WO2023038092A1 - 感光性組成物、それを用いた硬化膜、カラーフィルタ、光学フィルタ、画像表示装置、固体撮像素子、及び赤外線センサ - Google Patents

感光性組成物、それを用いた硬化膜、カラーフィルタ、光学フィルタ、画像表示装置、固体撮像素子、及び赤外線センサ Download PDF

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WO2023038092A1
WO2023038092A1 PCT/JP2022/033780 JP2022033780W WO2023038092A1 WO 2023038092 A1 WO2023038092 A1 WO 2023038092A1 JP 2022033780 W JP2022033780 W JP 2022033780W WO 2023038092 A1 WO2023038092 A1 WO 2023038092A1
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Prior art keywords
group
carbon atoms
alkyl group
hydrogen atom
meth
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PCT/JP2022/033780
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English (en)
French (fr)
Japanese (ja)
Inventor
慶一 近藤
慎太郎 櫻井
駿平 鈴木
秀平 河岡
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Toyo Visual Solutions Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyo Visual Solutions Co Ltd
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Application filed by Toyo Ink SC Holdings Co Ltd, Toyo Visual Solutions Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Priority to CN202280040746.8A priority Critical patent/CN117425857A/zh
Priority to KR1020237041811A priority patent/KR20240054920A/ko
Publication of WO2023038092A1 publication Critical patent/WO2023038092A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • One embodiment of the present invention relates to a photosensitive composition that can be cured at low temperatures.
  • Patent Literature 1 discloses a flexible display that uses color filters instead of circularly polarizing plates.
  • a color filter for suppressing external light reflection is laminated on the display device in which the above-mentioned organic EL display elements are laminated. Since the organic light-emitting layer has low heat resistance, it needs to be baked at a low temperature in order to form the colored pixels of the color filter on the organic EL element. Colored pixels of color filters laminated on conventional liquid crystal display elements are baked at a very high temperature of 230° C., but in some cases, they are baked at a lower temperature, for example, 100° C. or less. However, if the baking temperature of the colored pixels is lowered, the curing becomes insufficient, and when the colored pixels are formed in the next step, problems such as peeling of the colored pixels and surface roughness due to the solvent contained in the applied coloring composition occur. . On the other hand, when the exposure amount is increased, the reaction of the cross-linking component contained in the colored pixels progresses and curing progresses, but it is very difficult to obtain a good pattern shape.
  • a composition containing an alkali-soluble resin having a blocked isocyanato group and a reactive diluent Patent Document 2
  • a composition containing a polyfunctional thiol containing a hydroxyl group in an alkali-soluble resin having a blocked isocyanato group Patent Document 3
  • an isocyanato group having a specific block structure and a hydroxyl group in the same or different component A composition comprising (US Pat. No. 6,300,004) is disclosed.
  • compositions described in Patent Documents 1 to 4 satisfy all of the developability, substrate adhesion, pattern shape, and solvent resistance after the low-temperature baking step.
  • An object of one embodiment of the present invention is to provide a photosensitive composition capable of forming a cured film having excellent developability, adhesion to a substrate, pattern shape, and solvent resistance after a low-temperature baking step.
  • Another embodiment of the present invention aims to provide a cured film that is a cured product of a photosensitive composition, and a color filter, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor having the cured film.
  • One embodiment of the present invention comprises a dye, a binder resin, a polymerizable compound, a photoinitiator, a resin-type dispersant, and a leveling agent, wherein the binder resin comprises an alkali-soluble
  • the present invention relates to a photosensitive composition containing a binder resin, wherein the photopolymerization initiator comprises an O-acyloxime ester-based photopolymerization initiator).
  • the photosensitive composition is applied and dried at 90° C. for 1 minute to form a film having a thickness of 3 ⁇ m, and the illumination intensity is 500 mW/cm 2 and the irradiation dose is 200 mJ/cm 2 .
  • the photosensitive composition has a residual film rate of 75% or more in a cured film formed by heating at 90° C. for 30 minutes after exposure to ultraviolet rays at .
  • the residual film ratio is a value obtained by dividing the thickness of the cured film formed by heating at 90° C. for 30 minutes by the thickness of the cured film exposed to ultraviolet rays before heating at 90° C. for 30 minutes.
  • Another embodiment of the present invention relates to the photosensitive composition, wherein the polymerizable compound contains an alkali-soluble group-containing polymerizable compound.
  • another embodiment of the present invention relates to the photosensitive composition, wherein the resin-type dispersant contains an acidic resin-type dispersant
  • Another embodiment of the present invention relates to the photosensitive composition, wherein the acidic resin-type dispersant contains a photocrosslinkable acidic resin-type dispersant.
  • the O-acyloxime ester photopolymerization initiator is represented by the following general formula (1), general formula (2), general formula (3), general formula (4),
  • the photosensitive composition contains at least one compound having a structure selected from the group consisting of general formula (5), general formula (6), and general formula (7).
  • R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group.
  • R 3 represents —COR 5 , a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group.
  • R5 represents a phenyl group and a thienyl group having a substituent.
  • R 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the alkyl group, cyclic alkyl group, acyl group, and phenyl group of R 1 to R 4 above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group.
  • a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group.
  • the hydrogen atoms of the substituents in R 1 to R 4 may be further substituted with another substituent R 6 .
  • R6 represents a halogen atom, fluorine atom, alkyl group, cyclic alkyl group, acyl group, nitro group, sulfo group and phenyl group.
  • R 1 and R 2 may each independently have a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic substituent having 3 to 20 carbon atoms.
  • R 3 is a hydrogen atom, a group having an O-acyloxime structure, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, acetoxy; or sulfo group.
  • R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
  • the hydrogen atom of the aryl group or arylalkyl group represented by R 4 may be further substituted with R 21 , —OR 21 , —COR 21 , hydroxyl group, nitro group, cyano group, halogen atom, or —COOR 21 Often, R 21 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group or aryl group represented by R 21 , the hydrogen atom of the arylalkyl group may be further substituted with a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or a carboxyl group.
  • the alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group.
  • the hydrogen atoms of the substituents in R 1 to R 4 may be further substituted with other substituents.
  • R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group.
  • R 3 and R 5 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show.
  • the alkyl group, acyl group and phenyl group of R 1 to R 3 may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group.
  • R 4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, or —COR 6 .
  • R 6 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 4 to 20 carbon atoms.
  • the hydrogen atoms of the substituents in R 1 to R 6 may be further substituted with other substituents.
  • R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group.
  • R 3 and R 5 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show.
  • R 4 is a hydrogen atom or an alkoxy group, and the alkoxy group may contain a linear or branched alkyl group having 1 to 20 carbon atoms or a hydroxyl group.
  • the alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group.
  • the hydrogen atoms of the substituents in R 1 to R 5 may be further substituted with other substituents.
  • R 1 and R 2 each independently represent R 11 or -COR 11
  • R 11 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 4 to 20 carbon atoms
  • the alkyl moiety of the represented alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl
  • R 3 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 4 to 20 carbon atoms, and is represented by R 3
  • the alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side
  • the hydrogen atom of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R 21 , R 22 and R 23 is further a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or may be substituted with a carboxyl group, and the alkylene portion of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R 21 , R 22 and R 23 may be -O-, -S-, - COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, an oxygen atom is adjacent 1 to 5 may be included in conditions that do not match, R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group
  • R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms
  • R 3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, an acetoxy group or a sulfo group.
  • R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an optionally substituted cyclic alkyl group having 3 to 20 carbon atoms, a phenyl group, a tolyl group, or a xylyl group. indicates m is 0 or 1; ]
  • another embodiment of the present invention relates to a cured film, which is a cured product of the photosensitive composition.
  • Another embodiment of the present invention relates to a color filter having the cured film.
  • Another embodiment of the present invention relates to an optical filter having the cured film.
  • Another embodiment of the present invention relates to an image display device having the cured film.
  • Another embodiment of the present invention relates to a solid-state imaging device having the cured film.
  • Another embodiment of the present invention relates to an infrared sensor having the cured film.
  • a photosensitive composition capable of forming a cured film having excellent developability, adhesion to a substrate, pattern shape, and solvent resistance after a low-temperature baking step.
  • a cured film that is a cured product of a photosensitive composition, and a color filter, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor having the cured film are provided. can.
  • FIG. 1 shows a schematic cross-sectional view of an image display device provided with a cured film of this embodiment.
  • FIG. 2 shows a schematic cross-sectional view of an infrared sensor provided with the cured film of this embodiment.
  • (meth)acryloyl means, unless otherwise specified, 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” do.
  • C.I means a color index (C.I.; published by The Society of Dyers and Colorists).
  • a polymerizable unsaturated group is a group containing an ethylenically unsaturated double bond.
  • a monomer is an ethylenically unsaturated bond-containing compound that can be polymerized to form a resin.
  • a monomer is an unreacted compound, and a monomer unit is a partial structure forming a resin after polymerization of the monomer.
  • the molecular weight of the compound in the present embodiment is a value calculated by calculation, or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry) for a low-molecular compound whose molecular weight can be specified, and a compound having a molecular weight distribution. is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.
  • the photosensitive composition of the present embodiment can be used for forming a cured film of a color filter or an optical filter having a cured film formed by a heating process at 180° C. or less after pattern formation by photolithography.
  • the photosensitive composition includes a dye (hereinafter also referred to as “dye (A)”), a binder resin (hereinafter also referred to as “binder resin (B)”), a polymerizable compound (hereinafter referred to as “polymerizable compound (C )”.), a photopolymerization initiator (hereinafter also referred to as “photopolymerization initiator (D)”), a resin-type dispersant (hereinafter also referred to as “resin-type dispersant (Z)”), and A leveling agent (hereinafter also referred to as “leveling agent (E)”) is included.
  • the binder resin (B) contains an alkali-soluble binder resin having a structural unit having a blocked isocyanato group (hereinafter also referred to as “alkali-soluble binder resin (Bb)”), and the photopolymerization initiator (D) is O-acyloxy (hereinafter also referred to as “O-acyl oxime ester photopolymerization initiator (D1)").
  • the photosensitive composition of this embodiment contains a dye (A).
  • A the transmittance of each wavelength region can be controlled, and the transmission wavelength of the cured film, which is the cured product of the photosensitive composition, can be easily controlled.
  • the transmittance may be controlled for areas other than the visible region, and the material may be colorless and transparent as long as the transmittance is controlled.
  • the pigment (A) may be any of pigments, dyes, and near-infrared absorbing pigments. These can be used together.
  • pigment is a compound classified as a pigment in the Color Index. Pigments include, for example, red pigments, orange pigments, blue pigments, green pigments, blue pigments, purple pigments, black pigments, and the like.
  • the red pigment is, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81: 3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 2
  • C.I. I. Pigment Red 48 1,122,177,224,242,269,254,291,295,296, the pigment described in JP-A-2014-134712, the pigment described in Patent No. 6368844 is preferable, C. I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are more preferable.
  • An orange pigment is, for example, C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.
  • a yellow pigment is, for example, C.I. I. Pigment Yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 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,
  • a green pigment is, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 and the like. Among these, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 are preferred.
  • a blue pigment is, for example, C.I. I. 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 and the like.
  • C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.
  • a purple pigment is, for example, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
  • C.I. I. Pigment Violet 19, 23 are preferred.
  • a black pigment is, for example, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. At least two pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and violet pigments may be used as the black colorant.
  • Inorganic pigments which are a kind of pigment, include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, Cobalt green, amber, synthetic iron black and the like.
  • Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Moreover, these derivatives and lake pigments obtained by turning dyes into lakes can also be used as the dye (A).
  • Acid dyes preferably have acidic groups such as sulfonic acid and carboxylic acid groups. Further, it is preferable to use 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, as the dye (A).
  • a salt-forming compound which is a salt of a resin component having these functional groups and an acid dye, is also preferred.
  • the salt-forming compound is sulfonamidated to be modified into a sulfonic acid amide compound, thereby easily obtaining a photosensitive composition having excellent resistance (light resistance and solvent resistance).
  • a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent resistance (light resistance and solvent resistance).
  • the compound having an onium base is preferably a resin having a cationic group.
  • salt-forming compounds that form salts with organic acids, perchloric acid, and metal salts thereof are preferred.
  • Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance and solvent resistance) and affinity with pigments.
  • the anion component that works as a counterion is organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus anion compound, fluorine group-containing boron anion compound, cyano group-containing nitrogen anion compound, halogenated carbon
  • a salt-forming compound obtained by salt-forming an anion compound having a conjugate base of an organic acid having a hydrogen group and an acid dye is preferred. It should be noted that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.
  • Chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.).
  • dyes anthrapyridone dyes, etc.
  • carbonium dyes diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.
  • quinoneimine dyes oxazine dyes, thiazine dyes, etc.
  • azine dyes polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes
  • Dye structures derived from dyes selected from dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, metal complex dyes thereof, and the like.
  • azo dyes xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes
  • a dye structure derived from a dye selected from quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes.
  • a dye structure derived from the selected dye is more preferred.
  • a near-infrared absorbing dye is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm.
  • a near-infrared absorbing dye is a pigment (also referred to as a near-infrared absorbing pigment) or a dye (also referred to as a near-infrared absorbing dye).
  • a near-infrared absorbing pigment and a near-infrared absorbing dye may be used in combination.
  • the near-infrared absorbing pigment is preferably a near-infrared absorbing pigment.
  • the solubility of the near-infrared absorbing pigment is preferably less than 2 g, more preferably less than 1 g, still more preferably 0.5 g or less per 100 g of propylene glycol monomethyl ether acetate at 25°C.
  • Examples of near-infrared absorbing dyes include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds.
  • cyanine compounds cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds.
  • naphthalocyanine compounds, pyrrolopyrrole compounds and squarylium compounds are preferred, and naphthalocyanine compounds and squarylium compounds are more preferred.
  • Cyanine compounds WO 2006/006573, WO 2010/073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; JP-A-4-23868, JP-A-06-192584, JP-A-2000-63691, International Publication No. 2014/208514, etc.; JP, JP 2009-29955 A, International Publication No.
  • the squarylium compound is preferably a compound represented by the following general formula (SQ1).
  • R 1 to R 4 each independently represent a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR 10 , — COR 11 , —COOR 12 , —OCOR 13 , —NR 14 R 15 , —NHCOR 16 , —CONR 17 R 18 , —NHCONR 19 R 20 , —NHCOOR 21 , —SR 22 , —SO 2 R 23 , —SO 2 represents OR 24 , —NHSO 2 R 25 , —SO 2 NR 26 R 27 , —B(OR 28 ) 2 , or —NHBR 29 R 30 ; R 10 to R 30 each independently represent a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group,
  • R 12 of —COOR 12 is hydrogen (ie, carboxyl group)
  • the hydrogen atom may be dissociated (ie, carbonate group), or it may be in the form of a salt.
  • R 24 of —SO 2 OR 24 is a hydrogen atom (ie, sulfo group)
  • the hydrogen atom may be dissociated (ie, sulfonate group) or in a salt state.
  • R 1 and R 2 , R 3 and R 4 may combine with each other to form a ring.
  • a “substituent” includes, for example, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR 100 , —COR 101 , —COOR 102 , —OCOR 103 , —NR 104 R 105 , —NHCOR 106 , —CONR 107 R 108 , —NHCONR 109 R 110 , —NHCOOR 111 , —SR 112 , —SO 2 R 113 , —SO 2 OR 114 , —NHSO 2 R 115 or —SO 2 NR 116 R 117 .
  • R 100 to R 117 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group.
  • R 102 of —COOR 102 is hydrogen (ie, carboxyl group)
  • the hydrogen atom may be dissociated (ie, carbonate group) or may be in a salt state.
  • R 114 of —SO 2 OR 114 is a hydrogen atom (ie, sulfo group)
  • the hydrogen atom may be dissociated (ie, sulfonate group) or in a salt state.
  • Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
  • the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-12, even more preferably 1-8.
  • Alkyl groups may be linear, branched or cyclic.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms.
  • Alkenyl groups may be linear, branched or cyclic.
  • the alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms.
  • Alkynyl groups may be linear, branched or cyclic.
  • the number of carbon atoms in the aryl group is preferably 6-25, more preferably 6-15, even more preferably 6-10.
  • the alkyl portion of the aralkyl group is the same as the alkyl group described above.
  • the aryl portion of the aralkyl group is the same as the above aryl group.
  • the number of carbon atoms in the aralkyl group is preferably 7-40, more preferably 7-30, even more preferably 7-25.
  • the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1-3.
  • a heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.
  • a heteroaryl group is preferably a 5- or 6-membered ring.
  • the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3-30, more preferably 3-18, even more preferably 3-12.
  • Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, and aralkyl groups may have a substituent or may be unsubstituted. Examples of the substituent include the "substituent" described above.
  • the squarylium compound is more preferably a compound represented by the following general formula (SQ2).
  • R 5 to R 8 are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR 50 , — COR51 , -COOR52 , -OCOR53 , -NR54R55 , -NHCOR56 , -CONR57R58 , -NHCONR59R60 , -NHCOOR61 , -SR62 , -SO2R63 , -SO2 represents OR 64 , —NHSO 2 R 65 or —SO 2 NR 66 R 67 , —B(OR 68 ) 2 and —NHBR 69 R 70 ; R 50 to R 70 each independently represent a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group
  • R 52 of —COOR 52 is hydrogen (ie, carboxyl group)
  • the hydrogen atom may be dissociated (ie, carbonate group), or it may be in the form of a salt.
  • R 64 of —SO 2 OR 64 is a hydrogen atom (ie, sulfo group)
  • the hydrogen atom may be dissociated (ie, sulfonate group) or may be in a salt state.
  • R 5 and R 6 and R 7 and R 8 may combine with each other to form a ring.
  • the pyrrolopyrrole compound is preferably a compound represented by the following general formula (PP1).
  • R 1x and R 1y each independently represent an alkyl group, an aryl group or a heteroaryl group
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent
  • R 2 and R 3 may combine with each other to form a ring
  • R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group
  • R 4 is It may be covalently or coordinately bonded to at least one selected from the group consisting of R 1x , R 1y and R 3
  • R 4x R 4y each independently represents a substituent.
  • Examples of the compound represented by the general formula (PP1) include compounds described in JP-A-2009-263614, JP-A-2011-68731, and International Publication No. 2015/166873.
  • R 1x and R 1y are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group.
  • the alkyl group, aryl group and heteroaryl group represented by R 1x and R 1y may have a substituent or may be unsubstituted.
  • substituents include alkoxy groups, hydroxy groups, halogen atoms, cyano groups, nitro groups, —OCOR 11 , —SOR 12 , —SO 2 R 13 and the like.
  • R 11 to R 13 each independently represent a hydrocarbon group or a heteroaryl group.
  • substituents include substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614.
  • substituents are alkoxy groups, hydroxy groups, halogen atoms, cyano groups, nitro groups, -OCOR 11 , -SOR 12 and -SO 2 R 13 .
  • the group represented by R 1x and R 1y is preferably an alkoxy group having a branched alkyl group or an aryl group having a group represented by —OCOR 11 as a substituent.
  • the branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.
  • At least one of R 2 and R 3 is preferably an electron-withdrawing group, more preferably R 2 represents an electron-withdrawing group and R 3 represents a heteroaryl group.
  • a heteroaryl group is preferably a 5- or 6-membered ring.
  • the heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring with 2 to 8 condensed numbers, more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2.
  • Heteroatoms include, for example, nitrogen atoms, oxygen atoms, and sulfur atoms.
  • Heteroaryl groups preferably have one or more nitrogen atoms.
  • Two R 2 groups in general formula (PP1) may be the same or different.
  • Two R 3 groups in general formula (PP1) may be the same or different.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR 4x R 4y , and is represented by a hydrogen atom, an alkyl group, an aryl group, or -BR 4x R 4y is more preferred, and a group represented by —BR 4x R 4y is even more preferred.
  • the substituent represented by R 4x R 4y is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and still more preferably an aryl group. These groups may further have a substituent.
  • Two R 4 groups in general formula (PP1) may be the same or different.
  • pyrrolopyrrole compounds are shown below.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • the pyrrolopyrrole compound paragraphs 0016 to 0058 of JP-A-2009-263614, paragraphs 0037-0052 of JP-A-2011-68731, paragraphs 0014-0027 of JP-A-2014-130343, International Publication No. 2015/166873, paragraphs 0010-0033.
  • this embodiment is not limited to these.
  • naphthalocyanine compound ((naphthalocyanine compound))
  • the naphthalocyanine compound is preferably a compound represented by the following general formula (NPc1).
  • R 1 to R 24 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted C 6 to 20 aryl group, substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, —OR 25 or —SR 26 , wherein R 25 and R 26 each independently represent a hydrogen atom or a substituent; represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
  • Halogen atoms represented by R 1 to R 24 in general formula (NPc1) include, for example, fluorine, chlorine, bromine and iodine atoms.
  • the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in the general formula (NPc1) is not particularly limited as long as it is a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. .
  • the alkyl group may be branched or may form a ring.
  • alkyl groups having 1 to 20 carbon atoms represented by R 1 to R 24 in general formula (NPc1) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl, neo-pentyl, 1,2-dimethyl-propyl, n-hexyl, isohexyl, sec-hexyl group, n-heptyl group, iso-heptyl group, sec-heptyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 1-t-butyl-2-methylpropyl group, n -nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-do
  • the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in the general formula (NPc1) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and a linear or branched carbon Alkyl groups of numbers 1 to 8 are more preferred.
  • the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in general formula (NPc1) may have a substituent.
  • substituents which may be present include, but are not limited to, an alkoxy group, a halogen group, an amino group, a cyano group, a nitro group and the like.
  • the phrase "having a substituent" in an alkyl group having 1 to 20 carbon atoms having a substituent means that a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms has one or It means that two or more hydrogen atoms are substituted with substituents such as, for example, the alkoxy groups, halogen groups, amino groups, cyano groups, nitro groups, etc. described above, and the phrase “unsubstituted” It means that a hydrogen atom of a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is not substituted with a substituent such as an alkoxy group, a halogen group, an amino group, a cyano group or a nitro group.
  • the phrases "having a substituent" and “unsubstituted” are used with the same meaning as explained here.
  • the aryl group having 6 to 20 carbon atoms represented by R 1 to R 24 in the general formula (NPc1) is not particularly limited as long as it is a residue obtained by removing one hydrogen atom from an aromatic ring having 6 to 20 carbon atoms. not something.
  • Specific examples include phenyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, A benzhydryl group, a trityl group, a pyrenyl group and the like can be mentioned, and a phenyl group is particularly preferred.
  • the aryl group having 6 to 20 carbon atoms represented by R 1 to R 24 in general formula (NPc1) may have a substituent.
  • substituents which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in the general formula (NPc1) may have.
  • the heterocyclic group having 4 to 20 carbon atoms represented by R 1 to R 24 in the general formula (NPc1) is particularly a residue obtained by removing one hydrogen atom from a heterocyclic ring having 4 to 20 carbon atoms. It is not limited. Specific examples include pyridyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyrimidinyl, pyridazinyl, and pyrazinyl groups.
  • a triazinyl group an indolyl group, an isoindolyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinolyl group, an isoquinolyl group, a purinyl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group and a phenothiazinyl group. is particularly preferred.
  • the heterocyclic groups having 4 to 20 carbon atoms represented by R 1 to R 24 in general formula (NPc1) may have a substituent.
  • substituents which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in the general formula (NPc1) may have.
  • the alkyl group having 1 to 20 carbon atoms represented by R 25 and R 26 in general formula (NPc1) includes the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in general formula (NPc1). The same can be mentioned.
  • the alkyl group having 1 to 20 carbon atoms represented by R 25 and R 26 in general formula (NPc1) may have a substituent.
  • substituents which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in formula (NPc1) may have.
  • the aryl group having 6 to 20 carbon atoms represented by R 25 and R 26 in general formula (NPc1) includes an aryl group having 6 to 20 carbon atoms represented by R 1 to R 24 in general formula (NPc1). The same can be mentioned.
  • the aryl group having 6 to 20 carbon atoms represented by R 25 and R 26 in general formula (NPc1) may have a substituent. Examples of the substituent which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 24 in the general formula (NPc1) may have.
  • R 1 to R 24 in general formula (NPc1) are preferably each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. all of R 1 to R 24 are hydrogen atoms, or R 1 , R 2 to R 5 , R 7 , R 8 to R 11 , R 13 , R 14 to R 17 , R 19 and R 20 to R 23 is a hydrogen atom, and R 6 , R 12 , R 18 and R 24 are unsubstituted aryl groups having 6 to 20 carbon atoms, or R 2 to R 5 , R 6 , R 8 to R 11 , R 12 , R 14 to R 17 , R 18 , R 20 to R 23 and R 24 are hydrogen atoms, and R 1 , R 7 , R 13 and R 19 are unsubstituted aryl groups having 6 to 20 carbon atoms is more preferable.
  • R 1 to R 24 are hydrogen atoms, or R 1 , R 2 to R 5 , R 7 , R 8 to R 11 , R 13 , R 14 to R 17 , R 19 and R 20 to R 23 is a hydrogen atom and R 6 , R 12 , R 18 and R 24 are phenyl groups, or R 2 to R 5 , R 6 , R 8 to R 11 , R 12 , R 14 to R 17 , More preferably, R 18 , R 20 to R 23 and R 24 are hydrogen atoms, and R 1 , R 7 , R 13 and R 19 are phenyl groups.
  • M represents two hydrogen atoms, metal atoms, metal oxides or metal halides.
  • M represents two hydrogen atoms
  • a structure is formed in which the N—M—N portion in general formula (NPc1) is indicated as two N—H.
  • Metal atoms represented by M in the general formula (NPc1) include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium and tin.
  • metal oxides represented by M in the general formula (NPc1) include titania and vanadia.
  • Examples of the metal halide represented by M in the general formula (NPc1) include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride and silicon chloride.
  • M in the general formula (NPc1) is preferably copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride or tin (II) chloride, more preferably copper, zinc, vanadia or titania. Vanadia is preferred, and vanadia is particularly preferred.
  • the method for producing the compound represented by the general formula (NPc1) is not particularly limited, and conventionally known methods can be appropriately used.
  • a method of synthesizing a naphthalocyanine having a metal at the center from a corresponding naphthalenedicarboxylic acid or its derivative (acid anhydride, diamide, dinitrile, etc.) by direct cyclization in the presence of a metal compound is known (e.g. , Chemistry-A European Journal, Vol. 9, pp. 5123-5134 (published 2003)).
  • a catalyst for example, ammonium molybdate
  • it can be synthesized using a metal compound as described later.
  • the above cyclization reaction can be carried out without solvent, it is preferably carried out in an organic solvent.
  • the organic solvent that can be used in the cyclization reaction is not particularly limited as long as it has low reactivity with naphthalenedicarboxylic acid or a derivative thereof as a starting material, but an inert solvent that does not exhibit reactivity is preferred.
  • organic solvents such as inert solvents such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o-chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol and benzonitrile; methanol , ethanol, 1-propanol, 2-propanol, 1-butanol, 1-hexanol, 1-pentanol and 1-octanol; pyridine, N,N-dimethylformamide, N,N-dimethylacetamide , N-methyl-2-pyrrolidinone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethylsulfoxide and sulfolane.
  • inert solvents such as benzene, toluene, xylene, nitrobenzen
  • 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene, benzonitrile and sulfolane are preferred, and 1-octanol, dichlorobenzene, benzonitrile and sulfolane are more preferred.
  • One of these solvents may be used alone, or two or more thereof may be used in combination.
  • the amounts of the naphthalenedicarboxylic acid or derivative thereof and the metal compound used in the cyclization reaction are not particularly limited as long as the reaction proceeds.
  • the acid or its derivative is usually used in the range of 1 to 500 parts by mass, preferably 10 to 350 parts by mass, and the metal compound is usually 0.25 to 0.5 mol per 1 mol of the naphthalene dicarboxylic acid or its derivative. , preferably in the range of 0.25 to 0.4 mol.
  • the conditions for the cyclization reaction are also not particularly limited, but the reaction temperature is preferably in the range of 30 to 250°C, more preferably in the range of 80 to 200°C.
  • the reaction time is preferably 1 to 30 hours.
  • the cyclization reaction may be carried out in an air atmosphere, but is preferably carried out in an inert gas atmosphere (for example, under circulation of nitrogen gas, helium gas, argon gas, etc.).
  • the ratio of the raw materials used is 0.00 metal compound per 1 mol of the metal-free naphthalocyanine. It is preferably used in an amount of 1 to 10 mol, more preferably 0.5 to 5 mol, even more preferably 1 to 3 mol.
  • the metal compound inorganic and organic metal compounds can be used, and specific examples thereof include halides (e.g., chlorides, bromides), sulfates, acetates, metal acetylacetonates, etc., preferably They are halides and acetates, and more preferably halides.
  • the compound obtained by the above reaction may be subjected to crystallization, filtration, washing, drying, etc. according to conventionally known methods. By such operation, the naphthalocyanine compound represented by the general formula (NPc1) can be efficiently obtained with high purity.
  • the naphthalocyanine compounds represented by general formula (NPc1) can be used singly or in combination.
  • the naphthalocyanine compound represented by the general formula (NPc1) preferably has a maximum absorption wavelength in the wavelength range of 750 to 1500 nm, and more preferably has a maximum absorption wavelength in the wavelength range of 780 to 1000 nm.
  • naphthalocyanine compound is preferably a compound represented by the following general formula (NPc2).
  • R 1 to R 24 each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, or a substituent.
  • optionally substituted aryl group, optionally substituted cycloalkyl group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl represents a group.
  • Z is a polymer moiety containing a monomer unit represented by general formula (NPc3) or a phosphorus compound moiety represented by general formula (NPc4).
  • X represents -CONH-R 25 -, -COO-R 26 -, -CONH-R 27 -O-, or -COO-R 28 -O-
  • R 25 to R 28 represents an alkylene group or an arylene group optionally linked by -O-, -CO-, -COO-, -OCO-, -CONH- or -NHCO- between carbon atoms.
  • R31 represents a hydrogen atom or a methyl group.
  • n is 0 or an integer from 1 to 10; * is a bond with Al in the general formula (NPc2).
  • R 29 and R 30 each independently represent a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted It represents an alkoxyl group or an optionally substituted aryloxy group, and R 29 and R 30 may combine with each other to form a ring.
  • * is a bond with Al in the general formula (NPc2).
  • the near-infrared absorbing dyes can be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to use at least two types of compounds having different maximum absorption wavelengths. As a result, compared with the case of using one type of near-infrared absorbing dye, the waveform of the absorption spectrum is broadened, and near-infrared rays in a wide wavelength range can be absorbed.
  • the dye (A) can be used alone or in combination of two or more.
  • the content of the dye (A) is preferably 0.5 to 80% by mass, more preferably 1 to 55% by mass, based on 100 parts by mass of the nonvolatile matter of the photosensitive composition.
  • the method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, dissolution precipitation, and the like can be used. Among these, the salt milling treatment by the kneader method, which is one 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 and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.
  • the salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill.
  • a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill.
  • This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent.
  • the water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling.
  • Water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate, etc., and sodium chloride (salt) is preferable from the point of view of price.
  • the amount of the water-soluble inorganic salt to be used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, in terms of both processing efficiency and production efficiency.
  • the water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used.
  • a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety.
  • the amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.
  • a resin may be added to the salt milling process as needed.
  • the type of the resin is not particularly limited, and includes natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. Among these, it is preferable that they are solid at room temperature, insoluble in water, and partially soluble in the above organic solvents.
  • the amount of the resin to be added is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.
  • the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive composition is 500 mass ppm or less with respect to the total amount of the photosensitive composition. is preferably
  • the total content of the specific metal elements contained in the photosensitive composition is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, relative to the total amount of the photosensitive composition.
  • the lower limit of the total content of the specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more. If it is within the above range, it is possible to obtain a photosensitive composition capable of suppressing costs, excellent in storage stability, and capable of forming a color filter that suppresses the generation of foreign substances and the decrease in brightness.
  • the content of each specific metal element contained in the photosensitive composition is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, relative to the total amount of the photosensitive composition.
  • the metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that constitute the pigment also have few impurities that do not function effectively, and can be removed in the same manner as the specific metal elements by the following method. I can. Further, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc. mixed with materials (for example, catalysts) used in the production process of various raw materials of the photosensitive composition are also low.
  • the content of specific metal elements can be measured by inductively coupled plasma atomic emission spectrometry (ICP).
  • ICP inductively coupled plasma atomic emission spectrometry
  • a dye derivative can be used in the photosensitive composition, if desired.
  • a dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue.
  • Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups.
  • Organic dyes include, for example, diketopyrrolopyrrole pigments; anthraquinone pigments; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; isoindole-based pigments; isoindolinone-based pigments; quinophthalone-based pigments; naphthol-based pigments; threne-based pigments; metal complex-based pigments; .
  • diketopyrrolopyrrole-based dye derivatives JP 2001-220520, WO 2009/081930, WO 2011/052617, WO 2012/102399, JP JP 2017-156397, the phthalocyanine dye derivative, JP 2007-226161, WO 2016/163351 pamphlet, JP 2017-165820, Japanese Patent No.
  • These dye derivatives can be used alone or in combination of two or more.
  • the amount of the dye derivative used is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and further preferably 5 to 50 parts by mass with respect to 100 parts by mass of the dye (A). preferable.
  • the dye derivative By adding a dye derivative to the dye (A) and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., the dye derivative is adsorbed on the surface of the pigment, and the dye derivative is added.
  • the primary particles of the pigment can be made finer than when they are not used.
  • the dye derivative By adding a dye derivative to the dye (A) and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the dye derivative adsorbs to the pigment surface and the pigment surface becomes polar. Promotes adsorption of the dispersant, improves compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives, and disperses stability and viscosity over time when used as a colored composition or colored curable composition Improves stability.
  • the coating film has excellent stability over time when the colored curable composition is applied to a glass substrate, etc., and the waiting time from application of the colored curable composition to exposure (PCD: Post Coating delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay).
  • PCD Post Coating delay
  • PED Post Exposure Delay
  • the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress the precipitation of crystals due to aggregation and sublimation of the pigment when the coating film is heated and baked. Furthermore, development time variations and development residues are suppressed.
  • the photosensitive composition of this embodiment contains a resin-type dispersant (Z).
  • the resin-type dispersant (Z) is preferably used for dispersing the pigment (A).
  • the resin-type dispersant (Z) has a dye (A) affinity site that has the property of adsorbing to the dye (A) and a relaxation site that has an affinity with components other than the dye (A).
  • the resin-type dispersant (Z) is, for example, a urethane-based dispersant such as polyurethane, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, or a polycarboxylic acid ammonium salt.
  • polycarboxylic acid alkylamine salts polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, or modified products thereof, poly (lower alkyleneimine) and a polyester having a free carboxyl group Formed amides or oily dispersants such as salts thereof, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols water-soluble resins or water-soluble high-molecular weight compounds such as poly(vinylpyrrolidone), polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters, and the like. These can be used alone or in combination of two or more.
  • the resin type dispersant (Z) is preferably a graft resin (also called a comb resin) or a block copolymer.
  • grafted resin refers to a resin having, as a side chain, a polymer different from the main chain on a molecular chain that serves as the main chain. . . . is a polymer having BB).
  • block copolymer refers to a copolymer composed of a linear polymer having a plurality of different homopolymers as partial constituents (blocks), for example, (AA...AA)-(BB...BB )-(AA...AA).
  • the main chain may be made of a polymer or the like, and preferably made of polyester, for example.
  • the resin-type dispersant (Z) is not a random copolymer but a graft resin or a block copolymer, so that it can exhibit its function as a resin-type dispersant (Z) more effectively. That is, in both the graft resin and the block copolymer, since the affinity site and the relaxation site are present as a group, it is assumed that the dispersing function is likely to be exhibited.
  • the resin-type dispersant (Z) includes an acidic resin-type dispersant (ZA) and a basic resin-type dispersant (ZB) depending on the difference in polar groups.
  • Acidic resin-type dispersant examples include resin-type dispersants having an aromatic carboxylic acid structure.
  • Acidic resin-type dispersants (ZA) are WO 2008/007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, It can be produced by known methods such as JP-A-2009-251481, JP-A-2007-23195, and JP-A-8-143651.
  • the acidic resin dispersant (ZA) includes, for example, a photocrosslinkable acidic resin dispersant having a photocrosslinkable group (ZAUV-1) and a non-photocrosslinkable acidic resin dispersant having no photocrosslinkable group (ZA -2).
  • the photocrosslinkable acidic resin type dispersant (ZAUV-1) includes, for example, a dispersant having a vinyl polymer moiety having an aromatic carboxylic acid structure in the main chain and a (meth)acryloyl group in the side chain.
  • the photocrosslinkable acidic resin-type dispersant is, for example, (1) an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, and separately (2) reacting the acid anhydride group in the acid anhydride with a hydroxyl group-containing thiol, and starting from the thiol group of the thiol; Examples include a method of polymerizing a monomer to form a vinyl polymer moiety.
  • the photocrosslinkable acidic resin-type dispersant (ZAUV-1) is, in other words, a dispersant composed of a polyester portion having a carboxyl group and a vinyl polymer portion obtained by polymerizing a monomer, wherein the vinyl polymer portion includes (meth)acryloyl It is a dispersant having a group.
  • Photocrosslinkable acidic resin-type dispersants (ZAUV-1) include, for example, comb-type dispersants described in JP-A-2011-157416. As another method, a comb-type dispersant described in Japanese Patent No. 6782309 can also be used.
  • Tetracarboxylic dianhydrides are, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6 -tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, aliphatic tetracarboxylic dianhydride such as bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxy
  • Tricarboxylic anhydrides include, for example, benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic acid Anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride etc.), 3,4,4′-benzophenonetricarboxylic anhydride, 3,4,4′-biphenylethertricarboxylic anhydride, 3,4,4′-biphenyltricarboxylic anhydride, 2,3,2′- biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride,
  • the (meth)acryloyl group-containing vinyl polymer moiety can be synthesized by reacting the hydroxyl group of the vinyl polymer moiety with the isocyanate group in the isocyanate group-containing monomer. As a result, photocurability can be imparted to the vinyl polymer portion, which is the relaxation portion.
  • isocyanate group-containing monomers examples include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate and the like.
  • the hydroxyl group-containing thiol is preferably a compound having two hydroxyl groups and one thiol group.
  • hydroxyl group-containing thiols include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2- mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.
  • the monomer used for synthesizing the vinyl polymer moiety includes, for example, at least one thermally crosslinkable functional group selected from the group consisting of hydroxyl group, oxetane group, t-butyl group and blocked isocyanato group, carboxyl group-containing monomer, mers and other monomers.
  • Hydroxyl-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono hydroxyalkyl (meth)acrylates such as (meth)acrylates and alkyl- ⁇ -hydroxyalkyl acrylates such as ethyl- ⁇ -hydroxymethyl acrylate;
  • (Meth)acrylamide-based monomers having a hydroxyl group include, for example, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl) ( N-(hydroxyalkyl)(meth)acrylamides such as meth)acrylamide; Vinyl ether monomers having a hydroxyl group, such as hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxy
  • Oxetane group-containing monomers include, for example, (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, [(meth)acryloyloxyalkyl]alkyloxetane, (3-ethyloxetane-3-yl)methyl methacrylate etc. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred.
  • Examples of monomers having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.
  • Block isocyanato group-containing monomers include, for example, 2-(O-[1′-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and the like. is mentioned.
  • the amount of the thermally crosslinkable functional group-containing monomer used is preferably 1 to 90 parts by mass, more preferably 5 to 60 parts by mass, based on the total amount of monomers. When used in an appropriate amount, the solvent resistance of the film is further improved.
  • carboxyl group-containing monomers examples include (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid. Among these, (meth)acrylic acid is preferred.
  • Other monomers include (meth)acrylic acid esters, nitrogen-containing group monomers, and vinyl monomers.
  • (Meth) acrylic acid esters for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate and other (meth)acrylic acid alkyl esters; cyclohexyl (meth)acrylate, tertiarybutylcyclohexyl (meth)acrylate, Alicyclic (meth)acrylates such as dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and
  • Nitrogen-containing group monomers include, for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, N-substituted (meth)acrylamides such as acryloylmorpholine; amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; meth)acrylonitrile, etc. Nitriles of.
  • Vinyl monomers include, for example, styrenes such as styrene and ⁇ -methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; vinyl acetate, vinyl propionate and the like. Examples include fatty acid vinyls.
  • the non-photocrosslinkable acidic resin-type dispersant (ZA-2) is preferably a dispersant having an aromatic carboxylic acid structure in the main chain and a vinyl polymer moiety having no (meth)acryloyl group in the side chain.
  • the resin-type dispersant (ZA-2) preferably has a structure obtained by removing (meth)acryloyl groups from the structure of the resin-type dispersant (ZAUV-1).
  • Resin-type dispersants (ZA-2) include, for example, comb-type dispersants described in Japanese Patent No. 4396777 and Japanese Patent No. 5181664.
  • the blending amount is preferably 20 parts by mass or more in 100 parts by mass of the resin-type dispersant (Z) from the viewpoint of developability.
  • the blending amount is preferably 40 parts by mass or more in 100 parts by mass of the acidic resin-type dispersant (ZA) from the viewpoint of solvent resistance.
  • the basic resin type dispersant (ZB) is, for example, a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic resin having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain. system block copolymers and urethane polymer dispersants.
  • a resin-type dispersant having an aromatic carboxyl group and a vinyl-based resin having a tertiary amino group are combined. Combination use is also mentioned as a preferable example.
  • the amine value (mgKOH/g) of the resin type dispersant (Z) is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, from the viewpoint of developability and pigment dispersibility.
  • “Amine value” is the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize the basic nitrogen contained in 1 g of solid dispersant, and is determined by potentiometric titration according to ASTM D 2074. can be done.
  • the resin-type dispersant (Z) can be used in combination with dispersants other than those described above.
  • Other dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, or modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups or oily dispersants such as salts thereof, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid
  • the resin-type dispersant (Z) can be used alone or in combination of two or more.
  • the amount of the resin-type dispersant (Z) used is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, relative to 100 parts by mass of the dye (A). When used in an appropriate amount, the film formability is further improved.
  • the content of the resin-type dispersant (Z) is preferably 2 to 33% by mass based on 100 parts by mass of the non-volatile content of the photosensitive composition.
  • the polystyrene-equivalent weight-average molecular weight of the resin-type dispersant (Z) is 4,000 or more and less than 100,000 from the viewpoint of dispersion stability, development stains, solvent resistance, and development speed, although the molecular weight is not limited as long as the problem can be solved. is preferred, and 5,000 to 30,000 is more preferred.
  • the binder resin (B) contains an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group, and as an optional component, an alkali-soluble binder resin (B1) having no structural unit having a blocked isocyanato group. can contain.
  • the alkali-soluble binder resin (Bb) is preferably a random copolymer.
  • the molecular structure of a random copolymer is generally chain-like.
  • random copolymer refers to a copolymer in which two or more constitutional units are randomly arranged.
  • Block polymers and comb-shaped polymers have functional sites such as dye adsorption sites and steric repulsion sites, so molecules tend to aggregate due to the action of intermolecular forces between functional sites.
  • functional sites such as dye adsorption sites and steric repulsion sites
  • random polymers two or more constitutional units are randomly arranged, so it is speculated that the action of intermolecular forces is weak and the molecules tend to spread indefinitely.
  • the random polymer exists diffusely throughout the photosensitive composition. Therefore, the photosensitive composition of the present embodiment can form a film having a smooth surface and high cohesion. This contributes to the improvement of substrate adhesion, pattern shape, and solvent resistance after the low-temperature baking step.
  • the photosensitive composition of the present embodiment includes, as the binder resin (B), an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group, thereby forming a film using the photosensitive composition. is cured by treatment such as exposure, a cured film having good developability, substrate adhesion, pattern shape, and solvent resistance after low-temperature baking can be obtained.
  • a structural unit (Bb-1) having a blocked isocyanato group is a structural unit derived from a monomer containing a blocked isocyanato group.
  • the blocked isocyanato group-containing monomer is a compound obtained by blocking the isocyanato groups in the isocyanato group-containing monomer with a blocking agent.
  • the reaction between the isocyanate compound and the blocking agent can be carried out with or without the presence of a solvent. When using a solvent, it is necessary to use a solvent that is inert to the blocked isocyanato groups.
  • an organic metal salt such as tin, zinc or lead, or a tertiary amine may be used as a catalyst.
  • the reaction can generally be carried out at -20 to 150°C, preferably at 0 to 100°C.
  • Examples of blocked isocyanato group-containing monomers include compounds represented by the following formula (8).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents -CO-, -COOR 3 - (wherein R 3 is an alkylene group having 1 to 6 carbon atoms) or —COO—R 4 O—CONH—R 5 — (wherein R 4 is an alkylene group having 2 to 6 carbon atoms, and R 5 is an alkylene group having 2 to 12 carbon atoms which may have a substituent or an arylene group having 6 to 12 carbon atoms).
  • R 2 is preferably -COOR 3 -, where R 3 is preferably an alkylene group having 1 to 4 carbon atoms.
  • Compounds represented by the above formula (8) include, for example, 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 2-isocyanato-1- Methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, (meth)acryloyl isocyanate and the like.
  • An equimolar (1 mol:1 mol) reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used.
  • the alkyl group of the 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, more preferably an ethyl group.
  • the diisocyanate compounds include, for example, hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3- isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, lysine diisocyanate and the like.
  • the blocking agents include, for example, lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, alcohols such as benzyl alcohol, phenylcellosolve, furfuryl alcohol and cyclohexanol; Phenols such as p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; malon active methylene-based compounds such as dimethyl acid, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and
  • the blocking agent protects the highly reactive isocyanato groups, but heating dissociates the blocked isocyanato groups and regenerates the isocyanato groups.
  • the isocyanato group is a reactive functional group contained in the resin type dispersant (Z), the binder resin (B), and the polymerizable compound (C), that is, an acid group or a hydroxy group optionally contained , and amino groups to form a cured film with a high cross-linking density.
  • the dissociation rate of the blocked isocyanato group when the blocked isocyanato group-containing (meth)acrylate is heat-treated at 100° C. for 30 minutes is preferably 5 to 99% by mass, more preferably 8 to 97% by mass, and 10 to 95% by mass. % is more preferred.
  • the dissociation rate of the blocked isocyanato group of the blocked isocyanato group-containing (meth)acrylate was obtained by preparing an n-octanol solution having a concentration of 20% by mass of the blocked isocyanato group-containing (meth)acrylate, and adding 1 After adding dibutyltin laurate equivalent to 3% by mass and phenothiazine (polymerization inhibitor) equivalent to 3% by mass, heating at 100° C. for 30 minutes, mass reduction rate of the blocked isocyanato group-containing (meth)acrylate was analyzed by HPLC.
  • Blocking agents for blocked isocyanato group-containing (meth)acrylates having such a dissociation rate include ⁇ -butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methylethylketoxime, 3,5 - dimethylpyrazole and diethyl malonate.
  • these blocking agents diethyl malonate, 3,5-dimethylpyrazole and methyl ethyl ketoxime are more preferable from the viewpoint of low-temperature curability.
  • the dissociation temperature of the blocked isocyanato group is preferably 80°C or higher.
  • a blocked isocyanato group-containing (meth)acrylate having a dissociation temperature of 80° C. or higher is used, the stability of the copolymer during synthesis can be sufficiently ensured, and unintended cross-linking reaction can be prevented during the modification reaction described later. can be reduced.
  • the dissociation temperature of the blocked isocyanato group is 160° C. or less, the baking temperature can be sufficiently lowered and the solvent resistance of the cured coating film can be sufficiently secured.
  • the dissociation temperature of the blocked isocyanato group is preferably 80°C to 160°C, more preferably 80°C to 120°C, and particularly preferably 80°C to 100°C.
  • the dissociation temperature of the blocked isocyanato group was determined by preparing an n-octanol solution with a concentration of 20% by mass of the blocked isocyanato group-containing (meth)acrylate, adding 1% by mass of dibutyltin laurate and 3 After adding phenothiazine (polymerization inhibitor) corresponding to % by mass, the mixture was heated at a predetermined temperature, and after 30 minutes the mass reduction rate of the blocked isocyanato group-containing (meth)acrylate was measured by HPLC analysis. The temperature at which the rate of decrease is 80% by mass or more is defined as the dissociation temperature of the blocked isocyanato group.
  • Examples of the blocked isocyanato group-containing (meth)acrylate include Karenz (registered trademark) MOI-DEM (reaction product of methacryloyloxyethyl isocyanate and diethyl malonate) represented by the following formula (21), Showa Denko K.K.
  • the ratio of the structural unit (Bb-1) having a blocked isocyanato group contained in the binder resin (B) is not particularly limited, but is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, most preferably is 3 to 25 mol %.
  • the ratio of the structural unit (Bb-1) having a blocked isocyanato group is 1 to 40 mol%, the solvent resistance of the cured coating film is improved and the storage stability of the binder resin (B) is maintained.
  • the polystyrene-equivalent weight-average molecular weight of the alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group is preferably 5,000 or more and less than 80,000 from the viewpoint of development speed, solvent resistance, and development speed. ,000 or more and less than 50,000 is more preferable.
  • the acid value of the alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group is preferably 20-200 mgKOH/g, more preferably 40-150 mgKOH/g, from the viewpoint of developability.
  • the "acid value” is the number of mg of potassium hydroxide required to neutralize 1 g of resin solid content, and can be obtained by potentiometric titration according to JIS K 0070.
  • the alkali-soluble binder resin (B1) may be any resin that dissolves in an alkali developer, and known resins can be used.
  • the alkali-soluble binder resin (B1) preferably has a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm.
  • the alkali-soluble binder resin (B1) include thermoplastic resins, active energy ray-curable resins having ethylenically unsaturated double bonds, and the like.
  • the alkali-soluble binder resin (B1) can have thermosetting properties.
  • the thermosetting group includes an epoxy group and an ocetanyl group.
  • thermoplastic resins include resins having acidic groups such as carboxyl groups, sulfone groups, and phosphoric acid groups.
  • resins include acrylic resins having acidic groups, ⁇ -olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/ (anhydrous) maleic acid copolymer and the like.
  • At least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly alkali-soluble resins having acidic groups and/or hydroxyl groups, has good developability, solvent resistance, and transparency. is high, it is preferably used.
  • Methods for adding ethylenically unsaturated double bonds to the alkali-soluble binder resin (B1) include, for example, the following methods (i) to (iii).
  • Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidiether, 3,4-epoxybutyl (meth)acrylate, 3-methyl- 3,4-epoxybutyl (meth)acrylate, 3-ethyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxy Hexyl (meth)acrylate, ⁇ -ethyl acrylate glycidyl, allyl glycidyl ether, crotonyl glycidyl ale, (iso)crotonate glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, N-(3,5) -dimethyl-4-glycidyl)benz
  • glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether represented by the following general formula (9) are preferable, and the concentration of ethylenically unsaturated groups can be increased.
  • Glycidyl (meth)acrylate is more preferable in that it can easily cure with UV rays in a coating film formed from the photosensitive composition.
  • R6 is a hydrogen atom or a methyl group, l is an integer of 0 or 1;
  • Carboxyl group-containing monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among these, acrylic acid and methacrylic acid are preferred.
  • the site obtained by adding the carboxyl group of the carboxyl group-containing monomer to the epoxy group of the epoxy group-containing monomer is synthesized, and the site obtained by reacting the polybasic acid anhydride is derived from the polybasic acid anhydride. It is called a structural unit (b1-2). From the viewpoint of developability, the structural unit (b1-2) is preferable as the structural unit (b1-1) derived from the epoxy group-containing monomer.
  • polybasic acid anhydrides examples include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.
  • Hydroxyl group-containing monomers for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth)
  • Examples include acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate.
  • isocyanate group-containing monomers examples include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.
  • the epoxy group-containing monomer may be used as a copolymerization component in the step of forming the binder resin (B), or may be introduced into the binder resin by addition reaction with the carboxyl groups of the binder resin.
  • a hydroxyl group produced by an addition reaction with an epoxy group or a carboxyl group contributes to the dispersion stability of the pigment and enhances the solvent shock resistance.
  • the alkali-soluble binder resin (B1) may contain a structural unit (b2) having an aromatic ring group.
  • the structural unit (b2) having an aromatic ring group has a cyclic structure with an aromatic ring group represented by general formula (10) or general formula (11), and a pigment and a dye, or a pigment and a dye and a dispersant, etc. It functions as an affinity site for the pigment composition consisting of.
  • the content of the structural unit (b2) having an aromatic ring group is preferably 2 to 80 mol% of the total structural units of the binder resin (B). This improves developability and further suppresses solvent shock.
  • R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring.
  • the dashed line in general formula (11) indicates a cyclic structure containing one or more saturated or unsaturated heterocyclic rings which may have a substituent, adjacent to the benzene ring.
  • Monomers constituting the structural unit (b2) having an aromatic ring group include styrene, ⁇ -methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, and bisphenol A diglycidyl ether di(meth)acrylate. , monomers and oligomers such as (meth)acrylic acid esters of methylolated melamine, and monomers represented by the general formula (12).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkylene group having 2 or 3 carbon atoms
  • R 3 is the number of carbon atoms which may have a benzene ring. It is an alkyl group of 1-20 and n is an integer of 1-15.
  • Aronix M-101A [phenol EO-modified (n ⁇ 2) acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : hydrogen atom, n ⁇ 2], M-102 [phenol EO-modified (n ⁇ 4) acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : hydrogen atom, n ⁇ 4], M-110 [paracumylphenol EO-modified (n ⁇ 1) acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : paracumyl, n ⁇ 1], M-111 [n-nonylphenol EO-modified (n ⁇ 1) acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : n -nonyl group, n ⁇ 1], M-113 [n-nonylphenol EO-modified (n ⁇ 4) acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3
  • the number of carbon atoms in the alkyl group of R 3 is preferably 1-20, more preferably 1-10.
  • Alkyl groups include not only linear alkyl groups, but also branched alkyl groups and alkyl groups having a benzene ring as a substituent.
  • the alkyl group becomes an obstacle and suppresses the approach of the resins to promote adsorption/orientation to the pigment. The steric hindrance effect increases, and it tends to hinder even the adsorption/orientation of the benzene ring to the pigment.
  • n is preferably an integer of 1-15. If n exceeds 15, the hydrophilicity increases and the solvation effect decreases, the viscosity of the vinyl resin increases, and the viscosity of the coloring composition using this increases, which may affect fluidity. There is From the viewpoint of solvation, n is more preferably 1-4.
  • the precursor of the structural unit (b2) having an aromatic ring group is styrene, ⁇ -methylstyrene, benzyl acrylate, benzyl methacrylate, or A monomer represented by the general formula (12) is preferred.
  • the side chain benzene ring is oriented to the pigment, which promotes resin adsorption to the pigment and also functions to suppress aggregation of the pigment.
  • benzyl acrylate and/or benzyl methacrylate are preferred from the viewpoint of developability, dispersion stability, and solvent shock.
  • the content of the structural unit (b2) having an aromatic ring group is preferably 2 to 80 mol%, based on the total monomer units of the alkali-soluble binder resin (B1), from the viewpoint of solvent shock resistance and developability. 60 mol % is more preferred, and 2 to 40 mol % is even more preferred. When contained in an appropriate amount, development resistance and substrate adhesion are further improved.
  • the alkali-soluble binder resin (B1) may contain a structural unit (b3) having an aliphatic ring group.
  • the structural unit (b3) having an alicyclic group has a cyclic structure with an alicyclic group represented by the following formulas (b31) and (b32). They are not compatible as affinity sites for dispersants of pigments and dyes and to alkaline developers.
  • the content of the structural unit (b3) having an alicyclic group is preferably 2 to 80 mol% of the total monomer units of the binder resin (B1). This improves developability and further suppresses solvent shock.
  • the dicyclopentane moiety in the structure of the structural unit (b3) having an aliphatic ring group does not have a planar ring structure, and sterically hinders the aggregation of molecules in the filter segment. You can expect to give
  • Examples of the precursor of the structural unit (b3) having an aliphatic ring group include monomers represented by general formula (b33), monomers represented by general formula (b34), and the like.
  • R 4 is a hydrogen atom or a methyl group
  • R 5 is an alkylene group having 2 or 3 carbon atoms
  • m is an integer of 0 to 2.
  • the content of the structural unit (b3) having an aliphatic ring group is preferably 2 to 80 mol%, more preferably 2 to 60 mol%, more preferably 2 to 80 mol% of the total monomer units of the alkali-soluble binder resin (B1). 40 mol % is more preferred. When contained in an appropriate amount, developability, development resistance, and substrate adhesion are improved, and solvent shock can be further suppressed.
  • the carboxyl group-containing structural unit (b4) has a carboxyl group and functions as an alkali-soluble site during development.
  • the carboxyl group-containing structural unit (b4) preferably accounts for 2 to 60 mol% of all monomer units in the alkali-soluble binder resin (B1). Developability, development resistance, and substrate adhesion can be improved when contained in an appropriate amount.
  • the precursor of the carboxyl group-containing structural unit (b4) is an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, or ⁇ -chloroacrylic acid, or an unsaturated dicarboxylic acid such as maleic acid or fumaric acid.
  • carboxyl group-containing monomers Compounds obtained by half-esterification of unsaturated dicarboxylic acid anhydrides such as maleic anhydride with hydroxyl group-containing (meth)acrylic compounds such as hydroxyalkyl (meth)acrylates are also included. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of polymerizability (ease of control of molecular weight and the like).
  • the alkali-soluble binder resin (B1) can contain a structural unit (b5) other than the structural units (b1) to (b4). However, the structural unit (Bb-1) having a blocked isocyanato group is excluded.
  • Other monomers forming the structural unit (b5) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate ) acrylates, phenoxydiethylene glycol (meth)acrylates, methoxypolypropylene glycol (meth)acrylates, ethoxypolyethylene glycol (meth)acrylates and other (meth)acrylates; 2-hydroxyethyl (meth) acrylate, 2-
  • the raw materials for synthesizing the alkali-soluble binder resin (B1) can be used alone or in combination of two or more.
  • the content of the alkali-soluble binder resin (B1) is preferably 5 to 95 parts by mass or less, and 10 to 90 parts by mass or less in 100 parts by mass of the alkali-soluble binder resin (B) from the viewpoint of developability and substrate adhesion. is more preferred.
  • the alkali-soluble binder resin (B1) can be used alone or in combination of two or more.
  • the polystyrene equivalent weight average molecular weight of the alkali-soluble binder resin (B1) is preferably 5,000 or more and less than 80,000, more preferably 6,000 or more and less than 17,000, from the viewpoint of development stains, solvent resistance, and development speed. .
  • the glass transition temperature (hereinafter also referred to as Tg) of the alkali-soluble binder resin (B1) is preferably ⁇ 50 to 150° C., more preferably ⁇ 10 to 150° C., from the viewpoint of development stains, solvent resistance, and development speed. -10 to 80°C is more preferable.
  • a measured Tg obtained by actual measurement can be applied to the glass transition temperature.
  • the measured Tg can use a value measured by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the resin to be calculated is assumed to be a copolymer of n kinds of monomer components from W 1 to W n , W n is the weight fraction of the n-th monomer, Tg n is n is the glass transition temperature (absolute temperature) of the homopolymer of the first monomer.
  • the value of the glass transition temperature of a homopolymer (hereinafter also referred to as a homopolymer) of each monomer is described in Brandrup, J.; Immergut, E.; H. The values given in the ed. "Polymer Handbook, Third edition, John wiley & sons, 1989" are used.
  • the alkali-soluble binder resin (B1) preferably has a (meth)acryloyl group from the viewpoint of developability and substrate adhesion.
  • the (meth)acryloyl group is preferably a structural unit (b1-1) derived from an epoxy group-containing monomer. 2 to 90 mol% of the structural unit (b1-1) derived from an epoxy group-containing monomer, 2 to 80 mol% of the aromatic ring-containing structural unit (b2) in all structural units, an aliphatic ring It is preferable to contain the contained structural unit (b3) in an amount of 2 to 80 mol % of all structural units.
  • the structural unit derived from the epoxy group-containing monomer is a structural unit obtained by reacting an epoxy group in the epoxy group-containing monomer with a carboxyl group.
  • the acid value of the alkali-soluble binder resin (B1) is preferably 20-200 mgKOH/g, more preferably 40-150 mgKOH/g, from the viewpoint of developability.
  • the photosensitive composition of the present embodiment can contain, as the binder resin (B), an alkali-soluble binder resin (B2) other than the alkali-soluble binder resin (B1) within a range that does not impair the effects of the present embodiment.
  • the content of the binder resin (B) is preferably 1 to 80% by mass based on 100 parts by mass of non-volatile matter in the photosensitive composition.
  • the mass ratio of the resin (X) having a blocked isocyanato group to the resin (Y) not having a blocked isocyanato group is the resin (X) having a blocked isocyanato group/the resin (Y) not having a blocked isocyanato group. From the viewpoint of development stains, it is preferably 0.04 to 0.95, more preferably 0.07 to 0.90, and particularly preferably 0.12 to 0.85.
  • the binder resin (B) can be used alone or in combination of two or more.
  • the photosensitive composition of this embodiment contains a polymerizable compound (C).
  • the polymerizable compound (C) mainly contributes to improving the pattern shape and the solvent resistance after the low-temperature baking step.
  • the polymerizable compound (C) is a monomer or oligomer having a polymerizable unsaturated group and having a molecular weight of 2,000 or less. In addition, the molecular weight is usually 100 or more.
  • Examples of polymerizable unsaturated groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups. Among these, a (meth)acryloyl group is preferable from the viewpoint of improving chemical resistance.
  • the polymerizable compound (C) is preferably a polymerizable compound having 2 to 5 polymerizable unsaturated groups, more preferably a compound having 2 to 4 polymerizable unsaturated groups, and 2 to 3 polymerizable unsaturated groups. Further preferred are compounds having This further improves the chemical resistance. When a polymerizable compound having 6 or more polymerizable unsaturated groups is used, sufficient chemical resistance may not be obtained after heating at 180° C. or less. Therefore, it is preferable to use a polymerizable compound containing 6 or more polymerizable unsaturated groups as long as the effects of the present embodiment are not impaired.
  • a polymerizable compound having one polymerizable unsaturated group can be used for the purpose of introducing a functional group or the like to the terminal of the polymerizable component in the photopolymerization reaction in the exposure step.
  • Developability and chemical resistance can be improved by appropriately using a polymerizable compound having one polymerizable unsaturated group containing an acid group, a hydroxyl group, or a steric hindrance group.
  • the polymerizable compound (C) is, for example, styrene, vinyl acetate, (meth)acrylamide, N-vinylformamide, acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate.
  • phenoxydiethylene glycol acrylate polyethylene glycol di(meth)acrylate, 2-ethylhexyl (meth)acrylate, ethoxylated-O-phenylphenol acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol diacrylate, tricyclodecanedimethanol Diacrylate, tricyclodecanyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, ethoxylated bisphenol A diacrylate, ethoxylated glycerin triacrylate, tris-(2-acryloxyethyl) isocyanurate, 1,6- Hexanediol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, various (meth)acrylic acid esters such as urethane acrylate, triethylene glycol di(meth)acrylate,
  • trimethylolpropane triacrylate, trimethylolpropane PO-modified triacrylate, and trimethylolpropane EO-modified triacrylate have poor solvent resistance and do not solve the problem, so (meth)acrylate is introduced into trimethylolpropane. It is preferable not to use, as the polymerizable compound (C), a polymerizable compound obtained by introducing an alkylene oxide group into a (meth)acrylate of trimethylolpropane.
  • the polymerizable compound (C) preferably has an alkali-soluble group.
  • Alkali-soluble groups include hydroxyl group, phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkyl carbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, tris(alkylsulfonyl) A methylene group, an alkylene oxide group, a phosphoric acid group, a lac
  • hydroxyl group phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group (preferably hexafluoroisopropyl group), sulfonimide group, bis(alkylcarbonyl)methylene group, alkylene oxide group (e.g., ethylene oxide chain or propylene oxide chain) and the like).
  • developability and pattern formability are further improved.
  • the alkali-soluble group is preferably an acid group such as a carboxyl group or a carboxylic anhydride group.
  • the acid value is preferably 10-300 mgKOH/g, more preferably 10-200 mgKOH/g, even more preferably 10-120 mgKOH/g. When the acid value is within this range, the development residue is suppressed and the pattern shape is improved.
  • Polymerizable compounds having an acid group include, for example, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-(meth) ) acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxyethyl acid phosphate, ⁇ -carboxyethyl (meth)acrylate, and the like.
  • polymerizable compounds having an acid group include, for example, Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., Aronix M-5400, M-5700, M-510, M-520, M- manufactured by Toagosei Co., Ltd. 521, light acrylate HOA-MPL (N), HOA-HH (N), HOA-MPE (N), HOMS (N), P-1A, P-1M, P-2M, etc. manufactured by Kyoeisha Chemical Co., Ltd. mentioned.
  • Polymerizable compounds having a hydroxyl group include, for example, N-hydroxymethyl (meth)acrylamide, 1,4-cyclohexanedimethanol monoacrylate, bisphenol A diglycidyl ether di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2 - hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol caprolactone modified penta ( meth) acrylate, glycerin di(meth) acrylate, bis-(2-acryloxyethyl) isocyanurate, 2-hydroxy-3-methacrylpropyl acrylate, 2-(meth) acryloyl
  • polymerizable compounds having a hydroxyl group include, for example, KAYARAD R-128H manufactured by Nippon Kayaku Co., Ltd., Aronix MT-3560, M-305, M-306, M-313, M-313 and M-313 manufactured by Toagosei Co., Ltd.
  • a lactone-modified polymerizable compound is a compound having a lactone-modified structure in its molecule. Heat resistance is improved by using a lactone-modified polymerizable compound.
  • the lactone-modified polymerizable compound includes polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethritol, tripentaerythritol, glycerin, diglycerol, and trimetholmelamine, and ( It is obtained by esterifying meth)acrylic acid and ⁇ -caprolactone or other lactone compounds.
  • the lactone-modified polymerizable compound is preferably a compound represented by the following general formula (13).
  • R 1 represents a hydrogen atom or a methyl group
  • m is an integer of 1 or 2
  • * is a bond that bonds to the oxygen atom in general formula (13).
  • R 1 represents a hydrogen atom or a methyl group
  • * is a bond that bonds with the oxygen atom in general formula (13).
  • Lactone-modified polymerizable compounds are commercially available, for example, as KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd.
  • DPCA-20 in the above general formulas (13) to (15)
  • m 1, general formula ( 14)
  • the number of groups represented by 2
  • R 1 are all hydrogen atoms
  • DPCA-30 in the above general formulas (13) to (15)
  • DPCA-60 in the above general formulas (13) to (15)
  • DPCA-120 in the above general formulas (13) to (15)
  • the content of the lactone-modified polymerizable compound is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and 20 to 60 parts by mass in 100 parts by mass of the polymerizable compound (C). Part is more preferred.
  • lactone-modified polymerizable compounds include KARARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. manufactured by Nippon Kayaku Co., Ltd.
  • the photosensitive composition of the present embodiment preferably contains a polymerizable compound having a urethane bond as the polymerizable compound (C).
  • the polymerizable compound having a urethane bond is, for example, a urethane (meth)acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or a polyhydric alcohol with a polyfunctional isocyanate and further having a hydroxyl group.
  • (Meth)acrylates having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, Examples include glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, and hydroxyl
  • polyfunctional isocyanate examples include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; Alternatively, burettes, isocyanate nurates, trimethylolpropane adducts, and the like thereof can be mentioned.
  • aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate
  • aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate
  • alicyclic diisocyanates such as isophorone diisocyanate
  • the polymerizable compound having a urethane bond further has an acid group.
  • acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among them, a carboxyl group is preferred.
  • a method for introducing an acid group into a polymerizable compound having a urethane bond is, for example, to react the (meth)acrylate having a hydroxyl group with the polyfunctional isocyanate. Then, it can be synthesized by adding a mercapto compound having a carboxyl group to the product.
  • Mercapto compounds having a carboxyl group include, for example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.
  • the number of polymerizable unsaturated groups in the polymerizable compound having a urethane bond is preferably 2 to 10, more preferably 2 to 8.
  • the content of the polymerizable compound having a urethane bond is preferably 1 to 70 parts by mass, more preferably 2 to 50 parts by mass, and 3 to 40 parts by mass in 100 parts by mass of the polymerizable compound (C). Parts by mass are more preferred.
  • polymerizable compounds having urethane bonds are AH-600, AT-600, AH-600, UA-306H, UA-306T, UA-306I, UA-1100H manufactured by Kyoeisha Chemical Co., Ltd., Toagosei Co., Ltd. and Aronix M-1100, M-1200, M-1600, etc. manufactured by Aronix.
  • the content of the polymerizable compound (C1) having an alkali-soluble group is preferably 5 to 95 parts by mass, preferably 5 to 90 parts by mass, based on 100 parts by mass of the polymerizable compound (C) from the viewpoint of developability and pattern formation. is more preferred.
  • the amine structure in the polymerizable compound (C2) having three or more (meth)acryloyl groups and an amine structure (hereinafter also simply referred to as the polymerizable compound (C2)) is a primary amine, secondary amine, or tertiary Where an amine is included, it is preferable to include a tertiary amine.
  • the amine structure of the polymerizable compound (C2) 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.
  • the number of (meth)acryloyl groups in the polymerizable compound (C2) is not particularly limited as long as it is 1 or more, but from the viewpoint of pattern formation, it is preferably 3 or more and 16 or less.
  • the polymerizable compound (C2) can be used alone or in combination of two or more.
  • the content of the polymerizable compound (C2) is preferably 0.5 parts by mass or more, more preferably 1 to 80 parts by mass based on 100 parts by mass of the polymerizable compound (C), from the viewpoint of pattern formability and solvent resistance. , 2 to 60 parts by weight are particularly preferred.
  • the polymerizable compound (C2) includes, for example, tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, (meth)acrylate compound (X) and A Michael addition reaction product with the amine compound (Y) and the like can be mentioned.
  • (Meth)acrylate compounds (X) are, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ) acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra (Meth)acrylates, trimethylolpropane alkylene oxide-modified tri(meth)acrylates, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth
  • the (meth)acrylate compound (X) can be used alone or in combination of two or more.
  • Amine compounds (Y) include, for example, n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m- primary amines such as aminophenol and p-aminophenol; Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, 4 - secondary amines such as anilinephenol;
  • the amine compound (Y) can be used alone or in combination of two or more.
  • 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 known methods can be used. For example, methods described in International Publication No. 2006/075754, Japanese Patent Publication No. 2008-545859, Japanese Patent Application Laid-Open No. 2017-066347, and the like can be mentioned.
  • the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure may have an acidic group and/or a hydroxyl group.
  • a method of introducing an acidic group and/or a hydroxyl group includes, for example, a method of using a compound having an acidic group and/or a hydroxyl group in (meth)acrylate compound (X) or an amine compound (Y), or a Michael addition reaction followed by A method of adding an acid anhydride and the like can be mentioned.
  • C2 Commercially available products of the polymerizable compound (C2) include Aronix MT-3041, 3042 and Aron DA manufactured by Toagosei Co., Ltd., EBECRYL 80 and 7100 manufactured by Daicel-Ornex, and CN371, CN550, and CN551 manufactured by SARTOMER. be done.
  • the polymerizable compound (C) can be used alone or in combination of two or more.
  • the polymerizable compound (C) may contain one or more selected from the group consisting of a lactone-modified polymerizable compound and a polymerizable compound having a urethane bond, from the viewpoints of developability, pattern formability, and heat resistance. .
  • the blending amount of the polymerizable compound (C) is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass based on 100 parts by mass of the dye (A), from the viewpoint of photocurability and developability.
  • the content of the polymerizable compound (C) is preferably 15 to 60% by mass based on 100 parts by mass of the non-volatile matter of the photosensitive composition.
  • Polymerizable compound (C)/binder resin (B), which is the mass ratio of polymerizable compound (C) and binder resin (B), is preferably 0.01 or more, and more preferably 0.83 or more from the viewpoint of developability stains. .
  • the photosensitive composition of the present embodiment contains an O-acyloxime ester photopolymerization initiator (D1).
  • O-acyl oxime ester photopolymerization initiator (D1) absorbs ultraviolet rays, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure.
  • O-acyl oxime ester photopolymerization initiator (D1) examples include compounds represented by the following general formulas (1) to (7).
  • R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group.
  • R 3 represents —COR 5 , a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group.
  • R5 represents a phenyl group and a thienyl group having a substituent.
  • R 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the alkyl group, cyclic alkyl group, acyl group and phenyl group of R 1 to R 4 above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group.
  • the hydrogen atoms of the substituents in R 1 to R 4 may be further substituted with another substituent R 6 .
  • R6 represents a halogen atom, fluorine atom, alkyl group, cyclic alkyl group, acyl group, nitro group, sulfo group and phenyl group.
  • Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R 1 to R 4 in the general formula (1) are, for example, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl , t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl , cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexyle
  • OXE-02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)) is a compound in which R 1 is methyl. However, it does not contain a methyl group because the film has poor light resistance and does not solve the problem.
  • phenyl group having a substituent represented by R 5 in the general formula (1) is, for example, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, chemical formula (1-A). and the like.
  • Cyclic alkyl groups having 3 to 20 carbon atoms represented by R 1 to R 4 in general formula (1) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl groups.
  • the oxime-based photopolymerization initiator (D1-1) represented by general formula (1) is, for example, 1-[9-ethyl-6-benzoyl-9. H. -carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H.
  • R 1 and R 2 may each independently have a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic substituent having 3 to 20 carbon atoms.
  • R 3 is a hydrogen atom, a group having an O-acyloxime structure, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, acetoxy; or sulfo group.
  • R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
  • the hydrogen atom of the aryl group or arylalkyl group represented by R 4 may be further substituted with R 21 , —OR 21 , —COR 21 , hydroxyl group, nitro group, cyano group, halogen atom, or —COOR 21 Often, R 21 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group or aryl group represented by R 21 , the hydrogen atom of the arylalkyl group may be further substituted with a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or a carboxyl group.
  • the alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group.
  • the hydrogen atoms of the substituents in R 1 to R 4 may be further substituted with other substituents.
  • Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R 1 to R 4 in the general formula (2) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohe
  • Cyclic alkyl groups having 3 to 20 carbon atoms represented by R 1 to R 4 in general formula (2) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl groups.
  • the aryl group having 6 to 30 carbon atoms represented by R 4 and R 21 in the above general formula (2) is, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, or any of the above alkyl groups. Examples include phenyl, biphenylyl, naphthyl, anthryl, etc., which are substituted one or more times.
  • Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R 4 in the general formula (2) include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and the like.
  • Examples of the oxime photopolymerization initiator (D1-2) represented by the general formula (2) include compounds represented by the following chemical formulas (2-1) to (2-6).
  • R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group.
  • R 3 and R 5 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show.
  • the alkyl group, acyl group and phenyl group of R 1 to R 3 may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group.
  • R 4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, or —COR 6 .
  • R 6 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 4 to 20 carbon atoms.
  • the hydrogen atoms of the substituents in R 1 to R 6 may be further substituted with other substituents.
  • Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R 1 to R 5 in the general formula (3) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohe
  • Cyclic alkyl groups having 3 to 20 carbon atoms represented by R 1 to R 5 in general formula (3) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl groups.
  • the heterocyclic groups having 4 to 20 carbon atoms represented by R 4 and R 7 in the general formula (3) are, for example, benzofuran, isobenzofuran, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzo 5- to 7-membered heterocycles such as oxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl and morpholinyl.
  • the aryl group having 6 to 30 carbon atoms represented by R 6 in the general formula (3) is, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, substituted with one or more of the above alkyl groups. phenyl, biphenylyl, naphthyl, anthryl and the like.
  • Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R 6 in the general formula (3) include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and the like.
  • Examples of the oxime photopolymerization initiator (D1-3) represented by the general formula (3) include compounds represented by the following chemical formulas (3-1) to (3-3).
  • R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group.
  • R 3 and R 5 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show.
  • R 4 is a hydrogen atom or an alkoxy group, and the alkoxy group may contain a linear or branched alkyl group having 1 to 20 carbon atoms or a hydroxyl group.
  • the alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group.
  • the hydrogen atoms of the substituents in R 1 to R 5 may be further substituted with other substituents.
  • Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R 1 to R 5 in the general formula (4) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclo
  • Cyclic alkyl groups having 3 to 20 carbon atoms represented by R 1 , R 2 , R 3 and R 5 in the general formula (4) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl. and the like.
  • the oxime-based photopolymerization initiator (D1-4) represented by the general formula (4) is, for example, 1,2-heptanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime ), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1,2-octanedione, 1-[4-(benzoyl)phenyl]-, 2 -(O-benzoyloxime), ethanone, 1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(2-methylphenylthio)phenyl]- Octan-1-one-2-one oxime-O-acetate, 1-[4-(2,4,6-trimethylphenylthio)phenyl]-octan-1-one-2-one oxime
  • R 1 and R 2 each independently represent R 11 or -COR 11
  • R 11 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 20 carbon atoms
  • the alkyl moiety of the represented alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl
  • R 3 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 20 carbon atoms, and is represented by R 3
  • the alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may
  • the hydrogen atom of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R 21 , R 22 and R 23 is further a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or may be substituted with a carboxyl group, and the alkylene portion of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R 21 , R 22 and R 23 may be -O-, -S-, - COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, an oxygen atom is adjacent 1 to 5 may be included in conditions that do not match, R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group
  • the alkyl groups having 1 to 20 carbon atoms represented by R 3 , R 11 , R 21 , R 22 , R 23 and R 24 in the general formula (5) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclo
  • the aryl group having 6 to 30 carbon atoms represented by R 3 , R 11 , R 21 , R 22 , R 23 and R 24 in the general formula (5) is, for example, phenyl, tolyl, xylyl, ethylphenyl , naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.
  • the arylalkyl groups having 7 to 30 carbon atoms represented by R 3 , R 11 , R 21 , R 22 , R 23 and R 24 in the general formula (5) are, for example, benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and the like.
  • the heterocyclic groups having 2 to 20 carbon atoms represented by R 3 , R 11 , R 21 , R 22 , R 23 and R 24 in the general formula (5) are, for example, pyridyl, pyrimidyl, furyl, thienyl , tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, 5- to 7-membered heterocycles such as morpholinyl. .
  • the method for producing the oxime-based photopolymerization initiator (D1) represented by general formula (5) is not particularly limited, and known methods can be used. For example, the method described in WO2015/152153 can be used.
  • Examples of the oxime-based photopolymerization initiator (D1-5) represented by the general formula (5) include compounds represented by the following chemical formulas (5-1) to (5-3).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carbon It represents an alkoxy group of 1 to 20 carbon atoms, an arylalkyl group of 7 to 30 carbon atoms or a heterocyclic group of 4 to 20 carbon atoms.
  • Examples of the oxime-based photopolymerization initiator (D1-6) represented by general formula (6) include compounds represented by chemical formulas (6-1) to (6-4) below.
  • R 1 and R 2 are each independently a hydrogen atom, a linear or branched alkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms
  • R 3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, an acetoxy group or a sulfo group.
  • R 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an optionally substituted cyclic alkyl group having 3 to 20 carbon atoms, a phenyl group, a tolyl group, or a xylyl group. indicates m is 0 or 1;
  • Examples of the oxime-based photopolymerization initiator (D1-7) represented by general formula (7) include compounds represented by chemical formulas (7-1) to (7-7) below.
  • IRGACURE OXE-05, NCI-730, NCI-930, IRGACURE OXE-04, SPI-05, NCI-831, TRONLY TR-PBG-345, chemical formula (7-3) is preferred, and SPI-05, NCI-831, TRONLY TR-PBG-345, and chemical formula (7-3) are more preferred.
  • the content of the O-acyl oxime ester photopolymerization initiator (D1) is 0.4 to 10 parts by weight per 100 parts by weight of the photopolymerization initiator (D) from the viewpoint of development stains, chemical resistance, and taper formation. Preferably, 0.5 to 5 parts by mass is more preferable.
  • Photopolymerization initiators other than the above include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4- morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1 - acetophenone compounds such as butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl
  • the photopolymerization initiator (D) can be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (D) is 0.02 to 200 parts by mass with respect to 100 parts by mass of the dye (A) from the viewpoint of development speed, solvent resistance, substrate adhesion, development stains, and tapered shape. parts is preferred, and 0.05 to 100 parts by mass is more preferred. When blended in an appropriate amount, solvent resistance, substrate adhesion and development stains are further improved.
  • the content of the photopolymerization initiator (D) is preferably 0.2 to 15% by mass based on 100 parts by mass of the nonvolatile matter of the photosensitive composition.
  • the photosensitive composition of this embodiment can contain a leveling agent (E). This further improves the wettability and dryability of the substrate during coating.
  • the leveling agent (E) include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.
  • the photosensitive composition containing an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group has a high affinity between the blocked isocyanato group and the developer, and stains appear on the surface of the coating film after development. Easy to cause (development stains).
  • the combination of the O-acyl oxime ester photopolymerization initiator (D1) and the above leveling agent significantly improved the performance.
  • Silicone-based surfactants include, for example, linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
  • Fluorosurfactants include, for example, surfactants or leveling agents having fluorocarbon chains.
  • Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate
  • cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.
  • Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenylether disulfonates, and monoethanol lauryl sulfate.
  • amine triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.
  • Amphoteric surfactants include, for example, lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.
  • Amphithol 20AB Commercially available products include Amphithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.
  • the leveling agent (E) can be used alone or in combination of two or more.
  • the content of the leveling agent (E) is preferably 0.001 to 3.0 parts by mass, more preferably 0.005 to 1.2 parts by mass, based on 100 parts by mass of the nonvolatile matter of the photosensitive composition.
  • the silicone-based surfactant (E1) and the fluorine-based surfactant (E2) are particularly preferred.
  • BYK-330, BYK-323 and 348 manufactured by BYK Chemie, FZ-2122 and SH-8400 manufactured by Dow Corning Toray, and Futergent 601ADH2 manufactured by Neos Co., Ltd. are used from the viewpoint of development stains and tapered shape.
  • the company Megafac F-554 is more preferred.
  • the photosensitive composition of the present embodiment may contain a thermal base generator together with an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group.
  • a thermal base generator together with an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group.
  • thermal base generator known or commonly used curing accelerators can be used without particular limitation, but examples include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and salts thereof (e.g., phenol salts, octylate salts, p-toluenesulfonate salts, formate salts, tetraphenylborate salts); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and its Salts (eg phenol salts, octylate, p-toluenesulfonate, formate, tetraphenylborate salts); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethyl Tertiary amines such as cyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-
  • DBU
  • the photosensitive composition of the present embodiment preferably contains a sensitizer (G).
  • Sensitizers include, for example, chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzyl and camphorquinone, benzoin compounds, and fluorene.
  • Polymethines such as polymethine-based compounds, naphthoquinone-based compounds, anthraquinone-based compounds, xanthene-based compounds, thioxanthene-based compounds, xanthone-based compounds, thioxanthone-based compounds, coumarin-based compounds, ketocoumarin-based compounds, cyanine-based compounds, merocyanine-based compounds, and oxonol-based compounds dyes, acridine-based compounds, azine-based compounds, thiazine-based compounds, oxazine-based compounds, indoline-based compounds, azulene-based compounds, azulenium-based compounds, squarylium-based compounds, porphyr
  • Thioxanthone compounds (G1) include, for example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. be done. Among these, 2,4-diethylthioxanthone is preferred.
  • Benzophenone compound (G2) Benzophenone compounds include, for example, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 2-aminobenzophenone and the like. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.
  • the sensitizer (G) can be used alone or in combination of two or more.
  • the content of the sensitizer (G) is preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (D).
  • thermosetting compound (H) The photosensitive composition of this embodiment can contain a thermosetting compound (H).
  • the thermosetting compound (H) reacts in the heating step, increasing the crosslink density and improving the heat resistance.
  • the thermosetting compound (H) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin.
  • Thermosetting compounds (H) include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.
  • Epoxy compounds (H1) include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene , alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymerization of phenols and various diene compounds (di)
  • the content of the epoxy compound (H1) is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, based on 100 parts by mass of the nonvolatile content of the photosensitive composition. is more preferred.
  • the oxetane compound (H2) is a known compound having an oxetane group.
  • Oxetane compounds include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.
  • Monofunctional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3- ⁇ [3-(triethoxy silyl)propoxy]methyl ⁇ oxetane and the like.
  • Examples of commercially available products include OXE-10, 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 212 manufactured by Toagosei Co., Ltd., and the like.
  • Bifunctional oxetane compounds include, for example, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3 -ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)- 5-oxa-nonane, 1,2-bis[(3-eth
  • Examples of commercially available products include OXBP and OXTP manufactured by UBE Corporation, and OXT-121 and 221 manufactured by Toagosei Co., Ltd.
  • Trifunctional or higher oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-o
  • the content of the oxetane compound (H2) is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, based on 100 parts by mass of the non-volatile matter of the photosensitive composition.
  • a melamine compound is a compound having a melamine ring structure.
  • the melamine compound is preferably a methylol-type or ether-type compound, more preferably a melamine compound having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. Having an appropriate number of methylol groups or ether groups facilitates obtaining just the right amount of heat resistance.
  • thermosetting compound (H) can be used alone or in combination of two or more.
  • the photosensitive composition of the present embodiment can be used together with a curing agent (curing accelerator) to assist curing of the thermosetting compound (H).
  • Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like.
  • Curing agents include, for example, amine compounds (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and their salts (e.g., imidazole, 2 -methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -methylimi
  • the curing agent can be used alone or in combination of two or more.
  • the content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (H).
  • the photosensitive composition of this embodiment can contain a thiol chain transfer agent (I).
  • thiol-based chain transfer agent (I) When the thiol-based chain transfer agent (I) is used in combination with the photopolymerization initiator (D), thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the photosensitivity of the photosensitive composition is improved. do.
  • the thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having 2 or more thiol groups (SH groups), more preferably a polyfunctional thiol having 4 or more. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.
  • Polyfunctional thiols are, for example, hexanedithiol, decanedithiol, 1,4-butanedi-rubisthiopropionate, 1,4-butanedi-rubisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate.
  • the thiol-based chain transfer agent (I) can be used alone or in combination of two or more.
  • the content of the thiol-based chain transfer agent (I) is 100 parts by mass of the nonvolatile matter of the photosensitive composition, preferably 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass, and further 2 to 8 parts by mass. preferable. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.
  • the photosensitive composition of the present embodiment can contain an adhesion improver (J). This improves the adhesion between the cured film and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography.
  • the adhesion improver (J) includes, for example, a silane coupling agent.
  • Silane coupling agents include, for example, vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxy
  • KBM-403, KBM-803, X-12-1154, X-12-1156, X-12-1048, X-12- 1150 is preferred.
  • the adhesion improver (J) can be used alone or in combination of two or more.
  • the content of the adhesion improver (J) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the nonvolatile matter of the photosensitive composition.
  • the photosensitive composition of this embodiment can contain a polymerization inhibitor (K).
  • the polymerization inhibitor (K) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol , 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol , 4-t-butylcatechol, 3,5-di-t-butylcatechol and other alkylcatechol compounds; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 - Alkylresorcinol compounds such as propylresor
  • the content of the polymerization inhibitor (K) is preferably 0.01 to 0.4 mass in 100 mass parts of the non-volatile matter of the photosensitive composition.
  • the photosensitive composition of this embodiment can contain an ultraviolet absorber (L).
  • the ultraviolet absorber (L) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylate-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. compounds and the like.
  • Benzotriazole compounds include, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′- Hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1- dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
  • TINUVIN P for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan Co., Ltd., and Adekastab LA-29, LA-31RG manufactured by ADEKA Corporation. , LA-32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.
  • Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate, 2,4-bis'2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-tri
  • KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd.
  • TINUVIN 400 405, 460, 477, 479, 1577ED manufactured by BASF Japan
  • Adekastab LA-46, LA-F70 manufactured by ADEKA Corporation Sun Chemical CYASORB UV-1164 manufactured by Co., Ltd. can be mentioned.
  • Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 5-sulfonic acid-3, water temperature, 2-hydroxy-4-n-octo xybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octa decyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. .
  • salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate.
  • the content of the ultraviolet absorber (L) is preferably 5 to 90 parts by weight based on the total of 100 parts by weight of the photopolymerization initiator (D) and the ultraviolet absorber (L).
  • the photosensitive composition of this embodiment can contain an antioxidant (M).
  • the antioxidant (M) prevents the photopolymerization initiator (D) or the thermosetting compound (I) from yellowing due to oxidation during thermal curing or ITO annealing.
  • the concentration of the photosensitive coloring pigment (A) is high, the content of the polymerizable compound (C) is relatively decreased. Then, the cured film tends to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.
  • Antioxidant (M) is preferably a compound containing no halogen atom.
  • Antioxidants include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.
  • Hindered phenol antioxidants include, for example, 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)stearylpropionate, 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]
  • Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensates of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , Poly[[6-[
  • Phosphorus antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15alkyl)-4,4' -Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(
  • Sulfur antioxidants include, for example, 2,2-bis ⁇ [3-(dodecylthio)-1-oxopropoxy]methyl ⁇ propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′- ditridecyl thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o- cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like.
  • the antioxidant (M) can be used alone or in combination of two or more.
  • the content of the antioxidant (M) is preferably 0.5 to 5.0 parts by mass based on 100 parts by mass of the non-volatile matter of the photosensitive composition. When contained in an appropriate amount, transmittance, spectral characteristics, and sensitivity are improved.
  • Storage stabilizer (N) The photosensitive composition of this embodiment can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive composition over time.
  • Storage stabilizers (N) include, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenyl and the like. organic phosphines, phosphites, and the like.
  • the content of the storage stabilizer (N) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of non-volatile matter in the photosensitive composition.
  • the photosensitive composition of this embodiment can contain an organic solvent (Q).
  • the organic solvent (Q) is, for example, 1,2,3-trichloropropane, allyl alcohol, 1-methoxy-2-propanol, ethyl lactate, ethyl acetate, 2-butanol, 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-cyclohexene-1- On, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl Acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-
  • ethyl lactate propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like are preferred from the viewpoint of pigment dispersibility and alkali-soluble resin solubility.
  • Glycol acetates alcohols such as benzyl alcohol, diacetone alcohol, propylene glycol monomethyl ether and propylene glycol monoethyl ether; and ketones such as cyclohexanone are preferred.
  • a solvent with higher drying properties is used. It is appropriately selected and used according to the conditions of the heating process.
  • Solvents with higher drying properties include, for example, ethyl acetate (boiling point 77° C.), 2-propanol (boiling point 83° C.), isobutyl alcohol (boiling point 108° C.), propyl acetate (boiling point 102° C.), propylene glycol monomethyl ether (boiling point 121° C. ° C.), n-butyl acetate (boiling point 126° C.), isobutyl acetate (boiling point 118° C.), allyl alcohol (boiling point 97° C.), 2-butanol (boiling point 100° C.) and the like.
  • solvents thermal energy during low-temperature heating can be efficiently used to form a cured film, and solvent resistance is improved.
  • the organic solvent (Q) can be used alone or in combination of two or more.
  • a pigment (A), a resin-type dispersant (Z), an organic solvent (Q), and the like are added and subjected to dispersion treatment to produce a dispersion.
  • the binder resin (B), the polymerizable compound (C), the photopolymerization initiator (D) and the like are added to the dispersion and mixed to produce the dispersion.
  • the timing of blending each material is arbitrary.
  • distribution process can also be performed in multiple times.
  • Examples of the dispersing machine that performs the dispersing process include a two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor.
  • the average dispersed particle size (secondary particle size) of the near-infrared absorbing dye in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm.
  • a suitable particle size facilitates obtaining a photosensitive composition with high dispersion stability.
  • the method for measuring the average dispersed particle size is, for example, using a Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method), and the particle permeability is measured by an absorption model.
  • the particle shape is non-spherical
  • the D50 particle diameter is the average diameter.
  • the organic solvent used for dispersion as the diluent solvent for the measurement, and to measure the ultrasonically treated sample immediately after the sample preparation, because it is easy to obtain results with little variation.
  • the photosensitive composition is separated by means of centrifugation, filtration with a sintered filter, membrane filter, or the like to remove coarse particles of 5 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and contaminants. It is preferable to remove the dust that has accumulated.
  • the photosensitive composition of the present embodiment preferably does not substantially contain particles of 0.5 ⁇ m or more, and more preferably does not contain particles of 0.3 ⁇ m or less.
  • the photosensitive composition of the present embodiment can form a cured film even when baked at a low temperature.
  • the photosensitive composition can form a good cured film even when baked at a low temperature of 100°C.
  • a film with a thickness of 3 ⁇ m was formed, exposed to ultraviolet light with an ultrahigh-pressure mercury lamp at an illuminance of 500 mW/cm 2 and an irradiation dose of 200 mJ/cm 2 , and then heated at 90° C. for 30 minutes. , is preferably 75% or more.
  • the cured film of the present embodiment can be obtained by curing the film formed using the photosensitive composition of the present embodiment through treatment such as exposure.
  • the method for producing the cured film is not particularly limited.
  • a step (3) of alkali developing the exposed portion to form a patterned cured film and a step (4) of heat-treating (post-baking) the pattern can be carried out.
  • a photosensitive composition is applied onto a substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and if necessary, an oven, Using a hot plate or the like, it is dried (pre-baked) at a temperature of 50 to 120° C. for 10 to 120 seconds.
  • the substrate include a glass substrate and a silicon substrate.
  • the silicon substrate may have, for example, an imaging element such as a CCD or CMOS formed on its surface.
  • an undercoat layer may be provided on the substrate for improving adhesion with the upper layer, preventing diffusion of substances, and flattening the surface of the substrate.
  • the thickness of the layer after drying is preferably 0.05 to 10.0 ⁇ m, more preferably 0.3 to 5 ⁇ m.
  • Step (2) In the exposure step, the film obtained in step (1) is exposed to a specific pattern through a mask.
  • a mask for example, an exposure device such as a stepper is used. Radiation used for exposure includes, for example, ultraviolet rays such as g-line, h-line and i-line.
  • Step (3) The film that has undergone step (2) is subjected to alkali development treatment, whereby the unexposed portions of the film are eluted in an alkaline aqueous solution, leaving only the cured portions to obtain a patterned film.
  • Developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include alkaline compounds such as pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene.
  • the concentration of the 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 11-13, more preferably 11.5-12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed, and the residual film rate after development can be improved.
  • Developing methods include, for example, the dipping method, the spraying method, and the paddle method.
  • the developing temperature is preferably 15 to 40°C.
  • Step (4) In the heat treatment (post-baking), the patterned coating obtained in step (3) is sufficiently cured by heating.
  • the post-baking temperature is 180° C. or lower, preferably 160° C. or lower, more preferably 140° C. or lower, and even more preferably 120° C. or lower.
  • the lower limit of the post-baking temperature is not particularly limited as long as the film can be cured.
  • the post-baking time is preferably about 2 minutes to 1 hour, more preferably about 5 minutes to 1 hour.
  • the cured film of this embodiment can be used for color filters and optical filters.
  • optical filters an infrared cut filter and an infrared transmission filter are preferable.
  • the color filters and optical filters in this specification can be manufactured by the same method as the cured film described above.
  • the cured film of this embodiment can be used in an image display device.
  • the form used for the image display device is not particularly limited, but it can be used as a near-infrared cut filter, a near-infrared pass filter, a color filter, or a black matrix.
  • a black matrix is a solid-state imaging device, a black edge provided at the peripheral portion of an image display device such as a liquid crystal display device; a lattice-like and/or striped black portion between red, blue, and green pixels; TFT light shielding dot-shaped and/or linear black patterns for .
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of an image display device provided with a cured film.
  • the image display device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged facing each other with a gap between them, and a liquid crystal LC is enclosed between them.
  • a TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon.
  • An alignment layer 14 is provided on the transparent electrode layer 13 .
  • a polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .
  • a color filter 22 is formed on the inner surface of the second transparent substrate 21 .
  • the red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).
  • a transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.
  • a polarizing plate 25 is formed on the outer surface of the transparent substrate 21 .
  • a backlight unit 30 is provided below the polarizing plate 15 .
  • the liquid crystal LC is oriented according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence).
  • a TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of ITO, for example, is formed thereon.
  • An alignment layer 14 is provided on the transparent electrode layer 13 .
  • a polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .
  • a color filter 22 is formed on the inner surface of the second transparent substrate 21 .
  • the red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).
  • a transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.
  • a polarizing plate 25 is formed on the outer surface of the transparent substrate 21 .
  • a backlight unit 30 is provided below the polarizing plate 15 .
  • the white LED light source 31 there is one in which a fluorescent filter is formed on the surface of a blue LED, or one in which a phosphor is contained in a resin package of a blue LED. ( ⁇ 3), a wavelength ( ⁇ 4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, and a wavelength ( ⁇ 5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and The ratio (I4/I3) of the emission intensity I3 at the wavelength ⁇ 3 to the emission intensity I4 at the wavelength ⁇ 4 is 0.2 or more and 0.4 or less, and the ratio (I5/ A white LED light source (LED1) having a spectral characteristic in which I3) is 0.1 or more and 1.3 or less, and a wavelength ( ⁇ 1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and 530 nm to 580 nm.
  • a white LED light source (LED2) with properties is preferred.
  • LED 1 examples include NSSW306D-HG-V1 and NSSW304D-HG-V1 manufactured by Nichia Corporation.
  • LED 2 examples include NSSW440 and NSSW304D manufactured by Nichia Corporation.
  • the solid-state imaging device of this embodiment has a cured film.
  • the configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.
  • the solid-state imaging device includes, for example, a plurality of photodiodes and polysilicon that constitute a light receiving area of the solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on a substrate.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • a light-shielding film is provided on the photodiode and the transfer electrode so that only the light-receiving portion of the photodiode is opened, and nitriding is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode.
  • a configuration having a device protective film made of silicon or the like and having a color filter on the device protective film is preferable.
  • the color filter preferably has a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
  • the partition wall preferably has a low refractive index for each color pixel.
  • Imaging devices including a solid-state imaging device include, for example, devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654. Applications of the imaging device include digital cameras, electronic devices having an imaging function (mobile phones, etc.), in-vehicle cameras, surveillance cameras, and the like.
  • FIG. 2 is a schematic cross-sectional view showing a configuration example of an infrared sensor.
  • An infrared sensor 300 shown in FIG. 2 includes a solid-state imaging device 310 .
  • An imaging area provided on the solid-state imaging device 310 is configured by combining an infrared cut filter 311 and a color filter 312 .
  • the infrared absorption filter 311 transmits light in the visible 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 1300 nm).
  • the color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light region. For example, pixels of red (R), green (G), and blue (B) are formed. A color filter or the like is used.
  • the infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and the cured film of the present embodiment containing the above-described near-infrared absorption dye can be used.
  • 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 1300 nm, for example.
  • a microlens 315 is arranged on the incident light side of the color filter 312 and the infrared transmission filter 313 .
  • a planarization film 316 is formed to cover the microlenses 315 .
  • the cured film of the present embodiment can be used as a light shielding film such as the edge and / or side of the surface of the infrared cut filter 311, and if it is used for the inner wall of the infrared sensor, it does not affect the internal reflection and / or the light receiving part. It prevents light from entering and improves sensitivity.
  • this infrared sensor image information can be captured at the same time, so it is possible to perform motion sensing etc. by recognizing the target to detect movement.
  • distance information can be obtained with this infrared sensor, it is possible to take an image including 3D information.
  • this infrared sensor can also be used as a biometric sensor.
  • the cured film of this embodiment can also be used as a colored spacer.
  • a colored spacer For example, when spacers are used in a TFT-type LCD, light incident on the TFT may cause the TFT to malfunction as a switching element, and the colored spacer is used to prevent this.
  • the colored spacers can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.
  • the cured film of the present embodiment can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, it is suitably used for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members imparting light shielding properties and antireflection properties. Examples of micro LEDs and micro OLEDs include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.
  • the cured film of this embodiment can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for optical filters and optical films used in quantum dot displays, as well as members imparting light shielding properties and antireflection properties.
  • embodiments of the present invention include various embodiments not described here. For example, including configuration for:
  • One configuration of the present invention is a photosensitive coloring composition containing a dye (A), a binder resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a leveling agent (E),
  • the binder resin (B) contains an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group
  • the photopolymerization initiator (D) is an O-acyl oxime ester system represented by the above general formula (1), general formula (2), general formula (3), general formula (4) or general formula (5) It is a photosensitive coloring composition that is a photopolymerization initiator (D1).
  • Another configuration of the present invention is the photosensitive coloring composition, wherein the leveling agent (E) contains either one of a silicone-based surfactant and a fluorine-based surfactant.
  • the binder resin (B) further includes an alkali-soluble binder resin (B1) having a polystyrene-equivalent weight average molecular weight of 5,000 or more and less than 50,000 (however, the alkali-soluble binder resin (Bb) The above photosensitive coloring composition, except for the case where
  • Another configuration of the present invention is the photosensitive coloring composition, wherein the alkali-soluble binder resin (B1) contains a structural unit (b3) having an alicyclic group.
  • the structural unit (b3) having an aliphatic ring group in the alkali-soluble binder resin (B1) has a ring represented by the above formula (b31) or (b32). It is a photosensitive coloring composition.
  • Another aspect of the present invention is the photosensitive coloring composition, wherein the alkali-soluble binder resin (B1) further contains a structure (b1-2) derived from a polybasic acid anhydride.
  • Another aspect of the present invention is the photosensitive coloring composition, which further contains a resin-type dispersant (Z).
  • Another configuration of the present invention is the photosensitive coloring composition, wherein the resin-type dispersant (Z) contains an acidic resin-type dispersant (ZA).
  • Another aspect of the present invention is the photosensitive coloring composition, wherein the acidic resin-type dispersant (ZA) contains a photocrosslinkable acidic resin-type dispersant (ZAUV-1).
  • ZA acidic resin-type dispersant
  • ZAUV-1 photocrosslinkable acidic resin-type dispersant
  • Another aspect of the present invention is a cured film, which is a cured product of the photosensitive coloring composition.
  • Another configuration of the present invention is a color filter having the cured film.
  • Another configuration of the present invention is an optical filter having the cured film.
  • Another configuration of the present invention is an image display device having the cured film.
  • Another configuration of the present invention is a solid-state imaging device having the cured film.
  • Another configuration of the present invention is an infrared sensor having the cured film.
  • a numerical range indicated using “to” indicates a range that includes the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the upper limit or lower limit of the numerical range in one step can be arbitrarily combined with the upper limit or lower limit of the numerical range in another step.
  • the present invention relates to the subject matter of Japanese Patent Application No. 2021-148439 filed on September 13, 2021, the entire disclosure of which is incorporated herein by reference.
  • non-volatile matter or non-volatile matter concentration refers to the mass residue after standing in an oven at 280° C. for 30 minutes.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g), amine value (mgKOH/g), and glass transition temperature (Tg) of the resin are measured as follows.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder resin and dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector.
  • GPC gel permeation chromatography
  • HLC-8220GPC manufactured by Tosoh Corporation
  • TEZ-GEL SUPER HZM-N was used as both packing materials, and the oven temperature was 40.
  • a tetrahydrofuran (THF) solution was used as an eluent, and the flow rate was 0.35 ml/min.
  • Samples were dissolved in a solvent consisting of 1 wt % of the above eluent and injected at 20 microliters.
  • a molecular weight is a polystyrene conversion value.
  • Acid value of binder resin and dispersion resin 80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the binder resin and dispersion resin solution and stirred to dissolve uniformly. 555" manufactured by HIRANUMA Co., Ltd.), and the acid value (mgKOH/g) was measured according to the method of JIS K 0070. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile content of the resin solution.
  • the amine value of the dispersing resin is a value obtained by converting the total amine value (mgKOH/g) measured according to the method of ASTM D 2074 into nonvolatile matter.
  • Glass-transition temperature The glass transition temperature of the binder resin (B) was measured using a differential scanning calorimeter by weighing 5 mg of a sample into a sample pan and measuring the temperature from ⁇ 20 to 200° C. at a heating rate of 10° C./min under a nitrogen stream.
  • the resulting kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , 98 parts of finely divided pigment (A-Y1) were obtained.
  • azobarbituric acid precursor (Production of yellow pigment (A-Y4)) (azobarbituric acid precursor)
  • An azobarbituric acid precursor was prepared according to the synthetic method described in JP-A-2017-171915. (Instruction 1) 46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were introduced into 1100 g of distilled water at 85°C. The pH was then adjusted to about pH 5 using aqueous potassium hydroxide and stirring continued for 90 minutes.
  • the azobarbituric acid precursor (0.3 mol) prepared in Instruction 1 was mixed with 1500 parts of distilled water at 82°C. 10 parts of 30% strength hydrochloric acid are then added dropwise to adjust the pH to 2-2.5. 79.4 parts of melamine (0.63 mol) were then introduced. 0.3 mol of an approximately 25% strength nickel chloride solution was then added dropwise. After 3 hours at 82° C., the pH was adjusted to approximately 5.5 using KOH. This was followed by dilution with about 100 parts distilled water at 90°C. 21 parts of 30% strength hydrochloric acid are then added dropwise and a temperature of 90° C. is maintained for 12 hours.
  • yellow pigment (Y4-2) "0.3 mol of about 25% strength nickel chloride solution” of the preparation example of yellow pigment (Y4-1) was replaced with "0.225 mol of 25% strength nickel chloride + 0.075 mol of 25% strength chloride
  • yellow pigment (Y4-3) "0.3 mol of about 25% strength nickel chloride solution” of the preparation example of yellow pigment (Y4-1) was replaced with "0.150 mol of 25% strength nickel chloride + 0.150 mol of 25% strength chloride
  • yellow pigment (Y4-4) "0.3 mol of about 25% strength nickel chloride solution” of the preparation example of yellow pigment (Y4-1) was replaced with "0.075 mol of 25% strength nickel chloride + 0.225 mol of 25% strength chloride
  • a yellow pigment (Y4-4) was obtained in the same manner as the yellow pigment (Y4-1) except that it was replaced with "mixed solution of zinc”
  • yellow pigment (Y4-4) zinc/melamine of nickel azobarbituric acid adduct, a hybrid compound with components of 50 mol % Zn and 50 mol % nickel).
  • yellow refined pigment (A-Y4) 25 parts of yellow pigment (Y4-1), 25 parts of yellow pigment (Y4-2), 25 parts of yellow pigment (Y4-3), 25 parts of yellow pigment (Y4-4), 1000 parts of sodium chloride, and 120 parts of diethylene glycol
  • a 1-gallon stainless steel kneader manufactured by Inoue Seisakusho Co., Ltd. was charged and kneaded at 70° C. for 8 hours. This mixture is poured into 2000 parts of warm water, heated to about 80°C and stirred with a high speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated at 80°C for 24 hours. After drying, a yellow finely divided pigment (A-Y4) was obtained.
  • Pigment Green 59 100 parts, sodium chloride: 1,200 parts, and diethylene glycol: 120 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80° C. for a day and night. A finely divided green pigment (A-G59) was obtained by drying and pulverizing.
  • Pigment Green 62 100 parts, sodium chloride: 1,200 parts, and diethylene glycol: 120 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a fine green pigment (A-G62).
  • Pigment Green 63 100 parts, sodium chloride: 1,200 parts, and diethylene glycol: 120 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a fine green pigment (A-G63).
  • a colorant (dye 1) was obtained as a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain. At this time, C.I. I. The content of the active coloring component derived from Acid Red 52 was 25% by mass.
  • Dye solutions AD2 and AD3 were prepared in the same manner as dye solutions AD1, respectively, using colorants (dye 2 and dye 3).
  • NIR1 Near-infrared absorbing dye
  • A-NIR1 Near-infrared absorbing dye 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed with 400 parts of toluene and mixed in a nitrogen gas atmosphere. The mixture was heated with stirring and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, a dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol.
  • A-NIR1 Near-infrared absorbing dye
  • the resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was stirred in a nitrogen gas atmosphere. The mixture was heated and stirred in the medium, and the reaction was carried out under reflux for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the resulting reaction mixture.
  • A-NIR1 near-infrared absorbing dye represented by the following chemical formula (17).
  • the kneaded mixture is put into hot water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, dried at 80°C for a day and night, and pulverized.
  • A-NIR1 a fine near-infrared absorbing dye
  • A-NIR2 Near-infrared absorbing dye
  • the resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was stirred in a nitrogen gas atmosphere. The mixture was heated and stirred in the medium, and the reaction was carried out under reflux for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the resulting reaction mixture.
  • a near-infrared absorbing dye (A-NIR2) represented by the following chemical formula (18). rice field.
  • a near-infrared absorbing dye (A-NIR2) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR2) in the same manner as for A-NIR1.
  • This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain a compound of the following chemical formula (19).
  • 5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50°C.
  • 10 parts of the compound of the following chemical formula (19) was gradually added, and the mixture was stirred at 90°C for 120 minutes.
  • this reaction solution is poured into 2000 parts of water, and the resulting precipitate is filtered, washed with water, dried, and near-infrared absorbing dye (A-NIR3) represented by the following chemical formula (20). got A near-infrared absorbing dye (A-NIR3) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR3) in the same manner as for A-NIR1.
  • Near-infrared absorbing dye (A-NIR32) 6 parts of bis(4-bromophenyl)phosphoric acid was added to 200 parts of N-methylpyrrolidone, thoroughly stirred and mixed, and then heated to 50°C. To this solution, 10 parts of the compound of chemical formula (19) was gradually added and stirred at 90° C. for 120 minutes. Thereafter, this reaction solution is poured into 2000 parts of water, and the resulting precipitate is filtered, washed with water, dried, and near-infrared absorbing dye (A-NIR32) represented by the following chemical formula (201). got A near-infrared absorbing dye (A-NIR32) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR32) in the same manner as for A-NIR1.
  • Near infrared absorbing dye (A-NIR33) 4 parts of diphenylphosphinic acid was added to 200 parts of N-methylpyrrolidone, thoroughly stirred and mixed, and then heated to 50°C. To this solution, 10 parts of the compound of chemical formula (19) was gradually added and stirred at 90° C. for 120 minutes. Then, this reaction solution is poured into 2000 parts of water, and the resulting precipitate is filtered, washed with water, dried, and near-infrared absorbing dye (A-NIR33) represented by the following chemical formula (202). got A near-infrared absorbing dye (A-NIR32) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR33) in the same manner as for A-NIR1.
  • a near-infrared absorbing dye (A-NIR4) A near-infrared absorbing dye (A-NIR4) represented by the chemical formula (21) was obtained according to the description of International Publication No. 2019/058882.
  • a near-infrared absorbing dye (A-NIR4) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR4) in the same manner as A-NIR1.
  • binder resin (B) Alkali-soluble binder resin (B1-1) solution
  • PGMAc propylene glycol monomethyl ether acetate
  • styrene (hereinafter referred to as St)
  • GMA glycidyl methacrylate
  • DCPMA dicyclopentanyl methacrylate
  • AIBN isobutyronitrile
  • GMA-AA and THPA were esterified to introduce a structure (b1-2) derived from fatty acid anhydride-modified polybasic acid anhydride (hereinafter referred to as GMA+AA+THPA).
  • GMA+AA+THPA fatty acid anhydride-modified polybasic acid anhydride
  • PGMAc was added so that the non-volatile content was 20% to prepare a random polymer alkali-soluble binder resin (B1-1) solution.
  • Alkali-soluble binder resins (B1-2) to (B1-11) Alkali-soluble binder resins (B1-2) to (B1-11) are synthesized by changing the raw materials, composition ratios, and amounts shown in Tables 1-1 and 1-2, and PGMAc is added. and the non-volatile content was set at 20%. In addition, the numerical value in a table
  • Tg glass transition temperature ranges of the binder resins shown in Tables 1-1 and 1-2 are as follows. A: -50°C or higher and -10°C or lower B: -10°C or higher and 80°C or lower C: 80°C or higher and lower than 150°C D: -50°C or lower, or 150°C or higher
  • the mixture was stirred at 78° C. for 3 hours to carry out a copolymerization reaction to generate a random copolymer.
  • propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20%, to obtain an alkali-soluble binder resin solution (Bb-1) having a structural unit having a blocked isocyanato group.
  • the weight average molecular weight of the copolymer in the obtained polymer composition was 8,000, and the acid value was 75 KOHmg/g.
  • Alkali-soluble binder resin solutions (Bb-2) to (Bb-4) having a structural unit having a blocked isocyanato group) A random copolymerization reaction is performed under the same conditions as for the alkali-soluble binder resin solution (Bb-1) having a structural unit having a blocked isocyanato group, except that the raw materials listed in Table 1-3 are used, and the block isocyanato group is obtained. Alkali-soluble binder resin solutions (Bb-2 to 4) having structural units were obtained. Table 1-3 shows the weight average molecular weight and acid value of the random copolymer in the resulting polymer composition.
  • Karenz MOI-BM is 2-[O-(1'-methylproprideneamino)carboxyamino]ethyl methacrylate (manufactured by Showa Denko KK), and Karenz MOI-DEM is Malon. Acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester (manufactured by Showa Denko KK).
  • the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
  • 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate as a second block (A block) monomer (manufactured by Showa Denko Materials Co., Ltd., Funcryl FA-711MM ) was added, and the mixture was stirred while maintaining the temperature at 110° C. under a nitrogen atmosphere to continue the reaction.
  • ZA-1 solution 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate are charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and nitrogen gas is introduced. replaced with The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added.
  • the temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by measuring the non-volatile content that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and heated at 100°C. Reacted for 7 hours.
  • a solution of a resin-type dispersant (ZA-1) having a comb-shaped structure with a molecular weight of 70 mgKOH/g and a weight average molecular weight of 8,500 was obtained.
  • a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko KK), and ETERNACOLL OXMA. (manufactured by UBE Co., Ltd.) and 100 parts of propylene glycol monomethyl ether acetate were charged and purged with nitrogen gas.
  • the inside of the reaction vessel is heated to 80° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added. and reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted.
  • BPAF 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N (Hydroxyl value 112 mgKOH/g, manufactured by Kuraray Co., Ltd.)) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, 1,8-diazabicyclo-[5.4.0]-7-undecene 0.40 as a catalyst parts were added and reacted at 100° C. for 7 hours.
  • Dispersion 1 After stirring and mixing the following raw materials uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill ("Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.), Dispersion 1 was produced by filtering through a filter with a pore size of 1.0 ⁇ m. Finely divided pigment (A-R177): 11.0 parts Resin type dispersant (ZAUV-1): 30.0 parts Organic solvent (PGMAc): 59.0 parts
  • Dispersions 2 to 36 were produced in the same manner as Dispersion 1, except that the raw materials and amounts shown in Tables 2-1 to 2-5 were changed.
  • Photosensitive composition 1 The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 ⁇ m to produce a photosensitive composition 1.
  • Example 1 (Photosensitive composition 3) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 ⁇ m to produce a photosensitive composition 3.
  • Photosensitive compositions 4 to 96 Photosensitive compositions 4 to 98 were produced in the same manner as in Example 1 except that the photosensitive composition 3 of Example 1 was changed to the raw materials and amounts shown in Tables 3-1 to 3-11.
  • the alkali-soluble binder resin solution (Bb) having a structural unit having a blocked isocyanato group is referred to as binder resin solution (Bb)
  • the alkali-soluble binder resin (B1) is referred to as binder resin (B1).
  • [Alkali-soluble group-containing polymerizable compound (C1)] (Hydroxyl group-containing polymerizable compound (C1-1)): 34 parts of dipentaerythritol pentaacrylate, 33 parts of pentaerythritol triacrylate, "G201-P” (2-hydroxy-3-methacrylpropyl acrylate; manufactured by Kyoeisha Chemical Co., Ltd.)
  • D1-1-1 compound of the above chemical formula (1-1)
  • D1-1-2 compound of the above chemical formula (1-2)
  • D1-1-3 compound of the above chemical formula (1-3)
  • D1- 1-4 Compound of the above chemical formula (1-4)
  • D1-1-10 Compound of the above chemical formula (1-10)
  • D1-1-11 Compound of the above chemical formula (1-11)
  • D1-1- 12 compound of the above chemical formula (1-12)
  • D1-1-M a mixture of 8.3 parts each of the above chemical formulas (1-1) to (1-12) (represented by general formula (2)
  • D1-2-1 compound of the above chemical formula (2-1)
  • D1-2-2 compound of the above chemical formula (2-2)
  • D1-2-3 compound of the above chemical formula (2-3)
  • D1- 2-4 The compound of the above chemical formula (2-4)
  • D1-2-M A mixture of 25 parts each of the above chemical formula
  • Leveling agent (E) "BYK-330" (polyether-modified polydimethylsiloxane, silicone-based leveling agent; manufactured by BYK-Chemie)
  • E-2 "Megafac F-554" (copolymer of polyisobutylene glycol monoacrylate and 2-(perfluorohexyl)ethyl acrylate, fluorine-based leveling agent; manufactured by DIC Corporation)
  • the resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) having a size of 100 mm ⁇ 100 mm and a thickness of 0.7 mm by a spin coating method so that the film thickness after drying was 2.5 ⁇ m. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed through a photomask having a stripe pattern of 100 ⁇ m width with an illuminance of 30 mW/cm 2 and a dose of 100 mJ/cm 2 using an extra-high pressure mercury lamp. After that, the substrate was subjected to spray development using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C.
  • a potassium hydroxide solution concentration: 0.04% by mass
  • the resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) having a size of 100 mm long, 100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness was 2.5 ⁇ m. It was dried on a hot plate at 70°C for 1 minute. Then, using an ultra-high pressure mercury lamp, it was exposed to ultraviolet rays through a photomask having a square pattern of 100 ⁇ m square with an illumination intensity of 30 mW/cm 2 and an irradiation dose of 100 mJ/cm 2 . Furthermore, after cooling this substrate to room temperature, it was spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C.
  • a potassium hydroxide solution concentration: 0.04% by mass
  • the resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) having a size of 100 mm long, 100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness was 2.5 ⁇ m. It was dried on a hot plate at 70°C for 1 minute. Then, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet rays through a photomask having a stripe pattern of 100 ⁇ m width at an illumination intensity of 30 mW/cm 2 and an irradiation dose of 100 mJ/cm 2 .
  • this substrate After cooling this substrate to room temperature, it is spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C. for a development time of 40 seconds, washed with deionized water, and air-dried with clean air. Then, a substrate for evaluation was obtained. On the photocured portion remaining after the development, a 5 ⁇ 5 cm area at the center of the substrate was observed with an optical microscope at a magnification of 50, and the portion where the color was locally changed was observed as a development stain.
  • the evaluation criteria are as follows, and 3 or more is practical. [Evaluation criteria] 5: No development spots are observed in the entire photocured portion. 4: Development stains were observed in less than 10% of the area of the entire photocured portion as 100%.
  • Development stains were observed in 10% or more and less than 20% of the area of the entire photocured portion as 100%.
  • Development stains were observed in 20% or more and less than 50% of the area of the entire photocured portion as 100%.
  • Development stains were observed in 50% or more of the area of the entire photocured portion as 100%.
  • the resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) having a size of 100 mm long, 100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness was 2.5 ⁇ m. It was dried on a hot plate at 70°C for 1 minute. Then, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet light through a photomask having a stripe pattern of 100 ⁇ m width at an illumination intensity of 30 mW/cm 2 and an irradiation dose of 50 mJ/cm 2 .
  • this substrate After cooling this substrate to room temperature, it is spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C. for a development time of 40 seconds, washed with deionized water, and air-dried with clean air. Then, a substrate for evaluation was obtained. On the photocured portion remaining after the development, a 5 ⁇ 5 cm area at the center of the substrate was observed with an optical microscope at a magnification of 50, and the portion where the color was locally changed was observed as a development stain.
  • the evaluation criteria are as follows, and 3 or more is practical. [Evaluation criteria] 5: No development spots are observed in the entire photocured portion. 4: Development stains were observed in less than 10% of the area of the entire photocured portion as 100%.
  • Development stains were observed in 10% or more and less than 20% of the area of the entire photocured portion as 100%.
  • Development stains were observed in 20% or more and less than 50% of the area of the entire photocured portion as 100%.
  • Development stains were observed in 50% or more of the area of the entire photocured portion as 100%.
  • the resulting photosensitive composition was applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) having a size of 100 mm ⁇ 100 mm and a thickness of 0.7 mm by a spin coating method so that the film thickness after drying was 2.5 ⁇ m. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed through a striped pattern photomask with a width of 5 to 25 ⁇ m in increments of 5 ⁇ m with an illuminance of 30 mW/cm 2 and a dose of 100 mJ/cm 2 using an ultra-high pressure mercury lamp.
  • the substrate was developed by spraying with a potassium hydroxide solution (concentration: 0.04% by mass) at 23°C, washed with deionized water, air-dried with clean air, and heated in a clean oven at 90°C for 30 minutes.
  • a substrate for adhesion evaluation was obtained.
  • Spray development was carried out for the shortest time for pattern formation without development residue for each photosensitive composition film, and this was taken as the proper development time.
  • a thin line pattern with a width of 5 to 25 ⁇ m among the patterns of the adhesion evaluation substrate was observed with an optical microscope to confirm the minimum line width of the remaining thin line pattern.
  • the evaluation criteria are as follows, and 3 or more is practical. [Evaluation criteria] 4: Fine lines of 15 ⁇ m or less remain. 3: Fine lines exceeding 15 ⁇ m and 20 ⁇ m or less remain. 2: Fine lines exceeding 20 ⁇ m and 25 ⁇ m or less remain. 1: Fine lines do not remain.
  • the photosensitive composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 2.5 ⁇ m, and dried at 70° C. for 1 minute. 2 ml of an aqueous potassium hydroxide solution (concentration: 0.04% by mass) at 23° C. is added dropwise to the coating film, and the time until the coating film dissolves is measured to evaluate the development speed of the photosensitive composition. bottom.
  • the evaluation criteria are as follows, and 3 or more is practical. [Evaluation criteria] 4: Less than 35 seconds 3: 35 seconds or more and less than 45 seconds 2: 45 seconds or more and less than 55 seconds 1: 55 seconds or more
  • Film thickness change rate
  • photosensitive compositions 3 to 96 were applied and dried at 90° C. for 1 minute to form a film with a thickness of 3 ⁇ m .
  • the residual film ratio of the cured film formed by heating at 90° C. for 30 minutes after exposure to ultraviolet rays was good, being in the range of 85 to 100%.
  • Image display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Orientation layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Orientation layer 25 Polarizing plate 30 Backlight unit 31
  • White LED light source LC Liquid crystal 300
  • Infrared sensor 310
  • Solid-state imaging device 311
  • Infrared cut filter 312
  • Color filter 313
  • Infrared absorption transmission filter 314

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CN119707775A (zh) * 2023-09-26 2025-03-28 常州强力先端电子材料有限公司 一种咔唑肟酯光引发剂及其制备方法和应用

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