the monomer represented by general formula (1) is preferably at least one selected from the compounds represented by the above formulae (1-1), (1-2), (1-3), (1-4), (1-9), (1-10), (1-11), (1-12), (1-13) and (1-14).

[0068] The monomer represented by formula (1) can be used alone or in combination of two or more kinds.

[0069] General formula (2) [ka]

[0070] In general formula (2), R 1represents a hydrogen atom or a methyl group.

[0071] In general formula (2), R 4 ~R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or a combination thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, R 4 and R 5 is preferably a hydrogen atom, R 6 is preferably a methyl group, an ethyl group, or an n-propyl group.

[0072] In general formula (2), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include a methylene group, an ethylene group, an n-propylene 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, and a tetramethylethylene group. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0073] The method for producing the monomer represented by the general formula (2) is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2022 / 145298 can be mentioned.

[0074] Specific examples of the monomer represented by formula (2) include compounds represented by formulas (2-1) to (2-6), although the present invention is not limited thereto.

[0075] [ka]

[0076] The monomer represented by formula (2) can be used alone or in combination of two or more kinds.

[0077] General formula (3) [ka]

[0078] In general formula (3), R 1 represents a hydrogen atom or a methyl group.

[0079] In general formula (3), R 7 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0080] In general formula (3), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include a methylene group, an ethylene group, an n-propylene 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, and a tetramethylethylene group. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0081] The method for producing the monomer represented by the general formula (3) is not particularly limited, and a known method can be used, for example, the method described in Coatings Technology, Vol. 62, by Witzeman, JS, and Dell Rector, FJ.

[0082] Specific examples of the monomer represented by formula (3) include compounds of formulas (3-1) to (3-4), although the present invention is not limited thereto.

[0083] [ka]

[0084] The monomer represented by formula (3) can be used alone or in combination of two or more kinds.

[0085] General formula (4) [ka]

[0086] In general formula (4), R 1 represents a hydrogen atom or a methyl group.

[0087] In general formula (4), R 8 ~R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. 8 ~R 10At least one of them 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 after low-temperature heating, a methoxy group and an ethoxy group are preferred. From the viewpoint of resistance after low-temperature heating, R 8 ~R 10 At least two of them are preferably alkoxy groups having 1 to 6 carbon atoms.

[0088] In general formula (4), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include a methylene group, an ethylene group, an n-propylene 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, and a tetramethylethylene group. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0089] Specific examples of the monomer represented by formula (4) include compounds of formulas (4-1) to (4-6), although the present invention is not limited thereto.

[0090] [ka]

[0091] Commercially available products of the monomer represented by the general formula (4) include, for example, KBM-502, 503, 5103, 5803, KBE-502, 503, and the like manufactured by Shin-Etsu Chemical Co., Ltd.

[0092] The monomer represented by formula (4) can be used alone or in combination of two or more kinds.

[0093] General formula (5) [ka]

[0094] In general formula (5), R 1 represents a hydrogen atom or a methyl group.

[0095] In general formula (5), R 11 ~R 13 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, the methyl group is preferred.

[0096] In general formula (5), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, a group having --NH--, or a combination thereof. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include a methylene group, an ethylene group, an n-propylene 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, and a tetramethylethylene group. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0097] Specific examples of the monomer represented by formula (5) include compounds of formulas (5-1) to (5-6), although the present invention is not limited thereto. [ka]

[0098] The monomer represented by formula (5) can be used alone or in combination of two or more kinds.

[0099] From the viewpoints of storage stability and resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit (b1) is more preferably a monomer unit formed from one or more of the monomers represented by general formula (1) and the monomers represented by general formula (2).

[0100] The thermally crosslinkable group-containing monomer unit (b1) can be formed by using the monomers represented by the general formulae (1) to (5) alone or in combination of two or more kinds.

[0101] The thermally crosslinkable group-containing monomer unit (b1) can be a combination of a monomer unit formed of a monomer represented by any one of the general formulae (1) to (5) and a monomer unit formed of a monomer other than the monomer represented by any one of the general formulae (1) to (5).

[0102] Examples of the monomer other than the monomers represented by the general formulas (1) to (5) include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, and the like.

[0103] The content of the thermally crosslinkable group-containing monomer unit (b1) is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, of the total monomer units of the alkali-soluble resin (B1) from the viewpoints of storage stability and resistance after low-temperature heating.

[0104] The alkali-soluble resin (B1) may contain, in addition to the thermally crosslinkable group-containing monomer unit (b1), for example, an acidic group-containing monomer unit (b2), a hydroxyl group-containing monomer unit (b3), an aliphatic condensed ring structure-containing monomer unit (b4), a polymerizable unsaturated group-containing monomer unit (b5), and other monomer units (b6).

[0105] [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. The acidic group-containing monomers can be used alone or in combination of two or more kinds.

[0106] From the viewpoint of alkali solubility, the content of the acidic group-containing monomer unit (b2) is preferably from 1 to 40 mol %, and more preferably from 5 to 30 mol %, of all the constituent units of the alkali-soluble resin (B1).

[0107] In addition, the method of introducing the acidic group-containing monomer unit (b2) into the alkali-soluble resin (B1) may be a method of adding an acid anhydride (modifying compound) to the hydroxyl group contained in the resin (precursor) other than the method of copolymerizing a thermally crosslinkable group-containing monomer and an acidic group-containing monomer. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0108] [Hydroxyl group-containing monomer unit (b3)] 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. The hydroxyl group-containing monomers can be used alone or in combination of two or more kinds.

[0109] From the viewpoint of resistance after low-temperature heating, the content of the hydroxyl group-containing monomer units (b3) is preferably 1 to 60 mol %, more preferably 5 to 50 mol %, of all monomer units in the alkali-soluble resin (B1).

[0110] The method for introducing the hydroxyl group-containing monomer unit (b3) into the alkali-soluble resin (B1) may include, other than copolymerizing a thermally crosslinkable group-containing monomer with a hydroxyl group-containing monomer, a method for adding a compound having a carboxyl group (modifying compound) to an epoxy group contained in the resin (precursor), or a method for adding a compound having an epoxy group (modifying compound) to a carboxyl group contained in the resin (precursor).

[0111] [Aliphatic condensed ring structure-containing monomer unit (b4)] 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. The aliphatic fused ring structure-containing monomers can be used alone or in combination of two or more kinds.

[0112] [Polymerizable unsaturated group-containing monomer unit (b5)] Methods for incorporating the polymerizable unsaturated group-containing monomer unit (b5) into the alkali-soluble resin (B1) include, for example, the following methods (i) to (iii).

[0113] <Method (i)> In the method (i), for example, a precursor having an epoxy group is first synthesized, and then a monomer having a carboxyl group, among the above-mentioned acid group-containing monomers, is added to the epoxy group of the precursor.

[0114] It is also possible to further react an acid anhydride with the above precursor obtained by adding a monomer having a carboxyl group to the epoxy group of the precursor.

[0115] Examples of the acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0116] <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 of the precursor.

[0117] 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.

[0118] <Method (iii)> In the method (iii), for example, first, a precursor having a hydroxyl group-containing monomer (b3) is synthesized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0119] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0120] [Other monomer units (b6)] 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-bismaleimidoethane, 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N- N-substituted maleimides such as (4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples of such dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate include diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. The other monomers can be used alone or in combination of two or more.

[0121] 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.

[0122] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the alkali-soluble resin (B1) is preferably from 1.2 to 3.0, more preferably from 1.3 to 2.8.

[0123] 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.

[0124] The alkali-soluble resin (B1) can be used alone or in combination of two or more kinds.

[0125] 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 storage stability and resistance after low-temperature heating.

[0126] (Alkali-soluble resin (B2) not having a thermal crosslinking group-containing monomer unit (b1)) From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains, as the alkali-soluble resin (B), an alkali-soluble resin (B2) that does not have a thermally crosslinkable group-containing monomer unit (b1) (hereinafter, also simply referred to as alkali-soluble resin (B2)).

[0127] The alkali-soluble resin (B2) is not particularly limited as long as it does not have the thermal crosslinking group-containing monomer unit (b1), and the alkali-soluble resins already described can be used. For example, an alkali-soluble resin having at least one of the monomer units (b2) to (b6) described above can be used. Among them, from the viewpoint of resistance after low-temperature heating, it is preferable to have the polymerizable unsaturated group-containing monomer unit (b5).

[0128] 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.

[0129] 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.

[0130] The alkali-soluble resin (B2) can be used alone or in combination of two or more kinds.

[0131] The content of the alkali-soluble resin (B2) is preferably from 10 to 90 mass %, more preferably from 20 to 80 mass %, in 100 mass % of the alkali-soluble resin (B), from the viewpoints of storage stability and resistance after low-temperature heating.

[0132] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0133] The polymerizable compound (C) may be a monomer or oligomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and an acryloyloxy group having an ethylenically unsaturated double bond.

[0134] The polymerizable compound (C) is not particularly limited, and a known compound can be used. For example, a polymerizable compound (C1) having an amine structure, a polymerizable compound (C2) having a hydroxyl group, a polymerizable compound (C3) having a dendrimer structure or a hyperbranch 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) can be mentioned.

[0135] The polymerizable compound (C) may be used alone or in combination of two or more kinds.

[0136] 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.

[0137] (Polymerizable compound (C1) having an amine structure) From the viewpoint of resistance after low-temperature heating, the photosensitive composition of the present invention preferably contains a polymerizable compound (C1) having an amine structure. It is presumed that the polymerizable compound (C1) 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 (C1) 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 resistance. It is also presumed that the amine structure has polarity, and therefore adhesion to the substrate is improved.

[0138] The amine structure of the polymerizable compound (C1) 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 (C1) 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.

[0139] Examples of the polymerizable compound (C1) 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).

[0140] 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.

[0141] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0142] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, 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.

[0143] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0144] 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.

[0145] The polymerizable compound (C1) 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.

[0146] Commercially available polymerizable compounds (C1) 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.

[0147] The polymerizable compound (C1) having an amine structure can further have 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.

[0148] 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).

[0149] 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; Polyisocyanate compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0150] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0151] 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.

[0152] The polymerizable compound (C1) having an amine structure can be used alone or in combination of two or more kinds.

[0153] The content of the polymerizable compound (C1) having an amine structure is preferably from 0.1 to 80 mass %, more preferably from 0.5 to 60 mass %, in 100 mass % of the polymerizable compound (C).

[0154] (Polymerizable compound having a hydroxyl group (C2)) From the viewpoint of resistance after 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). The resistance is improved by the reaction between the hydroxyl group of the polymerizable compound (C2) having a hydroxyl group and the thermal crosslinking group of the alkali-soluble resin (B1).

[0155] Examples of the polymerizable compound (C2) 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.

[0156] Examples of commercially available polymerizable compounds (C2) 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.

[0157] The polymerizable compound (C2) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0158] The content of the polymerizable compound (C2) 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).

[0159] (Polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure) From the viewpoint of resistance after 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 assumed to react sufficiently even when the amount of polymerization initiator or the amount of exposure is small, improving resistance.

[0160] 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.

[0161] 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 SIRIUS-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.

[0162] The polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more kinds.

[0163] 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).

[0164] (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.

[0165] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0166] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0167] 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.

[0168] 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.

[0169] (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.

[0170] 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.

[0171] 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 diisocyanate such as isophorone diisocyanate, as well as biuret forms, isocyanurate forms, and trimethylolpropane adducts thereof.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] (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.

[0177] 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.

[0178] (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.

[0179] 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.

[0180] 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.

[0181] From the viewpoint of resistance after low-temperature heating, the polymerizable compound (C) preferably contains one or more compounds selected from the group consisting of a polymerizable compound (C1) having an amine structure, a polymerizable compound (C2) having a hydroxyl group, and a polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure.

[0182] The total content of the polymerizable compound (C1) having an amine structure, the polymerizable compound (C2) having a hydroxyl group, and the polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure is preferably 10 to 100 mass%, and more preferably 20 to 100 mass%, in 100 mass% of the polymerizable compound (C).

[0183] [Polymerization initiator (D)] The photosensitive composition of the present invention contains a polymerization initiator (D).

[0184] 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 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.

[0185] 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; triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 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.

[0186] 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.

[0187] 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); Examples of the organic peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 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.

[0188] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0189] 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.

[0190] (Bisoxime ester polymerization initiator (D1)) The photosensitive composition of the present invention contains a bisoxime ester polymerization initiator (D1) (hereinafter, also simply referred to as polymerization initiator (D1)) which is a photopolymerization initiator, as the polymerization initiator (D).

[0191] The bisoxime ester polymerization initiator (D1) is not particularly limited as long as it is a compound having two oxime ester groups in the molecule, and a known compound can be used. For example, a compound represented by the following general formula (6) can be mentioned.

[0192] General formula (6) [ka]

[0193] In the general formula (6), X1 and X2 each independently represent a carbonyl bond or a single bond. Among these, from the viewpoint of solubility in the organic solvent (E), it is preferable that at least one of X1 and X2 is a carbonyl bond, and it is more preferable that both of them are carbonyl bonds.

[0194] In formula (6), X3 represents a single bond, an oxygen atom, or a sulfur atom. Among these, X3 is preferably a single bond or a sulfur atom, more preferably a single bond.

[0195] In general formula (6), R1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group represented by the following general formula (7). The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, a 9-fluorenylmethyl group, etc. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc. Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, and a morpholinyl group.

[0196] General formula (7) [ka]

[0197] In formula (7), X4 represents an oxygen atom or a sulfur atom.

[0198] In the general formula (7), R8 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

[0199] In general formula (7), * represents a bond to the nitrogen atom.

[0200] Among these, R1 is preferably an alkyl group having 1 to 20 carbon atoms or a group represented by general formula (7), and more preferably a group represented by general formula (7).

[0201] In general formula (6), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, a 9-fluorenylmethyl group, etc. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc. Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, and a morpholinyl group.

[0202] In general formula (6), R4 and R5 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a 9-fluorenylmethyl group. The arylalkyl group may be a group substituted with a halogen atom, an amino group, a nitro group, and the like. Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, and a morpholinyl group.

[0203] In formula (6), R6 and R7 each independently represent a hydrogen atom or a nitro group. Among these, R6 and R7 are preferably hydrogen atoms.

[0204] The method for producing the compound represented by the general formula (6) is not particularly limited, and can be synthesized by a known method. For example, the methods described in International Publication No. 2015 / 139604, International Publication No. 2015 / 139601, International Publication No. 2017 / 200354, JP 2021-011486 A, JP 2021-155642 A, and International Publication No. 2020 / 139042 can be mentioned.

[0205] Specific examples of the bisoxime ester polymerization initiator (D1) are shown below, which are represented by the formulae (D1-1) to (D1-13), although the present invention is not limited thereto.

[0206] [ka]

[0207] [ka]

[0208] The bisoxime ester polymerization initiator (D1) can be used alone or in combination of two or more kinds.

[0209] The content of the bisoxime ester polymerization initiator (D1) is preferably from 5 to 100 mass%, and more preferably from 10 to 90 mass%, in 100 mass% of the polymerization initiator (D).

[0210] (Polymerization initiator (D2) other than bisoxime ester polymerization initiator (D1)) From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains, as the polymerization initiator (D), a polymerization initiator (D2) other than the bisoxime ester polymerization initiator (D1) (hereinafter also simply referred to as polymerization initiator (D2)).

[0211] The polymerization initiator (D2) is not particularly limited as long as it is other than the bisoxime ester polymerization initiator (D1), and a known compound can be used. In this specification, from the viewpoint of resistance after low-temperature heating, a compound having one oxime ester group is preferred, and a compound having one oxime ester group and having an absorption coefficient of 5.0×10 for light having a wavelength of 365 nm in propylene glycol monomethyl ether acetate is preferred. 3 Compounds with a density of 1000 L / mol·cm or more are more preferred.

[0212] Specific examples of the polymerization initiator (D2) are shown below, which are represented by the formulae (D2-1) to (D2-12), although the present invention is not limited thereto.

[0213] [ka]

[0214] [ka]

[0215] The polymerization initiator (D2) can be used alone or in combination of two or more kinds.

[0216] The content of the polymerization initiator (D2) is preferably from 10 to 90 mass % in 100 mass % of the polymerization initiator (D).

[0217] [Organic solvent (E)] The photosensitive composition of the present invention contains an organic solvent (E).

[0218] The organic solvent (E) is not particularly limited, and known compounds can be used. For example, 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-methyl butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl Benzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, 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, etc.,

[0219] The organic solvent (E) can be used alone or in combination of two or more kinds.

[0220] The content of the organic solvent (E) is preferably such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0221] (Hansen solubility parameter hydrogen bond term is 10MPa 1 / 2 (E1)) The photosensitive composition of the present invention has a hydrogen bond term of the Hansen solubility parameter of 10 MPa. 1 / 2 The organic solvent (E1) described above (hereinafter, simply referred to as organic solvent (E1)) is contained in an amount of 0.1 to 20 mass % relative to 100 mass % of the organic solvent (E).

[0222] Here, the Hansen solubility parameter is a solubility parameter introduced by Hildebrand, which is divided into three components, a dispersion term (hereinafter also referred to as δd), a polar term (hereinafter also referred to as δp), and a hydrogen bond term (hereinafter also referred to as δh), and expressed in three-dimensional space. The dispersion term indicates the effect due to dispersion forces, the polar term indicates the effect due to dipole-dipole forces, and the hydrogen bond term indicates the effect due to hydrogen bonding forces.

[0223] The definition and calculation of Hansen solubility parameters are described in "Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)" by Charles M. Hansen. In addition, the Hansen solubility parameters can be calculated from chemical structures using computer software "Hansen Solubility Parameters in Practice (HSPiP)". For the organic solvent (E1) of the present invention, the values ​​in Hansen Solubility Parameters; A Users Handbook, Second Edition are used, and for those not described, the calculated values ​​using "Hansen Solubility Parameters in Practice (HSPiP)" are used.

[0224] Examples of the organic solvent (E1) include dipropylene glycol monobutyl ether (δh=10.0), diethylene glycol hexyl ether (δh=10.0), butyl lactate (δh=10.2), propylene glycol monoethyl ether (δh=10.5), diethylene glycol monobutyl ether (δh=10.6), diacetone alcohol (δh=10.8), dipropylene glycol monopropyl ether (δh=11.0), dipropylene glycol monomethyl ether (δh=11.2), propylene glycol monomethyl ether (δh=11.6), diethylene glycol monoethyl ether (δh=12.2), ethylene glycol monobutyl ethyl ether (δh=12.3), 3-methyl-1-butanol (δh=13.3), ethyl lactate (δh=12.5), diethylene glycol monomethyl ether (δh=12.6), cyclohexanol (δh=13.5), 3-methoxy-1-butanol (δh=13.6), benzyl alcohol (δh=13.7), 2-methyl-1-butanol (δh=14.3), ethylene glycol monoethyl ether (δh=14.3), 2-butanol (δh=14.5), furfuryl alcohol (δh=15.1), 1-butanol (δh=15.8), ethylene glycol monomethyl ether (δh=16.4), ethanol (δh=19.4), etc.

[0225] The hydrogen bond parameter of the organic solvent (E1) is 10 to 20 MPa from the viewpoint of storage stability. 1 / 2 is preferable, and 10 to 16 MPa 1 / 2 is more preferred.

[0226] From the viewpoint of resistance after low-temperature heating, the organic solvent (E1) preferably has a vapor pressure at 20° C. of 100 Pa or more. Examples of organic solvents (E1) having a vapor pressure of 100 Pa or more at 20° C. include propylene glycol monoethyl ether (vapor pressure 900 Pa), diacetone alcohol (vapor pressure 108 Pa), propylene glycol monomethyl ether (vapor pressure 1,150 Pa), ethylene glycol monobutyl ether (vapor pressure 100 Pa), ethyl lactate (vapor pressure 360 ​​Pa), cyclohexanol (vapor pressure 130 Pa), 3-methoxy-1-butanol (vapor pressure 160 Pa), 2-methyl-1-butanol (vapor pressure 420 Pa), ethylene glycol monoethyl ether (vapor pressure 500 Pa), 1-butanol (vapor pressure 580 Pa), ethylene glycol monomethyl ether (vapor pressure 830 Pa), and ethanol (vapor pressure 5,800 Pa).

[0227] It is more preferable that the organic solvent (E1) contains at least two kinds.

[0228] From the viewpoint of storage stability, the content of the organic solvent (E1) is more preferably from 0.5 to 15 mass % in 100 mass % of the organic solvent (E).

[0229] (Organic solvent (E2) other than organic solvent (E1)) The organic solvent (E2) other than the organic solvent (E1) (also simply referred to as organic solvent (E2)) is not particularly limited, and any known compound can be used.

[0230] The organic solvent (E2) preferably contains one or more selected from the group consisting of propylene glycol diacetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, ethyl 3-ethoxypropionate, cyclopentanone, methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, cyclohexanone, and butyl acetate.

[0231] 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.

[0232] [Thiol-based chain transfer agents (F)] From the viewpoint of resistance after low-temperature heating, the photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent (F). It is presumed that this causes the generation of thiyl radicals that are not easily inhibited by oxygen in the exposure step, which promotes photocuring and improves resistance after low-temperature heating.

[0233] Examples of the thiol-based chain transfer agent (F) 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; Examples of polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0234] The thiol chain transfer agent (F) is preferably a monofunctional thiol compound having an acidic group.

[0235] The thiol chain transfer agent (F) can be used alone or in combination of two or more kinds.

[0236] The content of the thiol chain transfer agent (F) is preferably from 0.5 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0237] [Silane coupling agent (G)] From the viewpoint of resistance after low-temperature heating, the photosensitive composition of the present invention preferably contains a silane coupling agent (G). It is presumed that the silane coupling agent (G) reacts with functional groups on the substrate surface or functional groups of other components contained in the photosensitive composition, improving resistance after low-temperature heating.

[0238] The silane coupling agent (G) 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 (G) is not included in the alkali-soluble resin (B) and the polymerizable compound (C).

[0239] Examples of the silane coupling agent (G) 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.

[0240] Commercially available silane coupling agents (G) 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.

[0241] The silane coupling agent (G) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0242] 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.

[0243] The organic polymer type is a silane coupling agent (G) 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.

[0244] The silane coupling agent (G) preferably contains a compound represented by the following general formula (10). The compound represented by general formula (10) 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.

[0245] General formula (10) [ka]

[0246] In general formula (10), three R1 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 any one of the following general formulae (Q-1) to (Q-4), and n represents an integer of 1 to 10.

[0247] [ka]

[0248] 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 each independently represents a hydrogen atom or a methyl group. * represents a bond to an oxygen atom.

[0249] In the general formula (10), the three R1's are preferably methyl groups.

[0250] In the general formula (10), Q is preferably any of the general formulae (Q-1) to (Q-3).

[0251] The molecular weight (formula weight) or weight average molecular weight of the silane coupling agent (G) is preferably from 100 to 3,000, more preferably from 150 to 1,500.

[0252] The acid value of the silane coupling agent (G) is preferably 10 mgKOH / g or less.

[0253] The silane coupling agent (G) can be used alone or in combination of two or more kinds.

[0254] The content of the silane coupling agent (G) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0255] [Thermal crosslinkable compound (H)] The photosensitive composition of the present invention preferably contains a thermally crosslinkable compound (H) from the viewpoint of resistance after low-temperature heating. This allows the thermally crosslinkable compound (H) to crosslink upon heating, improving resistance. In this specification, the thermally crosslinkable compound (H) is not included in the alkali-soluble resin (B) and the polymerizable compound (C).

[0256] The thermally crosslinkable compound (H) is not particularly limited as long as it is a compound having a thermally crosslinkable 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.

[0257] The thermally crosslinkable compound (H) can be used alone or in combination of two or more kinds.

[0258] The content of the thermally crosslinkable compound (H) 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.

[0259] (Compound (H1) having an epoxy group) The thermally crosslinkable compound (H) preferably contains a compound (H1) having an epoxy group, whereby the epoxy group is crosslinked by heating, further improving resistance.

[0260] The epoxy group is a group having a three-membered cyclic ether structure, including an alicyclic epoxy group. Examples of compounds having an epoxy group include 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.

[0261] Commercially available products of the compound (H1) having an epoxy group include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., 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.

[0262] The compound (H1) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0263] The epoxy equivalent of the compound (H1) 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.

[0264] From the viewpoint of resistance after low-temperature heating, the compound (H1) having an epoxy group more preferably contains a compound represented by the following general formula (11).

[0265] General formula (11) [ka]

[0266] In formula (11), 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.

[0267] 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. 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 (11) may be the same or different.

[0268] The compound represented by the general formula (11) is, for example, 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.

[0269] The acid value of the compound (H1) having an epoxy group is preferably 10 mgKOH / g or less.

[0270] The compound (H1) having an epoxy group can be used alone or in combination of two or more kinds.

[0271] The content of the compound (H1) 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 thermally crosslinkable compound (H).

[0272] (Compound (H2) having a blocked isocyanate group) The thermally crosslinkable compound (H) preferably contains a compound (H2) having a blocked isocyanate group.

[0273] The compound (H2) 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.

[0274] The compound (H2) 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.

[0275] The blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, more preferably oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds, and particularly preferably active methylene compounds from the viewpoint of resistance after low-temperature heating. 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 temperatures, improving resistance.

[0276] The active methylene compound is preferably a compound represented by the following general formula (50). General formula (50) [ka] In general formula (50), R 11 , R 12 , R 13 , R 21 , R 22 , R 23 are each independently a hydrogen atom or an alkyl group which may contain one or more substituents selected from the group consisting of a hydroxyl group and an amino group. The wavy line represents a bond.

[0277] 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; Compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the aromatic compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further examples include biuret forms, isocyanurate forms, adduct forms, allophanate forms, and reaction products of these compounds with polyols.

[0278] 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.

[0279] Examples of the compound (H2) having a blocked isocyanate group include the following compounds: In the following structural formula, X represents a blocked isocyanate group, but the present invention is not limited thereto.

[0280] [ka]

[0281] The X (blocked isocyanate group) of the above compound may be, for example, any of the structures shown in (X-1) to (X-10) below. In the following structures, * represents a bond. However, the present invention is not limited to these.

[0282] [ka] TIFF2024174787000028.tif95162

[0283] Commercially available products of the compound (H2) having a blocked isocyanate group include, as compounds having an aliphatic structure, 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.

[0284] The compound (H2) having a blocked isocyanate group preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0285] The weight average molecular weight of the compound (H2) having a blocked isocyanate group is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0286] The acid value of the compound (H2) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0287] The compound (H2) having a blocked isocyanate group can be used alone or in combination of two or more kinds.

[0288] The content of the compound (H2) 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 thermally crosslinkable compound (H).

[0289] From the viewpoint of resistance after low-temperature heating, it is more preferable to use the thermally crosslinkable compound (H) in combination with a compound (H1) having an epoxy group and a compound (H2) having a blocked isocyanate group. The mass ratio of the compound (H1) having an epoxy group to the compound (H2) having a blocked isocyanate group is preferably from 5:95 to 95:5, and more preferably from 10:90 to 90:10.

[0290] [Dye (I)] The photosensitive composition of the present invention can contain a dye (I).

[0291] 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.

[0292] 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.

[0293] 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.

[0294] 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.

[0295] 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.

[0296] The dyes (I) can be used alone or in combination of two or more kinds.

[0297] 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.

[0298] [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.

[0299] 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. For example, compounds having an acidic substituent such as a sulfo group, a carboxyl 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.

[0300] For example, pyrrolopyrrole pigment derivatives are disclosed 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 disclosed in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A; and anthraquinone pigment derivatives are disclosed in JP 63-26 4674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009 / 025325; quinacridone pigment derivatives include JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine pigment derivatives include JP-A-2011-162662; thiazine indigo pigment derivatives include JP-A-2007-314785; triazine pigment derivatives include , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, as benzoisoindole pigment derivatives, JP-A-2009-57478, as quinophthalone pigment derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, as naphthol pigment derivatives, Examples of squarylium pigment derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo pigment derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, 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).

[0301] The pigment derivative (J) is preferably added during the micronization of the pigment (A) or during the dispersion treatment of the pigment (A).The average primary particle size of the pigment derivative (J) is preferably 5 to 200 nm.

[0302] The pigment derivative (J) can be used alone or in combination of two or more kinds.

[0303] 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).

[0304] [Dispersion resin (K)] The photosensitive composition of the present invention may contain a dispersing resin (K). This allows the pigment (A) to be stably dispersed. In this specification, the dispersing resin (K) is not included in the alkali-soluble resin (B).

[0305] 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.

[0306] 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.

[0307] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0308] 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.

[0309] 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.

[0310] From the viewpoint of resistance after low-temperature heating, the dispersing resin (K) preferably has a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a cyclic ether group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group.

[0311] Examples of the dispersing resin (K) include the resins described in paragraphs 0122 to 0155 of WO 2013 / 175978, 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.

[0312] 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.

[0313] The dispersing resin (K) can be used alone or in combination of two or more kinds.

[0314] 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).

[0315] [Sensitizer (L)] The photosensitive composition of the present invention can contain a sensitizer (L).

[0316] 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, benzoyl 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. , squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, or benzophenone compounds. Among these, thioxanthone compounds and benzophenone compounds are preferred.

[0317] The sensitizers (L) can be used alone or in combination of two or more kinds.

[0318] 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).

[0319] [Thermal crosslinking accelerator] The photosensitive composition of the present invention can be used in combination with a thermal crosslinking accelerator to assist the thermal crosslinking of the thermally crosslinkable compound (H). Examples of the thermal crosslinking accelerator include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the thermal crosslinking accelerator 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, etc.), and the like. , 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.).

[0320] The thermal crosslinking accelerators can be used alone or in combination of two or more kinds.

[0321] The content of the thermal crosslinking accelerator is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermal crosslinkable compound (H).

[0322] [Ultraviolet absorber (M)] The photosensitive composition of the present invention can contain an ultraviolet absorber (M).

[0323] The ultraviolet absorbent (M) 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.

[0324] Benzotriazole compounds 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 straight chain alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 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, etc. Commercially available products include, for example, Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, UVA-903KT manufactured by BASF Japan, and Adeka STAB LA-31RG, LA-31G, etc. manufactured by ADEKA Corporation.

[0325] Benzophenone compounds include, 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, diethylaminohydroxybenzoylhexyl benzoate, 4,4'-bis(dimethylamino)benzophenone, and the like. Non, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Commercially available products include, for example, Uvinal A, 3049, 3050, UVA-935LH manufactured by BASF Japan Ltd., and Adeka STAB 1413 manufactured by ADEKA Corporation.

[0326] Examples of the triazine compound 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, 2,4- Examples of the 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, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, etc. 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.

[0327] An example of the conjugated diene compound is UV503 manufactured by Daito Chemical Co., Ltd.

[0328] Examples of the methyldibenzoyl compound include 1,3-diphenyl-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione.

[0329] Examples of the coumarin compound include 4-hydroxycoumarin and 7-hydroxycoumarin.

[0330] The content of the ultraviolet absorber (M) is preferably from 0.1 to 5% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0331] [Polymerization inhibitor (N)] The photosensitive composition of the present invention may contain a polymerization inhibitor (N).

[0332] Examples of the polymerization inhibitor (N) 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.

[0333] The content of the polymerization inhibitor (N) is preferably from 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0334] [Antioxidants (O)] The photosensitive composition of the present invention can contain an antioxidant (O).

[0335] The antioxidant (O) prevents the polymerization initiator (D) and the thermally crosslinkable compound (H) in the photosensitive composition from being oxidized and yellowed by heat during the heating process or ITO annealing.

[0336] Examples of the antioxidant (O) include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. Among these, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds are preferred.

[0337] Examples of the hindered phenol compounds include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di -t-butyl-4-hydroxyphenyl)-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-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples of such phenols include 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), and 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol.

[0338] 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.

[0339] Examples of the hindered amine compound include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, and 1,2,2,6,6-pentamethoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate. 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-pi Ester of peridineethanol 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.

[0340] 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.

[0341] Examples of the phosphorus compound include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono(2 -ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene Diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 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, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, and the like.

[0342] Examples of commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan Ltd., and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0343] Examples of sulfur compounds 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.

[0344] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0345] The antioxidant (O) can be used alone or in combination of two or more kinds.

[0346] The content of the antioxidant (O) is preferably from 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0347] [Leveling agent (P)] The photosensitive composition of the present invention may contain a leveling agent (P), which improves the wettability and drying property of the composition to a substrate during application.

[0348] Examples of the leveling agent (P) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0349] 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.

[0350] 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.

[0351] The fluorosurfactant may be, for example, a surfactant or a leveling agent having a fluorocarbon chain.

[0352] 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.

[0353] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkyl alkanolamides, and alkyl imidazolines.

[0354] 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, manufactured by Kao Corporation. LS-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, T W-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 10 2, 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 copolymer Polyflour No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0355] 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.

[0356] Commercially available products include, for example, Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0357] Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0358] 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.

[0359] 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.

[0360] Commercially available products include Anhythol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0361] The leveling agents (P) can be used alone or in combination of two or more kinds.

[0362] The content of the leveling agent (P) is preferably from 0.001 to 2.0% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0363] [Storage stabilizer (Q)] The photosensitive composition of the present invention may contain a storage stabilizer (Q), which stabilizes the viscosity of the photosensitive composition over time.

[0364] Examples of the storage stabilizer (Q) 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.

[0365] The content of the storage stabilizer (Q) is preferably from 0.05 to 5% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0366] The photosensitive composition of the present invention may contain components other than those described above. Examples of the other components include an acid generator, a salt generator, a curing catalyst, a semiconductor nanocrystal, a semiconductor material, an organic electroluminescent material, an insulating material, etc. The content of the other components may be appropriately set within a range that does not impair the effects of the present invention.

[0367] [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.

[0368] A photosensitive composition in which the total amount of the specific metal elements is within the above range 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).

[0369] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less.

[0370] A photosensitive composition having a water content within the above range 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.

[0371] [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 (E) and then mixed successively. For example, a dispersion is produced by adding a pigment (A), a dispersing resin (K), an organic solvent (E), 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.

[0372] 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.

[0373] 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.

[0374] 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.

[0375] 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.

[0376] The photosensitive composition of the present invention is preferably used for forming a pattern by a photolithography method, although the present invention is not limited thereto.

[0377] <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 may also be used as a flat film without forming a pattern.

[0378] [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 an organic EL element can be maintained when an image display device uses an organic EL element as a light source, an image sensor uses an organic photoelectric conversion film, or a heat-sensitive base material such as a plastic film is used. The heating temperature is preferably 50°C or more.

[0379] In the production of the film, first, the photosensitive composition is applied onto a substrate. Examples of the substrate include glass, resin, silicon, and the like. The glass is preferably colorless and transparent. Depending on the application, colored glass such as blue glass may be used. The substrate may have an organic light-emitting layer. The substrate may also have an imaging element such as a CCD or CMOS. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0380] 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.

[0381] 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.

[0382] 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.

[0383] A method for forming a pattern by photolithography will be described in detail below. In the photolithography method, 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), and the unexposed parts are removed by alkaline development (development step), and the pattern is then heat-treated (heating step).

[0384] [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). In addition, a plurality of active energy rays can be used in combination, or exposure can be carried out in a plurality of separate steps.

[0385] [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.

[0386] [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.

[0387] <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.

[0388] <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.

[0389] 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.

[0390] <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 following liquid crystal display configuration can be given.

[0391] The liquid crystal display includes a color filter, a counter substrate having a TFT array substrate or the like, and a liquid crystal layer formed between the color filter and the counter substrate. Examples of driving methods for liquid crystal displays include the TN method, the IPS method, the OCB method, and the MVA method. The counter substrate can be appropriately selected according to the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropy and mixtures thereof according to the driving method.

[0392] Specifically, it is described in "Next Generation Liquid Crystal Display Technology" (by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994), "Electronic Display Devices" (by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0393] <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.

[0394] A substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like. A light shielding film with only the light receiving portion of the photodiodes open is provided on the photodiodes and the transfer electrodes. A device protection film is provided on this light shielding film, and the optical filter of the present invention is provided on this device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same applies below) below the optical filter (the side closer to the substrate) on the device protection film, or the light collecting means may be provided on the optical filter.

[0395] 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.

[0396] 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 .

[0397] 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).

[0398] 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.

[0399] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 capable of transmitting light of a wavelength transmitted through the infrared transmission filter 113 is disposed.

[0400] 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.

[0401] 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.

[0402] 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.

[0403] 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

[0404] 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.

[0405] Before describing the examples, each measurement method will be described.

[0406] 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.

[0407] (Molecular weight) 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.

[0408] (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.

[0409] (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.

[0410] (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.

[0411] <Production of Pigment (A)> (Near infrared absorbing pigment (A-14)) 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-14) represented by the following chemical formula (12). 50 parts of the obtained near-infrared absorbing pigment (A-14), 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-14).

[0412] Chemical formula (12) [ka]

[0413] (Near infrared absorbing pigment (A-15)) 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-15) which is a mixture of compounds represented by the following chemical formula (13) (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-14).

[0414] Chemical formula (13) [ka]

[0415] (Near infrared absorbing pigment (A-16)) According to the description of WO 2019 / 058882, a near infrared absorbing pigment (A-16) represented by the following chemical formula (14) was obtained. The near infrared absorbing pigment (A-16) was then micronized in the same manner as for the near infrared absorbing pigment (A-14). In the chemical formula (14), Ph represents a phenyl group.

[0416] Chemical formula (14) [ka]

[0417] (Near infrared absorbing pigment (A-17)) 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-17) which is a mixture of compounds represented by the following chemical formula (15) (mass ratio of dimer: trimer: tetramer = 81:17:2). Next, it was pulverized in the same manner as the near-infrared absorbing pigment (A-14).

[0418] Chemical formula (15) [ka]

[0419] <Production of alkali-soluble resin (B)> (Solution of alkali-soluble resin (B1-1) having thermal crosslinking group-containing monomer unit (b1)) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed, and the mixture was stirred while replacing with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of KarenzMOI-DEM (malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester manufactured by Showa Denko Co., Ltd.), 31.2 parts of 2-hydroxyethyl methacrylate (hereinafter, 2HEMA), 37.5 parts of dicyclopentanyl methacrylate (hereinafter, DCPMA), 20.7 parts of methacrylic acid (hereinafter, MAA), and 27.0 parts of methyl methacrylate (hereinafter, MMA), and 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 78 ° C for 3 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, and an alkali-soluble resin (B1-1) solution was prepared. The alkali-soluble resin (B1-1) had an acid value of 74 mgKOH / g and a weight average molecular weight of 8,000.

[0420] (Solution of alkali-soluble resin (B1-2) having thermal crosslinking group-containing monomer unit (b1)) An alkali-soluble resin (B1-2) was synthesized to have the composition ratio and weight average molecular weight shown in Table 2 in the same manner as for the alkali-soluble resin (B1-1), except that part of the DCPMA was replaced with glycidyl methacrylate (hereinafter, GMA). Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, thereby preparing an alkali-soluble resin (B1-2) solution. The weight-average molecular weight of the resin was adjusted by changing the amount of the polymerization initiator used.

[0421] (Solution of alkali-soluble resin (B1-3) having thermal crosslinking group-containing monomer unit (b1)) A resin (precursor) was synthesized in the same manner as the alkali-soluble resin (B1-1) by replacing a part of DCPMA with GMA. Then, the flask was replaced with air, and acrylic acid (hereinafter, AA), triphenylphosphine, and methylhydroquinone were added and reacted at 110°C for 10 hours. This introduced a monomer unit (hereinafter, GMA+AA) in which the epoxy group derived from GMA in the precursor reacted with the carboxyl group of AA. GMA+AA is a polymerizable unsaturated group-containing monomer unit (b5). Then, PGMAc was added so that the non-volatile content was 40% by mass, and an alkali-soluble resin (B1-3) solution was prepared.

[0422] (Solution of alkali-soluble resin (B1-4) having thermal crosslinking group-containing monomer unit (b1)) 28.5 parts of diethyl malate, 0.01 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.05 parts of dibutyltin dilaurate were added to a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, and the mixture was stirred and cooled to 15 to 20°C. Then, the temperature was maintained at 15 to 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 compound of the following chemical formula (16), which is a monomer represented by general formula (1), was obtained.

[0423] Chemical formula (16) [ka]

[0424] 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 the compound of chemical formula (16), 14 parts of MAA, 86 parts of n-butyl acrylate (hereinafter, nBMA), and 76 parts of MMA, 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 mass %, and an alkali-soluble resin (B1-4) solution was prepared.

[0425] (Solution of alkali-soluble resin (B1-5) having thermal crosslinking group-containing monomer unit (b1)) 0.1 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 was added to 100 parts of alkali-soluble resin (B1-4), and the temperature was raised to 80°C while stirring. After reacting at 80°C for 30 minutes, the reaction was terminated by cooling. As a result, an alkali-soluble resin (B1-5) having a thermal crosslinking group-containing monomer unit (b1) formed from the compound of the following chemical formula (17), which is a monomer represented by general formula (2), was obtained.

[0426] Chemical formula (17) [ka]

[0427] (Solution of alkali-soluble resin (B1-6) having thermal crosslinking group-containing monomer unit (b1)) In a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 190.2 parts of diethyl malate, 0.17 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.33 parts of dibutyltin dilaurate were added and stirred, and cooled to 15 to 20°C. Then, the temperature was maintained at 15 to 20°C, and 141.1 parts of 2-acryloyloxyethyl 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 compound of the following chemical formula (18), which is a monomer represented by general formula (1), was obtained.

[0428] Chemical formula (18) [ka]

[0429] 80 parts of PGMAc was placed in 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 78°C. Next, 48.8 parts of the compound of chemical formula (18), 24.7 parts of KarenzMOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate manufactured by Showa Denko K.K.), 25.5 parts of 2HEMA, 8.6 parts of 2-ethylhexyl acrylate (hereinafter, 2EHA), and 17.4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 78°C for 3 hours to react, and then 0.2 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 was added and stirred at 78°C for 30 minutes. As a result, a thermally crosslinkable group-containing monomer unit (b1) formed from a compound of the following chemical formula (19), which is a monomer represented by general formula (2), was introduced.

[0430] Chemical formula (19) [ka]

[0431] Next, 9.9 parts of succinic anhydride (hereinafter, SA) and 0.5 parts of lithium naphthenate (catalyst) were added and stirred at 78°C for 1 hour. This introduced a monomer unit in which SA was added to the hydroxyl group of 2HEMA (hereinafter, 2HEMA+SA). 2HEMA+SA is an acidic group-containing monomer unit (b2). Thereafter, PGMAc was added so that the non-volatile content was 40 mass%, and an alkali-soluble resin (B1-6) solution was prepared.

[0432] (Solution of alkali-soluble resin (B1-7) having thermal crosslinking group-containing monomer unit (b1)) KarenzMOI-BP was replaced with KarenzMOI-BM (2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate manufactured by Showa Denko K.K.), and similarly to the alkali-soluble resin (B1-6), an alkali-soluble resin (B1-7) was synthesized so as to have the composition ratio and weight average molecular weight shown in Table 2. Thereafter, PGMAc was added so that the non-volatile content was 40 mass %, and an alkali-soluble resin (B1-7) solution was prepared.

[0433] (Solution of alkali-soluble resin (B1-8) having thermal crosslinking 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 70 parts of PGMAc, and the mixture was stirred while replacing with nitrogen and heated to 90°C. Next, a mixture of 20.7 parts of 2-(acetoacetoxy)ethyl methacrylate (hereinafter, 2AAEM), which is a monomer represented by general formula (3), 26.7 parts of MAA, and 52.6 parts of DCPMA, and a mixture of 5.0 parts of V-601 added to 30 parts of PGMAc and dissolved therein were dropped into the flask from the dropping funnel. After the dropwise addition was completed, the mixture was stirred at 90°C for 6 hours to react. The mixture was then cooled to 40°C, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexylmethyl acrylate (hereinafter, ECHA), and 4.7 parts of triphenylphosphine were added, heated to 110°C, and stirred for 10 hours to react. This resulted in the introduction of a monomer unit in which the epoxy group of ECHA was added to the carboxyl group of MAA (hereinafter, MAA+ECHA). MAA+ECHA is a polymerizable unsaturated group-containing monomer unit (b5). Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, thereby preparing an alkali-soluble resin (B1-8) solution.

[0434] (Solution of alkali-soluble resin (B1-9) having thermal crosslinking group-containing monomer unit (b1)) 300 parts of PGMAc 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 (hereinafter, monomer A), a monomer represented by general formula (4), 40.8 parts of MAA, and 125 parts of MMA, and 27.3 parts of V-601 was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was reacted for 2 hours while stirring at 105°C. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, to prepare an alkali-soluble resin (B1-9) solution.

[0435] (Solution of alkali-soluble resin (B1-10) having a thermal crosslinking group-containing monomer unit (b1)) Monomer A was replaced with 3-methacryloyloxypropylmethyldiethoxysilane (hereinafter, monomer B), and an alkali-soluble resin (B1-10) was synthesized in the same manner as the alkali-soluble resin (B1-9) so as to have the composition ratio and weight average molecular weight shown in Table 2. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, thereby preparing an alkali-soluble resin (B1-10) solution.

[0436] (Solution of alkali-soluble resin (B1-11) having a thermal crosslinking group-containing monomer unit (b1)) 100 parts of PGMAc was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 90°C. Next, a mixture of 35 parts of tert-butyl methacrylate (hereinafter, tBMA), 5 parts of 2AAEM, 10 parts of N-benzylmaleimide (hereinafter, BzMI), 20 parts of 2HEMA, 17.1 parts of MAA and 2 parts of t-butylperoxy-2-ethylhexanoate (polymerization initiator) represented by general formula (5), and a mixture of 0.6 parts of n-dodecyl mercaptan and 20 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the temperature was kept at 90°C for 30 minutes, and then the temperature was raised to 115°C and the mixture was stirred for 90 minutes to react. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, thereby preparing an alkali-soluble resin (B1-11) solution.

[0437] (Solution of alkali-soluble resin (B1-12) having a thermally crosslinkable group-containing monomer unit (b1)) Karenz MOI-DEM was replaced with Karenz MOI-BP, and an alkali-soluble resin (B1-12) was synthesized in the same manner as the alkali-soluble resin (B1-1) so as to have the composition ratio and weight average molecular weight shown in Table 2. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, to prepare an alkali-soluble resin (B1-12) solution.

[0438] (Solution of alkali-soluble resin (B1-13) having a thermally crosslinkable group-containing monomer unit (b1)) Karenz MOI-DEM was replaced with GMA, and an alkali-soluble resin (B1-13) was synthesized in the same manner as the alkali-soluble resin (B1-1) so as to have the composition ratio and weight average molecular weight shown in Table 2. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, to prepare an alkali-soluble resin (B1-13) solution.

[0439] (Solution of alkali-soluble resin (B1-14) having a thermocrosslinkable group-containing monomer unit (b1)) Karenz MOI-DEM was dissolved in 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate (hereinafter, Monomer C) and 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-9-yl acrylate (hereinafter, monomer D) was used in place of the mixture (molar ratio 1:1), and alkali-soluble resin (B1-14) was synthesized in the same manner as alkali-soluble resin (B1-1) so as to have the constituent ratio and weight-average molecular weight shown in Table 2. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, thereby preparing an alkali-soluble resin (B1-14) solution.

[0440] (Solution of alkali-soluble resin (B1-15) having thermal crosslinking group-containing monomer unit (b1)) 28.3 parts of diisopropyl malonate, 0.01 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.05 parts of dibutyltin dilaurate were added to a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, and the mixture was stirred and cooled to 15 to 20°C. Then, the temperature was maintained at 15 to 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 the compound of the following chemical formula (200) was obtained.

[0441] Chemical formula (200) [ka]

[0442] In a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 32.5 parts of di-tert-butyl malonate, 0.01 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.05 parts of dibutyltin dilaurate were added and stirred, and cooled to 15 to 20°C. Then, the temperature was maintained at 15 to 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 the compound of the following chemical formula (210) was obtained.

[0443] Chemical formula (210) [ka]

[0444] A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while replacing with nitrogen and heated to 78 ° C. Next, a mixture of 13.7 parts of the compound of formula (200), 14.8 parts of the compound of formula (210), 31.2 parts of 2HEMA, 37.5 parts of DCPMA, 20.7 parts of MAA and 27.0 parts of MMA, and 12.0 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 78 ° C for 3 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, and an alkali-soluble resin (B1-15) solution was prepared. The alkali-soluble resin (B1-15) had an acid value of 74 mgKOH / g and a weight average molecular weight of 8,000.

[0445] [Table 2-1]

[0446] [Table 2-2] [Table 2-3]

[0447] The amount of each component in Tables 2-1, 2-2 and 2-3 is expressed in mole percent.

[0448] (Solution of alkali-soluble resin (B2-1) not having a thermocrosslinkable group-containing monomer unit (b1)) 100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120 ° C. while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 56.86 parts of GMA, 66.09 parts of DCPMA, and 31.25 parts of styrene (hereinafter, St), and a polymerization initiator dissolved in 5.0 parts of azobisisobutyronitrile in PGMAc was dropped from the dropping tube over 2.5 hours to carry out a polymerization reaction. After the dropwise addition was completed, the mixture was stirred at 120 ° C. for another 2 hours to carry out the reaction. Next, the inside of the flask was replaced with air, and 28.82 parts of AA, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the mixture was stirred at 120 ° C. for 5 hours to carry out the reaction. Further, 48.68 parts of tetrahydrophthalic anhydride (hereinafter, THPA) and 0.5 parts of triethylamine were added, and the mixture was reacted at 120° C. for 4 hours with stirring. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, to prepare an alkali-soluble resin (B2-1) solution. The resin had an acid value of 77 mgKOH / g and a weight average molecular weight of 10,000.

[0449] (Solution of alkali-soluble resin (B2-2) not having a thermal crosslinking group-containing monomer unit (b1)) A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 100 parts of PGMAc, heated to 80°C, and the atmosphere in the reaction vessel was replaced with nitrogen. From the dropping tube, a mixture of 25.1 parts of benzyl methacrylate (hereinafter, BzMA), 23.0 parts of nBMA, 14.3 parts of 2HEMA, 13.4 parts of MAA, 24.1 parts of Aronix M-110 (manufactured by Toagosei Co., Ltd., paracumylphenol ethylene oxide modified acrylate), and 1.1 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropwise addition, the mixture was stirred for another 3 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, to prepare an alkali-soluble resin (B2-2) solution. The resin had an acid value of 87 mgKOH / g and a weight average molecular weight of 25,000.

[0450] (Solution of alkali-soluble resin (B2-3) not having a thermal crosslinking group-containing monomer unit (b1)) 100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 109.25 parts of BzMA, 24.1 parts of MAA, 22.03 parts of DCPMA, 1.0 part of azobisisobutyronitrile as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours. After the dropwise addition, the mixture was stirred at 120°C for another 2 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, to prepare an alkali-soluble resin (B2-3) solution. The resin had an acid value of 98 mgKOH / g and a weight average molecular weight of 17,500.

[0451] <Production of Silane Coupling Agent (G)> (Silane coupling agent (G-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 stirred at 80°C for 4 hours to react. 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 (G-1) whose main component is represented by the following chemical formula (20) was obtained. In addition, as a secondary component, a dimer to decamer which is a condensation product of the chemical formula (20) was included.

[0452] Chemical formula (20) [ka]

[0453] <(Production of Compound (H2) Having Blocked Isocyanate Group)> (Production of blocked isocyanate compound H2-2) In a four-neck flask equipped with a thermometer, stirring blade, and reflux condenser, 100 parts by mass of hexamethylene diisocyanate (hereinafter also referred to as HDI) was charged under a nitrogen gas flow, and the temperature inside the reactor was maintained at 60°C while stirring, and 0.095 parts by mass of trimethylbenzylammonium hydroxide was added to carry out the reaction. After 4.5 hours, when the conversion rate reached 40% by mass, 0.02 parts by mass of phosphoric acid was added to stop the reaction. After filtering the reaction liquid, unreacted HDI was removed using a thin-film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter referred to as "H2-2 precursor"). The NCO content of the obtained H2-2 precursor was 22.0% by mass, the number average molecular weight was 655, and the average number of isocyanate groups was 3.43. The obtained H2-2 precursor also had the following characteristics: 1 H-NMR analysis confirmed the presence of isocyanurate groups. In a four-neck flask equipped with a thermometer, a stirring blade and a reflux condenser, 100 parts by mass of H2-2 precursor, diisopropyl malonate (70 mol% relative to 100 mol% of NCO groups), and di-tert-butyl malonate (30 mol% relative to 100 mol% of NCO groups) were charged under nitrogen gas flow, and butyl acetate was further added to adjust the solid content to 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was dropped, and the external bath was adjusted so that the solution temperature was 55°C, and the blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate composition H2-2 with a solid content of 60% by mass.

[0454] <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 heated to 80° C. over 1 hour, reacted for 2 hours, and cooled 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.

[0455] (Dye (I-2)) According to Example 30 of JP-A-05-345861, a compound represented by the following chemical formula (21) was obtained: In the chemical formula (21), Et represents an ethyl group.

[0456] Chemical formula (21) [ka]

[0457] <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% or more of the monomer 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.

[0458] (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 inside of 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 the monomer had reacted at 95% or more 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.

[0459] (Dispersed resin (K-3) solution) In a reactor equipped with a gas inlet tube, a condenser, an agitator, and a 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.

[0460] (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.

[0461] <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 (E2-1): 67.0 parts

[0462] (Dispersion 2~16) Dispersions 2 to 16 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts thereof were changed as shown in Tables 3-1 and 3-2.

[0463] [Table 3-1]

[0464] [Table 3-2]

[0465] The components listed in Tables 3-1 and 3-2 are as follows.

[0466] 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 179 A-12: CI Pigment Red 264 A-13: CI Pigment Red 254

[0467] Each of the pigments (A-1) to (A-13) was pulverized by salt milling, thoroughly washed with ion-exchanged water so as to have the specific metal content described above, and then dried before use.

[0468] [Pigment Derivatives (J)] [ka]

[0469] [Organic solvent (E)] (Organic solvent (E2)) E2-1:PGMAc

[0470] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive composition 1. The non-volatile content was 15.0 mass%. The blending amount (parts) of raw materials other than the dispersion was recorded as the non-volatile content, and the organic solvent contained in the raw materials was recorded as organic solvent (E). Dispersion 2, Dispersion 5, and Dispersion 9 used pigments A-2, A-5, and A-9, respectively, and in Table 4, the raw materials were broken down and entered, including other contained components. Dispersion 2: 1.0 part Dispersion 5: 21.0 parts Dispersion 9: 3.0 parts Alkali-soluble resin (B1-1): 2.56 parts Alkali-soluble resin (B2-2): 2.0 parts Polymerizable compound having an amine structure (C1-1): 0.5 parts Polymerizable compound having a hydroxyl group (C2-3): 1.4 parts Other polymerizable compounds (C7-2): 0.6 parts Polymerization initiator (D1-4): 0.1 part Polymerization initiator (D2-1): 0.05 parts Thiol chain transfer agent (F-1): 0.15 parts Thiol chain transfer agent (F-2): 0.15 parts Silane coupling agent (G-1): 0.35 parts Silane coupling agent (G-2): 0.09 parts Compound having an epoxy group (H1-1): 0.4 parts Compound (H2-1) having a blocked isocyanate group: 1.08 parts UV absorber (M-1): 0.15 parts UV absorber (M-2): 0.15 parts Leveling agent (P-1): 0.01 parts Leveling agent (P-2): 0.01 parts Organic solvent (E1-1): 3.0 parts Organic solvent (E1-5): 0.3 parts Organic solvent (E2-1): 45.65 parts Organic solvent (E2-2): 8.0 parts Organic solvent (E2-3): 8.0 parts Organic solvent (E2-4): 0.3 parts

[0471] [Examples 2 to 73 and Comparative Examples 1 to 3] (Photosensitive composition 2-76) Photosensitive compositions 2 to 76 were produced in the same manner as in Example 1 using the raw materials and amounts shown in Tables 4-1 to 4-8.

[0472] [Table 4-1]

[0473] [Table 4-2]

[0474] [Table 4-3]

[0475] [Table 4-4]

[0476] [Table 4-5]

[0477] [Table 4-6]

[0478] [Table 4-7]

[0479] [Table 4-8]

[0480] The respective raw materials listed in Tables 4-1 to 4-8 are as follows.

[0481] [Polymerizable compound (C)] (Polymerizable compound (C1) having an amine structure) C1-1: Aronix MT-3041 (manufactured by Toagosei Co., Ltd., a multifunctional acrylate having a tertiary amine structure)

[0482] (Polymerizable compound having a hydroxyl group (C2)) C2-1: Isocyanuric acid EO modified diacrylate C2-2: Glycerol diacrylate C2-3: Pentaerythritol triacrylate C2-4: Dipentaerythritol pentaacrylate

[0483] (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)

[0484] (Other polymerizable compounds (C7)) C7-1: Isocyanuric acid EO modified triacrylate C7-2: Pentaerythritol tetraacrylate C7-3: Dipentaerythritol hexaacrylate C7-4: Trimethylolpropane triacrylate C7-5: Dipentaerythritol EO modified hexaacrylate

[0485] [Polymerization initiator (D)] (Polymerization initiator (D1)) D1-1: The above-mentioned compound (D1-1) D1-2: The above-mentioned compound (D1-2) D1-3: The above-mentioned compound (D1-3) D1-4: The above-mentioned compound (D1-4) D1-5: The above-mentioned compound (D1-5) D1-6: The above-mentioned compound (D1-6) D1-7: The above-mentioned compound (D1-7) D1-8: The above-mentioned compound (D1-8) D1-9: The above-mentioned compound (D1-9) D1-10: The above-mentioned compound (D1-10)

[0486] (Polymerization initiator (D2)) D2-1: The above compound (D2-1) (absorption coefficient of light with a wavelength of 365 nm is 18,334 L / mol cm) D2-2: The above compound (D2-2) (absorption coefficient of light with a wavelength of 365 nm is 18,900 L / mol cm) D2-3: The above compound (D2-3) (absorption coefficient of light at a wavelength of 365 nm is 7,051 L / mol cm) D2-4: The above compound (D2-4) (absorption coefficient of light at a wavelength of 365 nm is 18,767 L / mol cm) D2-5: The above compound (D2-5) (absorption coefficient of light with a wavelength of 365 nm is 2,401 L / mol cm)

[0487] [Organic solvent (E)] (Organic solvent (E1)) E1-1: Propylene glycol monomethyl ether (δh=11.6, vapor pressure 1,150 Pa) E1-2: Propylene glycol monoethyl ether (δh=10.5, vapor pressure 900 Pa) E1-3: Ethyl lactate (δh=12.5, vapor pressure 360 ​​Pa) E1-4: 3-Methoxy-1-butanol (δh=13.6, vapor pressure 160Pa) E1-5: 1-butanol (δh=15.8, vapor pressure 580Pa) E1-6: Ethanol (δh=19.4, vapor pressure 5,800 Pa) E1-7: Diethylene glycol monoethyl ether (δh=12.2, vapor pressure 19 Pa)

[0488] (Organic solvent (E2)) E2-1:PGMAc E2-2: Ethyl 3-ethoxypropionate E2-3: Cyclohexanone E2-4: Butyl acetate

[0489] [Thiol chain transfer (F)] F-1: Mercaptosuccinic acid F-2: Pentaerythritol tetrakis(3-mercaptopropionate)

[0490] [Silane coupling agent (G)] G-2: KBM-803 (Shin-Etsu Silicone Co., Ltd., 3-mercaptopropyltrimethoxysilane) G-3: KBM-5103 (Shin-Etsu Silicone Co., Ltd., 3-acryloxypropyltrimethoxysilane)

[0491] [Thermal crosslinkable compound (H)] (Compound (H1) having an epoxy group) H1-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by general formula (11), with an average of 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq)

[0492] (Compound (H2) having a blocked isocyanate group) H2-1: Duranate MF-K60B (Asahi Kasei Corporation, a compound blocked with an active methylene compound)

[0493] [Ultraviolet absorber (M)] M-1: 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol M-2: 4,4'-bis(diethylamino)benzophenone

[0494] [Leveling agent (P)] P-1: BYK-330 (BYK-Chemie, polyether-modified dimethylsiloxane) P-2: Block copolymer having the following structure (n:m=50:50 (mol%))

[0495] [ka]

[0496] <Evaluation of Photosensitive Composition> The following evaluations were carried out on the obtained photosensitive compositions 1 to 76. The evaluation results are shown in Table 5.

[0497] [Storage stability evaluation (1): Viscosity] The obtained photosensitive composition was placed in a sealed container and stored at 40°C for 10 days. The rate of change in viscosity before and after storage was calculated and evaluated using the following formula. The viscosity was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. The evaluation criteria are as follows, with 3 or more being considered practical. [Change rate of viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 5: The rate of change was less than 3%. 4: The rate of change was 3% or more but less than 6%. 3: The rate of change was 6% or more but less than 9%. 2: The rate of change was 9% or more but less than 12%. 1: The rate of change was 12% or more.

[0498] [Storage stability evaluation (2): Sensitivity] 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 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 100 μm-wide stripe pattern 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, 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 the shortest time possible to form a pattern without leaving any residual development for the coating of each photosensitive composition. The width of the pattern was measured using a scanning electron microscope, and this was taken as the initial pattern width. The obtained photosensitive composition was separately placed in a sealed container and stored at 40°C for 10 days. A pattern after storage was created using the photosensitive composition after storage under the same conditions as for the formation of the initial pattern. The width after storage was measured in the same manner as before storage. The evaluation criteria are as follows, with 3 or more being considered practical. 5: The pattern width after storage was in the range of 98% to 102% of the initial pattern width. 4: The pattern width after storage was 96% or more and less than 98% of the initial pattern width, or was in the range of more than 102% and less than 104%. 3: The pattern width after storage was 94% or more and less than 96% of the initial pattern width, or was in the range of more than 104% and less than 106%. 2: The pattern width after storage was 92% or more and less than 94% of the initial pattern width, or was in the range of more than 106% and less than 108%. 1: The pattern width after storage was less than 92% or more than 108% of the initial pattern width.

[0499] [Storage stability evaluation (3): 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 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 100 μm-wide stripe pattern 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% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The spray development was carried out for the shortest time possible for forming a pattern without leaving any residual development for each photosensitive composition coating, and this was defined as the initial development time. The obtained photosensitive composition was placed in a separate sealed container and stored at 40° C. for 10 days. After storage, the photosensitive composition was developed under the same conditions as the initial evaluation described above and evaluated according to the following criteria. A score of 3 or higher is considered to be usable. 5: The development time after storage was within the range of 90% to 110% of the initial development time. 4: The development time after storage was in the range of 80% or more but less than 90% of the initial development time, or more than 110% but less than 120%. 3: The development time after storage was in the range of 70% or more but less than 80% of the initial development time, or more than 120% but less than 130%. 2: The development time after storage was in the range of 60% or more but less than 70% of the initial development time, or more than 130% but less than 140%. 1: The development time after storage is below 60% or exceeds 140% of the initial development time.

[0500] [High temperature and humidity resistance evaluation] 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 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 an ultra-high pressure mercury lamp 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., 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 or more but less than 10. 2: 10 or more but less than 15. 1:15 or more.

[0501] [Solvent resistance evaluation] 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 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 100 μm-wide stripe pattern 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 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.

[0502] [Evaluation of high temperature and humidity resistance after storage, and solvent resistance] The obtained photosensitive composition was separately placed in a sealed container and stored for 10 days at 40° C. Then, the high temperature and high humidity resistance and the solvent resistance of the photosensitive composition after storage were evaluated in the same manner as before storage.

[0503] [Table 5] [Explanation of symbols]

[0504] 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), a polymerization initiator (D), and an organic solvent (E), the alkali-soluble resin (B) contains an alkali-soluble resin (B1) having a thermally crosslinkable group-containing monomer unit (b1), the polymerization initiator (D) contains a bisoxime ester polymerization initiator (D1); In the organic solvent (E) 100% by mass, the hydrogen bond term of the Hansen solubility parameter is 10 MPa １／２ The photosensitive composition contains the organic solvent (E1) described above in an amount of 0.1 to 20 mass %.

2. The photosensitive composition according to claim 1, wherein the thermally crosslinkable group-containing monomer unit (b1) is a monomer unit formed from at least one monomer unit selected from the group consisting of monomers represented by the following general formulas (1) to (5): 【Chemistry 1】 (In general formulas (1) to (5), R １ each independently represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. In general formula (1), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms. ２ represents a single bond or an oxygen atom. ３ and L ４ each independently represents a single bond or a divalent organic group. In general formula (2), R ４ ~R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In general formula (3), R ７ represents an alkyl group having 1 to 10 carbon atoms. In general formula (4), R ８ ~R １０ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. ８ ~R １０ At least one of these is an alkoxy group having 1 to 6 carbon atoms. In general formula (5), R １１ ~R １３ each independently represents an alkyl group having 1 to 10 carbon atoms.

3. 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 an amine structure, a polymerizable compound (C2) having a hydroxyl group, and a polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure.

4. The photosensitive composition according to claim 1 , wherein the bisoxime ester polymerization initiator (D1) comprises a compound represented by the following general formula (6): General formula (6) 【Chemistry 2】 (In general formula (6), X １ and X ２ each independently represents a carbonyl bond or a single bond. ３ represents a single bond, an oxygen atom, or a sulfur atom. １ R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a group represented by the following general formula (7). ２ and R ３ R each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. ４ and R ５ R each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. ６ and R ７ each independently represents a hydrogen atom or a nitro group. General formula (7) 【Chemistry 3】 (In general formula (7), X ４ represents an oxygen atom or a sulfur atom. ８ represents an alkyl group having 1 to 10 carbon atoms. * represents a bond to the nitrogen atom.)

5. The photosensitive composition of claim 1 , further comprising a thiol-based chain transfer agent (F).

6. The photosensitive composition according to claim 1 , further comprising a silane coupling agent (G).

7. A film formed from the photosensitive composition according to any one of claims 1 to 6.

8. An optical filter comprising the film according to claim 7.

9. A solid-state imaging device comprising the optical filter according to claim 8.

10. An image display device comprising the optical filter according to claim 8.

11. An infrared sensor comprising the optical filter according to claim 8.

Images